Mixture of elastomeric composites and methods of obtaining them
Abstract
Elastomer composite blends are produced by novel wet/dry mixing methods and apparatus. In the wet mixing step or stage, fluid streams of particulate filler and elastomer latex are fed to the mixing zone of a coagulum reactor to form a mixture in semi-confined flow continuously from the mixing zone through a coagulum zone to a discharge end of the reactor. The particulate filler fluid is fed under high pressure to the mixing zone, such as to form a jet stream to entrain elastomer latex fluid sufficiently energetically to substantially completely coagulate the elastomer with the particulate filler prior to the discharge end. Highly efficient and effective elastomer coagulation is achieved without the need for a coagulation step involving exposure to acid or salt solution or the like. Elastomer composites are produced. Such elastomer composites may be cured or uncured, and combine material properties, such as choice of filler, elastomer, level of filler loading, and macro-dispersion, nor previously achieved. The coagulum produced by such wet mixing step, with or without intermediate processing steps, is then mixed with additional elastomer in a dry mixing step or stage to form elastomer composite blends. The additional elastomer to the coagulum may be the same as or different from the elastomer(s) used in the wet mixing step. <IMAGE>

Term
Term ended
Expired 28 September 2018, 8 years ago.
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7 claims: 1 independent, 6 dependent
- 1Sposób wytwarzania mieszanki kompozytów elastomerowych zawierającej elastomer, ziarnisty napełniacz i ewentualnie inne składniki, polegający na tym, że wprowadza się w ciągłym przepływie pierwszy płyn zawierający lateks elastomeru do strefy mieszania reaktora koagulatu, wprowadza się w ciągłym przepływie drugi płyn zawierający ziarnisty napełniacz pod ciśnieniem do strefy mieszania reaktora koagulatu w celu wytworzenia mieszaniny ziarnistego napełniacza z lateksem elastomeru, przy czym ziarnisty napełniacz powoduje koagulację lateksu, a mieszanie pierwszego płynu z drugim płynem w strefie mieszania dostarcza energii wystarczającej do zasadniczo całkowitego skoagulowania lateksu elastomeru z ziarnistym napełniaczem w reaktorze koagulatu;i odbiera się zasadniczo w ciągłym przepływie kompozyt elastomerowy z reaktora koagulatu;znamienny tym, że kompozyt elastomerowy miesza się na sucho z dodatkowym elastomerem z wytworzeniem mieszaniny kompozytu elastomerowego.
- 2Sposób według zastrz. 1, znamienny tym, że lateks elastomeru i dodatkowy elastomer wybiera się niezależnie spośród kauczuku naturalnego, chlorowanego kauczuku naturalnego, homopolimeru, kopolimeru i terpolimerów 1,3butadienu, styrenu, izoprenu, izobutylenu, 2,3-dimetylo-l,3-butadienu, akrylonitrylu, etylenu i propylenu, rozcieńczonych olejem pochodnych dowolnych z nich i mieszaniny dowolnych z nich, ziarnisty napełniacz wybiera się spośród sadzy, koloidalnej krzemionki, krzemionki strącanej, powlekanych sadzy, sadzy z chemicznymi grupami funkcyjnymi, silikonowanej sadzy i mieszaniny dowolnych z nich.
- 3Sposób według zastrz. 1 albo 2, znamienny tym, że dodatkowy ziarnisty napełniacz wprowadza się podczas mieszania na sucho kompozytu elastomerowego z dodatkowym elastomerem.
- 4Sposób według zastrz. 3, znamienny tym, że dodatkowy ziarnisty napełniacz miesza się z dodatkowym elastomerem przed mieszaniem na sucho kompozytu elastomerowego z dodatkowym elastomerem.
- 5Sposób według zastrz. 1 albo 2, albo 4, znamienny tym, że do strefy mieszania reaktora koagulatu wprowadza się dodatek wybrany spośród antyozonantów, przeciwutleniaczy, zmiękczaczy, środków ułatwiających przetwórstwo, żywic, środków przeciwpalnych, olejów rozcieńczalników, środków smarnych i mieszanin dowolnych z nich.
- 6Sposób według zastrz. 1 albo 2, albo 4, znamienny tym, że lateks elastomerowy i dodatkowy elastomer wybiera się niezależnie spośród lateksu kauczuku naturalnego, lateksu kauczuku SBR, lateksu kauczuku butadienowego;dodatkowy elastomer występuje w ilości równej 50% do 90% wagowych w stosunku do całkowitej ilości elastomeru w mieszance kompozytu elastomerowego;i mieszanka kompozytu elastomerowego zawiera od 30 do 85 części wagowych sadzy na 100 części wagowych.
- 7Sposób według zaostrz. 1 albo 2, albo 4, znamienny tym, że reaktor koagulatu określa wydłużoną strefę koagulatu przechodzącą od strefy mieszania do końca odbioru ze stopniowo wzrastającym polem przekroju.
Independent claims7
1,790 paragraphs in 1 section, as filed
The present invention relates to a method of producing a blend of elastomer composites. More particularly, the invention relates to a method of making an elastomer composite blend having filler particles finely dispersed throughout the elastomer.
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Numerous products of commercial interest are formed from elastomeric compositions in which a particulate filler is dispersed throughout each of a variety of synthetic elastomers, natural rubber, or elastomeric mixtures. For example, carbon black is widely used as a reinforcing agent in natural rubber and other elastomers. It is common to use a masterbatch that is a premix of filler, elastomer, and various optional additives such as filler oil, and then in some cases, blending such masterbatch with additional elastomer in a subsequent mixing step. The carbon black masterbatch is made of various grades of commercially available carbon black that varies in both surface area per unit weight and "structure". Numerous products of commercial interest are formed from such elastomeric compositions with a carbon black particulate filler dispersed in natural rubber. Such products include, for example, automobile tires, which can use a variety of elastomer compositions for the tread portions, sidewalls, bead sheaths, and tire carcass. Other products include, for example, engine mount airbags, V-belts, windshield wipers and more. Although a wide range of performance characteristics can be achieved using currently available materials and manufacturing techniques, there has been a long-standing need in the industry to develop elastomer compositions having improved properties and to reduce the cost and complexity of current manufacturing techniques. In particular, it is known, for example, that the level of macro-dispersion, i.e. homogeneity of the dispersion of a carbon black or other filler in an elastomer, can significantly influence the performance characteristics. For elastomeric compositions made by vigorously mixing carbon black or other filler with natural rubber or other elastomer (such as in a Banbury mixer or the like), any increase in macrodispersion requires longer or more vigorous mixing and consequently has the disadvantages of increased energy costs, production time, and the like make it happen. For carbon black fillers with certain surface area and structural characteristics, dispersion beyond a certain degree was not possible or commercially practiced using known mixing equipment and techniques. In addition, such prolonged or more intense mixing destroys natural rubber by breaking the polymer chains of the natural rubber elastomer and thus reduces its molecular weight, making the final elastomeric compound undesirable for certain applications. When used in tire treads, for example, the reduced molecular weight results in an undesirable reduction in the so-called rolling resistance of the tread.
It is well known to use carbon blacks having a higher or lower structure and surface area to manipulate the performance characteristics of an elastomeric composition. Higher surface area carbon blacks are known to improve fracture growth resistance and delamination resistance as well as abrasion resistance in general and other performance qualities. The commercially available mixing techniques could not achieve perfect homogeneity of the carbon black dispersion in the elastomer, however, without unacceptable decomposition of the natural rubber. Indeed, for a common carbon black level in natural rubber, such as 45 to 75 parts per hundred parts by weight, and an oil content of 0 to 10 parts per hundred parts by weight, low structure carbon blacks such as carbon blacks with a DBPA of less than 110 cc / 100 g, especially those having a surface area greater than about 45 m<sup>2</sup>/ g up to 65 m<sup>2</sup>/ g (CTAB), it was not possible to achieve compounds having less than about 1% undispersed carbon black (measured as macrodispersion as described below), regardless of duration and mixing intensity.
Furthermore, while theoretical analysis has indicated desirable improvements in some performance characteristics of elastomeric compositions using higher surface area and lower structure carbon blacks, it has not been possible to use known physical milling or other mastic processes to obtain elastomeric compositions that achieve both well-preserved natural rubber molecular weight, as well as a satisfactory level of carbon black macrodispersion. It has generally been found that e.g. However, with extremely fine carbon blacks, it is known to encounter an abnormal condition in which the expected performance improvement is not achieved. It is understood that this results, at least in part, in the inability of conventional elastomer development techniques to adequately disperse the soot in the natural rubber without unnecessarily breaking up the elastomeric polymer. So in conse4
189 Thus, there has been an inability to fully benefit from the natural affinity of carbon black and natural rubber with each other for such carbon blacks.
Since good carbon black dispersion in natural rubber compounds has sometimes been recognized as one of the most important goals in achieving good product quality and consistent product performance, considerable effort has been made to design procedures to evaluate the dispersion quality in rubber. Planned methods include, for example, the Cabot Dispersion Chart and various image analysis procedures. The quality of the dispersion can be defined as the state of the mixing obtained. The ideal carbon black dispersion is the state where the carbon black agglomerates (or lumps) break down into aggregates (obtained by dispersion mixing) homogeneously separated from each other (obtained by separating mixing), with the surfaces of all carbon black aggregates completely embedded by a rubber matrix (usually quoted as an introduction).
Common problems in the rubber industry that often accompany poor macrodispersion can be classified into four main categories: product performance, product defects, surface appearance and dispersion performance. The functional performance and durability of the rubber formulation, such as the elastic force, fatigue life, wear resistance, are essentially influenced by the quality of the dispersion. Undispersed carbon black also causes surface defects on the final product, including visible defects. Removing the presence of surface defects is critical in cast thin parts for functional reasons and in extruded profiles for both aesthetic and functional reasons.
A commercial image analyzer, such as the model IBAS Compact image analyzer available from Kontron Electronic GmbH (Munich, Germany), can be used to measure carbon black or other filler macrodispersion. Typically, in quantitative macro-dispersion tests used in the rubber industry, the critical cut-off size is 10 micrometers. Defects greater than about 10 micrometers in size typically consist of undispersed soot or other filler, as well as any sand or other contaminants that can affect both visual and functional performance. Thus, measuring macrodispersion involves measuring surface defects (formed by microcuts, embossing, or cutting) greater than 10 microns in size through the entire area of such defects per unit area of interest using an image analysis procedure. The macrodispersion D (%) is calculated as follows:
% non-dispersed area (%)<sup>:</sup> ν<sup>-</sup>'»
N, πϋ where
AND<sub>m</sub> = total area of the test sample area
N, = number of lesions of size Dj
D, = diameter of the wheel having the same area as that of the damage (wheel diameter equivalent) m = number of shots
Macrodispersion of carbon black or other filler in uncured natural rubber or other suitable elastomer can be estimated by image analysis of the notched surface samples. Typically, five to ten arbitrarily selected optical images of the cut surface are taken for image analysis. Knife marks and others are preferably removed using a numerical filtering technique. Cut surface image analysis thus provides information including the dispersion quality of the carbon black inside the natural rubber compound. Specifically, the percent undispersed area D (%) indicates the quality of the carbon black macrodispersion. As the macro-dispersion quality decreases, the percentage of non-dispersed area increases. Thus, the dispersion quality can be improved by reducing the percentage of non-dispersed area. As noted above, mixing operations have a direct effect on mixing efficiency and on macrodispersion. Generally, a better carbon black macrodispersion is achieved in an elastomer, e.g. in a natural rubber suburb, by longer mixing and by more intensive mixing. However, achieving better macro-dispersion by longer and more vigorous agitation degrades the elastomer into which the soot is dispersed. This is especially problematic with rubber
189 105 natural, which is very susceptible to mechanical / thermal decomposition. Longer and more intensive mixing, using known mixing techniques and equipment, such as a Banbury mixer, reduces the molecular weight of the natural rubber premix composition. Thus, it is known that an improved carbon black macrodispersion in natural rubber is achieved with a corresponding, generally undesirable reduction in the molecular weight of the rubber.
In addition to dry mixing techniques, it is known to continuously add latex and a slurry of carbon black to an agitated coagulation tank. Such "dry" techniques are commonly used with a synthetic elastomer such as SBR. The coagulation tank contains a coagulant such as salt or an aqueous acid solution, typically having a pH of about 2.5 to 4. The latex and the carbon black slurry are mixed and coagulated in a coagulation tank into small spheres (usually a few millimeters in diameter) referred to as wet particles. The fines and the acidic influencing agent are separated, usually by a vibrating shaker screen or the like. The particles are then transferred to a second agitated tank where it is rinsed in order to obtain a neutral or near neutral pH. There, the particles are subjected to additional steps of vibrating screening and drying and the like. Variants of this method have been suggested in terms of coagulation of natural and synthetic elastomers. Hagopian et al., 4,029,633, to which Cabot Corporation is assigned to the present invention, describes a continuous process for making an elastomer masterbatch. An aqueous slurry of carbon black is prepared and mixed with a natural or synthetic elastomer latex. This mixture is subjected to a so-called creaming operation, optionally using any known creaming agent. After creaming, the carbon black / latex mixture is introduced as a single coherent stream into the core of the coagulating fluid stream. The solid stream of creamed carbon black / latex mixture is believed to be sheared and sprayed through a stream of coagulating fluid prior to coagulation and then passed to the appropriate reaction zone to complete coagulation. After such a coagulation step, the rest of the process is essentially conventional, including separating the fines from the "serum" waste product and washing and drying the fines. A somewhat similar process is described in US Patent No. 3,048,559 to Heller et al. The aqueous carbon black slurry is continuously mixed with a stream of natural or synthetic elastomer or latex. The two streams are mixed under the conditions described as involving high hydraulic turbulence and impact. As in the above-mentioned Hagopian et al. Patent, the combined stream of the carbon black and latex elastomer slurry is then coagulated by adding acid or a coagulating salt solution.
US Patent 4,303,569 teaches the coagulation of an aqueous latex with an aqueous coagulant which may be an inorganic acid such as hydrochloric and sulfuric acid, and aqueous solutions of inorganic electrolytes such as alkali and alkaline earth metal sulfates and alum.
US 1611278 describes a rather typical older technology in which carbon black is dispersed in water and mixed with a natural latex, after which mechanical agitation must be applied to achieve coagulation, i.e. after mixing the liquid latex and the liquid filler. In addition, this specification uses a standard fluid mixer. Such use of the mixer in the above description is only for coagulation after mixing the components - carbon black and latex dispersion. Further, in step (c) claim 1 of the abovementioned description states, "mechanical agitation of the pre-mixed powdered component and latex to form a coagulum", which would lead the skilled person to the conclusion that the mixing of the latex and liquefied solid filler particles must have further steps, namely mechanical stirring or agitation, to achieve coagulation. .
There has long been a need in a variety of industries for elastomeric compounds with a particulate filler dispersed in a suitable elastomer, having improved macrodispersion, especially for example carbon black dispersed in natural rubber mixed with another elastomer. As discussed above, improved macro-dispersion can provide correspondingly improved aesthetic and functional characteristics. Particularly desirable are the new elastomeric compounds of carbon black in a mixture with a natural rubber and a synthetic elastomer in which an improved macro-dispersion is achieved together with a higher molecular weight of the natural rubber. It is an object of the present invention to meet some or all of these long felt needs.
189 105
According to the invention, a method for producing an elastomer composite blend containing elastomer, granular filler and optionally other ingredients, which comprises introducing a first fluid containing elastomer latex in a continuous flow into the mixing zone of the coagulum reactor, the second fluid containing the granular filler is continuously fed under pressure into the mixing zone of the coagulum reactor to form a granular filler-elastomer latex mixture, the granular filler causing the latex to coagulate and mixing the first fluid with the second fluid in the mixing zone provides substantially sufficient energy for the mixing zone. completely coagulating the elastomer latex with the granular filler in the coagulum reactor; discharging a substantially continuous flow of the elastomer composite from the coagulum reactor; characterized in that the elastomer composite is dry blended with the additional elastomer to form an elastomer composite blend.
Preferably, the elastomer latex and the additional elastomer are independently selected from natural rubber, chlorinated natural rubber, homopolymer, copolymer and terpolymers of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene and propylene, oil-diluted derivatives of any thereof, and mixtures of any thereof, the particulate filler is selected from carbon black, colloidal silica, precipitated silica, coated carbon blacks, chemically functional carbon black, siliconized carbon black, and mixtures of any thereof.
Preferably, additional granular filler is introduced while dry blending the elastomer composite with the additional elastomer.
Preferably, the additional granular filler is mixed with the additional elastomer prior to dry blending the elastomer composite with the additional elastomer.
Preferably, an additive selected from antiozonants, antioxidants, plasticizers, processing aids, resins, anti-flammable agents, diluent oils, lubricants and mixtures of any of these is introduced into the mixing zone of the coagulum reactor.
Preferably, the elastomer latex and the additional elastomer are independently selected from natural rubber latex, SBR rubber latex, butadiene rubber latex;
the additional elastomer is present in an amount of 50% to 90% by weight based on the total amount of elastomer in the elastomer composite blend; and the elastomer composite blend contains from 30 to 85 parts by weight of carbon black per 100 parts by weight.
Preferably, the coagulum reactor defines an elongated zone of the coagulum extending from the mixing zone to the end of discharge with a gradually increasing cross-sectional area.
According to a first aspect, the method of making elastomer composite blends comprises first forming an elastomer masterbatch by simultaneously feeding the particulate filler fluid and the elastomer latex fluid to the mixing zone of the coagulation reactor. Preferably, the coagulation reactor has an elongated coagulation zone which extends from the mixing zone, most preferably having a progressively increasing cross-sectional area downstream towards the exit of the coagulum reactor. The elastomer latex can be either natural or synthetic, and the particulate filler fluid includes carbon black or other particulate filler to effectively coagulate the latex. The particulate filler fluid is fed to the mixing zone, preferably in the form of a continuous high velocity injection of the injected fluid, while the latex fluid is fed at a slow speed. The velocity, flow rate, and particle concentration of the particulate filler fluid are sufficient to provide the mixture of high shear latex fluid and turbulent flow of the mixture in at least the upper portion of the coagulation zone so as to substantially completely coagulate the latex with the particulate filler upstream of the exit port. Substantially complete coagulation can thus be obtained, according to the preferred embodiments, without the need for the use of an acid or salt coagulation agent. The coagulated product of this wet blending step is then dry blended with additional elastomer to form an elastomer composite blend. Such additional elastomer may be the same or different from the elastomer used in the wet mixing step. Optionally, additional filler may be added during the dry mixing step. Such additional filler may be the same or different to the particulate filler used in the wet mixing step.
The elastomer composite blends are provided as a product of the process of the invention. The process of the invention provides novel elastomer composite blends having a macrodispersion level of the particulate filler, the molecular weight of the elastomer, the level of particle content, the choice of particulate filler (including e.g. a carbon black filler with an extremely high surface area and low structure) and / or other features not obtained earlier. In this regard, the elastomeric composite blends obtained by the process of the invention have excellent macro-dispersion, even with certain fillers such as carbon black having a structure to surface area ratio DBP: CTAB of less than 1.2, and even less than 1, in elastomers such as rubber. natural, etc., with little or no reduction in the molecular weight of the elastomer. In accordance with still other aspects of the invention, there are provided intermediates as well as end products that are formed from the blends of elastomer composites made by the process of the invention. Macrodispersion as used herein means the macrodispersion D (%) of the particulate filler, measured as a percentage of the undispersed area for damage greater than 10 micrometers. In the blends of elastomeric composites disclosed herein containing natural rubber, the molecular weight of the natural rubber, or Mw<sub>WITH(</sub>, and the (average weight) part of the sol is preferably at least about 300,000, more preferably at least about 400,000, with in some preferred embodiments between 400,000 and 900,000. The composite elastomer mixtures optionally include a filling oil, such as about 0 to 20 parts per hundred parts by weight, more preferably about 0 to 10 parts by weight of filling oil, and / or other ingredients such as are well known for optional use in the development of natural rubber and / or other elastomers with carbon black and / or other fillers. As discussed further below in connection with certain preferred exemplary embodiments, the novel elastomer composite blends disclosed herein can provide highly desirable physical properties and performance characteristics. Accordingly, the invention represents a significant technological advance.
These and other aspects and advantages of the various embodiments of the invention will become apparent. from a detailed discussion of certain preferred embodiments.
The following discussion of some preferred embodiments will make reference to the accompanying drawings in which:
Fig. 1 is a schematic illustration of a flowchart of an apparatus and method for producing elastomeric masterbatch in accordance with certain preferred embodiments;
Fig. 2 is a partially schematic elevation view of the preferred embodiment according to the schematic illustration of the flowchart of Fig. 1;
Fig. 3 is a partially schematic elevation view of an alternative embodiment according to the schematic and illustration of the flowchart of Fig. 1;
Fig. 4 is a partially sectioned elevational view of the mixing head / coagulum reactor assembly according to the embodiment of Fig. 3;
Fig. 5 is an elevation view, partially in section, corresponding to that of Fig. 4, illustrating an alternative preferred embodiment;
Fig. 6 is a section through the line 6-6 in Fig. 5;
Fig. 7 is a sectional view of a mixing head suitable for use in an alternative preferred embodiment;
Fig. 8 is a graph showing the surface area and structure properties (CTAB and DBPA) of the carbon black used in some highly preferred masterbatch compositions in accordance with the present invention;
Figures 9-25 are graphs showing macrodispersion, molecular weight of natural rubber, and / or other characteristics of the novel elastomer composites of this invention, including the carbon blacks shown in Figure 8, together with data relating to controls for comparison in some cases. an exemplary listing of the significant improvements in physical and performance characteristics achieved by elastomer composites;
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Figures 26-29 are graphs showing carbon black morphological properties, i.e. structure (DBPA) and surface area (CTAB), and identifying carbon black regions or zones (by such morphological properties) that are suitable for specific product applications; and
Figures 30 and 31 are graphs showing macrodispersion and molecular weight of natural rubber of the novel elastomer composites of this invention, together with controls for comparison.
It should be understood that the attached drawings are not necessarily necessary for the assessment. Certain features can be increased or decreased for the convenience or clarity of the illustration. Directional references used in the following discussion are based on the orientation of the components illustrated in the drawings, unless otherwise specified or otherwise indicated in the context. In general, the device in accordance with various embodiments of the invention may be used in a variety of settings. From the following description, it is possible to determine appropriate dimensions and directions for the device of the invention using routine technical feasibility and taking into account well-known factors determined for the intended application, such as desired production volumes, material selection, duty cycle, and the like. Reference numbers used in one drawing may be used in other drawings for the same feature or element.
Based on the method and equipment disclosed herein, elastomer composite blends are prepared including (i) a continuous flow made elastomer masterbatch containing elastomer latex and particulate filler blend fluids at a level of turbulence and flow control conditions sufficient to achieve coagulation. even without the use of traditional coagulating agents, and (ii) additional elastomer added to such elastomer masterbatch in a dry blending step. In fact, the great commercial benefit will be known immediately: (A) that elastomer masterbatch particles are obtained, i.e., a coagulated latex is obtained according to the "wet blending" step of the present method, without the need for extensive dry mastication of the elastomer with a filler, or exposure of the liquid latex / particulate composition to a stream or tank a coagulant, and (B) that an elastomer composite mixture is obtained by a "dry blending" step, including dry blending such a masterbatch with additional elastomer. Thus, in routine commercial implementation, the cost and complication of using acidic coagulation solutions can be avoided. Prior techniques involving pre-mixing of latex and particles, such as in the aforementioned Heller et al. And Hagopian et al., Do not even recognize the possibility of obtaining coagulation without exposing the latex / particle mixture to a conventional coagulant solution with its associated cost and impossibility. remove defects.
The preferred flexibility is achieved by the wet / dry mixing method disclosed in the lesser for making the elastomer composite blend. In particular, flexibility is provided by selecting the elastomer (s) used in the fluid or "wet-blending" step and selecting the elastomer (s) used in the subsequent "dry-mixing" step. The same mixture of elastomer (or elastomers) may be used in the wet and dry mixing steps, or alternatively, different elastomers may be used in any suitable relative weight ratio. Additional flexibility is provided by the fact that additional filler can optionally be added during the dry blending step. Such additional filler may be the same as or different from the particulate filler used in the wet mixing step. Preferably, in the preferred embodiments of the process disclosed herein, the excellent macrodispersion of the particulate filler obtained in the filler premix produced by the wet mixing step is maintained or even further improved in the subsequent dry mixing step. Without wishing to be bound by theory, it is now understood that, at least in certain preferred embodiments, the multiphase composite elastomer blend is produced by the wet / dry process disclosed herein. That is, despite difficulties with identification or observation using techniques generally used in the elastomer industry, it is understood that the elastomer composite blend comprises at least one elastomeric phase formed during the dry blending step. The degree of mixing of the two phases, and the degree to which the boundary layers between the two phases are more or less different, will depend on many factors, including e.g. the mutual affinity of the elastomer from the wet and dry mixing step, the level of the particle content, the selection of the particulate filler (s), whether additional filler was added during the dry mixing step, the relative weight fraction of the elastomer in the wet mixing step and the elastomer from the step dry mixing, etc.
The advantageous flexibility obtained by the present invention and its use to better control the distribution of the filler between two different elastomeric phases in the elastomer composite blend can be seen in the example of the elastomer composite mixture containing natural rubber. butadiene rubber (referred to in this discussion, in some cases as "BR"); and carbon black filler. In accordance with previously known dry / wet blending techniques, the carbon black may be blended with the natural rubber using blending techniques followed by addition and further blending of BR. Disadvantageously, much of the carbon black will migrate to the BR phase because of its affinity for the BR phase and less than the desired macrodispersion of the carbon black in the natural rubber phase. In comparison, the improved performance properties of comparable elastomer composite blends made by the wet / dry mixing method disclosed herein indicate that more carbon black is retained in the natural rubber phase when the carbon black is mixed with the natural rubber in the initial mixing step followed by the addition of BR in the next dry mixing stage.
In the wet mixing step of the method disclosed herein, the feed rate of the latex fluid and particulate filler fluid to the mixing zone of the coagulation reactor can be precisely measured to obtain high rates of throughput, with little free latex and little undispersed filler in the product particles at outlet end of the coagulation reactor. Without wishing to be bound by theory, it is now known that a more or less monophasic system is established in the mixing zone, except that coagulated solids are formed there and / or downstream of them in the coagulation zone. The extremely high speed of feeding the particulate filler fluid into the mixing zone of the coagulation reactor, and the differential speed to the latex fluid feed, are considered important in obtaining sufficient turbulence, i.e. sufficient shear energy of the latex by impinging the injection of the particulate filler fluid for thorough mixing and particle dispersion in the latex fluid, and coagulation. The high agitation energy produces product premix particles with excellent dispersion, along with controlled product delivery. A coagulum is formed and then formed into the desired extrudate. The particulate filler fluid and elastomer latex are preferably fed continuously, meaning that the flow of the coagulated premix from the mixing zone to the outlet of the coagulation reactor is established while the flow of the feed fluids is kept uninterrupted. Typically, the uninterrupted flow of the feed fluids and the simultaneous discharge of the coagulated premix are maintained for one or several hours, preferably, e.g., greater than 24 hours, and even possibly for a week or more.
Some preferred embodiments of the methods and apparatus for making the novel blends of the elastomeric composites disclosed herein are discussed below. Although the various preferred embodiments of the invention may employ a wide variety of fillers and elastomers, certain portions of the following detailed description of an aspect of the method and apparatus of the invention will in some cases, for convenience, describe a masterbatch comprising natural rubber and carbon black. One skilled in the art will be able, using this description, to utilize the method and apparatus disclosed herein in accordance with the principles of the operation discussed herein to make elastomer composite masterbatch and blends containing numerous alternative or additional elastomers, fillers, and other materials. Briefly, preferred methods for making an elastomeric masterbatch include feeding a carbon black or other filler slurry and natural rubber latex fluid or other suitable elastomeric fluid simultaneously to the mixing zone of the coagulation reactor. The coagulation zone extends from the mixing zone, preferably progressively increasing the cross-sectional area downward from the inlet end to the outlet opening. The slurry is fed to the mixing zone preferably as a continuous high velocity injection of the injected fluid, while the natural rubber latex fluid is fed at a relatively low velocity. High speed, flow rate
189 105 and the particle content of the filler slurry are sufficient to cause the mixture to cause high shear latex fluid, turbulence in the mixture flow in at least the upper part of the coagulation zone, and substantially complete coagulation of the elastomer latex upstream of the outlet. In this way, substantially complete coagulation can be achieved, according to the preferred embodiments, without the need for acid or salt coagulation agents. The preferred method for producing continuous flow elastomer composites involves continuously and simultaneously feeding the latex fluid and filler slurry to the mixing zone of the coagulation reactor, establishing a continuous, semi-restricted flow of the latex mixture and filler slurry in the coagulation zone. The elastomeric composite particles in the form of "worms" or globules are discharged from the outlet of the coagulation reactor in the form of a substantially constant flow simultaneously with the passing of the latex streams and the soot slurry to the mixing zone of the coagulation reactor. In particular, plug-type flow and atmospheric or near atmospheric pressure conditions at the outlet of the coagulation reactor are highly advantageous, facilitating the control of the elastomer composite product, such as for immediate or subsequent further processing steps. The feed rate of the natural rubber latex fluid and the carbon black slurry into the mixing zone of the coagulation reactor can be accurately metered to obtain high rates of efficiency, with little free latex and little undispersed filler in the product particles at the exit of the coagulation reactor. Without wishing to be bound by theory, it is now known that a more or less monophasic system is established in the mixing zone, except that coagulated solids are formed there and / or further in the coagulation zone. The extremely high speed of feeding the particulate filler fluid to the mixing zone of the coagulation reactor and the differential speed to the latex fluid feeding are considered important in obtaining sufficient turbulence, i.e. sufficient shear energy of the latex by the injection momentum of the particulate filler fluid for thorough mixing and particle dispersion in the latex fluid, and coagulation. The high mixing energy results in a new product with excellent dispersion, together with a controlled product delivery. A coagulum is formed and then formed into the desired extrudate.
The elastomer composite produced by the above-described wet mixing technique and equipment forms the elastomer composite mixtures of the invention by sequential wet mixing with additional elastomer. Thus, the present invention can be described as involving a wet / dry process, while prior art techniques have used a dry / dry method in which a premix is first formed by dry blending and additional elastomer is added by additional dry blending. The dry mixing step of the wet / dry mixing method of the present invention may be performed with commercially available equipment and techniques, including, e.g., Bandura mixers and the like. The additional elastomer added during the dry blending step of the wet / dry blending method disclosed herein may be one or more elastomers that are the same or different from the elastomer (s) used to form the masterbatch. Other ingredients may also be added along with additional elastomer during the dry mixing step, including e.g., filling oil, additional particulate filler, hardeners, etc., in those embodiments where additional particulate filler is added during the dry mixing step, such additional the filler may be the same as or different from the filler (s) used in the premix formed by the wet mixing step.
The aforementioned preferred apparatus and techniques for making blends of elastomer composites disclosed herein are discussed in connection with the accompanying drawings, wherein the continuous-flow wet-blending step of making an elastomeric masterbatch employs a continuous, semi-restricted flow of elastomer latex, e.g. natural rubber latex. (half latex or concentrate) mixed with a filler suspension, e.g. an aqueous suspension of carbon black in a coagulation reactor forming an elongated coagulation zone which extends, with a preferably progressive increase in cross-sectional area, from the inlet end to the outlet end. The terms "semi-restricted" flow means that the flow path after the mixed latex fluid and the filler slurry in the coagulation reactor is closed or substantially closed upstream of the mixing zone and is open at the opposite, lower end of the reactor. coagulation, that is, at the outlet end of the coagulation reactor. The turbulence conditions at the top of the coagulation zone are maintained continuously, at least in a more or less steady state, together with substantially plug-type flow conditions at the open outlet end of the coagulation reactor. The discharge end is "open" at least in the sense that it allows the coagulum to discharge, generally at or near atmospheric pressure, and typically, by simple gravity drop (possibly inside a flow path with reinforcement or screen) to a suitable collection means, such as feed hopper of the dewatering extruder. Thus, the semi-restricted flow causes a turbulence gradient extending axially or longitudinally within at least a portion of the coagulation reactor. Without wishing to be bound by theory, it is now believed that the coagulation zone substantially allows for high turbulence mixing and coagulation at the top of the coagulation reactor, together with an essentially plug-type solid product outlet flow at the outlet end. The injection of carbon black or a slurry of other filler by continuous injection into the mixing zone occurs continuously simultaneously with the ease of collecting fines of elastomer masterbatch discharged under substantially plug-type flow conditions and generally ambient pressure at the discharge end of the coagulation reactor. Likewise, the axial velocities of the slurry through the slurry nozzle into the mixing zone and usually, at the upper end of the coagulation zone, are substantially higher than at the discharge end. The axial velocity of the slurry will typically be tens of meters per second upon entering the mixing zone, preferably from a feed pipe with a small axial bore diameter, in accordance with the preferred embodiments discussed below. The axial velocity of the resulting flow at the inlet end of the coagulation reactor with increasing cross-sectional area in a conventional application may be e.g. 1.5-6.1 m / s, typically 2.1-4.6 m / s. In contrast, at the outlet end, the axial velocity of the discharged product of the masterbatch fines will typically be about 0.30-3.0 m / s, and more generally 0.6-1.5 m / s. Thus, the above-mentioned semi-restricted turbulent flow achieves the very significant advantage that the latex of the natural rubber or other elastomer coagulates by mixing with carbon black or other filler even in the absence of post-treatment in the stream or reservoir of acid, salt or other coagulating solution, with controlled, preferably, delivery. more or less formed product from the coagulation reactor for subsequent treatment.
It should be understood in this regard that the reference to the coagulation reactor as "open" at the outlet end is not intended to mean that the outlet end is necessarily displayed or easily accessible by hand. Instead, it may be permanently or releasably attached to a collecting device or subsequent processing device, such as a divider (discussed further below), a dryer, etc. The outlet end of the coagulation reactor is open in the essential sense, wherein the turbulent flow inside the coagulation zone of the coagulation reactor which is under high pressure and sealed against any significant backward movement (i.e. upward) in the mixing zone, which allows the above-mentioned pressure to be established. and / or a velocity gradient as it travels towards and from the exit end.
It should also be recognized in this regard that the turbulence decreases with the coagulation reactor towards the outlet end, depending on factors such as percentage of capacity utilization, material selection and others. Reference herein to a substantially plug flow at or before the outlet end of the coagulation reactor should be understood in light of the fact that the outlet end flow consists primarily or entirely of premix particles, ie globules or "worms" of the coagulated elastomer masterbatch. The particles are usually more or less shaped into the interior of the coagulation zone at the point along the coagulation zone where the flow essentially becomes plug flow. The still advancing mass of "worms" or globules preferably have a piston-type flow in the sense that they move generally or primarily axially towards the outlet end at any point in time in a given cross-section of the coagulation zone at the outlet end, have a completely uniform velocity, so that they are easily collected and inspected for further processing. Thus, the fluid phase mixing aspect disclosed herein may be advantageously applied
189 105 must be performed under steady-state or more or less steady-state conditions, which results in a high level of product uniformity.
A preferred embodiment of wet mixing according to the method and apparatus disclosed herein is schematically illustrated in Fig. 1. Various aspects of the system configuration, component selection and so on will depend to some extent on the particular characteristics of the intended applications. Thus, for example, factors such as maximum batch capacity and flexibility in material selection will affect the size and distribution of system components. Generally, such considerations will be possible for those skilled in the art using the present specification. It can be seen that the system illustrated in Fig. 1 comprises means for feeding natural rubber latex or other elastomer latex fluid at low pressure and low velocity continuously into the mixing zone of the coagulation reactor. More particularly, there is provided a pressure vessel 10 for maintaining the latex supply under pressure. Alternatively, a latex storage tank provided with a peristaltic pump or a plurality of pumps or other suitable feed means adapted to maintain a fluid supply of elastomer latex via feed line 12 to mixing zone of coagulation reactor 14 may be used. The latex fluid in reservoir 10 may be held under air or nitrogen or other pressure such that the latex fluid is fed to the mixing zone at a line pressure of preferably less than 68.9 kPa, preferably about 13.8-55.2 kPa, and typically about 34.5 kPa. Latex supply pressure and flow lines, connections etc. Latex supply means should be set to cause shear in the flowing latex fluid as low as reasonably possible. Preferably, all flow lines, e.g., are smooth, with only large radius twists, if any, and smooth or streamlined connections between the lines. The pressure is selected so as to obtain a flow velocity of me greater than about 3.7 m / s.
Suitable elastomer latex fluids include both natural and synthetic elastomer latexes and latex mixtures. Of course, the latex must be suitable for coagulation by the particulate filler selected and must be suitable for the intended purpose or use of the final rubber product. Those skilled in the art will be able to select a suitable elastomer latex or a suitable blend of elastomeric latexes for use in the methods and devices disclosed herein using this specification. Exemplary elastomers include, but are not limited to, rubbers, polymers (e.g., homopolymers, copolymers, and / or terpolymers) of 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3-butadiene, acrylonitrile, ethylene, and propylene, and similar. The elastomer may have a glass transition temperature (Tg) as measured by Differential Scanning Calorimetry (DSC), ranging from about -120 ° C to about 0 ° C. Examples include, but are not limited to, styrene-butadiene rubber (SBR), natural rubber and its derivatives such as chlorinated rubber, polybutadiene, polyisoprene, poly (styrene-co-butadiene), and filler oil derivatives of either. Mixtures of any of the above can also be used. Latex may be present in the aqueous carrier fluid. Alternatively, the fluid carrier may be a hydrocarbon solvent. In any event, the elastomer latex fluid must be suitable for controlled continuous feeding at the appropriate speed, pressure and concentration to the mixing zone. Particular suitable synthetic rubbers include: copolymers having from about 10 to about 70% by weight of styrene and from about 90 to about 30% by weight of butadiene, such as a copolymer comprising 19 parts of styrene and 81 parts of butadiene, a copolymer comprising 43 parts of styrene and 57 parts of butadiene and a copolymer consisting of 50 parts styrene and 50 parts butadiene; conjugated diene polymers and copolymers such as polybutadiene, polyisoprene, polychloroprene, and others, and copolymers of such conjugated dienes with an ethylene group-copolymerizable monomer such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, 5-vinylpyridine, -2-vinyl-5-pyridine, 5-ethyl-2-vinylpyridine. 2-methyl-5-vinylpyridine , alkyl substituted acrylates, vinyl ketone, methyl isopropyl ketone, methyl vinyl ether, alpha methylene carboxylic acids and their esters, and amides such as acrylic acid and dialkylacrylic acid amide. Also suitable for adaptations herein are ethylene and other alpha olefin copolymers such as propylene, butene-1, and pentene-1.
The additional elastomer added during the dry blending step disclosed in the present wet / dry blending method may be any elastomer or blend.
189 105 elastomers suitable for the intended use or application, including those listed above for use in the wet mixing step. According to certain preferred embodiments, the elastomer latex used in the wet mixing step is natural rubber latex and the additional elastomer used in the dry mixing step is butadiene rubber (BR). In such preferred embodiments, the butadiene rubber preferably forms the minor phase or component of the elastomer composite blend, most preferably being from 10% to 50% by weight of the total elastomer in the elastomer composite blend. In accordance with certain other preferred embodiments, the elastomer latex used in the wet mixing step is natural rubber latex and the additional elastomer used in the dry mixing step is styrene butadiene rubber (SBR). In such preferred embodiments, SBR preferably forms the main phase or component of the elastomer composite blend, most preferably 50% to 90% by weight of the total elastomer in the elastomer composite blend. In accordance with certain other preferred embodiments, the additional elastomer is natural rubber. In accordance with certain other preferred embodiments, the elastomer latex used in the wet mixing step is butadiene rubber latex and the additional elastomer used in the wet mixing step is SBR. In such preferred embodiments, SBR is preferably present in 10% to 90% by weight of the total elastomer in the elastomer composite blend. In accordance with certain other preferred embodiments, the elastomer latex used in the wet mixing step is rubber butadiene latex, and the additional elastomer used in the dry mixing step is natural rubber. In such preferred embodiments, the natural rubber preferably forms the minor component or phase of the elastomer composite mixture, most preferably from 10% to 50% by weight of the total elastomer in the elastomer composite mixture. In accordance with certain other preferred embodiments using rubber butadiene latex in the wet mixing step, the additional elastomer is additional butadiene rubber.
In accordance with certain other preferred embodiments, the elastomer latex used in the wet mixing step is SBR and the additional elastomer is butadiene rubber. In such preferred embodiments, the butadiene rubber preferably ranges from 10% to 90% by weight of the total elastomer in the elastomer composite blend. In accordance with certain other preferred embodiments, the elastomer latex used in the wet mixing step is SBR and the additional elastomer is natural rubber. In such preferred embodiments, the natural rubber preferably comprises the minor component or phase, most preferably from 50% to 90% by weight of the total elastomer in the elastomer composite blend. Certain other preferred embodiments use SBR in both the wet and dry mixing steps, thus being substantially 100% elastomer in the elastomer composite blend.
As noted further below, the rubber compositions of the present invention may contain, in addition to the elastomer and filler, curing agents, a coupling agent and optionally various processing aids, oil fillers and anti-degradation agents. In this regard, it should be understood that the elastomer composite blends disclosed herein include vulcanized (VR) compositions, thermoplastic vulcanizates (TPV), thermoplastic elastomers (TPE), and thermoplastic polyolefins (TPO). TPV, TPE and TPO materials are further classified by being extruded and poured several times without substantially losing performance characteristics. Thus, in making elastomer composite mixtures, one or more curing agents may be used, such as, for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other systems used to effect vulcanization of the elastomer composition.
If the elastomer latex used in the wet-blending step comprises a natural rubber latex, the natural rubber latex may include a half latex or a concentrate (made, e.g., by evaporation, swirling, or standing). Natural rubber latex, of course, must be suitable for soot coagulation. The latex is usually supplied in an aqueous carrier fluid. Alternatively, the fluid carrier may be a hydrocarbon solvent. In any event, the natural rubber latex fluid must be capable of being towed, continuously fed at the appropriate speed, pressure and concentration to the mixing zone. The well-known instability of natural rubber latex is preferably accommodated in that it is subjected to a relatively low pressure and low wall in the system until it is prepared for the above-mentioned semi-restricted turbulent flow after encountering the extremely high velocity and kinetic energy of the carbon black suspension in the mixing zone. In some preferred embodiments, e.g. the natural rubber is fed to the mixing zone at a pressure of about 35.5 kPa), at a speed in the range of about 0.9-3.7 m / s, more preferably about 1.2-1.8 m / s. The selection of a suitable latex or latex mixtures will be able to be made by one skilled in the art, taking advantage of the present description and knowledge of selection criteria generally well known in the industry.
A particulate filler fluid, e.g. a carbon black slurry, is fed to the mixing zone at the inlet end of coagulation reactor 14 via feed line 16. The slurry may include any suitable filler in a suitable carrier fluid. The choice of the carrier fluid will depend mainly on the choice of the particulate filler and the system parameters. Both aqueous and non-aqueous fluids may be used, and aqueous fluids are preferred in many embodiments for reasons of cost, availability, and suitability for use in the production of carbon black and certain other filler slurries.
If a carbon black filler is used, the choice of the carbon black will depend largely on the intended use of the elastomer composite mixture. Optionally, the carbon black filler may also contain any material that may be a slurry and may be fed to the mixing zone in accordance with the principles disclosed herein. Suitable additional particulate fillers include e.g. conductive fillers, reinforcing fillers, fillers, containing short fibers (usually having an L / D aspect ratio of less than 40), flakes, etc. Thus, examples of particulate fillers that can be used to make an elastomer masterbatch in accordance with the methods and apparatus disclosed herein are carbon black, colloidal silica, precipitated silica, coated carbon black, chemically functionalized carbon blacks such as those having organic groups attached, and siliconized soot. either singly or in combination with each other. Suitable chemically functionalized carbon blacks include those described in International Application No. PCT / US 95/16194 (WO 9618688), the description of which is hereby incorporated by reference. In silicon carbon blacks, silicon-containing moieties, such as silicon oxide or carbide, are distributed across at least a portion of the carbon black aggregate as the interior of the carbon black.
Conventional carbon blacks exist in the form of aggregates, each aggregate consisting of a single phase, which is carbon. This phase may exist in the form of graphite crystallite and / or amorphous carbon, and is usually a mixture of the two forms. As discussed elsewhere herein, carbon black aggregates can be modified by leaving silicon-containing moieties such as silica on at least a portion of the surface of the carbon black aggregates. The result can be described as silicon-coated carbon blacks. The materials described herein as siliconized carbon blacks are not carbon black aggregates that have been coated or otherwise modified, but actually represent a different type of aggregate. In siliconized carbon blacks, aggregates contain two phases. One phase is carbon which will still be present as graphite crystallite and / or amorphous carbon while the second phase is silica (and possibly another silicon containing moiety). Thus, the phase of the silicon-containing moieties in the siliconized carbon black is an internal part of the aggregate: distributed over at least parts of the aggregate. It will be seen that the multiphase aggregates are quite different from the silicon-coated carbon blacks mentioned above, which consist of preformed single-phase carbon black aggregates having silicon-containing moieties deposited on their surface. Such carbon blacks can be surface treated to place silica functional groups on the surface of the carbon black aggregate. In this process, an existing aggregate is treated to deposit or coat silica (as well as possibly other silicon-containing species) on at least a portion of the aggregate surface. For example, an aqueous sodium silicate solution may be used to deposit amorphous silica on the surface of carbon black aggregates in an aqueous slurry at a high pH, such as 6 or higher, as discussed in Japanese Unexamined Disclosed Publication (Kokai) No. 63-63755. More specifically, the carbon black can be dispersed in water to obtain
189 An aqueous slurry containing, for example, about 5% by weight of carbon black and 95% by weight of water. The slurry is heated to above about 70 ° C, such as to 85-95 ° C, and the pH is adjusted to above 6, such as in the range 10-11, with a basic solution. A separate formulation is made from a sodium silicate solution containing the amount of silica desired to be deposited on the carbon black, and an acidic solution to bring the sodium silicate solution to neutral pH. The sodium silicate acid solutions are added dropwise to the slurry, which is maintained at its starting pH value with an acid or base solution as needed. The temperature of the solution is also maintained. The suggested rate of addition of the sodium silicate solution is to calibrate the dropwise addition to add about 3% by weight of silicic acid, based on the total amount of carbon black, per hour. The slurry should be stirred during the addition, and afterwards, for a few minutes (such as 30) to several hours (ie 2-3). In contrast, siliconized carbon blacks can be obtained by producing carbon black in the presence of volatile silicon-containing compounds. Such carbon blacks are preferably produced in a modular or "staged" furnace carbon black reactor having a combustion zone followed by a reduced diameter zone, a restricted diameter feedstock injection zone, and a reaction zone. The extinguishing zone lies behind the reaction zone.
Typically, the quenching fluid, generally water, is sprayed onto the stream of newly formed carbon black particles flowing from the reaction zone. In the production of silicon carbon black, the above-mentioned volatile silicon containing compound is introduced into the carbon black reactor at a point upstream of the quenching zone. Useful compounds are volatile compounds at the carbon black reactor temperatures. Examples include, but are not limited to, silicates such as tetraoxyorthosilicate (TEDS) and tetramethoxyorthosilicate; silanes such as tetrachlorosilane and trichloromethylsilane; and volatile silicone polymers such as octamethylcyclo-tetrasiloxane (OMTS). The volatile flow rate will determine the weight percent silicon in the treated carbon black. The weight percentage of silicon in the treated carbon black is typically from about 0.1 to 25%, preferably about 0.5% to about 10%, and more preferably about 2% to about 6%. The volatile compounds may be pre-mixed with the carbon black feed material and introduced with the feed material to the reaction zone. Alternatively, the volatile compound may be introduced into the reaction zone separately, either upstream or downstream of the feed material injection point.
As noted above, additives can be used, and in this regard, useful coupling agents for coupling silica or carbon black should be expected to be useful in treating carbon black with silicon. Carbon blacks and numerous additional suitable particulate fillers are commercially available and known to those skilled in the art.
The choice of a particular filler or blend of particulate fillers will depend primarily on the intended use of the elastomer composite blends. As used herein, the particulate filler may include any material that may be a slurry and may be fed to the mixing zone in accordance with the principles disclosed herein. Suitable additional particulate fillers include e.g. conductive fillers, reinforcement fillers, short fiber fillers (usually having an L / D aspect ratio less than 40), flakes, etc. In addition to the carbon black and silica type fillers mentioned above, the fillers can be formed from clay, glass, polymer such as aramid fiber e.t.c. It is possible to select a suitable particulate filler for use in the method and apparatus disclosed herein using the present specification, and it is expected that any filler suitable for use in elastomeric compositions can be incorporated into elastomer composites using the teachings of the present description. It is of course also possible to use mixtures of different particulate fillers.
The preferred embodiments of the invention according to FIG. 1 are particularly well suited for the production of a particulate filler fluid, including aqueous carbon black suspensions. In accordance with known principles, it will be understood that carbon blacks having a lower surface area per unit weight must be used at higher concentrations in the particle suspension in order to achieve the same coagulation efficiency as lower concentrations of carbon black having a higher surface area per unit weight. The mixing tank 18 receives water and carbon black, e.g., optionally granulated carbon black, to form the fluid of the initial mixture. This fluid mixture passes through the discharge port 20 to a fluid line 22 provided with pumping devices 24, such as a diaphragm pump or the like. Line 28 carries the liquid mixture to the grinder
189 105 of colloid 32, or alternatively tubular or other mill through inlet 30. Carbon black is dispersed into aqueous carrier fluid to form a dispersion fluid that is passed through outlet 31 and fluid line 33 to homogenizer 34. Pumping devices 36, preferably including an expanding or other pump is provided in line 33. The homogenizer 34 further disperses the carbon black in the carrier fluid to form a soot slurry which is fed to the mixing zone of the coagulation reactor 14. This has an inlet 37 for fluid communication with the line 33 from the colloid mill 32. The homogenizer 34 may preferably include e.g. commercially available from Microfluidics International Corporation (Newton, Massachusetts. USA). Also suitable are homogenizers such as the MS 18, MS45 and MC 120 series homogenizer models available from APV Homogenizer Divisions from APV Gaulin, Inc. (Wilmington, Massachusetts, USA). Other suitable homogenizers are. commercially available and will be apparent to one skilled in the art using this description. Typically, the carbon black in water made according to the above-described system will have at least about 90% agglomerates less than about 30 microns in size, more preferably at least 90% agglomerates less than about 20 microns in size. Preferably, the carbon black is broken down to an average size of 5-15 microns, e.g., about 9 microns. Exit 38 carries the carbon black slurry from the homogenizer to the mixing zone via fluid line 16. The slurry may reach 68.9-103.4MPa in the homogenizer step and exits the homogenizer at about 4.13MPa or more. Preferably, a high carbon black content is used to reduce the task of removing excess water or other carrier. Typically about 10 to 30% by weight of carbon black is recommended. The carbon black content (weight percent) of the slurry and the flow rate of the slurry into the mixing zone should be coordinated with the flow rate of the natural rubber latex into the mixing zone to achieve the desired amount of carbon black (parts per hundred parts) in the premix. The carbon black content will be selected according to known principles in order to obtain material characteristics and performance properties suited to the intended use of the product. Usually e.g. Carbon blacks with a CTAB value of 10 or greater are used in sufficient amount to provide a carbon black content of the premix of at least about 30 parts per hundred parts of the premix.
The slurry is preferably used in the preparation of the premix directly during manufacture. The fluid lines carrying the slurry and any optional holding tank and the like should establish or maintain conditions that substantially ensure the dispersion of the carbon black in the slurry. That is, substantial re-agglomeration or precipitation of the particulate filler in the suspension should be prevented or reduced to a reasonably practicable size.
Preferably, all flow lines are e.g. smooth, with smooth connections between lines. Optionally, an accumulator is provided between the homogenizer and the mixing zone to reduce pressure fluctuations or slurry velocity at the end of the slurry inlet nozzle in the mixing zone.
Natural rubber latex fluid or fluid with another elastomer passed to the mixing zone through feed line 12 and a carbon black slurry fed to the mixing zone through feed line 16 at the correct processing parameters, as discussed above, can form a new elastomer composite, specifically elastomer masterbatch particles. Means may also be provided for incorporating various additives into the elastomer masterbatch. Additional fluid, containing one or more additives, may be fed to the mixing zone as a separate feed stream. One or more additives may also be pre-mixed, if desired, with the carbon black slurry, or more typically, with the elastomer latex fluid. The additives may also be mixed with the premix sequentially, i.e. during the dry blending step. Those skilled in the art are well aware of the numerous extras, including antioxidants, anti-ozone agents, plasticizers, processing aids (e.g., liquid polymers, oils, and the like), resins, flame retardants, filling oils, lubricants, and mixtures of each. The general use and selection of such additives are well known to those skilled in the art. Their use in the system disclosed herein will be well understood when using this specification. In accordance with some alternative embodiments, vulcanizing agents may also be incorporated in a similar manner to make the possible
189 105 vulcanizable elastomeric composite which may be cited as a vulcanizable base compound.
The elastomer masterbatch particles are transferred from the outlet end of the coagulation reactor 14 to a suitable drying unit. In the preferred embodiment of Fig. 1, the masterbatch particles undergo a multi-stage drying process. It first enters the dehydration extruder and then, via a conveyor belt or by simple gravity drop or other suitable means 41, to the drying extruder 42. In routine preferred embodiments according to that illustrated in Fig. 1, producing a natural rubber premix with a carbon black filler, the dewatering / drying operation will typically reduce the water content to about 0 to 1% by weight, more preferably, 0 to 5% by weight. Suitable dryers are well known and commercially available, including, for example, extruded dryers, fluid bed dryers, hot air dryers, or other oven dryers and the like, such as French Mills available from French Oil Machinery Co., (Piąua, Ohio, USA).
The dried premix particles from the drying extruder 42 are conveyed via a cooling conveyor 44 to a bale pressing machine 46. The baling machine is an optional advantageous feature of the apparatus of Fig. 1, where the dried premix particles are compressed in a chamber into stable compensated blocks. or the like. Typically, up to 11.3-34.0 kg of premix with elastom are compressed into blocks or bales for transport, further processing, etc. Alternatively, the product is provided in the form of granules, e.g. by churning off particles.
The dimensions and particular features of the design of the coagulation reactor 14, including a mixing zone / coagulation zone set up, suitable for the embodiment according to Fig. 1 will depend in part on design factors such as the desired batch capacity, choice of materials to be treated, etc. One preferred embodiment is illustrated. in Fig. 2, where the coagulation reactor 48 has a mixing head 50 connected to the coagulation zone 52 with a strong gasket at the connector 54. Fig. 2 schematically illustrates a first subsystem 56 feeding elastomer latex to the mixing zone, subsystem 57 feeding a soot slurry or other particulate filler fluid to the mixing zone, and subsystem 58 feeding optional additional fluid, pressurized air, etc. to the mixing zone. It can be seen that the mixing head 50 has three feed channels 60, 61, 62. Supply channel 60 is provided for natural rubber latex fluid and supply channel 62 is provided for direct supply of gas and / or additive fluid. In combination with the preferred embodiments using direct injection of additives, a significant advantage is achieved in combination with hydrocarbon additives or, more generally, water-immiscible additives. While it is well known to use intermediate emulsions to form secondary emulsions suitable for premixing with elastomer latex, preferred embodiments as described herein using direct injection of additives can eliminate not only the need for intermediate emulsions but also equipment such as tanks, dispersing devices, etc. previously used to form an emulsion. Thus, a reduction in production costs and complications can be achieved. As discussed further below, the feed channel 61 through which the slurry is fed to the mixing zone is preferably coaxial with the mixing zone and the coagulation zone of the coagulation reactor. Although only a single feed channel to receive the elastomer latex fluid is shown, any suitable number of feed channels may be positioned around the center channel through which the slurry is fed to the mixing zone. Thus, e.g. in the embodiment according to Fig. 2, a fourth supply channel could be provided through which ambient or high pressure air or other gas is fed to the mixing zone. Pressurized air may be injected as well as the slurry through the central axial supply channel 61. The secondary supply channels may be temporarily or permanently closed when not in use.
It can be seen that the coagulation zone 52 of the coagulation reactor 48 has a first portion 64 having an axis length that may be selected depending on the design objectives for the particular intended application. Optionally, the coagulation zone may have a constant cross-sectional area over all or substantially all of its axial length. Thus, for example, a coagulation reactor can define an easy, straight tubular flow channel from the mixing zone to the end of the outlet.
189 105 wego. Preferably, however, for the reasons discussed above, and as seen in the preferred embodiment illustrated in the drawings, the cross-sectional area of the coagulation zone 52 increases progressively from the inlet 66 to the outlet 68. More specifically, the cross-sectional area increases in the longitudinal direction from the entrance to the outlet. In the embodiment according to Fig. 2, the coagulation zone increases progressively in terms of cross-sectional area in the sense that it continuously increases behind a constant portion 64 of the cross-sectional area. References to the diameter and cross-section of the coagulation reactor (or more correctly, the coagulation zone defined inside the coagulation reactor) and other components, unless otherwise specified, are intended to mean the cross-sectional area of such an open flow corridor.
As can be seen, the elastomeric composite, namely the coagulated elastomer latex in the form of premix particles 72, is discharged from the coagulation reactor 48 through the divider 70. The divider 70 is an adjustable conductor attached to the coagulation reactor at the outlet 68. It is adjustable to selectively pass the fines of elastomer masterbatch 72 to each of the various other recipient sites. This feature advantageously facilitates the removal of pre-batch fines from the product stream, e.g. for testing or when starting a production run, where initial instability of the process may cause short term poor product quality. In addition, the splitter provides flexibility in the design, directing the product from the coagulation reactor to various routes through to production. According to the preferred embodiment of Fig. 1 the fines of the masterbatch 72 are discharged from the coagulation reactor 48 through the separator 70 which is seen to be obtained from the dryer 40.
As can be seen, the cross-sectional dimension of the coagulation reactor 48 increases by the overall angle? Between inlet 66 and outlet 68. The angle? Is greater than 0 ° and in preferred embodiments is less than 45 °, more preferably less than 15 °, most preferably 0.5. up to 5 °. As can be seen, the angle α is half angle, thus being measured from the central longitudinal axis of the coagulation zone, to the point A at the outer circle of the coagulation zone at the end of the coagulation reactor. In this regard, it should be understood that the cross-sectional area of the upper portion of the coagulation reactor, i.e. the inlet portion 66, preferably increases slowly enough to achieve approximately coagulum formation following the principles discussed above. Too large an expansion angle of the coagulation zone may result in the elastomer masterbatch not being produced from the particles to the desired form of globules or worms, but simply sprayed over the coagulation reactor. Increasing the orifice diameter of the coagulation reactor too slowly can, in some embodiments, cause the feed material and reaction product to be back-loaded or pooled in the mixing head. In the lower part of the mixing zone, where the latex has been substantially coagulated and the flow has become substantially plug flow, the coagulation zone may extend either with or without increasing the transverse area. Thus, reference herein to a coagulation zone in the preferred embodiments having a progressively increasing cross-sectional area should be understood as referring primarily to that part of the coagulation zone where the flow is essentially a plug flow.
The cross-sectional area of the coagulation zone (i.e., at least the top of the coagulation zone as discussed immediately above) may increase in a stepwise manner rather than continuously illustrated in the embodiment of Fig. 2.
In the embodiment illustrated in Fig. 3, the continuous flow system for producing an elastomer masterbatch according to the method and apparatus discussed herein comprises, as can be seen, a mixing head / coagulation zone assembly in which the cross-sectional area of the coagulation zone increases in a stepwise manner. Preferably, the individual sections of the coagulation zone in such a staged embodiment have flowing connections between adjacent sections. That is, they combine to form a smooth and generally continuous coagulation zone surface as opposed to, for example, a sharp or instantaneous increase in diameter from one section to the next. The coagulation zone of Fig. 3 increases in three stages so that there are four different sections or subzones 74-77. Following the principles of the plan discussed immediately above, the cross-sectional area of the coagulation zone 53 increases from entry 66 to point A at exit 68 at an overall angle that obtains the necessary flow control at the top of the coagulation reactor. The first section of 74 can
189 105 to be taken as comprising (a) a portion of constant diameter of the mixing head 50 immediately downstream of the mixing zone, and (b) a portion of the same or similar diameter connected to the connector 54 at the entrance 66. This first section has a constant cross-sectional diameter Di and dimension axial or Li length. In this first section 74, the length Li should be greater than three times the diameter Di, more preferably greater than five times the diameter Di, and most preferably from about 12 to 18 times the diameter Di. Each subsequent section preferably has a constant cross-sectional dimension and a cross-sectional area approximately double that of the previous (i.e. top) section. Thus, for example, section 75 has a constant cross-sectional dimension and a cross-sectional area that is twice that of section 74. Likewise, cross-sectional area 76 is twice that of section 75 and that cross-sectional area of section 77 is double that of section 76. In each of sections 75-77, the length is preferably greater than three times its diameter, more preferably about three to seven times its diameter and generally about five times its diameter. Thus, for example, in section 76, the longitudinal dimension L3 is preferably about five times its diameter D3.
The set of mixing head and coagulation zone corresponding to the embodiment according to Fig. 3 is shown in Fig. 4, partially in section. The mixing head 50 is integral with the extension of the coagulation zone 53 via the connector 54. This defines a mixing zone in which the multiple feed channels 60, 61, 62 form a connection to an elongated substantially cylindrical channel 80 substantially coaxial with a portion of the coagulation zone within the extension 53. It will be appreciated that it is not essential to the operability of the method and apparatus disclosed herein to accurately define the boundaries of the mixing zone and / or coagulation zone. Numerous variations are possible in the plan of the feed channel connection areas, as will be apparent from the present description. Therefore, a guiding line in embodiments of the type illustrated in Fig. 4 for example, the slurry tip 67 is generally above the starting cylindrical portion 80 that is approximately longitudinally centered at the junction of the feed channels. In such embodiments, preferably the minimum cross-sectional area defined by the imaginary cone 67 from the slurry tip to the circumference of the circle at the beginning of the cylindrical portion 80 is preferably greater than or at least equal to the latex 60 feed channel cross-sectional area. Preferably, both the channel 80 and at least the upper part of the coagulation zone in which the turbulent flow exists before substantially complete coagulation of the elastomer latex are circular in cross-section.
The devices for feeding the carbon black slurry or particulate filler, apparently, include a feed pipe 82 extending substantially coaxial with the mixing chamber to the opening or end of the slurry nozzle 67 which opens towards the coagulation zone. This is a highly advantageous feature of the preferred embodiment discussed herein. Carbon black, as noted above, is fed into the mixing zone at a very high speed relative to the latex feed rate, and the alignment of the narrow feed tube opening 82 causes excellent flow turbulence. Diameter D<sub>m</sub> channel 80 (which as noted above is preferably substantially equal to the diameter D1 immediately downstream of part of the coagulation zone section 74) preferably at least twice the internal diameter of the slurry feed pipe 82, preferably about four to eight times the diameter of the feed pipe 82, typically about seven to eight times that diameter. The feed tube 82 is seen to form a tight seal for the fluid with an entry port 83 at the upper end of the feed channel 61 of the mixing head 50. The diameter of the axial feed tube 82 is mainly determined by the volumetric flow rate required and the axial velocity of the slurry as it passes through the nozzle tip the slurries 67 into the mixing chamber. The correct or required volume and speed can be easily determined by one skilled in the art using this specification, and will be partly a function of concentration and choice of materials. Embodiments such as illustrated and discussed herein in which the feed pipe for the carbon black slurry is removable provide the desired flexibility to produce different masterbatch compositions at different times. The feed pipe used in one production run can be removed and replaced with a pipe with a larger or smaller bore diameter according to the next production. Given the pressure and the speed at which the slurry exits the feed pipe, it can be defined as a spray or injection into the mixing zone. It should be understood that this means at least some of it
189 In 105 embodiments, high velocity injection of the slurry into an area already substantially filled with fluid. Thus, it is a spray in terms of its immediate distribution as it passes the end of the slurry nozzle, and not necessarily in the sense of free-flying, straight-path material droplets.
Additional feed channels 60 and 62 are seen to form a connection 84, 85 to feed channel 60 and lower channel 80, respectively, at an angle β. The angle β may, in many embodiments, be from greater than 0 ° to less than 180 °. Typically, β can take from, for example, 30 ° -90 °. It is desirable to avoid negative pressure, i.e. cavitation, of the latex fluid as it is entrained by the high velocity of the slurry at the end of the slurry nozzle 67 as this can adversely result in incompatible mixing leading to incompatible premix product. Air or other gas may be injected or otherwise fed into the mixing zone to assist in breaking any such vacuum. In addition, an extended feed line for natural rubber latex leading to inlet port 86 of feed channel 60 preferably functions as a latex fluid reservoir. In the preferred embodiment of Fig. 4, the latex feed passage 60 intersects the mixing zone either before or after the end of the slurry nozzle 67.
A slurry of carbon black or other fluid with particulate filler is typically supplied to the feed pipe 82 at a pressure greater than about 2068 kPa, such as about 3447-34470 kPa), e.g., about 6890 kPa. Preferably, the liquid slurry is fed to the mixing zone through the end of the slurry nozzle 67 at a velocity of more than 30.5 m / s, preferably about 80.5-243.8 m / s, more preferably about 61-152.4 m / s, e.g. about 106.7 m / s. Arrows 51 in Fig. 4 represent the general direction of flow of elastomer latex and auxiliary feed materials through feed passages 60 and 62 into conduit 80 downstream of the end of slurry nozzle 67. Thus, the slurry and latex fluids are fed into the mixing zones at completely different feed flow rates according to the numbers set forth above. While not wishing to be bound by theory, it is now understood that the differential feed causes latex shear conditions in the mixing zone leading to good macrodispersion and coagulation.
An alternative preferred embodiment is illustrated in Figs. 5 and 6, in which a single axial feed pipe 82 of the Fig. 4 embodiment is changed to a plurality of axially extending feed pipes 90-92. Even larger numbers of feed pipes can be used, e.g. up to about 6 or 8 axially extending feed pipes. Preferably, production flexibility is achieved by using different feed pipes with different diameters to produce different formulations. Also, multiple feed pipes can be used simultaneously to achieve good turbulence within the mixing zone and the coagulation zone of the coagulation reactor.
An alternative embodiment of the mixing head is illustrated in Fig. 7. The mixing head 150 defines a mixing zone 179 as seen. An axial feed channel 161 connects to a feed pipe 182 adapted to feed a slurry of carbon black or other fluid with particulate filler at a high speed into the mixing chamber 179. It can be seen that the central opening in the feed pipe 182 ends at the end of the slurry nozzle 167. The constant diameter nozzle surface 168 is located just in front of the slurry nozzle 167 leading to a larger area of opening 169. Preferably, the axial diameter of surface 168 is about 2 to 6, e.g., about 5 times its diameter. A second feed channel 160 communicates 184 with mixing zone 179 at a 90 ° angle for feeding elastomer latex fluid to the mixing zone. The cross-sectional diameter of the latex fluid supply channel 160 is significantly larger than the cross-sectional diameter of the slurry nozzle tip 167 and surface 168. Without wishing to be bound by theory, the axial extension of the nozzle surface 168 coupled to a section having a widened bore diameter ahead of the nozzle surface is believed to be , favorable stability of the slurry flow through feed pipe 182 into mixing zone 179. The feed tube opening 182 has been found to function well with a 20 ° slant, i.e. a conical region 169 that extends upwardly at an angle of approximately 20 °. Downstream of mixing zone 179 is an elongated coagulation zone. In accordance with the principles discussed above, such a coagulation zone requires only a marginal lengthening. That is, its axial dimension should only be slightly longer than its diameter. However, preferably, a progressively increasing coagulation zone is used.
As discussed above, coagulation of the elastomer masterbatch is substantially complete at or before the end of the coagulation reactor. This means that coagulation occurs unnecessarily
189 105 adding a stream of coagulant or other solution. Coagulation may occur in the mixing zone. For this purpose, the mixing zone can be considered as all or part of the coagulation zone. Also, reference to substantially complete coagulation before the elastomer masterbatch exits the coagulation reactor does not exclude the possibility of subsequent treatment and subsequent treatment steps for each of the various purposes appropriate to the intended use of the final product. Therefore, substantially complete coagulation in the preferred embodiments of the new method disclosed herein using a natural rubber latex means that at least about 95 wt% of the rubber latex hydrocarbon is coagulated, more preferably at least about 97 wt%, and most preferably at least 99 wt%. % by weight is coagulated.
The masterbatch (or other elastomer composite) formed by the wet-blending step optionally passes through any suitable additional. treatment prior to addition of additional elastomer in the dry-blending step of the wet / dry process disclosed herein. Suitable equipment for the dry mixing step is commercially available and will be apparent to those skilled in the art making use of this description. Suitable dry mixing equipment includes e.g. Banbury mixers, mills, roller mixers, etc. Coagulum from the wet mixing step, with or without any additional intermediate treatment, is introduced into a Banbury mixer or other mixing device along with additional elastomer in any suitable order and proportion as appropriate to each other. intended use or application. One skilled in the art, using this description, will be able to determine the appropriate order of addition and relationship to the wet blend product and additional elastomer. Likewise, those skilled in the art will be able, making use of this description, to select suitable additional ingredients to be added during the dry mixing step as appropriate for the intended use or application, e.g. filling oil, vulcanizing agents, and other additives known to the use of elastomer composites and blends of elastomeric composites of the general type disclosed herein.
The method and apparatus disclosed and described herein produces blends of elastomeric composites having excellent physical properties and performance characteristics. The novel elastomer composite blends of the present invention include compositions made with the above-described process and apparatus as well as intermediates and end products made from such masterbatch compositions.
In particular, an elastomer masterbatch can be prepared using natural rubber latex (latex concentrate or mid-latex), together with various grades of carbon black filler, having excellent physical properties and performance characteristics. Currently, carbon blacks are successfully used in wide commercial use for applications such as tire tread, as well as carbon blacks so far considered unsuitable for commercial use with known equipment and methods. These inadequate carbon blacks, because their high surface area and low structure make them impractical for achieving an acceptable level of macrodispersion at the routine level of carbon black content and / or for preserving the molecular weight of the elastomer, are highly recommended for some applications of the novel elastomer composite blends disclosed herein. This elastomer composite mixture has been found to have an excellent dispersion of carbon black in the elastomer. Moreover, these favorable results have been obtained without the need for a coagulation step involving treatment with a tank or stream of an acid solution or other coagulant. Thus, not only can the cost and complication of such coagulant treatment be avoided, but the need to manipulate effluent streams during such operations is also avoided.
Prior art masticating techniques could not achieve an even dispersion of fillers in composite elastomer mixtures without significant molecular weight distribution, and thus do not produce novel natural rubber compositions made according to certain preferred embodiments of the present invention. Therefore, disclosed herein are novel elastomer composite blends having excellent carbon black macrodispersion in natural rubber, even carbon black, having a structure to surface area ratio of DBPA: CTAB below
1.2 and even less than 1.0 for the high molecular weight of natural rubber. Known mixing techniques in the past have not achieved such excellent carbon black macrodispersion without significant molecular weight distribution of the natural rubber and thus have not produced new composites22
189 105% of the masterbatch and other elastomer composites of the present invention. The preferred novel elastomer composite blends of this description, having a carbon black macrodistribution level not yet achieved, can be used in place of prior art elastomeric materials having less macrodispersion. Thus, the elastomer composite mixtures disclosed herein may be used as vulcanizing compounds in accordance with known techniques. Such new vulcanizing compounds, in the preferred embodiments, have been found to have physical characteristics and performance properties generally comparable and in some cases significantly better than other comparable vulcanized compounds, including a less macrodisperse masterbatch. The elastomer composite blends can be produced in accordance with the present invention with reduced mixing time, reduced energy input, and / or other cost savings.
As used herein, carbon black structure can be measured as Dibutylphthalate Adsorption (DBPA) value, expressed as DBPa cubic centimeters per 100 grams of carbon black, according to the procedure set forth in ASTM D2414. Carbon black surface area can be measured as CTAB expressed as square meters per gram of carbon black according to the procedure set forth in ASTM D3765-85. It will be appreciated that other factors affecting the level of dispersion obtained using the method and apparatus disclosed herein include the concentration of the carbon black in the slurry, the total energy input to the slurry, and the energy input when mixing the fluid streams, etc.
The macrodispersion quality of the carbon black in the natural rubber masterbatch disclosed herein is significantly higher than that of the prior art masterbatches with approximately Mw / (average weight). In some preferred embodiments, excellent carbon black distribution is achieved with Mw / i approximately equal to the weight of natural rubber in a field latex condition (e.g., about 1,000,000), not previously achieved. The advantage of the dispersion quality is especially important in the above-mentioned embodiments when using carbon black with a low structure and a high surface area, e.g. DBPA below 110 cc / 100 g, CTAB greater than 45 to 65 m<sup>2</sup>/ g, and DBPA: CTAB of less than 1.2 and preferably less than 1.0.
Examples
Test procedures
The following test procedures were used in the examples and comparisons provided below.
1. Bound rubber: A sample weighing 5 g ± 0.25 g is weighed and placed in 100 ml of toluene in a sealed flask and stored at ambient temperature for approximately 24 hours. Then the toluene is replaced with 100 ml of fresh toluene and the flask is kept for 4 days. The sample is then removed from the solvent and further dried in a vacuum oven at ambient temperature for 24 hours. The sample is then weighed and the bound gum is calculated from the weight loss data.
2. MWoi: As used in this description and claims, Mw<sub>AND</sub>j refers to the average molecular weight of the sol part of natural rubber. Standard GPC techniques for measuring molecular weight were followed as follows:
2.1 Two columns 10 pm 10<sup>6</sup> A. 10 µm column, 500 A and 10 µm mixed bed column from Polymer Laboratories, UK.
2.2 UV detection at '215 nm.
2.3. Solvent: tetrahydroiurane (THF)
2.4. Concentration, nominally 2 mg / ml in THF.
2.5. Samples are allowed to dissolve in THF for 3 days, and BHT is stabilized.
2.6 The solutions are centrifuged to separate any gels and the supernatant is injected onto the column.
2.7 Sample preparations. The sample preparation is designed to produce sol concentrations in the range 0.5 to 0.05 wt% to ensure a good detector response for accurate measurement of molecular weight distribution. Depending on the filler content, the weight of the sample is adjusted according to the following formula:
sample weight = (100 + filler content (parts per hundred parts) * 20/100 mg +/- 2 mg
189 105
The samples are placed in UV protected vials with 4 ml of stabilized tetrahydrofuran (THF) containing 0.02% butylated hydroxytoluene for three days. The dissolution supernatant, containing most of the sol, is transferred to Teflon centrifuge tubes and spun in an Avanti 30 centrifuge (Beckmann) for 60 minutes at 26,000 rpm (corresponding to a maximum field strength of 57.500 g). At this field strength, most of the gel phase is deposited, leaving the supernatant gel-free. This gel-free solution is diluted 1: 5, again using stabilized THF. At this point, samples are transferred to GPC vials and placed inside the Waters 717 Auto-Sampler (Waters Corporation, Milford, Massachusetts, USA) in the GPC test slide.
Determination of the molecular weight. The average molecular weight of a portion of the Mwz sol is then determined<sub>n</sub>]. Using Millenium software (available from Waters Corporation, Milford, Massachusetts, USA), a baseline is determined using the method min to min value within 15 and 35 minute time increments. This time increment is appropriate for the set of columns described in paragraph 2.1 above with the mobile phase flow rate set to 0.75 ml / min. Once a reasonable baseline is established, the distribution can be determined. The elution time is converted to molecular weight. Polystyrene solutions are prepared made from commercially available standards (EasiCal: Polymer Laboratories, UK), containing a series of molecular weights with a very narrow distribution. The conversion of polystyrene molecular weight into polyisoprene molecular weight equivalents is based on the universal calibration method of Benoit and colleagues. The hydrodynamic radius is proportional to the molecular weight product times the internal viscosity. After converting the molecular weights of polystyrene to polyisoprene equivalents, the calibration curve relates the absolute molecular weight to the elution time. Standards are run under conditions identical to the samples, and standards are integrated to assign the appropriate molecular weight for a given elution time based on the best fit for the given standards. After the time has been correctly converted from the distribution to molecular weight, the average of the respective molecular weight is calculated using the Millenium Waters program.
3. Mooney Viscosity: The standard procedures for ML (1 + 4) @ 100 ° C are followed.
4. Test sample vulcanization conditions: The test pieces are vulcanized to 150 ° C for the times indicated below:
4.1 Flat stretching: 20 minutes
4.2 Rebound: 23 minutes.
4.3 Hardness: 23 minutes
4.4. Heat Rise: 25 minutes.
5. Dispersion: The Cabot Dispersion Chart method is used with a subjective evaluation of 50x optical micrographs. (ASTM method D2663).
6. Strain Strain: Tested against BS903: A2 and ISO 37.
7. Hardness: Tested against ISO 48 (1994), temperature 23 ° C.
8. Resilience: Tested against BS903: A8 (1990), method A, temperature 23 ° C (8mm disc-shaped poured test piece).
9. Heat Rise: Tested against ASTM D2623, Method A.
9.1. Start temperature: 23 ° C
9.2. Static load: 11.35 kg
9.3 Impact: 0.57 cm
9.4. Frequency: 30 Hz
9.5 Run for 30 minutes.
10. Tangent 5: Measured on a Rheometrics® RDS II model. The described values are the maximum values for stress strains. Stress strain at 0 °, 30 ° and 60 ° C, 1 Hz and 0.1% to 60% stress.
11. Crack growth resistance: Measured in accordance with ASTM D3629-94
189 105
Example A
An elastomer masterbatch was produced in accordance with the invention. Specifically, an elastomer masterbatch was produced, including a standard Malaysia half natural rubber latex with 52.5 parts per hundred parts of a filler consisting of commercial grade N234 carbon black available from Cabot Corporation. The properties of the natural rubber field latex are provided in Table 1 below.
Table 1. Properties of natural rubber latex
<td>Additives</td><td>% dry rubber</td><td>% of total solids</td><td>% ash</td><td>Nitrogen ppm</td><td>Volatile fatty acid</td><td>ML (I + 4) @ 100 ° C</td>
<td>0.15% HNS<sup>and </sup>0.3% NH3, ZnO TMTD<sup>b</sup></td><td> 28,4</td><td> 34,2</td><td> 0,38</td><td> 0,366</td><td> 0,052</td><td> 68</td>
a. NS. neutral hydroxylamine sulfate, Mooney ZnO / TMrD 'viscosity stabilizer used as a biological preservative, typically 0.025% of the mixture 1 1
The full compound formulation is set out in Table 2 below, and represents a commercial truck tire tread known to have excellent resistance to reversal during vulcanization.
Table 1a 2. Masterbatch preparation
<td>Ingredient</td><td>Parts by weight</td>
<td>Gum</td><td> 100</td>
<td>Soot</td><td> 52,5</td>
<td>ZnO</td><td> 4,0</td>
<td>Stearic acid</td><td> 2,0</td>
<td>6PPD (antioxidant)</td><td> 2,0</td>
<td>Suproof Improved (wax)</td><td> 2,0</td>
<td>Ennerflex 74 (aromatic oil)</td><td> 3,0</td>
<td>Whole</td><td> 165,5</td>
The apparatus for producing the elastomer masterbatch was substantially identical to the apparatus described above with reference to Figures 1 and 7 of the drawings. The end of the slurry nozzle (see reference No. 167 in Figure 7) had a diameter of 0.1 mm with a body (see reference No. 168 in Figure 7) having an axial length of 5.1 mm. The coagulation zone had a diameter of 4.8 mm) and an axial length of 25 mm of constant diameter between the mixing zone and its exit orifice. The preparation of the masterbatch is described in more detail just below.
1. Preparation of a soot slurry. The bags of carbon black were mixed with deionized water in a carbon black suspension tank equipped with an agitator. The agitator shredded the granules into pieces and a crude slurry with an L 2.5% by weight of carbon black was formed. During operation, this slurry was continuously pumped by an air diaphragm pump into a colloid mill for the initial dispersion. The slurry was then fed via a pump from the increasing volume to a homogenizer, specifically a Model M3 homogenizer from APV Gaulin, Inc. The homogenizer produced a finely divided slurry. The flow rate of the slurry from the homogenizer to the mixing zone was set by the speed of the homogenizer, with the homogenizer acting as a high pressure positive displacement pump. The flow rate of the slurry was monitored with a Micromotion® mass flow meter. The carbon black slurry was fed to the homogenizer at a pressure ranging from 344.5-689 kPa and the homogenization pressure was set at 2756 kPa so that the slurry was injected into the mixing zone at a flow rate of 111.6-119.7 kg / h) and speeds of about 39.6 m / s.
2. Delivering latex. The latex was loaded into a pressure feed vessel with a volume of 0.38 m<sup>3</sup>. An antioxidant emulsion was added to the latex prior to loading. Antioxidants consisting of 0.3 parts of tris-nonylphenyl phosphite (TNPP) and 0.4 parts of Santoflek® 134 (alkylaryl-p-phenylenediamine mixture) were added. Each of the antioxidants was made into a 15 wt% emulsion using 3 parts potassium oleate to 100 parts antioxidant together with potassium hydroxide to adjust the pH of the emulsion to about 10. 3 phr of filler oil was also added. An air pressure of 351.6 kPa was used to transfer the latex from the feed vessel to the mixing zone of the coagulation reactor. The latex flow rate was 87.1-92.5 kg / h and about 1.2 m / s, measured automatically and controlled with a Micromotion® mass flow meter and rubber tube pinch valve. The desired carbon black content of 52.5 parts per hundred parts was obtained by maintaining the appropriate ratio between the latex feed rate and the carbon black slurry feed rate.
3. Mixing of carbon black and latex. The carbon black slurry and latex were mixed by entraining the latex into the carbon black slurry. During the entrainment, the carbon black was thoroughly mixed with the latex and the mixture was coagulated. The soft, moist, spongy coagulum "worms" left the coagulation reactor.
4. Drainage. The wet particles discharged from the coagulation reactor were about 79% water. The wet particles were dehydrated to about 5 to 10% moisture using a dehydration extruder (The French Oil Mill Machinery Company; 8.9 cm diameter). In the extruder, the wet particles were compressed and water was squeezed out of the particles through the gap of the extruder barrel.
5. Drying and cooling. The dehydrated particles were discharged into a second extruder where they were compressed again and heated. Water was discarded while the particles were expelled through the plate die of the extruder. The product starting temperature was about 149 ° C, the moisture content was about 0.5 to 1% by weight. The hot, dry particles were cooled rapidly (about 20 seconds) to about 38 ° C via a forced air vibrating conveyor. The resulting dry particles had about 66 wt% rubber solids and about 33 wt% carbon black.
Example B
A control premix was prepared by dry mastic. The control used the same formulations as in Example A (see Table 2 above), except that the natural gum was SMR 10 and not latex. It was prepared by pre-masticating the gum in an OOC Banbury mixer (about 3 kg) at 50 rpm using 10 parts of carbon black. A pre-mastic was performed for approximately 3 minutes to a total amount of 800 MJ / m3. Comparison of example A and example B
The masterbatch of Example A and the control masterbatch of Example B were prepared in a two-step mixing operation in an OOC Banbury mixer (approximately 3 kg). Table 3 below shows the mixing mode for the first step. It can be seen that the masterbatch of Example A followed a modified blending pattern.
Table 1 a 3. Stage 1 of the blending modes
<td>Time (minutes)</td><td>example A</td><td>Example B Dry control mixture</td>
<td> 1</td><td> 2</td><td> 3</td>
<td> 0,0</td><td>All ingredients</td><td>Pre-masticated rubber</td>
<td> 0,5</td><td></td><td>Soot and oil</td>
<td> 1,0</td><td>Deviation</td><td></td>
<td> 1,5</td><td></td><td>the other ingredients</td>
<td> 2,0</td><td></td><td></td>
189 105
continued from table 3
<td> 1</td><td> 2</td><td> 3</td>
<td> 2,5</td><td></td><td>Deviation</td>
<td> 3,0</td><td></td><td></td>
<td>X</td><td>Discharge at approximately 700 MJ / m<sup>3</sup></td><td>discharge at about 1,000 MJ / m3</td>
In a second step, the vulcanizing agents listed in Table 4 below were added with an additional mixing cycle of 500 MJ / m.
Table 4 Addition of vulcanizing agents in the last step
<td>Ingredient</td><td>Parts by weight</td>
<td>Compound from stage 1</td><td> 165,5</td>
<td>Goodyear Winstay 100 (antioxidant)</td><td> 1,0</td>
<td>TBBS (sulfur accelerator)</td><td> 1,8</td>
<td>Sulfur</td><td> 1,0</td>
<td>Whole</td><td> 169,3</td>
Thus, the Banbury agitation energy for developing Example A masterbatch was approximately 53% of the Banbury agitation energy required for pre-masticating and developing the control material of Example B. Despite the reduced energy input, Example A material had very good macrodispersion and molecular weight (average weight). ) of its sol part Mw<sub>From (5</sub>l was much higher than the one in the control. These data are summarized in Table 5 below.
TABLE 5. Development and vulcanization data
<td>A sample</td><td colspan="4">Mixing energy (MJ / m3)</td><td colspan="2">ML (1 + 4), 100 ° C</td><td>Mw</td>
<td></td><td>Initial mastic</td><td>Level 1</td><td>End</td><td>Whole</td><td>Level 1</td><td>End</td><td>Average weight</td>
<td>Example A</td><td> 0</td><td> 694</td><td> 500</td><td> 1,194</td><td> 102</td><td> 72</td><td> 444,900</td>
<td>Example B</td><td> 800</td><td> 965</td><td> 500</td><td> 2,265</td><td> 92</td><td> 67</td><td> 327,000</td>
Additional test results for the vulcanized (untreated) material of Example A and the control are set out in Table 6 below.
Table 6. Data of additional tests
<td>A sample</td><td>Hardness</td><td>100% mod</td><td>ł (MPa)</td><td>300% m</td><td>nodule (MPa)</td><td>Bending</td><td>(MPa)</td>
<td>Example A</td><td> 71</td><td colspan="2"> 2,82</td><td colspan="2"> 16,1</td><td colspan="2"> 28,7</td>
<td>Example B</td><td> 72</td><td colspan="2"> 3,12</td><td colspan="2"> 16,2</td><td colspan="2"> 28,5</td>
<td></td><td></td><td></td><td></td><td></td><td colspan="3">K ΛnIzay mnnnyę tratin-O yliiuiii y iuuŁvno</td>
<td colspan="3">Lengthen the resilience</td><td colspan="2">Increase</td><td></td><td>delta</td><td></td>
<td>A sample</td><td>breaking (%)</td><td> (%)</td><td colspan="2">thermal (° C)</td><td>60 ° C</td><td>30 ° C</td><td>0 ° C</td>
<td>Example A</td><td> 526</td><td> 56,5</td><td></td><td> 70,5</td><td> 0,203</td><td> 0,240</td><td> 0,290</td>
<td>Example B</td><td> 511</td><td> 57,6</td><td></td><td> 76,5</td><td> 0,206</td><td> 0,236</td><td> 0,286</td>
189 105
Example C
An elastomer masterbatch was produced in accordance with the invention. Specifically, an elastomer masterbatch was produced, comprising a standard Malaysia half natural rubber latex with 55 phr of a filler consisting of Regal® commercial grade carbon black available from Cabot Corporation. The formulation properties of the compound (excluding minor additives to the field latex) are summarized in Table 7 below.
Table 7
<td>Ingredient</td><td>Parts by weight</td>
<td>Gum</td><td> 100</td>
<td>Soot</td><td> 55</td>
<td>Santofleks 134 (antioxidant)</td><td> 0,4</td>
<td>TNPP (Antioxidant)</td><td> 0,3</td>
<td>Whole</td><td> 155,7</td>
The apparatus for producing the elastomer masterbatch was substantially identical to the apparatus described above with reference to Figures 1, 3 and 7 of the drawings. The end of the slurry nozzle (see reference No. 167 in Figure 7) had a diameter of 0.6 mm and the body (see reference No. 168 in Figure 7) having an axial length of 5 mm). The coagulation zone (see reference No.53 in Fig. 7) includes a first portion 4.8mm in diameter and approximately 25mm in axial length (partially inside the mix head and partially inside the sealed extension); a second portion 6.8 mm in diameter and 40.6 mm axial in length; a third part with a diameter of 9.6 mm and an axial length of 57 mm; and a fourth portion with a diameter of 13.5 mm and an axial length of 81.0 mm). In addition, there are short-axis spherical connections between the above-mentioned parts. The preparation of the masterbatch is described in more detail just below.
1. Preparation of a soot slurry. The bags of carbon black were mixed with deionized water in a soot slurry tank equipped with an agitator. The agitator broke the granules into pieces and a crude slurry of 14.9 wt% carbon black was formed. The crude slurry was recirculated using a tube mill. During operation, this slurry was continuously pumped by an air diaphragm pump into a colloid mill for the initial dispersion. The suspension was then fed from the increasing volume pump to a homogenizer, namely a Mrcroflurdizer Model M210 homogenizer from Microfluidics Internationa! Corporation to produce a finely divided slurry. The flow rate of the slurry from the microfluidizer to the mixing zone was set by the speed of the microfluidizer, with the microfluidizer acting as a high pressure positive displacement pump. The flow rate of the slurry was monitored with a Micromotion® mass flow meter. The carbon black slurry was fed to the microfuidizer at a pressure of about 896 kPa and the outlet pressure was set to 20682 kPa to the accumulator set to 3102 kPa inlet pressure so that the slurry was injected into the mixing zone by injection at a flow rate of about 106.1 kg / hr. speed of about 91.4 m / s.
2. Delivering latex. The latex was loaded into a tank, specifically a drum with a volume of 0.21m<sup>3</sup>. An antioxidant emulsion was added to the latex prior to loading. Antioxidants consisting of 0.3 parts of tris-nonylphenyl phosphite (TNPP) and 0.4 parts of Santoplex® 134 (alkylaryl-p-phenylenediamine mixture) were added. Each of the antioxidants was made into a 40 wt% emulsion using 4 parts potassium oleate to 100 parts antioxidant together with potassium hydroxide to adjust the pH of the emulsion to about 10. To transfer the latex from the feed tank to the mixing zone of the coagulation reactor, peristaltic pump. The latex flow rate was 87.1-89.8 kg / h and about 1.2 m / s as measured by an Endress + Hauser mass flow meter (Greenwood, Indiana, USA). The desired carbon black content of 55 parts per hundred parts was obtained by maintaining the appropriate ratio between the latex feed rate and the carbon black slurry feed rate.
189 105
3. Mixing of carbon black and latex. The carbon black slurry and latex were mixed by entraining the latex into the carbon black slurry. During the entrainment, the carbon black was thoroughly mixed with the latex and the mixture was coagulated. The soft, moist, spongy coagulum "worms" left the coagulation reactor.
4. Dewatering The wet particles discharged from the coagulation reactor were about 78% water. The wet particles were dehydrated to about 12 to 13% moisture using a dehydration extruder (The French Oil Mill Machinery Company; 8.9 cm diameter). In the extruder, the wet particles were compressed and the water was squeezed out of the particles and through the gap of the extruder barrel.
5. Drying and cooling. The dehydrated particles were discharged into a second extruder where they were compressed again and heated. Water was discarded while the particles were expelled through the plate die of the extruder. The starting temperature of the product was about 137.8-187.8 ° C) and the moisture content was about 0.3 to 0.4% by weight. The hot, dry particles were cooled rapidly (about 20 seconds) to a temperature of about 37.8 ° C via a forced air vibrating conveyor.
DiE examples
Two control dry mix masterbatches were prepared by dry masticating. Controls used the same formulations as Example C (see Table 7 above) except that in Example D, the gum was RSS1 NR rather than latex. In Example E, the gum was SMR 10 NR. Each was prepared by pre-masticating the gum in a BR Banbury mixer. The gum of Example D was masticated at 118 rpm for 10 minutes. The gum of Example E was masticated at 77 rpm for 4 minutes.
Comparison of examples C, D and E.
The masterbatch of Example C and the two control masterbatches of Example D and E were developed in a Br Banbury blender. Table 8 below lists the development modes.
Table 1a 8. Editing modes
<td>Masterbatch</td><td>Initial mastic</td><td>Stage 1 mixing</td><td>Stage II (final) mixing</td>
<td>Example C</td><td>Lack</td><td>Lack</td><td>Mixer BR Banbury 77 rpm 4.5 minutes</td>
<td>Example D</td><td>BR Banbury 118 rpm 10 minutes</td><td>BR Banbury 77 rpm 3 min</td><td>Mixer BR Banbury 77 rpm 4.5 minutes</td>
<td>Example E</td><td>Mixer BR Banbury 77 rpm 4 minutes</td><td>BR Banbury 77 rpm 8 minutes</td><td>Mixer BR Banbury 77 rpm 4.5 minutes</td>
The formulation development is given in Table 9 below.
Table 9: Stage II. Adding vulcanizing agents
<td>Ingredient</td><td>Parts by weight</td>
<td> 1</td><td> 2</td>
<td>The masterbatch from example 4</td><td> 155</td>
<td>Dry mixing from step 1 of example 5 or 6</td><td> 4,0</td>
<td>Azo 66 (zinc oxide)</td><td> 2,0</td>
<td>Hystyrene 5016 (stearic acid)</td><td> 2,0</td>
<td>Santoflex 13 (antioxidant)</td><td> 2,0</td>
<td>Sunproof Improved (wax)</td><td> 2,0</td>
189 105
continued from table 9
<td> 1</td><td> 2</td>
<td>Wmstay 100 (antioxidant)</td><td> 1,0</td>
<td>Santocure NS (sulfur accelerator)</td><td> 1,8</td>
<td>Sulfur</td><td> 1,0</td>
<td>Whole</td><td> 168,8</td>
All compounds showed well-preserved vulcanization with minimal inversion. Despite the reduced energy input, the material of Example C was found to have much better macro-dispersion than the dry-blended controls, and the molecular weight (average weight) of its part of the sol Mw<sub>o</sub>| he was much higher than the control. These data are summarized in Table 10 below.
Table 10: Masterbatch and compound properties
<td></td><td>Example C</td><td>Example D</td><td>Example E</td>
<td colspan="4">Masterbatch properties</td>
<td>Mooney viscosity ML (1 + 4) @ 100 ° C</td><td> 125</td><td> 124</td><td> 126</td>
<td>Bound rubber (%)</td><td> 50</td><td> 32</td><td> 44</td>
<td>MWzol</td><td> 0,678</td><td> 0,466</td><td> 0,463</td>
<td>Percentage of non-dispersed area (D%)</td><td> 0,12</td><td> 1,48</td><td> 2,82</td>
<td colspan="4">Properties of the relationship</td>
<td>Hardness</td><td> 62</td><td> 65</td><td> 62</td>
<td>Modulus of elasticity 100% (psi)</td><td> 239</td><td> 315</td><td> 270</td>
<td>Modulus of elasticity 300% (psi)</td><td> 1087</td><td> 1262</td><td> 1216</td>
<td>Tensile stress (psi)</td><td> 4462</td><td> 4099</td><td> 4344</td>
<td>Elongation%</td><td> 675</td><td> 591</td><td> 600</td>
<td>Maximum tangent delta @ 60 ° C (stress variation)</td><td> 0,189</td><td> 0,237</td><td> 0,184</td>
<td>Crack growth rate (cm / million cycles)</td><td> 0,8</td><td> 5,0</td><td> 5,8</td>
Additional examples and comparisons
Particularly preferred elastomer composites of the present invention have been produced in accordance with the method and apparatus disclosed herein. In particular, new natural rubber latex masterbatch and carbon black filler masterbatch compositions have been created having a much better macro-dispersion level and / or molecular weight of natural rubber than previously known compositions made from the same or similar starting materials. Fig. 8 shows the surface area and structure of the various carbon black fillers used in these preferred masterbatch compositions, specifically shows the CTAB surface area in square meters per gram of carbon black, on ASTM D3765-85, and the ibutyl phthalate (DBPA) absorption value in cubic centimeters of DBP per hundred grams of carbon black on ASTM D2414. As can be seen, Fig. 8 is divided into three different areas of carbon black. Area I contains carbon black, having a lower structure and higher surface area, being the most difficult to disperse in natural rubber and other elastomers using traditional dry-blending techniques. As a result, the area I carbon blacks are not used commercially as widely as other carbon blacks. The masterbatch and vulcanized elastomer compositions made with the Zone I carbon black using traditional dry-blending techniques have a lower macro-dispersion30
189 105 and usually the lower Mvol. Area II carbon blacks have a higher structure than area I. They typically achieve reasonably good natural rubber dispersion for vehicle and other tire products if subjected to such extended dry blending that the natural rubber Mzol is significantly lowered. The carbon blacks from area III in Fig. 8 have a lower surface area in relation to their structure. Accordingly, they are used with acceptable dispersion in natural rubber, by dry blending, but again with an undesirable reduction in Mzol. The dispersion of carbon black in all three regions of Fig. 8, specifically macrodispersion, is greatly improved in the elastomer composites disclosed herein, and according to preferred embodiments, a much higher Mvol of natural rubber can be obtained.
Controls 1-443
Controls were prepared by dry blending according to the following procedures to compare the elastomer composites of the present invention.
1. Natural rubber mastic.
To prepare dry premixes with a wide molecular weight range, logs of commercial natural rubber (RSS1, SMR CV and SMR 10) were pre-masticated in a BR Banbury mixer using the following conditions (fill factor: 0.75):
Table 11. Natural rubber mastic conditions
<td>Sample code</td><td>Mastic</td><td>Rotor speed (rpm)</td><td>Cooling water</td><td>Mastic time (minutes)</td>
<td>M1</td><td>no</td><td></td><td></td><td></td>
<td>M2</td><td>Yes</td><td> 77</td><td>is</td><td> 4</td>
<td>M3</td><td>Yes</td><td> 118</td><td>is</td><td> 6</td>
<td>M4</td><td>Yes</td><td> 118</td><td>is</td><td> 10</td>
2. Mixing of sczie with pre-yestykoweną graą actrrclaą
The following BR Banbury blending procedures were used to produce dry natural rubber masterbatches with varying levels of macro-dispersion quality. The fill factor was 0.70. The premix ingredients and mixing procedures are described in Table 12 as follows.
Table 12 Preparation of dry natural rubber premix
<td>Ingredient</td><td>phr (parts per hundred parts by weight of rubber)</td>
<td>Natural rubber</td><td> 100</td>
<td>Soot</td><td>see the tables below</td>
<td>Ofej</td><td>see the tables below</td>
<td>Santofex (antioxidant)</td><td> 0,4</td>
<td>TNPP (Antioxidant)</td><td> 0,3</td>
<td colspan="2">Mixing procedures minute 0. Add pre-masticated natural rubber (77 rpm, 45 ° C) minute 1 Add carbon black, oil and antioxidants</td>
Different levels of macrodispersion were produced by dry blending the pre-masticated natural rubber samples M1 through M4 for different mixing times as shown in Table 13 below. For example, the sample code M2D1 in Table 13 indicates the pre-masticated natural rubber control sample Ms (see Table 11 above). mixed for 10 minutes according to the preparation in Table 12.
189 105
T abe 1 a 13. Mixing times
<td>Natural rubber dry premix - sample code</td><td>Pre-masticated natural rubber</td><td>Time of mixing</td>
<td>M1D4</td><td>Ml</td><td> 4</td>
<td>M1D3</td><td>Ml</td><td> 6</td>
<td>M1D2</td><td>Ml</td><td> 8</td>
<td>MIDI</td><td>Ml</td><td> 10</td>
<td>M2D4</td><td>M2</td><td> 4</td>
<td>M2D3</td><td>M2</td><td> 6</td>
<td>M2D2</td><td>M2</td><td> 8</td>
<td>M2D1</td><td>M2</td><td> 10</td>
<td>M3D4</td><td>M3</td><td> 4</td>
<td>M3D3</td><td>M3</td><td> 6</td>
<td>M3D2</td><td>M3</td><td> 8</td>
<td>M3D1</td><td>M3</td><td> 10</td>
<td>M4D4</td><td>M4</td><td> 4</td>
<td>M4D3</td><td>M4</td><td> 6</td>
<td>M4D2</td><td>M4</td><td> 8</td>
<td>M4D1</td><td>M4</td><td> 10</td>
Final mixing of natural rubber masterbatch control samples
To evaluate compound performance, additional ingredients were added to the dry masticated natural rubber premix controls of Table 13 according to the formulation shown in Table 14.
Table 14. Additional ingredients for final blend
<td>Ingredient</td><td>Amount (phr)</td>
<td>Azo 66 (zinc oxide)</td><td> 4,0</td>
<td>Hyystere 5016 (stearic acid)</td><td> 2,0</td>
<td>Santoflex 13 (antioxidant)</td><td> 2,0</td>
<td>Sunproof Improved (wax)</td><td> 2,0</td>
<td>Wingstay 100 (antioxidant)</td><td> 1,0</td>
<td>Sanocure NS (sulfur accelerator)</td><td> 1,8</td>
<td>Sulfur</td><td> 1,0</td>
The compounds were vulcanized according to standard vulcanization techniques at 150 ° C until vulcanization is at least substantially complete, typically between 10 and 30 minutes. Therefore, the same or essentially the same final blend procedures were used for all control samples, including the formulations listed in Table 14 above, and all elastomer composite samples of the invention were prepared in a manner
189 105 described below (see "Examples of Preferred Embodiments") which were cured and tested for compound properties and performance characteristics.
The following Tables 15-23 show the molecular weight of the Mw sol<sub>ZO</sub>and and the macrodispersion D (%) of control samples 1 to 443. The samples were grouped into tables according to the selected carbon black. In the table given, the samples were grouped by natural rubber selection and the carbon black content and the oil content. The table headings display this information according to standard nomenclature. Thus, for example, the heading for Table 15 "N330 / 55phr / 0" indicates 55 phr of N330 carbon black without oil. The cells below the headings in the table show the natural rubber selection. Specifically, controls 1 to 450 as seen were made of RSS1, SMRCY and SMR10 standard grade natural rubber. A technical description of these natural gums is widely available, such as in Rubber World Magazme's Blue Book published by Lippincott and Pęto, Inc. (Akron, Ohio, USA). The molecular weight MW of the natural rubber before each pre-mastic (M1) and after the various amounts of pre-mastic (M2-M4) are also shown below in Tables 15-23.
Table 15
<td rowspan="3">Code</td><td colspan="6">N330 / 55phr / 0</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td>
<td>Sample No.</td><td>Mw<sub>ZO</sub>l (K)</td><td>D (%)</td><td>Sample No.</td><td>Mwzol (K)</td><td>D (%)</td>
<td>M1</td><td></td><td> 1300</td><td></td><td></td><td> 971</td><td></td>
<td>M2</td><td></td><td> 932</td><td></td><td></td><td> 725</td><td></td>
<td>M3</td><td></td><td> 664</td><td></td><td></td><td> 596</td><td></td>
<td>M4</td><td></td><td> 485</td><td></td><td></td><td> 482</td><td></td>
<td>M1D1</td><td> 1</td><td> 465</td><td> 4,24</td><td> 17</td><td> 426</td><td> 4,35</td>
<td>M1D2</td><td> 2</td><td> 571</td><td> 3,70</td><td> 18</td><td> 467</td><td> 3,89</td>
<td>M1D3</td><td> 3</td><td> 706</td><td> 4,79</td><td> 19</td><td> 486</td><td> 4,86</td>
<td>M1D4</td><td> 4</td><td> 770</td><td> 4,52</td><td> 20</td><td> 535</td><td> 478</td>
<td>M2D1</td><td> 5</td><td> 445</td><td> 3,66</td><td> 21</td><td> 380</td><td> 2,44</td>
<td>M2D2</td><td> 6</td><td> 490</td><td> 2,68</td><td> 22</td><td> 398</td><td> 3,71</td>
<td>M2D3</td><td> 7</td><td> 512</td><td> 3,68</td><td> 23</td><td> 433</td><td> 4,30</td>
<td>M2D4</td><td> 8</td><td> 581</td><td> 3,93</td><td> 24</td><td> 498</td><td> 5,81</td>
<td>M3D1</td><td> 9</td><td> 373</td><td> 1,33</td><td> 25</td><td> 342</td><td> 3,79</td>
<td>M3D2</td><td> 10</td><td> 402</td><td> 2,50</td><td> 26</td><td> 358</td><td> 4,35</td>
<td>M3D3</td><td> 11</td><td> 407</td><td> 2,98</td><td> 27</td><td> 371</td><td> 5,55</td>
<td>M3D4</td><td> 12</td><td> 452</td><td> 3,35</td><td> 28</td><td> 408</td><td> 5,01</td>
<td>M4D1</td><td> 13</td><td> 311</td><td> 3,63</td><td> 29</td><td> 311</td><td> 3,66</td>
<td>M4D2</td><td> 14</td><td> 337</td><td> 3,40</td><td> 30</td><td> 325</td><td> 5,31</td>
<td>M4D3</td><td> 15</td><td> 362</td><td> 5,03</td><td> 31</td><td> 344</td><td> 5,91</td>
<td>M4D4</td><td> 16</td><td> 382</td><td> 5,23</td><td> 32</td><td> 369</td><td> 5,67</td>
Table 16 Table 17
<td rowspan="3">Code</td><td colspan="6">Black Pearl 800 / 55phr / 0</td><td rowspan="3">Code</td><td colspan="3">N351 / 33phr / 20phr</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td><td colspan="3">RSS1</td>
<td>No samples</td><td>ABOUT _ £</td><td>D (%)</td><td>No samples</td><td>Mw<sub>ZO</sub>l (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td>Ml</td><td></td><td> 1041</td><td></td><td></td><td> 869</td><td></td><td></td><td></td><td></td><td></td>
<td>M2</td><td></td><td> 786</td><td></td><td></td><td> 662</td><td></td><td>Ml</td><td></td><td> 1300</td><td></td>
<td>M3</td><td></td><td> 663</td><td></td><td></td><td> 491</td><td></td><td>M2</td><td></td><td> 803</td><td></td>
<td>M4</td><td></td><td> 527</td><td></td><td></td><td> 420</td><td></td><td>M3</td><td></td><td> 601</td><td></td>
<td>M1D1</td><td> 113</td><td> 507</td><td> 12,20</td><td> 129</td><td> 418</td><td> 5,15</td><td></td><td></td><td></td><td></td>
<td>M1D2</td><td> 114</td><td> 551</td><td> 15,10</td><td> 130</td><td> 482</td><td> 4,94</td><td>M1D1</td><td> 401</td><td> 854</td><td> 2,08</td>
<td>M1D3</td><td> 115</td><td> 700</td><td> 10,20</td><td> 131</td><td> 515</td><td> 6,93</td><td>M1D2</td><td> 402</td><td> 969</td><td> 3,41</td>
<td>M1D4</td><td> 116</td><td> 786</td><td> 5,72</td><td> 132</td><td> 583</td><td> 8,74</td><td>M1D3</td><td> 403</td><td> 1040</td><td> 3,68</td>
<td>M2D1</td><td> 117</td><td> 420</td><td> 5,65</td><td> 133</td><td> 403</td><td> 2,60</td><td>M1D4</td><td> 404</td><td> 1130</td><td> 4,91</td>
<td>M2D2</td><td> 118</td><td> 441</td><td> 6,50</td><td> 134</td><td> 438</td><td> 2,74</td><td></td><td></td><td></td><td></td>
<td>M2D3</td><td> 119</td><td> 549</td><td> 7,70</td><td> 135</td><td> 434</td><td> 2,83</td><td>M2D1</td><td> 405</td><td> 648</td><td> 1,15</td>
<td>M2D4</td><td> 120</td><td> 606</td><td> 5,88</td><td> 136</td><td> 530</td><td> 3,88</td><td>M2D2</td><td> 406</td><td> 668</td><td> 2,16</td>
<td>M3D1</td><td> 121</td><td> 387</td><td> 3,26</td><td> 137</td><td> 366</td><td> 2,38</td><td>M2D3</td><td> 407</td><td> 675</td><td> 2,98</td>
<td>M3D2</td><td> 122</td><td> 409</td><td> 2,98</td><td> 138</td><td> 378</td><td> 2,83</td><td>M2D4</td><td> 408</td><td> 721</td><td> 4,70</td>
<td>M3D3</td><td> 123</td><td> 456</td><td> 3,61</td><td> 139</td><td> 399</td><td> 3,04</td><td></td><td></td><td></td><td></td>
<td>M3D4</td><td> 124</td><td> 483</td><td> 4,61</td><td> 140</td><td> 431</td><td> 2,39</td><td>M3D1</td><td> 409</td><td> 532</td><td> 1,10</td>
<td>M4D1</td><td> 125</td><td> 339</td><td> 2,13</td><td> 141</td><td> 311</td><td> 2,22</td><td>M3D2</td><td> 410</td><td> 537</td><td> 2,17</td>
<td>M4D2</td><td> 126</td><td> 367</td><td> 2,23</td><td> 142</td><td> 332</td><td> 2,27</td><td>M3D3</td><td> 411</td><td> 535</td><td> 2,45</td>
<td>M4D3</td><td> 127</td><td> 360</td><td> 2,60</td><td> 143</td><td> 344</td><td> 2,27</td><td>M3D4</td><td> 412</td><td> 558</td><td> 4,06</td>
<td>M4D4</td><td> 128</td><td> 403</td><td> 1,96</td><td> 144</td><td> 390</td><td><sup>2</sup>,<sup>73</sup></td><td></td><td></td><td></td><td></td>
Table 18A
<td rowspan="3">Code</td><td colspan="6">Regal 250 / 55phr / 0</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td>
<td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td> 1</td><td colspan="3"> 2</td><td colspan="3"> 3</td>
<td>Ml</td><td></td><td> 1332</td><td></td><td></td><td> 1023</td><td></td>
<td>M2</td><td></td><td> 896</td><td></td><td></td><td> 748</td><td></td>
<td>M3</td><td></td><td> 603</td><td></td><td></td><td> 581</td><td></td>
<td>M4</td><td></td><td> 408</td><td></td><td></td><td> 504</td><td></td>
<td>M1D1</td><td> 33</td><td> 585</td><td> 6,95</td><td> 49</td><td> 609</td><td> 1,93</td>
189 105
continued from Table 18A
<td> 1</td><td colspan="3"> 2</td><td colspan="3"> 3</td>
<td>M1D2</td><td> 34</td><td> 669</td><td> 8,03</td><td> 50</td><td> 634</td><td> 3,29</td>
<td>M1D3</td><td> 35</td><td> 759</td><td> 10,50</td><td> 51</td><td> 681</td><td> 2,21</td>
<td>M1D4</td><td> 36</td><td> 896</td><td> 14,1</td><td> 52</td><td> 702</td><td> 4,09</td>
<td>M2D1</td><td> 37</td><td> 580</td><td> 2,71</td><td> 53</td><td> 539</td><td> 2,14</td>
<td>M2D2</td><td> 38</td><td> 602</td><td> 2,61</td><td> 54</td><td> 569</td><td> 2,72</td>
<td>M2D3</td><td> 39</td><td> 631</td><td> 3,61</td><td> 55</td><td> 587</td><td> 4,75</td>
<td>M2D4</td><td> 40</td><td> 667</td><td> 5,43</td><td> 56</td><td> 595</td><td> 6,25</td>
<td>M3D1</td><td> 41</td><td> 457</td><td> 1,53</td><td> 57</td><td> 466</td><td> 2,88</td>
<td>M3D2</td><td> 42</td><td> 476</td><td> 2,09</td><td> 58</td><td> 449</td><td> 3,19</td>
<td>M3D3</td><td> 43</td><td> 493</td><td> 2,32</td><td> 59</td><td> 464</td><td> 4,53</td>
<td>M3D4</td><td> 44</td><td> 495</td><td> 3,54</td><td> 60</td><td> 500</td><td> 5,89</td>
<td>M4D1</td><td> 45</td><td> 372</td><td> 1,53</td><td> 61</td><td> 423</td><td> 2,89</td>
<td>M4D2</td><td> 46</td><td> 382</td><td> 2,09</td><td> 62</td><td> 433</td><td> 3,42</td>
<td>M4D3</td><td> 47</td><td> 381</td><td> 2,32</td><td> 63</td><td> 437</td><td> 4,39</td>
<td>M4D4</td><td> 48</td><td> 403</td><td> 3,54</td><td> 64</td><td> 447</td><td> 4,73</td>
Table 18B
<td rowspan="3">Code</td><td colspan="3">Regal 250 / 65phr / 0</td><td colspan="3">Regal 250 / 75phr / 0</td><td colspan="3">Regal 250 / 65phr / 10</td>
<td colspan="3">RSS1</td><td colspan="3">RSS1</td><td colspan="3">RSS1</td>
<td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Ml</td><td></td><td> 1138</td><td></td><td></td><td> 1138</td><td></td><td></td><td> 1138</td><td></td>
<td>M2</td><td></td><td> 901</td><td></td><td></td><td> 901</td><td></td><td></td><td> 901</td><td></td>
<td>M3</td><td></td><td> 660</td><td></td><td></td><td> 660</td><td></td><td></td><td> 660</td><td></td>
<td>M4</td><td></td><td> 483</td><td></td><td></td><td> 483</td><td></td><td></td><td> 483</td><td></td>
<td>M1D1</td><td> 65</td><td> 570</td><td> 1,50</td><td> 81</td><td> 539</td><td> 2,87</td><td> 97</td><td> 661</td><td> 1,89</td>
<td>M1D2</td><td> 66</td><td> 622</td><td> 3,25</td><td> 82</td><td> 624</td><td> 4,50</td><td> 98</td><td> 702</td><td> 2,69</td>
<td>M1D3</td><td> 67</td><td> 707</td><td> 7,50</td><td> 83</td><td> 685</td><td> 4,17</td><td> 99</td><td> 741</td><td> 3,14</td>
<td>M1D4</td><td> 68</td><td> 788</td><td> 4,77</td><td> 84</td><td> 763</td><td> 14,35</td><td> 100</td><td> 822</td><td> 5,24</td>
<td>M2D1</td><td> 69</td><td> 534</td><td> 1,62</td><td> 85</td><td> 484</td><td> 4,32</td><td> 101</td><td> 593</td><td> 0,91</td>
<td>M2D2</td><td> 70</td><td> 548</td><td> 4,19</td><td> 86</td><td> 512</td><td> 2,96</td><td> 102</td><td> 572</td><td> 3,48</td>
<td>M2D3</td><td> 71</td><td> 585</td><td> 4,31</td><td> 87</td><td> 227</td><td> 4,71</td><td> 103</td><td> 642</td><td> 4,23</td>
<td>M2D4</td><td> 72</td><td> 621</td><td> 6,21</td><td> 88</td><td> 605</td><td> 4,85</td><td> 104</td><td> 664</td><td> 5,35</td>
<td>M3D1</td><td> 73</td><td> 459</td><td> 3,64</td><td> 89</td><td> 429</td><td> 2,27</td><td> 105</td><td> 507</td><td> 2,65</td>
189 105
continued from Table 18B
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>M3D2</td><td> 74</td><td> 469</td><td> 5,79</td><td> 90</td><td> 446</td><td> 2,68</td><td> 106</td><td> 544</td><td> 2,96</td>
<td>M3D3</td><td> 75</td><td> 511</td><td> 5,30</td><td> 91</td><td> 466</td><td> 3,46</td><td> 107</td><td> 535</td><td> 3,69</td>
<td>M3D4</td><td> 76</td><td> 541</td><td> 9,13</td><td> 92</td><td> 491</td><td> 6,22</td><td> 108</td><td> 524</td><td> 3,27</td>
<td>M4D1</td><td> 77</td><td> 380</td><td> 2,34</td><td> 93</td><td> 368</td><td> 2,11</td><td> 109</td><td> 416</td><td> 1,85</td>
<td>M4D2</td><td> 78</td><td> 392</td><td> 2,86</td><td> 94</td><td> 372</td><td> 3,13</td><td> 110</td><td> 413</td><td> 3,18</td>
<td>M4D3</td><td> 79</td><td> 399</td><td> 4,59</td><td> 95</td><td> 375</td><td> 2,92</td><td> 111</td><td> 418</td><td> 6,96</td>
<td>M4D4</td><td> 80</td><td> 395</td><td> 4,57</td><td> 96</td><td> 388</td><td> 2,92</td><td> 112</td><td> 441</td><td> 6,46</td>
Table 19 Table 21 (A)
<td rowspan="3">Code</td><td colspan="6">N326 / 55phr / 0</td><td rowspan="3">Code</td><td colspan="3">S6740 / 55 / 0phr</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td><td colspan="3">RSS1</td>
<td>No samples</td><td>MWzol (K)</td><td>D (%)</td><td>No samples</td><td>MWzol (K)</td><td>D (%)</td><td>No samples</td><td>MW<sub>WITH</sub>ol (K)</td><td>D (%)</td>
<td>Ml</td><td></td><td> 1200</td><td></td><td></td><td> 1060</td><td colspan="2">1 M1</td><td></td><td> 108</td><td></td>
<td></td><td></td><td></td><td></td><td></td><td></td><td colspan="2"></td><td></td><td> 0</td><td></td>
<td>M2</td><td></td><td> 1030</td><td></td><td></td><td> 934</td><td colspan="2">1 M2</td><td></td><td> 837</td><td></td>
<td>M3</td><td></td><td> 724</td><td></td><td></td><td> 777</td><td colspan="2">And M3</td><td></td><td> 724</td><td></td>
<td>M4</td><td></td><td> 635</td><td></td><td></td><td> 644</td><td colspan="2">| M4</td><td></td><td> 532</td><td></td>
<td>M1D1</td><td> 145</td><td> 550</td><td> 3,49</td><td> 161</td><td> 644</td><td colspan="2">1J5 | M1D1</td><td> 412</td><td> 515</td><td> 1,24</td>
<td>M1D2</td><td> 146</td><td> 636</td><td> 3,54</td><td> 162</td><td> 661</td><td colspan="2">1.32 | M1D2</td><td> 413</td><td> 556</td><td> 1,32</td>
<td>M1D3</td><td> 147</td><td> 650</td><td> 5,89</td><td> 163</td><td> 697</td><td colspan="2">1.35 1 M1D3</td><td> 414</td><td> 633</td><td> 1,41</td>
<td>M1D4</td><td> 148</td><td> 724</td><td> 4,79</td><td> 164</td><td> 732</td><td colspan="2">2.01 | M1D4</td><td> 415</td><td> 732</td><td> 1,43</td>
<td>M2D1</td><td> 149</td><td> 517</td><td> 3,16</td><td> 165</td><td> 590</td><td colspan="2">1.50 | M2D1</td><td> 416</td><td> 433</td><td> 0,86</td>
<td>M2D2</td><td> 150</td><td> 572</td><td> 2,41</td><td> 166</td><td> 621</td><td colspan="2">1.56 | M2D2</td><td> 417</td><td> 451</td><td> 0,90</td>
<td>M2D3</td><td> 151</td><td> 613</td><td> 3,11</td><td> 167</td><td> 641</td><td colspan="2">2.22 | M2D3</td><td> 418</td><td> 495</td><td> 1,53</td>
<td>M2D4</td><td> 152</td><td> 696</td><td> 4,37</td><td> 168</td><td> 676</td><td colspan="2">2,: 31 | M2D4</td><td> 419</td><td> 542</td><td> 2,15</td>
<td>M3D1</td><td> 153</td><td> 489</td><td> 2,76</td><td> 169</td><td> 551</td><td colspan="2">1,: ^^ 1 M3D1</td><td> 420</td><td> 405</td><td> 0,25</td>
<td>M3D2</td><td> 154</td><td> 521</td><td> 1,93</td><td> 170</td><td> 550</td><td colspan="2">1.62 | M3D2</td><td> 421</td><td> 418</td><td> 0,50</td>
<td>M3D3</td><td> 155</td><td> 504</td><td> 3,14</td><td> 171</td><td> 563</td><td colspan="2">2.06 | M3D3</td><td> 422</td><td> 447</td><td> 0,75</td>
<td>M3D4</td><td> 156</td><td> 538</td><td> 2,81</td><td> 172</td><td> 578</td><td colspan="2">2.68 | M3D4</td><td> 423</td><td> 469</td><td> 0.73</td>
<td>M4D1</td><td> 157</td><td> 415</td><td> 1,74</td><td> 173</td><td> 487</td><td colspan="2">L96 J M4D1</td><td> 424</td><td> 371</td><td> 0,21</td>
<td>M4D2</td><td> 158</td><td> 447</td><td> 2,17</td><td> 174</td><td> 495</td><td colspan="2">2.22 | M4D2</td><td> 425</td><td> 387</td><td> 0,42</td>
<td>M4D3</td><td> 159</td><td> 466</td><td> 3,13</td><td> 175</td><td> 505</td><td colspan="2">2.99 | M4D3</td><td> 426</td><td> 382</td><td> 0,30</td>
<td>M4D4</td><td> 160</td><td> 469</td><td> 2,93</td><td> 176</td><td> 526</td><td colspan="2">3.337 | M4D4</td><td> 427</td><td> 396</td><td> 0,56</td>
189 105
Table 20 Table 21 (B)
<td rowspan="3">Code</td><td colspan="6">N110 / 55phr / 0</td><td rowspan="3">Code</td><td colspan="3">S6740 / 55 / 0phr</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td><td colspan="3">SMRCV</td>
<td>No samples</td><td>Mw<sub>WITH</sub>ol (K)</td><td>D (%)</td><td>No samples</td><td>Mw<sub>ZO</sub>l (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td>Ml</td><td></td><td> 937</td><td></td><td></td><td> 730</td><td colspan="2">And Ml</td><td></td><td> 876</td><td></td>
<td>M2</td><td></td><td> 764</td><td></td><td></td><td> 653</td><td colspan="2">M2</td><td></td><td> 754</td><td></td>
<td>M3</td><td></td><td> 569</td><td></td><td></td><td> 541</td><td colspan="2">1 M3</td><td></td><td> 574</td><td></td>
<td>M4</td><td></td><td> 449</td><td></td><td></td><td> 463</td><td colspan="2">And M4</td><td></td><td> 444</td><td></td>
<td>M1D1</td><td> 369</td><td> 360</td><td> 1,24</td><td> 3851</td><td> 334</td><td> 1,28</td><td>M1D1</td><td> 428</td><td> 433</td><td> 0,25</td>
<td>M1D2</td><td> 370</td><td> 426</td><td> 2,50</td><td> 386</td><td> 339</td><td> 1,60</td><td>M1D2</td><td> 429</td><td> 467</td><td> 0,34</td>
<td>M1D3</td><td> 371</td><td> 490</td><td> 2,69</td><td> 387</td><td> 372</td><td> 1,42</td><td>M1D3</td><td> 430</td><td> 633</td><td> 0,84</td>
<td>M1D4</td><td> 372</td><td> 618</td><td> 4,68</td><td> 388</td><td> 413</td><td> 2,80</td><td>M1D4</td><td> 431</td><td> 540</td><td> 1,43</td>
<td>M2D1</td><td> 373</td><td> 340</td><td> 0,69</td><td> 389</td><td> 309</td><td> 0,72</td><td>M2D1</td><td> 432</td><td> 399</td><td> 0,35</td>
<td>M2D2</td><td> 374</td><td> 356</td><td> 0,85</td><td> 390</td><td> 314</td><td> 1,17</td><td>M2D2</td><td> 433</td><td> 399</td><td> 0,41</td>
<td>M2D3</td><td> 375</td><td> 395</td><td> 0,90</td><td> 391</td><td> 342</td><td> 1,27</td><td>M2D3</td><td> 434</td><td> 422</td><td> 0,62</td>
<td>M2D4</td><td> 376</td><td> 433</td><td> 1,17</td><td> 392</td><td> 380</td><td> 2,94</td><td>M2D4</td><td> 435</td><td> 469</td><td> 0,44</td>
<td>M3D1</td><td> 377</td><td> 295</td><td> 0,81</td><td> 393</td><td> 271</td><td> 0,94</td><td>M3D1</td><td> 436</td><td> 340</td><td> 0,44</td>
<td>M3D2</td><td> 378</td><td> 313</td><td> 1,27</td><td> 394</td><td> 292</td><td> 0,93</td><td>M3D2</td><td> 437</td><td> 363</td><td> 0,81</td>
<td>M3D3</td><td> 379</td><td> 333</td><td> 1,20</td><td> 395</td><td> 314</td><td> 1,43</td><td>M3D3</td><td> 438</td><td> 377</td><td> 0,89</td>
<td>M3D4</td><td> 380</td><td> 353</td><td> 1,35</td><td> 396</td><td> 351</td><td> 1,77</td><td>M3D4</td><td> 439</td><td> 403</td><td> 0,86</td>
<td>M4D1</td><td> 381</td><td> 255</td><td> 1,12</td><td> 397</td><td> 260</td><td> 0,74</td><td>M4D1</td><td> 440</td><td> 363</td><td> 0,65</td>
<td>M4D2</td><td> 382</td><td> 269</td><td> 1,14</td><td> 398</td><td> 267</td><td> 0,93</td><td>M4D2</td><td> 441</td><td> 328</td><td> 1,05</td>
<td>M4D3</td><td> 383</td><td> 287</td><td> 1,30</td><td> 399</td><td> 284</td><td> 1,49</td><td>M4D3</td><td> 442</td><td> 342</td><td> 1,52</td>
<td>M4D4</td><td> 384</td><td> 316</td><td> 1,67</td><td> 400</td><td> 297</td><td> 1,83</td><td>M4D4</td><td> 443</td><td> 360</td><td> 1,99</td>
Table 22 (A)
<td rowspan="3">Code</td><td colspan="9">Regal 660 / 55phr / 0</td>
<td colspan="3">RSS1</td><td colspan="3">SMRCV</td><td colspan="3">SMR10</td>
<td>No samples</td><td>Mw<sub>WITH</sub>about] (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>MWzol (K)</td><td>D (%)</td>
<td> 1</td><td> 2</td><td>ABOUT J.</td><td> 4</td><td>c</td><td> 6</td><td>Ή 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Ml</td><td></td><td> 1110</td><td></td><td></td><td> 836</td><td></td><td></td><td> 746</td><td></td>
<td>M2</td><td></td><td> 844</td><td></td><td></td><td> 709</td><td></td><td></td><td> 632</td><td></td>
<td>M3</td><td></td><td> 609</td><td></td><td></td><td> 584</td><td></td><td></td><td> 492</td><td></td>
<td>M4</td><td></td><td> 522</td><td></td><td></td><td> 513</td><td></td><td></td><td> 416</td><td></td>
189 105
continuation of table 22 (A)
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>M1D1</td><td> 177</td><td> 674</td><td> 8,35</td><td> 193</td><td> 564</td><td> 1,87</td><td> 209</td><td> 501</td><td> 9,54</td>
<td>M1D2</td><td> 178</td><td> 792</td><td> 7,89</td><td> 194</td><td> 611</td><td> 2,50</td><td> 210</td><td> 572</td><td> 6,68</td>
<td>M1D3</td><td> 179</td><td> 891</td><td> 8,53</td><td> 195</td><td> 708</td><td> 3,08</td><td> 211</td><td> 681</td><td> 7,37</td>
<td>M1D4</td><td> 180</td><td> 676</td><td> 7,46</td><td> 196</td><td> 671</td><td> 2,31</td><td> 212</td><td> 594</td><td> 7,18</td>
<td>M2D1</td><td> 181</td><td> 598</td><td> 8,56</td><td> 197</td><td> 520</td><td> 5,28</td><td> 213</td><td> 463</td><td> 2,82</td>
<td>M2D2</td><td> 182</td><td> 602</td><td> 3,89</td><td> 198</td><td> 558</td><td> 4,85</td><td> 214</td><td> 483</td><td> 4,57</td>
<td>M2D3</td><td> 183</td><td> 697</td><td> 6,40</td><td> 199</td><td> 603</td><td> 2,88</td><td> 215</td><td> 565</td><td> 3,92</td>
<td>M2D4</td><td> 184</td><td> 659</td><td> 5,71</td><td> 200</td><td> 541</td><td> 4,25</td><td> 216</td><td> 550</td><td> 5,68</td>
<td>M3D1</td><td> 185</td><td> 473</td><td> 2,03</td><td> 201</td><td> 486</td><td> 2,79</td><td> 217</td><td> 395</td><td> 2,13</td>
<td>M3D2</td><td> 186</td><td> 506</td><td> 1,66</td><td> 202</td><td> 482</td><td> 2,76</td><td> 218</td><td> 393</td><td> 1,98</td>
<td>M3D3</td><td> 187</td><td> 562</td><td> 1,94</td><td> 203</td><td> 504</td><td> 3,54</td><td> 219</td><td> 443</td><td> 2,49</td>
<td>M3D4</td><td> 188</td><td> 559</td><td> 4,33</td><td> 204</td><td> 526</td><td> 2,41</td><td> 220</td><td> 449</td><td> 1,90</td>
<td>M4D1</td><td> 189</td><td> 401</td><td> 2,18</td><td> 205</td><td> 415</td><td> 3,16</td><td> 221</td><td> 335</td><td> 1,49</td>
<td>M4D2</td><td> 190</td><td> 426</td><td> 1,72</td><td> 206</td><td> 418</td><td> 2,92</td><td> 222</td><td> 345</td><td> 1,71</td>
<td>M4D3</td><td> 191</td><td> 466</td><td> 1,48</td><td> 207</td><td> 446</td><td> 2,80</td><td> 223</td><td> 363</td><td> 1,78</td>
<td>M4D4</td><td> 192</td><td> 449</td><td> 3,57</td><td> 208</td><td> 465</td><td> 3,13</td><td> 224</td><td> 374</td><td> 2,35</td>
Table 22 (B)
<td rowspan="3">Code</td><td colspan="3">Regal 660/45/0</td><td colspan="3">Regal 660/65/0</td><td colspan="3">Regal 660/65/10</td>
<td colspan="3">RSS1</td><td colspan="3">RSS1</td><td colspan="3">RSS1</td>
<td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>MW<sub>with</sub>ol (K)</td><td>D (%)</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Ml</td><td></td><td> 1245</td><td></td><td></td><td> 1245</td><td></td><td></td><td> 1245</td><td></td>
<td>M2</td><td></td><td> 876</td><td></td><td></td><td> 876</td><td></td><td></td><td> 876</td><td></td>
<td>M3</td><td></td><td> 625</td><td></td><td></td><td> 625</td><td></td><td></td><td> 625</td><td></td>
<td>M4</td><td></td><td> 482</td><td></td><td></td><td> 482</td><td></td><td></td><td> 482</td><td></td>
<td>M1D1</td><td> 225</td><td> 646</td><td> 3,45</td><td> 241</td><td> 563</td><td> 14,55</td><td> 257</td><td> 639</td><td> 1,63</td>
<td>M1D2</td><td> 226</td><td> 697</td><td> 3,04</td><td> 242</td><td> 638</td><td> 14,09</td><td> 256</td><td> 699</td><td> 3,55</td>
<td>M1D3</td><td> 227</td><td> 762</td><td> 7,70</td><td> 243</td><td> 691</td><td> 13,64</td><td> 259</td><td> 814</td><td> 5,44</td>
<td>M1D4</td><td> 228</td><td> 830</td><td> 6,75</td><td> 244</td><td> 790</td><td> 11,26</td><td> 260</td><td> 764</td><td> 11,25</td>
<td>M2D1</td><td> 229</td><td> 574</td><td> 4,79</td><td> 245</td><td> 469</td><td> 5,88</td><td> 261</td><td> 572</td><td> 2,77</td>
<td>M2D2</td><td> 230</td><td> 589</td><td> 3,02</td><td> 246</td><td> 507</td><td> 7,31</td><td> 262</td><td> 580</td><td> 4,39</td>
<td>M2D3</td><td> 231</td><td> 636</td><td> 6,41</td><td> 247</td><td> 558</td><td> 9,72</td><td> 263</td><td> 610</td><td> 5,51</td>
<td>M2D4</td><td> 232</td><td> 675</td><td> 6,55</td><td> 248</td><td> 543</td><td> 10,59</td><td> 264</td><td> 638</td><td> 7,29</td>
189 105
table continued 22 (B)
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>M3D1</td><td> 233</td><td> 471</td><td> 2,77</td><td> 249</td><td> 420</td><td> 5,48</td><td> 265</td><td> 474</td><td> 4,10</td>
<td>M3D2</td><td> 234</td><td> 481</td><td> 5,17</td><td> 250</td><td> 426</td><td> 6,97</td><td> 266</td><td> 485</td><td> 5,72</td>
<td>M3D3</td><td> 235</td><td> 510</td><td> 7,78</td><td> 251</td><td> 468</td><td> 8,81</td><td> 267</td><td> 502</td><td> 6,24</td>
<td>M3D4</td><td> 236</td><td> 518</td><td> 7,89</td><td> 252</td><td> 471</td><td> 9,55</td><td> 268</td><td> 495</td><td> 7,13</td>
<td>M4D1</td><td> 237</td><td> 388</td><td> 3,20</td><td> 253</td><td> 335</td><td> 5,19</td><td> 269</td><td> 390</td><td> 5,02</td>
<td>M4D2</td><td> 238</td><td> 392</td><td> 5,65</td><td> 254</td><td> 344</td><td> 6,06</td><td> 270</td><td> 365</td><td> 5,88</td>
<td>M4D3</td><td> 239</td><td> 397</td><td> 5,14</td><td> 255</td><td> 344</td><td> 5,59</td><td> 271</td><td> 410</td><td> 7,45</td>
<td>M4D4</td><td> 240</td><td> 403</td><td> 7,54</td><td> 256</td><td> 361</td><td> 8,54</td><td> 2,72</td><td> 388</td><td> 7,59</td>
Table 23 (A)
<td rowspan="3">Code</td><td colspan="9">N234 / 55phr / 0</td>
<td colspan="3">RSSJ</td><td colspan="3">SMRCV</td><td colspan="3">SMR10</td>
<td>No samples</td><td>Mw<sub>WITH</sub>ol (K)</td><td>D (%)</td><td>No samples</td><td>Mw<sub>WITH</sub>cl (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td>Ml</td><td></td><td> 1060</td><td></td><td></td><td> 845</td><td></td><td></td><td> 743</td><td></td>
<td>M2</td><td></td><td> 811</td><td></td><td></td><td> 712</td><td></td><td></td><td> 621</td><td></td>
<td>M3</td><td></td><td> 595</td><td></td><td></td><td> 577</td><td></td><td></td><td> 445</td><td></td>
<td>M4</td><td></td><td> 466</td><td></td><td></td><td> 477</td><td></td><td></td><td> 388</td><td></td>
<td>M1D1</td><td> 273</td><td> 350</td><td> 1,88</td><td> 289</td><td> 312</td><td> 0,61</td><td> 305</td><td> 325</td><td> 0,78</td>
<td>M1D2</td><td> 274</td><td> 476</td><td> 3,40</td><td> 290</td><td> 317</td><td> 0,64</td><td> 306</td><td> 363</td><td> 1,66</td>
<td>M1D3</td><td> 275</td><td> 459</td><td> 2,70</td><td> 291</td><td> 361</td><td> 1,03</td><td> 307</td><td> 400</td><td> 1,89</td>
<td>M1D4</td><td> 276</td><td> 665</td><td> 2,70</td><td> 292</td><td> 419</td><td> 1,56</td><td> 308</td><td> 459</td><td> 1,73</td>
<td>M2D1</td><td> 277</td><td> 323</td><td> 0,40</td><td> 293</td><td> 304</td><td> 0,76</td><td> 309</td><td> 294</td><td> 0,54</td>
<td>M2D2</td><td> 278</td><td> 371</td><td> 0,73</td><td> 294</td><td> 306</td><td> 0,72</td><td> 310</td><td> 321</td><td> 1,24</td>
<td>M2D3</td><td> 279</td><td> 398</td><td> 0,74</td><td> 295</td><td> 318</td><td> 0,74</td><td> 311</td><td> 354</td><td> 1,28</td>
<td>M2D4</td><td> 280</td><td> 464</td><td> 1,42</td><td> 296</td><td> 357</td><td> 1,30</td><td> 312</td><td> 363</td><td> 1,39</td>
<td>M3D1</td><td> 281</td><td> 278</td><td> 0,47</td><td> 297</td><td> 260</td><td> 0,53</td><td> 313</td><td> 260</td><td> 0,69</td>
<td>M3D2</td><td> 282</td><td> 304</td><td> 0,83</td><td> 298</td><td> 272</td><td> 0,65</td><td> 314</td><td> 268</td><td> 0,48</td>
<td>M3D3</td><td> 283</td><td> 323</td><td> 0,82</td><td> 299</td><td> 295</td><td> 0,58</td><td> 315</td><td> 289</td><td> 1,38</td>
<td>M3D4</td><td> 284</td><td> 260</td><td> 1,06</td><td> 300</td><td> 302</td><td> 1,14</td><td> 316</td><td> 303</td><td> 0,78</td>
<td>M4D1</td><td> 285</td><td> 251</td><td> 0,61</td><td> 301</td><td> 244</td><td> 0,53</td><td> 317</td><td> 236</td><td> 1,00</td>
<td>M4D2</td><td> 286</td><td> 266</td><td> 0,51</td><td> 302</td><td> 253</td><td> 0,81</td><td> 318</td><td> 239</td><td> 0,77</td>
<td>M4D3</td><td> 287</td><td> 273</td><td> 0,64</td><td> 303</td><td> 266</td><td> 0,62</td><td> 319</td><td> 257</td><td> 0,72</td>
<td>M4D4</td><td> 288</td><td> 282</td><td> 0,53</td><td> 304</td><td> 296</td><td> 0,88</td><td> 320</td><td> 268</td><td> 1,30</td>
189 105
Table 23 (B)
<td rowspan="3">Code</td><td colspan="3">N234 / 45/0</td><td colspan="3">N234 / 65/0</td><td colspan="3">N234 / 65/10</td>
<td colspan="3">RSS1</td><td colspan="3">RSS1</td><td colspan="3">RSS1</td>
<td>No samples</td><td>Mw<sub>z0</sub>l (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td><td>No samples</td><td>Mwzol (K)</td><td>D (%)</td>
<td>Ml</td><td></td><td> 1185</td><td></td><td></td><td> 1185</td><td></td><td></td><td> 1185</td><td></td>
<td>M2</td><td></td><td> 828</td><td></td><td></td><td> 828</td><td></td><td></td><td> 828</td><td></td>
<td>M3</td><td></td><td> 623</td><td></td><td></td><td> 623</td><td></td><td></td><td> 623</td><td></td>
<td>M4</td><td></td><td> 462</td><td></td><td></td><td> 462</td><td></td><td></td><td> 462</td><td></td>
<td>M1D1</td><td> 321</td><td> 507</td><td> 7,33</td><td> 337</td><td> 336</td><td> 3,44</td><td> 353</td><td> 395</td><td> 5,51</td>
<td>M1D2</td><td> 322</td><td> 598</td><td> 8,15</td><td> 338</td><td> 458</td><td> 5,09</td><td> 354</td><td> 478</td><td> 7,68</td>
<td>M1D3</td><td> 323</td><td> 731</td><td> 8,97</td><td> 339</td><td> 479</td><td> 8,17</td><td> 355</td><td> 555</td><td> 9,46</td>
<td>M1D4</td><td> 324</td><td> 772</td><td> 12,02</td><td> 340</td><td> 706</td><td> 9,90</td><td> 356</td><td> 637</td><td> 8,39</td>
<td>M2D1</td><td> 325</td><td> 486</td><td> 3,48</td><td> 341</td><td> 255</td><td> 3,22</td><td> 357</td><td> 292</td><td> 0,58</td>
<td>M2D2</td><td> 326</td><td> 479</td><td> 5,44</td><td> 342</td><td> 288</td><td> 3,34</td><td> 357</td><td> 352</td><td> 1,23</td>
<td>M2D3</td><td> 327</td><td> 527</td><td> 5,51</td><td> 343</td><td> 295</td><td> 4,65</td><td> 359</td><td> 394</td><td> 1,35</td>
<td>M2D4</td><td> 328</td><td> 566</td><td> 7,70</td><td> 344</td><td> 393</td><td> 5,45</td><td> 360</td><td> 449</td><td> 2,37</td>
<td>M3D1</td><td> 329</td><td> 419</td><td> 0,88</td><td> 345</td><td> 237</td><td> 1,50</td><td> 361</td><td> 292</td><td> 0,86</td>
<td>M3D2</td><td> 330</td><td> 423</td><td> 1,24</td><td> 346</td><td> 252</td><td> 1,78</td><td> 362</td><td> 286</td><td> 1,14</td>
<td>M3D3</td><td> 331</td><td> 431</td><td> 2,55</td><td> 347</td><td> 270</td><td> 2,88</td><td> 363</td><td> 313</td><td> 2,19</td>
<td>M3D4</td><td> 332</td><td> 458</td><td> 4,03</td><td> 348</td><td> 304</td><td> 3,92</td><td> 364</td><td> 340</td><td> 2,51</td>
<td>M4D1</td><td> 33</td><td> 341</td><td> 0,62</td><td> 349</td><td> 226</td><td> 1,18</td><td> 365</td><td> 265</td><td> 0,83</td>
<td>M4D2</td><td> 334</td><td> 338</td><td> 1,13</td><td> 350</td><td> 214</td><td> 1,81</td><td> 366</td><td> 273</td><td> 0,99</td>
<td>M4D3</td><td> 335</td><td> 319</td><td> 1,37</td><td> 351</td><td> 233</td><td> 2,97</td><td> 367</td><td> 291</td><td> 1,39</td>
<td>M4D4</td><td> 336</td><td> 354</td><td> 2,06</td><td> 352</td><td> 258</td><td> 3,83</td><td> 368</td><td> 307</td><td> 2,41</td>
Examples of recommended forms of implementation
Additional samples of the elastomer composites of the present invention were produced. Specifically, the # 1-32 series of natural rubber elastomer composites in accordance with the present invention were made using the apparatus and procedures generally as in Example A above. The elastomeric composites included half a natural rubber latex from Malaysia with the properties shown in Table 24 below. Each of the elastomer composites contained a carbon black with morphological properties (structure and surface area) from Regions I, II or III of Fig. 8. Specifically, the following carbon blacks were used: Regal® 660, N234, N326, NI 10, Regal® 250, N330, Black Pearl® 800, Sterling® 6740 and N351. The carbon black contents ranged from 30 to 75 phr and the filling oil contents ranged from Odo 20 phr. Details of the preparation of elastomer composite sample No. 1-32 are shown in Table 25.
As noted above, the apparatus and procedures used to make elastomer composites # 1-32 were generally consistent with those of Example A, including the masterbatch formulation additives shown in Table 2. A more detailed description of the apparatus and procedures used for Elastomeric composites # 1-32 is provided. below.
189 105
1. Equipment
Inventive specimens 1-32 were prepared using a masterbatch preparation apparatus essentially of the inventive apparatus described above with reference to Figs. 1, 4 and 7. The diameter of the tip of the slurry nozzle (see item 167 in Fig. 7) and the length The body (see item 168 in Fig. 7) is given in Table 25 for each of samples Nos. 1-32. The coagulation zone of the device had four zones of progressively increasing diameter from the mixing zone to the exit orifice. The diameter and axial length of each of the four zones (the first being partially inside the mixing head and partially inside the sealed extension) is shown in Table 25. There were short axis spherical joints between the zones.
2. Preparation of a soot slurry.
The bags of carbon black were mixed with deionized water in a carbon black suspension tank equipped with an agitator. The agitator shredded the granules into pieces and a crude carbon black slurry was formed. The concentration of the carbon black (as a percentage by weight) in the carbon black slurry for each sample is given in Table 25. During the operation, this slurry was continuously pumped by an air diaphragm pump into the grinder for initial dispersion. The slurry was then fed via an air diaphragm pump to a colloid mill which was then fed to a progressively ascending chamber pump to a homogenizer, namely a Microfluidizer Model M210 homogenizer from Microfluidics International Corporation. The microfluidicator produced a finely divided slurry. The flow rate of the slurry from the microfluidizer to the mixing zone was set by the speed of the microfluidizer, with the microfluidizer acting as a high pressure positive displacement pump. The flow rate of the slurry was monitored with a Micromotion® mass flow meter. The pressure at which the carbon black slurry was fed to the homogenizer and the homogenizer output pressure (all pressures in kPa) were reported for each sample in Table 25. From the homogenizer, the carbon black slurry was fed to the accumulator to reduce any fluctuation in slurry pressure at the end of the slurry nozzle in the mixing zone. The terminating pressure of the slurry nozzle and the flow rate at which the slurry was fed to the mixing zone for each sample are given in Table 25.
3. Delivering latex
The latex was charged to a 0.21 m3 feed tank. The antioxidant emulsion was added to the latex prior to loading and mixed prior to loading. Antioxidants were added consisting of 0.3 phr of tris-nonylphenyl phosphite (TNPP) and Santoplex® 134 (a mixture of alkylaryl-p-phenylenediamine) in the amount shown in Table 25. Each of the antioxidants was made into a 40 wt% emulsion using 4 parts potassium oleate to 100 parts antioxidant together with potassium hydroxide to adjust the pH of the emulsion to about 10. Filling oil, if any, was added as shown in Table 25. For latex transfer. from the feed vessel to the mixing zone of the coagulation reactor, a peristaltic pump was used. The latex flow rate and velocity are shown in Table 25. The flow rate was measured automatically with an Endress + Hauser mass flow meter (Greenwood, Indiana, USA). The desired carbon black content was obtained by maintaining the appropriate ratio between the latex feed rate and the carbon black slurry feed rate.
4. Mixing of carbon black and latex.
The carbon black slurry and latex were mixed by entraining the latex into the carbon black slurry. During the entrainment, the carbon black was thoroughly mixed with the latex and the mixture was coagulated. The soft, moist, spongy coagulum "worms" left the coagulation reactor.
5. Drainage.
The water content of the wet particles discharged from the coagulation reactor is shown in Table 25. The wet particles were dehydrated using a dewatering extruder (The French Oil Mill Machinery Company; 8.9 cm diameter). In the extruder, the wet particles were compressed and the particles squeezed out water through the slot of the extruder barrel. The final particle moisture content is shown in Table 25 for each of the samples of the invention.
189 105
Drying and cooling.
The dehydrated particles were discharged into the second extruder, where they were compressed again and heated. Water was discarded while the particles were expelled through the lamellar matrix of the extruder. Product exit temperature and moisture content are shown in Table 25. The hot, dry particles were cooled rapidly (approximately 20 seconds) to approximately 37.8 ° C via a forced air vibrating conveyor.
Table 24. Properties of natural rubber latex
<td>Type latex</td><td>Source</td><td>Additives</td><td>% dry rubber</td><td>% of total solids</td><td>% ash</td><td>Nitrogen ppm</td><td>Volatile fatty acid</td>
<td>Concentrate</td><td>T1T1 latex SDN.BHD</td><td>0.35% NH3 ZnO, TMTD 0.1% HHS</td><td> 60</td><td> 62,0</td><td> 0,15</td><td> 0,29</td><td> 0,022</td>
<td>Latex field</td><td>RRIM 9/94</td><td>0.15% HNS<sup>C. </sup>0.3% NH3, ZnO.TMTD<sup>b</sup></td><td> 28,4</td><td> 34,2</td><td> 0,38</td><td> 0,366</td><td> 0,052</td>
a RR1M stands for Rubber Research Institute of Malaysia b ZnO / TMTD used as a biological preservative, typically 0.025% 1: 1 mixture c NS neutral hydroxylamine sulfate, Mooney viscosity stabilizer
Table 25 Details of the sample preparation according to the invention
<td rowspan="3">The sample according to the invention no</td><td colspan="4">Cabot elastomer composite</td><td colspan="2">Termination of the slurry nozzle</td><td colspan="2">Microfluidizer</td>
<td rowspan="2">Latex type</td><td colspan="2">Soot</td><td rowspan="2">Oil content (phr)</td><td rowspan="2">Diameter (mm)</td><td rowspan="2">Length body (mm)</td><td rowspan="2">Pressure inlet (kPa)</td><td rowspan="2">Pressure outlet (kPa)</td>
<td>Type</td><td>Content phr</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 1</td><td>Half latex</td><td>N330</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1390</td><td> 20682</td>
<td> 2</td><td>Half latex</td><td>N330</td><td> 55</td><td> 0</td><td> 1,0</td><td> 25,4</td><td> 2068</td><td> 0</td>
<td></td><td>Half latex</td><td>N330</td><td> 55</td><td> 0</td><td> 1,0</td><td> 25,4</td><td> 2068</td><td> 0</td>
<td> 4</td><td>Half latex</td><td>REGAL 250</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1241</td><td> 24129</td>
<td> 5</td><td>Half latex</td><td>REGAL 250</td><td> 65</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 2068</td><td> 68940</td>
<td> 6</td><td>Half latex</td><td>REGAL 250</td><td> 75</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1379</td><td> 89622</td>
<td> 7</td><td>Half latex</td><td>REGAL 250</td><td> 65</td><td> 10</td><td> 0,6</td><td> 12,7</td><td> 1723</td><td> 82728</td>
<td> 8</td><td>Half latex</td><td>BLACK PEARL 800</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12.7</td><td> 1379</td><td> 27576</td>
<td> 9</td><td>Half latex</td><td>N326</td><td> 55</td><td> 0</td><td> 0,6</td><td> 25,4</td><td> 1723</td><td> 20682</td>
<td> 10</td><td>Half latex</td><td>REGAL 660</td><td> 55</td><td> 0</td><td> 0,6</td><td> 25,4</td><td> -</td><td> -</td>
189 105 cd from Table 25
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 11</td><td>Half latex</td><td>REGAL 660</td><td> 45</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1379</td><td> 86175</td>
<td> 12</td><td>Half latex</td><td>REGAL 660</td><td> 65</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1792</td><td> 103410</td>
<td> 13</td><td>Half latex</td><td>REGAL 660</td><td> 65</td><td> 10</td><td> 0,6</td><td> 12,7</td><td> 1379</td><td> 82728</td>
<td> 14</td><td>Half latex</td><td>N234</td><td> 55</td><td> 0</td><td> 0,6</td><td> 25,4</td><td> 1241</td><td> 37917</td>
<td> 15</td><td>Half latex</td><td>N234</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> -</td><td> 99963</td>
<td> 16</td><td>Half latex</td><td>N234</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> -</td><td> 99963</td>
<td> 17</td><td>Half latex</td><td>N234</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> -</td><td> 99963</td>
<td> 18</td><td>Half latex</td><td>N234</td><td> 45</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1379</td><td> 89622</td>
<td> 19</td><td>Half latex</td><td>N234</td><td> 65</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1517</td><td> 89622</td>
<td> 20</td><td>Half latex</td><td>N234</td><td> 65</td><td> 10</td><td> 0,6</td><td> 12,7</td><td> 2068</td><td> 99963</td>
<td> 21</td><td>Ponytail is half</td><td>N110</td><td> 55</td><td> 0</td><td> 0,6</td><td> 25,4</td><td> 827</td><td> 31023</td>
<td> 22</td><td>Concentrate latex</td><td>N351</td><td> 33</td><td> 20</td><td> 0,6</td><td> 12,7</td><td> 1723</td><td> 86175</td>
<td> 23</td><td>Half latex</td><td>STERL1NG 6740</td><td> 55</td><td> 0</td><td> 0,6</td><td> 12,7</td><td> 1723</td><td> 82728</td>
<td> 24</td><td>Half latex</td><td>N234</td><td> 48</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> 1723</td><td> 75834</td>
<td> 25</td><td>Half latex</td><td>N234</td><td> 53</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> 1723</td><td> 75834</td>
<td> 26</td><td>Half latex</td><td>N234</td><td> 58</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> 1723</td><td> 75834</td>
<td> 27</td><td>Half latex</td><td>N234</td><td> 63</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> 1723</td><td> 75834</td>
<td> 28</td><td>Half latex</td><td>N234</td><td> 68</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> 1723</td><td> 75834</td>
<td> 29</td><td>Concentrate latex</td><td>N234</td><td> 49</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> -</td><td> 75834</td>
<td> 30</td><td>Concentrate latex</td><td>N234</td><td> 54</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> -</td><td> 75834</td>
<td> 31</td><td>Concentrate latex</td><td>N234</td><td> 63</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> -</td><td> 75834</td>
<td> 32</td><td>Concentrate latex</td><td>N234</td><td> 65</td><td> 5</td><td> 0,58</td><td> 12,7</td><td> -</td><td> 75834</td>
Table 25 (continued)
<td rowspan="3">A sample according to invention no</td><td colspan="8">Coagulation zone</td><td rowspan="3">Suspension soot concentration soot (%)</td>
<td colspan="2">Part one</td><td colspan="2">Part two</td><td colspan="2">Part three</td><td colspan="2">Part four</td>
<td>Diameter (mtn)</td><td>Length (mm)</td><td>Diameter (mm)</td><td>Length (mm)</td><td>Diameter (mm)</td><td>Length (mm)</td><td>Diameter (mm)</td><td>Length (mm)</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td> 1</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,2</td>
189 105
continued from Table 25
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td> 2</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,9</td>
<td> 3</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,9</td>
<td> 4</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 19,0</td>
<td> 5</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 21,0</td>
<td> 6</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 21,0</td>
<td> 7</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 21,0</td>
<td> 8</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,0</td>
<td> 9</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,8</td>
<td> 10</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,9</td>
<td> 11</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,2</td>
<td> 12</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,2</td>
<td> 13</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,2</td>
<td> 14</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,8</td>
<td> 15</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,7</td>
<td> 16</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,7</td>
<td> 17</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,7</td>
<td> 18</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,6</td>
<td> 19</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,6</td>
<td> 20</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,6</td>
<td> 21</td><td> 4,8</td><td> 27,9</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 11,8</td>
<td> 22</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 15,0</td>
<td> 23</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 14,7</td>
<td> 24</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,5</td>
<td> 25</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,5</td>
<td> 26</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,5</td>
<td> 27</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,5</td>
<td> 28</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 13,5</td>
<td> 29</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 12,8</td>
<td> 30</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 12,8</td>
<td> 31</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 12,8</td>
<td> 32</td><td> 4,8</td><td> 76,2</td><td> 6,9</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td><td> 12,8</td>
Table 25 (continued)
<td rowspan="3">A sample according to invention no</td><td rowspan="3">Nozzle hang. Pressure tip (kPa)</td><td colspan="6">Mixing zone</td>
<td rowspan="2">Rate flow suspensions (kg / h)</td><td rowspan="2">Speed suspensions (m / s)</td><td colspan="2">Antioxidant</td><td rowspan="2">Rate flow latex kg / h</td><td rowspan="2">Speed latex (m / s)</td>
<td>TNPP (phr)</td><td>Santoflex (phr)</td>
<td> 1</td><td> 9652</td><td> 125,2</td><td> 102,4</td><td> 0,3</td><td> 0,4</td><td> 127,9</td><td> 2,1</td>
<td> 2</td><td> 2930</td><td> 223,1</td><td> 75,3</td><td> 0,3</td><td> 0,4</td><td> 242,2</td><td> 4,0</td>
<td> 3</td><td> 2930</td><td> 223,1</td><td> 75,3</td><td> 0,3</td><td> 0,4</td><td> 242,2</td><td> 4,0</td>
<td> 4</td><td> 10341</td><td> 130,6</td><td> 104,9</td><td> 0,3</td><td> 0,4</td><td> 182,3</td><td> 3,0</td>
<td> 5</td><td> 10341</td><td> 141,5</td><td> 112,8</td><td> 0,3</td><td> 0,4</td><td> 185,0</td><td> 3,0</td>
<td> 6</td><td> 10858</td><td> 141,5</td><td> 112,8</td><td> 0,3</td><td> 0,4</td><td> 160,5</td><td> 2,6</td>
<td> 7</td><td> 10686</td><td> 141,5</td><td> 112,8</td><td> 0,3</td><td> 0,4</td><td> 187,7</td><td> 3,04</td>
<td> 8</td><td> 12409</td><td> 141,5</td><td> 115,8</td><td> 0,3</td><td> 0,4</td><td> 133,3</td><td> 2,2</td>
<td> 9</td><td> 4136</td><td> 114,3</td><td> 93,9</td><td> 0,3</td><td> 0,4</td><td> 108,8</td><td> 1.8</td>
<td> 10</td><td> -</td><td> 108,8</td><td> 89,3</td><td> 0,3</td><td> 0,4</td><td> 98,0</td><td> 1,6</td>
<td> 11</td><td> 10341</td><td> 138,8</td><td> 113,7</td><td> 0,3</td><td> 0,4</td><td> 190,5</td><td> 3,1</td>
<td> 12</td><td> 8962</td><td> 130,6</td><td> 107,0</td><td> 0,3</td><td> 0,4</td><td> 125,2</td><td> 2,0</td>
<td> 13</td><td> 9471</td><td> 133,3</td><td> 109,1</td><td> 0,3</td><td> 0,4</td><td> 130,6</td><td> 2,1</td>
<td> 14</td><td> 6205</td><td> 144,2</td><td> 118,3</td><td> 0,3</td><td> 0,4</td><td> 130,6</td><td> 2,1</td>
<td> 15</td><td> 9652</td><td> 155,1</td><td> 128,0</td><td> 0,3</td><td> 0,4</td><td> 146,9</td><td> 2,4</td>
<td> 16</td><td> 9652</td><td> 155,1</td><td> 128,0</td><td> 0,3</td><td> 0,4</td><td> 146,9</td><td> 2,4</td>
<td> 17</td><td> 9652</td><td> 155,1</td><td> 128,0</td><td> 0,3</td><td> 0,4</td><td> 146,9</td><td> 2,4</td>
<td> 18</td><td> 11090</td><td> 141,5</td><td> 116,1</td><td> 0,3</td><td> 0,4</td><td> 176,9</td><td> 2,9</td>
<td> 19</td><td> 11375</td><td> 144,2</td><td> 118,3</td><td> 0,3</td><td> 0,4</td><td> 122,4</td><td> 2,0</td>
<td> 20</td><td> 11283</td><td> 144,2</td><td> 118.3</td><td> 0,3</td><td> 0,4</td><td> 125,2</td><td> 2,0</td>
<td> 21</td><td> 6205</td><td> 144,2</td><td> 120,1</td><td> 0,3</td><td> 0,4</td><td> 111,6</td><td> 1,8</td>
<td> 22</td><td> 10686</td><td> 138,8</td><td> 113,7</td><td> 0,3</td><td> 0,4</td><td> 138,8</td><td> 2,3</td>
<td> 23</td><td> 10686</td><td> 141,5</td><td> 116,1</td><td> 0,3</td><td> 0,4</td><td> 155,1</td><td> 2,5</td>
<td> 24</td><td> 14650</td><td> 138,8</td><td> 135,3</td><td> 0,3</td><td> 0,4</td><td> 156,0</td><td> 2,7</td>
<td> 25</td><td> 15512</td><td> 138,8</td><td> 135,3</td><td> 0,3</td><td> 0,4</td><td> 149,7</td><td> 2,4</td>
<td> 26</td><td> 14650</td><td> 138,8</td><td> 135,3</td><td> 0,3</td><td> 0,4</td><td> 136,1</td><td> 2,2</td>
<td> 27</td><td> 15580</td><td> 138,8</td><td> 135,3</td><td> 0,3</td><td> 0,4</td><td> 125,2</td><td> 2,0</td>
<td> 28</td><td> -</td><td> 138,8</td><td> 135,3</td><td> 0,3</td><td> 0,4</td><td> 114,3</td><td> 1,9</td>
<td> 29</td><td> 16201</td><td> 144,2</td><td> 141,1</td><td> 0,3</td><td> 0,4</td><td> 70,7</td><td> 1,2</td>
<td> 30</td><td> 16270</td><td> 144,2</td><td> 141,1</td><td> 0,3</td><td> 0,4</td><td> 62,6</td><td> 1,0</td>
<td> 31</td><td> 16201</td><td> 144,2</td><td> 141,1</td><td> 0,3</td><td> 0,4</td><td> 57,1</td><td> 0,9</td>
<td> 32</td><td> 16683</td><td> 144,2</td><td> 141,1</td><td> 0,3</td><td> 0,4</td><td> 54,4</td><td> 0,9</td>
189 105
Table 25 (continued)
<td rowspan="2">The sample according to the invention no</td><td colspan="2">Drainage</td><td colspan="2">Drying and cooling</td>
<td>Initial particle moisture (%)</td><td>Final particle moisture (%)</td><td>Product temperature (° C)</td><td>Product moisture (%)</td>
<td> 1</td><td> 77,6</td><td> 8,5</td><td> 155,6</td><td> 0,3</td>
<td> 2</td><td> 78,7</td><td> -</td><td> 232,2</td><td> 0,2</td>
<td> 3</td><td> 78,7</td><td> 7,8</td><td> 204,4</td><td> 0,2</td>
<td> 4</td><td> 74,9</td><td> -</td><td> 193,3</td><td> 0,3</td>
<td> 5</td><td> 76,2</td><td> 7,9</td><td> 154,4</td><td> 0,2</td>
<td> 6</td><td> 76,4</td><td> 11,4</td><td> -</td><td> 0,2</td>
<td> 7</td><td> 75,8</td><td> 8,8</td><td> 168,3</td><td> 0,3</td>
<td> 8</td><td> 77,7</td><td> 6,5</td><td> 154,4</td><td> 0,2</td>
<td> 9</td><td> 77,9</td><td> 8,9</td><td> 173,9</td><td> 0,2</td>
<td> 10</td><td> 77,8</td><td> -</td><td> -</td><td> 0,4</td>
<td> 11</td><td> 78,7</td><td> 9,7</td><td> 140,6</td><td> 0,5</td>
<td> 12</td><td> 79,7</td><td> -</td><td> 168,3</td><td> 0,2</td>
<td> 13</td><td> 79,1</td><td> -</td><td> -</td><td> 0,9</td>
<td> 14</td><td> 77,9</td><td> 8,4</td><td> 165,6</td><td> 0,1</td>
<td> 15</td><td> 79,2</td><td> -</td><td>kiln dried</td><td> -</td>
<td> 16</td><td> 79,2</td><td> 10,3</td><td>kiln dried</td><td> -</td>
<td> 17</td><td> 79,2</td><td> 11,2</td><td>kiln dried</td><td> -</td>
<td> 18</td><td> 79,0</td><td> 15,0</td><td> 187,8</td><td> 0,4</td>
<td> 19</td><td> 80,0</td><td> 3,6</td><td> 162,8</td><td> 0,3</td>
<td> 20</td><td> 79,5</td><td> 9,4</td><td> 173,9</td><td> 0,5</td>
<td> 21</td><td> 80,5</td><td> 9,5</td><td> 193,3</td><td> 0,2</td>
<td> 22</td><td> 65,1</td><td> 9,1</td><td> 137,8</td><td> 0,3</td>
<td> 23</td><td> 78,1</td><td> 6</td><td> 165,6</td><td> 0,8</td>
<td> 24</td><td> 77,4</td><td> -</td><td> 193,3</td><td> 0,3</td>
<td> 25</td><td> 77,8</td><td> -</td><td> 198,9</td><td> 0,4</td>
<td> 26</td><td> 78,1</td><td> -</td><td> 204,4</td><td> 0,7</td>
<td> 27</td><td> 78,4</td><td> -</td><td> 210,0</td><td> 0,4</td>
<td> 28</td><td> 78,7</td><td> -</td><td> 215,6</td><td> 1,1</td>
<td> 29</td><td> 71,2</td><td> -</td><td> 204,4</td><td> 0,6</td>
<td> 30</td><td> 72,3</td><td> -</td><td> 215,6</td><td> 0,4</td>
<td> 31</td><td> 73,3</td><td> -</td><td> 204,4-232,2</td><td> 0,9</td>
<td> 32</td><td> 74,1</td><td> -</td><td> 204,4-232,2</td><td> 0,2</td>
189 105
It should be noted that samples 2 and 3 were produced with almost no outlet pressure at the outlet of the microfluidizer etc. to determine the macrodispersion under reverse process conditions.
The excellent macrodispersion of the carbon black in the obtained masterbatches is demonstrated by the quality of these macrodispersion and the molecular weight of the sol part Mwzo
Table 26 below shows Mw<sub>WITH</sub>ol macro dispersion values for inventive samples 1-32, along with soot and oil (if any) used in each of the samples. The carbon black content and oil content are shown as phr values in Table 26.
Table 26: Sol Molecular Weight and Non-Dispersed Area in Samples of the Invention
<td>Sample according to</td><td>The soot / oil content of the invention no</td><td>Mwzol</td><td>D (%)</td>
<td> 1</td><td>N330755 / 0</td><td> 305</td><td> 0,26</td>
<td> 2</td><td>N330 / 55/0</td><td> 726</td><td> 0,54</td>
<td> 3</td><td>N330 / 55/0</td><td> 544</td><td> 0,40</td>
<td> 4</td><td>R250 / 55/0</td><td> 876</td><td> 0,08</td>
<td> 5</td><td>R250 / 65/0</td><td> 670</td><td> 0,16</td>
<td> 6</td><td>R250 / 75/0</td><td> 655</td><td> 0,03</td>
<td> 7</td><td>R250 / 65/10</td><td> 519</td><td> 0,02</td>
<td> 8</td><td>BP800 / 55/0</td><td> 394</td><td> 0,14</td>
<td> 9</td><td>N326 / 55/0</td><td> 666</td><td> 0,20</td>
<td> 10</td><td>R660 / 55/0</td><td> 678</td><td> 0,12</td>
<td> 11</td><td>R660 / 45/0</td><td> 733</td><td> 0,05</td>
<td> 12</td><td>R660 / 65/0</td><td> 568</td><td> 0,04</td>
<td> 13</td><td>R660 / 65/10</td><td> 607</td><td> 0,02</td>
<td> 14</td><td>N234 / 55/0</td><td> 433</td><td> 0,15</td>
<td> 15</td><td>N234 / 55/0</td><td> 1000</td><td> 0,10</td>
<td> 16</td><td>N234 / 55/0</td><td> 500</td><td> 0,15</td>
<td> 17</td><td>N234 / 55/0</td><td> 550</td><td> 0,10</td>
<td> 18</td><td>N234 / 45/0</td><td> 495</td><td> 0,17</td>
<td> 19</td><td>N234 / 65/0</td><td> 359</td><td> 0,20</td>
<td> 20</td><td>N234 / 65/10</td><td> 350</td><td> 0,11</td>
<td> 21</td><td>SUN 10/55/0</td><td> 612</td><td> 0,17</td>
<td> 22</td><td>N351 / 33/20</td><td> 800</td><td> 0,10</td>
<td> 23</td><td>S6740 / 55/0</td><td> 630</td><td> 0.10</td>
<td> 24</td><td>N234 / 48/5</td><td> 569</td><td> 0,05</td>
<td> 25</td><td>N234 / 53/5</td><td> 485</td><td> 0,12</td>
<td> 26</td><td>N234 / 58/5</td><td> 447</td><td> 0,12</td>
<td> 27</td><td>N234 / 63/5</td><td> 403</td><td> 0,13</td>
<td> 28</td><td>N234 / 58/5</td><td>378 J / O</td><td> 0,16</td>
<td> 29</td><td>N234 / 49/5</td><td> 618</td><td> 0,12</td>
<td> 30</td><td>N234 / 54/5</td><td> 482</td><td> 0,16</td>
<td> 31</td><td>N234 / 63/5</td><td> 390</td><td> 0,17</td>
<td> 32</td><td>N234 / 65/5</td><td> 325</td><td> 0,20</td>
189 105
The results for all samples according to the invention having a carbon black content of 55 phr are shown in the semi-log decrease in Fig. 9 together with the values for macrodispersion and Mw<sub>WITH</sub>ol for the corresponding natural rubber control sample series as described above prepared by dry-blending techniques. At least one data showing a sample of the invention having 55 phr of each carbon black is shown in Fig. 9, along with all control samples having a carbon black content of 55 phr. (Controls 401 through 412, also shown in Fig. 9, used 33 phr of N351 carbon black and 20 parts of loading oil).
It can be seen from Table 26 and Fig. 9 that the samples according to the invention have excellent macro-dispersion. Specifically, the samples of the invention have D (%) values generally less than 0.2% even at Mzol values above 0.85 x 1 (0 ', while the control samples never achieved such perfect macrodispersion under any Mzol. the data shown in Fig. 9 clearly disclose that the macrodispersion quality of the new elastomer composites over a wide range of Mvapol values is much higher than that achievable with comparable ingredients in previously known dry blending methods.
The symbols used for the various data points shown in FIG. 9, and used in the subsequent discussion of FIGS. 10-25, are explained in the following legend.
Fig. 9. Quality of dispersion and Mw-y of NR premixes controls from 177 to 224 A controls from 283 to 320 Θ controls from 145 to 176
Δ controls from 369 to 400 o controls from 33 to 64 x controls from 1 to 32 o controls from 113 to 144 controls from 412 to 443 <► controls from 401 to 412 s samples according to the present invention
Fig. 10. Quality of dispersion and Mwzol of NR masterbatches (area I)
Ά control samples from 177 to 224
O the sample of the present invention □ controls 145 to 176
Θ sample 9 according to the present invention o control samples from 33 to 64 □ sample 4 according to the present invention x control samples from 1 to 32 sample 1 according to the present invention control samples from 113 to 144 o sample 8 according to the present invention
Fig 11. Quality of dispersion and Mw ^ u, masterbatches NR 25 (area II)
A controls from 2'73 to 320 and sample 14 according to the present invention
∆ controls from 369 to 400 □ sample 21 according to the present invention 3 0
Fig; 12 Quality of dispersion and Mvou of NR masterbatches (area III) ♦ controls 401 to 412 and sample 22 according to the present invention controls 412 to 443 □ sample 23 according to the present invention
Fig; 13. Quality of dispersion and Mw<sub>WITH</sub>olu premix NR (carbon black N330, 55 parts by weight per 100 parts by weight) © controls from 1 to 32 s samples according to the invention from 1 to 3
189 105
Fig. 14. Quality of dispersion and Mw ^ u of NR premixes (Regal 250 carbon black) ® control samples from 33 to 64 B sample 4 according to the present invention o control samples from 65 to 80 □ sample 5 according to the present invention 0 controls from 81 to 96
A sample 6 according to the present invention ❖ controls 97 to 112
Δ sample 7 according to the present invention
Fig. 15. Quality of dispersion and Mw<sub>WITH</sub>ol<sub>AT</sub> premix NR (Black Pearl Carbon Black 800.55 parts by weight per 100 parts by weight) ® controls 113 to 144 o sample 8 according to the present invention
Fig. 16. Dispersion quality and Mw of NR masterbatches (carbon black N326, 55 parts by weight per 100 parts by weight). 145 to 176 g sample 9 according to the present invention
Fig. 17. Quality of dispersion and Mw ^ u of premixes NR (Regal 660 carbon black) © controls 177 to 224 and sample 10 of the present invention controls 225 to 240 □ samples 11 of the present invention 0 controls 241 to 256
A sample 12 according to the present invention ❖ controls 257 to 272
A sample 13 according to the present invention
Fig. 18. Quality of dispersion and Mw ^ u, premix NR (carbon black N234) © controls 273 to 320b samples 14 to 17 according to the present invention o controls 337 to 352 o samples 19 according to the present invention controls 321 to 336 A sample 18 of the present invention Φ controls 353 to 368 A sample 20 of the present invention
Fig. 19. Quality of dispersion and Mw<sub>WITH</sub>ol<sub>AT</sub> premix NR (carbon black N110, 55 parts by weight per 100 parts by weight) © controls from 369 to 400 E3 sample 21 according to the present invention
Fig :. 20. Dispersion quality and Mw2 of NR premixes (carbon black N351, 33 parts by weight per 100 parts by weight), Control samples 401 to 412, Sample 22 according to the present invention
Fig. 21 Quality of dispersion and Mw<sub>o</sub>and in NR premixes (Sterling carbon black 6740, 55 parts by weight per 100 parts by weight) © controls 412 to 443 b sample 23 according to the present invention
Fig. 22. Effect of Mzole on crack growth rate (NR blends containing 55 parts by weight of N234® carbon black per 100 parts by weight) ® controls 273 to 288 63 Sample 16 according to the present invention
189 105
N234
Fig 23. Effect of Mwżol on crack growth rate (NR blends containing 55 parts by weight of N326® carbon black per 100 parts by weight) © controls 145 to 160 o sample 9 according to the present invention
Fig. 24. Effect of MW sol on crack growth rate (NR blends containing 55 parts by weight of Regal 660® carbon black per 100 parts by weight) © controls 177 to 192 □ sample 10 according to the present invention stresses @ 60 ° C) mixtures containing various amounts of carbon black samples from 24 to 28 according to the present invention samples from 29 to 32 according to the present invention controls from 444 to 450
Fig. 30. Quality of the macro-dispersion and MW of the sol part of the NR masterbatch containing the double phase aggregates (carbon black / silica) o control samples 451 to 455 b sample 33 according to the present invention o control samples 459 to 466 □ sample 34 according to the present invention
Fig. 31. Macrodispersion quality and M in sol part of NR masterbatches containing the blend of carbon black with silica ® controls 491 to 496 b sample 38 according to the minor invention 0 controls 483 to 490 □ sample 3 7 according to the present invention o controls 475 to 482, sample 36 according to the present invention ® controls 467 to 474 and sample 35 according to the present invention
The macro-dispersion values of the elastomer composites of the present invention shown in Fig. 9 are described by the following equations:
D,% <0.2% (1) when Mw<sub>WITH</sub>ol is below 0.45 x 10<sup>6</sup>; and log (D) <log (0.2) + CMw<sub>with</sub>o - (0.45 x 106)] x 1 θ '<sup>6</sup> (2) when 0.45 x 106 <Mw<sub>ro</sub>l <1.1x 10<sup>6</sup>.
Based on the discussion above, it is assumed that the macrodispersion D,%, in equation (1) above is the percentage of undispersed area measured for defects greater than 10 µm. From Fig. 9 it can be seen that D,%, equal to 0.2% is the limiting macro-dispersion quality for all of the carbon blacks in Regions I, II and III for the dry natural rubber masterbatches. That is, none of the dry masticated masterbatches achieved a macrodispersion quality of 0.2% at any Mw<sub>WITH(</sub>Even after sufficient mixing for a degradation of Mwj »l below 0.45 x 106, this is described by the above equation (1). When the Mzol of the dry masterbatch control samples shown in Fig. 9 is between 0.45 x 106 and 1.1<sub>χ</sub> 10 * 6, the dispersion quality is even worse, while surprisingly, the dispersion quality of the samples of the present invention having an Mzol in this range remains excellent. None of the preferred embodiments shown in Fig. 9 having Mzol between 0.45 x 106 1.1<sub>χ</sub> 106 does not exceed a preferred macrodispersion limit of 0.2%. In this regard, it should be assumed that the data points for the preferred embodiments of the present invention which are shown in Fig. 9 (and the other Figures discussed below) lie on the X-axis (i.e., for a D,% value of 0.1%) may be have a dispersion quality of 0.1 or even better (i.e. lower D,%).
189 105
Area I soot samples
Samples of the invention containing carbon blacks having morphological properties (i.e., the structures and surface areas in Area I in Fig. 8 and the corresponding controls as described above, produced with such Carbon blacks from Area I) were compared on the semi-log plot in Fig. 10. . 10 shows the macrodispersion and Mzol values of the samples according to the invention and the corresponding control samples containing carbon blacks Regal® 660, N326, Regal® 250, N330 and Black Pearl® 800 with a carbon black content ranging from 30 to 75 parts by weight per 100 parts by weight and an oily diluent content ranging from 0 to 20 parts by weight per 100 parts by weight. You can see the perfect soot dispersion in Fig. 10 for all samples of the present invention showing preferred variations of the elastomer composites of the present invention.
All samples according to the invention are preferably below line 101 in Fig. 10, while all controls are inferior in dispersion and above line 101. Thus, the preferred embodiments shown in Fig. 10, even if they contain carbon black in the most difficult-to-disperse Area I are all below the D% value of 0.3%. All the most preferred embodiments have a D,% value not exceeding 0.2%, even for Mvol values preferably above 0.7 x 10<sup>6</sup>. The data of Fig. 10 clearly shows that the macrodispersion qualities of the novel elastomer composites disclosed herein and incorporating the Area I carbon blacks with a wide range of MWol s are significantly superior to those achieved with comparable components in prior art dry mastic methods. The macro-dispersion values of the elastomer composites according to the invention presented in Fig. 10 are described by the following equations:
D,% <1.0% (3) when the Mzol is below 0.7 x 10<sup>6</sup>; and log (D) <log (1.0) + 2.5 x [Mw2 - (0.7 x 10<sup>6</sup>)] x 1 (4) when 0.7 x 106 <Mzol <1.1 x 106.
D,%, is assumed to be the percentage of undispersed area measured for defects greater than 10 µm and that 1% is the limiting macrodispersion quality for all Area I carbon blacks for the natural rubber masterbatches of the present invention. That is, none of the dry masticated masterbatches achieved a macrodispersion quality of 1.0% or better at any Mzol even after dry blending sufficient to degrade the Mw<sub>WITH</sub>oi less than 0.7 x 106 as described in equation (3) above. When the Mvol of the control dry masterbatch samples shown in Fig. 10 is between 0.7 x 10) 6 and 1.1 x 106, the dispersion quality is even worse. However, surprisingly, the dispersion quality of the samples of the present invention having an Mzol in this range remains excellent. The preferred embodiment shown in Fig. 10 having Mzola between 0.7 x 1.1 x 106 is well below the preferred 0.2% macrodispersion limit. It can be seen that the elastomer composites of the invention containing the Zone I carbon blacks have a heretofore unattainable balance between macrodispersion quality and MW value.
Area II soot samples.
Samples of the invention containing carbon blacks with morphological properties (i.e., the structures and surface areas in Area II in Fig. 8 and the corresponding controls as described above, produced with such Carbon blacks from Area I) were compared on the semi-log plot in Fig. 11. . 11 shows the macrodispersion and Mzol values of the samples according to the invention and the corresponding control samples containing carbon blacks N234 and N110 with a carbon black content ranging from 40 to 70 parts by weight per 100 parts by weight and an oily diluent content ranging from 0 to 10 parts by weight per 100 parts by weight. You can see the perfect soot dispersion in Fig. 11 for all samples of the present invention showing preferred variations of the elastomer composites of the present invention. The inventive samples are preferably below line 111 on Fig. 11, while all controls have poorer dispersion and are above line 111. Thus, the preferred embodiments shown in Fig. 11 containing the Zone II carbon blacks are below the D,% value. equal to 0.3%. The most preferred embodiments have a D,% value not exceeding 0.2% for any Mzol value. The data of Fig. 11 shows
189 It is clear that the macrodispersion quality of the novel elastomer composites disclosed herein and incorporating the Area II carbon blacks having a wide range of Mwzol values is significantly superior to that achieved with comparable ingredients in prior art dry mastic methods. The macro-dispersion values of the elastomer composites according to the invention presented in Fig. 11 are described by the following equations:
D,% <0.3% (5) when Mw<sub>WITH</sub>about! is below 0.35 x 10<sup>6</sup>; and log (D) <log (0.3) + 2.8 x JMwz! - (0.35 x 106)] x 10 '<sup>6</sup> (6) when 0.35 x 106 <Mzol <1.1 x 10 <sup>6</sup>.
D,%, equal to 0.30% is assumed to be the limiting macro-dispersion quality for all Zone II carbon blacks for the natural rubber masterbatches of the present invention, and a value of 0.35 x 106 is the limiting Mso value. That is, none of the dry masterbatches achieved a macrodispersion quality of 0.30% or better at any Mwzol even after dry blending sufficient to degrade the Mwzol below 0.35 x 106, such as<sub>this </sub>is described by the above equation (5). When the Mvol of the control dry masterbatch samples shown in Fig. 11 is between 0.35 x 10<sup>6</sup> 1 1.1 x 106, the dispersion quality is even worse. However, surprisingly, the dispersion quality of the samples of the present invention having an Mzol in this range remains excellent. The preferred embodiments shown in Fig. 11 having Mzole between 0.35 x 106 and 1.1<sub>χ</sub> 106 fall well below the favorable macrodispersion limit of 0.2%. It can be seen that the elastomer composites according to the invention containing the Zone II carbon blacks have a hitherto unattainable balance between macro-dispersion quality and pattern value.
Area III soot samples.
Samples of the invention containing carbon blacks with morphological properties (i.e., structures and surface areas) in Area III in Fig. 8 and the corresponding controls as described above produced with such Area III carbon blacks were compared in the semi-log plot of Fig. 12. . 12 shows the macrodispersion and Mzol values of the samples according to the invention and the corresponding N351 and Sterling carbon black control samples with a carbon black content ranging from 30 to 70 parts by weight per 100% by weight and an oily diluent content ranging from 0 to 20 parts by weight per 100 parts by weight. You can see the perfect soot dispersion in Fig. 12 for all samples of the present invention showing preferred variations of the elastomer composites of the present invention. All the samples of the invention are preferably below line 121 in Fig. 12, while all controls have poorer dispersion and are above line 121. Thus, the preferred embodiments shown in Fig. 12 containing carbon blacks from Zone DI, are at or below the value of D,%, equal to 0.1 even for the value of Mzol, preferably above 0.3 x 1061 even above 0.7 x 10<sup>6</sup>. The data of Fig. 12 show; clearly, that the macrodispersion quality of the novel elastomer composites disclosed herein and containing the Zone III carbon blacks, over a wide range of Mzol values, is significantly superior to that achieved using comparable components in the prior art dry blending methods. The macro-dispersion values of the elastomer composites according to the invention presented in Fig. 12 are described by the following equations:
D,% <0.1% (() when Mw<sub>WITH</sub>ol is below 0.35 x 106; and log D <log (0.1) + 2.0 x [Mzol - (0.30 x 106)] x 10 '<sup>6</sup> (^) when 0.30 x 1 () 6 <Mzol <1.1 x 106.
It is assumed that D,%, equal to 0.1% is the limiting macro-dispersion quality for all Zone III carbon blacks for all natural rubber masterbatches according to the present invention, and that a value of 0.3 x 106 is the limiting value of Mwzol. This means that none of the dry sponges has a macrodispersion and 0.1% at the proofs of the Mvolume, rraw ^ ett after a mixture of dry ay / sessile weaves below 0.35 × 10, such as is described by the above equation (7). When Mw<sub>WITH</sub>The ol of the control samples of the dry pre-dews shown in Fig. 12 is between 0.3 x 106 ij, j <sub>χ</sub> J0<sup>6</sup>, the quality of the dispersion is even worse. Surprisingly, however, the dispersion quality of the samples according to the present invention is 52
189 105 Mw, o. [In this respect, she remains perfect. The preferred embodiments shown in Fig. 12 having Mzole between 0.30 x10 and 1.1 x 106 are well below the preferred macrodispersion limit of 0.2% and also below the D,% value of 0.1%. It can be seen that the elastomer composites according to the invention containing the Zone I carbon blacks have a hitherto unattainable balance between the quality of the macrodispersion and the Mwzol value.
Additional sample comparison
The macrodispersion values for the inventive samples are graphically represented in the semi-logarithmic plots of Figs. 13 to 21 as a function of their Mwzol values, as in Figs. 8 to 12 discussed above. In particular, Figs. 13 to 21 show all the samples of the invention containing particular carbon black (limited to samples containing the specified amounts of carbon black) together on one semi-log plot along with the corresponding controls. (See the legends above for reference numbers to the samples of the invention and the control samples included in each Figure). Thus, Fig. 13 shows the dispersion quality and Mzol of the samples according to the invention and the controls described above containing 55 parts by weight of N330 carbon black per 100 parts by weight. Data Fig. 13 clearly show that the macrodispersion quality of the new elastomer composites according to the invention, containing the N330 carbon black, over a wide range of Mwzol values, is significantly better than that of the control samples. The macrodispersion of the elastomer composites of the invention containing the N330 carbon black as shown in Fig. 13 is described by the following equations:
D,% & lt; 1% (9) when Mzol & lt; 0.6 x 106; and log D <log (1) + 2.5 x [Mzol - (0.6 x 10 6)] x 10<sup>6</sup> (10) when 0.6 x 106 <M and <1.1 x 106.
None of the dry masticated masterbatches achieved a macrodispersion quality of 1.0% with any Mvolol even after dry blending sufficient to degrade the Mvol below 0.6 x 106 (see equation 9 above). In the controls containing 55 parts by weight of N330 carbon black per 100 parts by weight, where the Mvolol value was kept between 0.6 x 106 and 1.1 x 106, the D,% value is even greater, such as greater than 4% undispersed area.
Fig. 14 shows the dispersion and Mzol quality of the inventive samples and the controls described above containing Regal® 250 carbon black. Selected inventive samples and the controls shown in Fig. 14 contained oil as stated above. The data in Fig. 13 clearly shows that the macrodispersion quality of the novel elastomer composites of the invention containing the Regal® 250 carbon black over a wide range of Mwzol values is significantly superior to that of the control samples. The macrodispersion values of the elastomer composites of the invention containing the Regal® 250 carbon black as shown in Fig. 14 are described by the following equations:
D,% & lt; 1% (9) when Mvol. & Lt; 0.6 x 106; and log D <log (l) + 2.5 x [Mzol - (0.6 × 10<sup>6</sup>)] x 10'6 (10) when 0.6 x 106 <M and <1.1 x 106.
None of the control samples achieved a macrodissircrsjj 1.0% ll ^ lb quality better with any Mwzol even after dry blending sufficient to degrade the Mwzol below 0.6 x 106. In contrast, the elastomer composites of the invention containing Regal® 250 carbon black and having Mwzol values above 0 . 6 x 106 have an excellent macro-dispersion such as D% less than 0.2%. Properties of the mixtures and characteristics of the samples according to the invention and the control samples shown in Fig. 14, containing the Regal® 250 carbon black, are given in Table 27, below. It can be seen that sample 4 according to the invention has an extremely good crack growth resistance as indicated by the very low crack growth rate value of only 0.92 cm / million cycles. Thus, the sample according to the invention is significantly superior to the corresponding control samples. It is assumed that this is mainly due to the better Mzol value and the better macrodispersion of the carbon black in the sample of the invention as discussed above.
189 105
Table 27. Properties of blends of NR compositions containing 55 parts by weight of Regal® 250 carbon black per 100 parts by weight
<td>sample no</td><td>Mooney ML (1 + 4) @ 100C</td><td>hardness</td><td>E100 (psi)</td><td>E300 (psi)</td><td>stretching (psi)</td><td>EB,%</td>
<td>counter 33</td><td> 60,63</td><td> 55,35</td><td> 181,26</td><td> 999,82</td><td> 4090,24</td><td> 675,0</td>
<td>counter 34</td><td> 73,58</td><td> 57,80</td><td> 235,14</td><td> 1293,88</td><td> 3978,24</td><td> 595,0</td>
<td>counter 35</td><td> 81,49</td><td> 58,65</td><td> 243,66</td><td> 1265,26</td><td> 4103,41</td><td> 613,0</td>
<td>counter 36</td><td> 84,04</td><td> 59,95</td><td> 244,23</td><td> 1215,87</td><td> 360,32</td><td> 614,0</td>
<td>counter 37</td><td> 57,35</td><td> 56,75</td><td> 218,70</td><td> 1259,99</td><td> 4119,85</td><td> 502,0</td>
<td>counter 38</td><td> 60,10</td><td> 57,05</td><td> 216,75</td><td> 1206,60</td><td> 4023,65</td><td> 620,0</td>
<td>counter 39</td><td> 68,28</td><td> 57,25</td><td> 225,44</td><td> 125,23</td><td> 413,06</td><td> 621,0</td>
<td>counter 40</td><td> 77,40</td><td> 59,10</td><td> 255,15</td><td> 1330,87</td><td> 4059,87</td><td> 597,0</td>
<td>counter 41</td><td> 44,40</td><td> 56,25</td><td> 216,00</td><td> 1214,78</td><td> 4038,68</td><td> 618,0</td>
<td>counter 42</td><td> 47,96</td><td> 56,50</td><td> 214,53</td><td> 1202,93</td><td> 3944,04</td><td> 613,0</td>
<td>counter 43</td><td> 49,84</td><td> 57,05</td><td> 221,26</td><td> 1229,07</td><td> 4018,24</td><td> 611,0</td>
<td>counter 44</td><td> 50,10</td><td> 56,60</td><td> 210,50</td><td> 1140,90</td><td> 4058,33</td><td> 638,0</td>
<td>counter 45</td><td> 36,82</td><td> 52,90</td><td> 177,47</td><td> 982,86</td><td> 3790,56</td><td> 533,0</td>
<td>counter 46</td><td> 38,23</td><td> 54,50</td><td> 198,63</td><td> 1111,04</td><td> 3860,56</td><td> 629,0</td>
<td>counter 47</td><td> 35,35</td><td> 54,60</td><td> 199,03</td><td> 1110,00</td><td> 3871,49</td><td> 505,0</td>
<td>counter 4 8</td><td> 40,58</td><td> 55,50</td><td> 204,52</td><td> 113,94</td><td> 3961,06</td><td> 632,0</td>
<td>by Wynal. 4</td><td> 71,97</td><td> 57,00</td><td> 218,18</td><td> 1230,30</td><td> 4036,30</td><td> 611,0</td>
1psi = 6.89476x103 Pa
Table 27 (continued)
<td>sample no</td><td>resilience</td><td>crack growth rate, cm / million cycles</td><td>abrasion, g</td><td>tg δ @ 0 ° C</td><td>tg 8 @ 60 ° C</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 33</td><td> 64,50</td><td> 2,00</td><td> 0,191</td><td> 0,167</td><td> 0,091</td>
<td>counter 34</td><td> 64,55</td><td> 1,83</td><td> 0,182</td><td> 0,155</td><td> 0,083</td>
<td>counter 35</td><td> 63,75</td><td> 2,38</td><td> 0,192</td><td> 0,150</td><td> 0,091</td>
<td>counter 36</td><td> 63,30</td><td> 1,42</td><td> 0,180</td><td> 0,162</td><td> 0,091</td>
<td>counter 37</td><td> 64,65</td><td> 3,00</td><td> 0,168</td><td> 0,176</td><td> 0,100</td>
<td>counter 38</td><td> 63,45</td><td> 2,99</td><td> 0,163</td><td> 0. 184</td><td> 0,099</td>
<td>counter 39</td><td> 63,90</td><td> 2,17</td><td> 0,186</td><td> 0. 170</td><td> 0,092</td>
<td>counter 40</td><td> 62,30</td><td> 1,69</td><td> 0,182</td><td> 0,175</td><td> 0,093</td>
<td>counter 41</td><td> 64,20</td><td> 2,84</td><td> 0,190</td><td> 0. 189</td><td> 0,102</td>
<td>counter 42</td><td> 64,20</td><td> 3,24</td><td> 0,182</td><td> 0.18</td><td> 0,103</td>
<td>counter 43</td><td> 64,50</td><td> 3,52</td><td> 0,177</td><td> 0,182</td><td> 0,101</td>
189 105
continued from table 27
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 44</td><td> 63,90</td><td> 3,50</td><td> 0,179</td><td> 0,185</td><td> 0,104</td>
<td>counter 45</td><td> 63,80</td><td> 3,86</td><td> 9,199</td><td> 0,107</td><td> 0,104</td>
<td>counter 46</td><td> 64,30</td><td> 3,94</td><td> 0,191</td><td> 0,184</td><td> 0,107</td>
<td>counter 47</td><td> 64,35</td><td> 3,81</td><td> 0,192</td><td></td><td> 0,106</td>
<td>counter 48</td><td> 63,65</td><td> 3,46</td><td> 0,180</td><td> 0,182</td><td> 0,110</td>
<td>by Wynal. 4</td><td> 64,70</td><td> 0,92</td><td> 0,190</td><td> 0,148</td><td> 0,096</td>
Figure 15 shows the dispersion and Mzol quality of the inventive and control samples described above containing 55 parts by weight of Black Pearl® 800 carbon black per 100 parts by weight. The data of Fig. 15 clearly shows that the macrodispersion quality of the new elastomer composites of the invention containing Black Pearl® 800 carbon black is significantly better than that of the controls. The macro-dispersion values of the elastomer composites of the invention containing Black Pearl® 800 carbon black, as shown in Fig. 15, are described by the following equations:
D,% <1.5% (11) when Mzol <0.65 x 10<sup>6</sup>; and log D <log (1.5) + 2.5 x [M Mzol - (0.65 x 10<sup>6</sup>)] x 10 '<sup>6</sup> (12) when 0.65 x 106 <Mw<sub>WITH</sub>Oi <1.1 x 106.
None of the control samples achieved a macrodispersion quality of 1.0% or better at any Mwzol even after dry blending sufficient to degrade the Mwzol below 0.65 x 106. In contrast, the inventive elastomer composites containing Black Pearl® 800 carbon blacks and having a Mwzol above 0 . 65 x 106 have an excellent macro-dispersion such as D% less than 0.2%. Properties of the mixtures and characteristics of the samples according to the invention and the control samples shown in Fig. 15, containing Black Pear1® 800 carbon black, are given in Table 28, below. It can be seen that sample 8 according to the invention has exceptionally good crack growth resistance as indicated by the very low crack growth rate value of only 0.27 cm / million cycles. Thus, the sample according to the invention is significantly superior to the corresponding control samples. It is assumed that this is mainly due to the better Mzol value and the better macrodispersion of the carbon black in the sample of the invention as discussed above.
Table 28. Properties of blends of NR compositions containing 55 parts by weight of Black Pearl® 800 Carbon Black per 100 parts by weight
<td>Sample No.</td><td>Mooney ML (1 + 4) @ 100C</td><td>Hardness</td><td>E100 (psi)</td><td>E300 (psi)</td><td>Stretching (psi)</td><td>EB,%</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>
<td>counter 113</td><td> 110,5</td><td> 66,4</td><td> 345,0</td><td> 1333,0</td><td> 3878,0</td><td> 598</td>
<td>counter 114</td><td> 109,0</td><td> 67,3</td><td> 367,0</td><td> 1427,0</td><td> 4033,0</td><td> 606</td>
<td>counter 115</td><td> 106,4</td><td> 67,2</td><td> 363,0</td><td> 1311,0</td><td> 3896,0</td><td> 610</td>
<td>counter 116</td><td> 105,7</td><td> 69,0</td><td> 322,0</td><td> 1202,0</td><td> 3856,0</td><td> 626</td>
<td>counter 117</td><td> 110,6</td><td> 67,1</td><td> 316,0</td><td> 1400,0</td><td> 4180,0</td><td> 616</td>
<td>counter 118</td><td> 118,9</td><td> 67,1</td><td> 310,0</td><td> 1395,0</td><td> 3967,0</td><td> 607</td>
<td>counter 119</td><td> 111,9</td><td> 67,7</td><td> 309,0</td><td> 1323,0</td><td> 4149,0</td><td> 634</td>
189 105
continued from Table 28
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>
<td>counter 120</td><td> 110,6</td><td> 67,6</td><td> 373,0</td><td> 1188,0</td><td> 4199,0</td><td> 653</td>
<td>counter 121</td><td> 114,7</td><td> 66,3</td><td> 287,0</td><td> 1262,0</td><td> 4329,0</td><td> 667</td>
<td>counter 122</td><td> 110,6</td><td> 65,8</td><td> 288,0</td><td> 1223,0</td><td> 4217,0</td><td> 659</td>
<td>counter 123</td><td> 115,0</td><td> 67,5</td><td> 280,0</td><td> 1282,0</td><td> 4071,0</td><td> 624</td>
<td>counter 124</td><td> 116,5</td><td> 66,5</td><td> 309,0</td><td> 1388,0</td><td> 4166,0</td><td> 623</td>
<td>counter 125</td><td> 113,4</td><td> 65,4</td><td> 281,0</td><td> 1274,0</td><td> 3978,0</td><td> 631</td>
<td>counter 126</td><td> 101,4</td><td> 66,8</td><td> 280,0</td><td> 1228,0</td><td> 4206,0</td><td> 656</td>
<td>counter 127</td><td> 105. 5</td><td> 66,4</td><td> 262,0</td><td> 1150,0</td><td> 4167,0</td><td> 670</td>
<td>counter 128</td><td> 110,7</td><td> 66,8</td><td> 292,0</td><td> 1301,0</td><td> 4209,0</td><td> 643</td>
<td>by Wynal. 8</td><td> 131,3</td><td> 63,5</td><td> 227,0</td><td> 1291,0</td><td> 3418,0</td><td> 532</td>
psi = 6.89476x103 Pa
Table 28 (continued)
<td>Sample No.</td><td>Resilience</td><td>Crack growth rate, cm / million cycles</td><td>Abrasion, g</td><td>tg δ @ 0 ° C</td><td>tan δ @ 60 ° C</td>
<td>counter 113</td><td> 44,7</td><td> 3,14</td><td> 0,148</td><td> 0,281</td><td> 0,184</td>
<td>counter 114</td><td> 45,0</td><td> 2,72</td><td> 0,125</td><td> 0,274</td><td> 0,185</td>
<td>counter 115</td><td> 47,0</td><td> 2,54</td><td> 0,163</td><td> 0,233</td><td> 0,171</td>
<td>counter 116</td><td> 46,6</td><td> 2,41</td><td> 0,194</td><td> 0,244</td><td> 0,163</td>
<td>counter 117</td><td> 40,9</td><td> 4,56</td><td> 0,088</td><td> 0,327</td><td> 0,214</td>
<td>counter 118</td><td> 41,8</td><td> 2,80</td><td> 0,112</td><td> 0,335</td><td> 0,225</td>
<td>counter 119</td><td> 41,7</td><td> 4,33</td><td> 0,091</td><td> 0,321</td><td> 0,216</td>
<td>counter 120</td><td> 42,1</td><td> 3,89</td><td> 0,095</td><td> 0,301</td><td> 0,207</td>
<td>counter 121</td><td> 39,2</td><td> 3,38</td><td> 0,075</td><td> 0,312</td><td> 0,256</td>
<td>counter 122</td><td> 38,7</td><td> 4,58</td><td> 0,108</td><td> 0,344</td><td> 0,236</td>
<td>counter 123</td><td> 40,2</td><td> 4,79</td><td> 0,103</td><td> 0,329</td><td> 0,232</td>
<td>counter 124</td><td> 41,7</td><td> 3,78</td><td> 0,102</td><td> 0,321</td><td> 0,209</td>
<td>counter 125</td><td> 38,9</td><td> 3,40</td><td> 0,076</td><td> 0,352</td><td> 0,248</td>
<td>counter 126</td><td> 38,1</td><td> 5,57</td><td> 0,070</td><td> 0,355</td><td> 0,241</td>
<td>counter 127</td><td> 38,2</td><td> 4,79</td><td> 0,073</td><td> 0,346</td><td> 0,254</td>
<td>counter 128</td><td> 39,4</td><td> 3,40</td><td> 0,113</td><td> 0,357</td><td> 0,23</td>
<td>according to invented 8</td><td> 44,8</td><td> 0,27</td><td> 0,130</td><td> 0,297</td><td> 0,199</td>
Figure 16 shows the dispersion and Mzol quality of the inventive and control samples described above containing 55 parts by weight per 100 parts by weight of N326 carbon black. The data of Fig. 16 clearly show that the macrodispersion quality of the new elastomer composites of the invention containing NM326 carbon black is significantly better than that of the control samples. Macrodispersion values of elastomer composites according to
189 105 of the invention containing the N326 carbon black as shown in Fig. 16 are described by the following equations:
D,% <1% (13) when Mwz <0.7 x 10<sup>6</sup>; and log D <log (1) + 2.5 x [Mw<sub>WITH</sub>oi - (0.7 x 106)] x 10- (14) when 0.7 x 106 <Mwjoi <1.1 x 106.
None of the controls achieved a macrodispersion quality of 1.0% or better at any Mw2O1 even after dry blending sufficient to degrade Mw2O1 less than 0.7 x 106. In contrast, elastomer composites of the invention containing carbon black N326 and having a Mw2ol greater than 0.7 x 106 <sub>m</sub>They have an excellent macrodispersion such as D% below 0.2%. The properties of the blends and the characteristics of the inventive samples and the control samples shown in Fig. 16 containing the N326 carbon black are given in Table 29, below. It can be seen that sample 9 of the invention has an extremely good crack growth resistance as indicated by the very low crack growth rate value of only 0.77 cm / million cycles. Thus, the sample according to the invention is significantly superior to the corresponding control samples. It is assumed that this is mainly due to the better Mzol value and the better macrodispersion of the carbon black in the sample of the invention as discussed above.
Table 29. Properties of blends of NR compositions containing 55 parts by weight of N326 carbon black per 100 parts by weight
<td>Sample No.</td><td>Mooney ML (1 + 4) @ 100C</td><td>Hardness</td><td>E100 (psi)</td><td>E300 (psi)</td><td>Stretching (psi)</td><td>EB,%</td>
<td>counter 145</td><td> 64,6</td><td> 60,5</td><td> 289</td><td> 1713</td><td> 3921</td><td> 548</td>
<td>counter 146</td><td> 88,2</td><td> 62,4</td><td> 340</td><td> 1802</td><td> 4094</td><td> 553</td>
<td>counter 147</td><td> 91,7</td><td> 63,3</td><td> 391</td><td> 1917</td><td> 3991</td><td> 528</td>
<td>counter 148</td><td> 96,8</td><td> 4,3</td><td> 326</td><td> 1664</td><td> 4045</td><td> 572</td>
<td>counter 149</td><td> 62,4</td><td> 61,5</td><td> 310</td><td> 1763</td><td> 4029</td><td> 552</td>
<td>counter 150</td><td> 67,7</td><td> 62.6</td><td> 326</td><td> 1855</td><td> 4055</td><td> 551</td>
<td>counter 151</td><td> 76,5</td><td> 60,6</td><td> 287</td><td> 1641</td><td> 4015</td><td> 575</td>
<td>counter 152</td><td> 79,4</td><td> 63,6</td><td> 329</td><td> 1720</td><td> 3980</td><td> 559</td>
<td>counter 153</td><td> 57,2</td><td> 60,1</td><td> 282</td><td> 1623</td><td> 3968</td><td> 579</td>
<td>counter 154</td><td> 75,2</td><td> 62,8</td><td> 254</td><td> 1889</td><td> 3879</td><td> 525</td>
<td>counter 155</td><td> 57,3</td><td> 62,2</td><td> 323</td><td> 1763</td><td> 3975</td><td> 556</td>
<td>counter 156</td><td> 60,1</td><td> 61,9</td><td> 310</td><td> 1667</td><td> 3918</td><td> 564</td>
<td>counter 157</td><td> 45,1</td><td> 61,2</td><td> 328</td><td> 1748</td><td> 4768</td><td> 533</td>
<td>counter 158</td><td> 50,1</td><td> 50,6</td><td> 315</td><td> 1740</td><td> 3871</td><td> 546</td>
<td>counter 159</td><td> 53,2</td><td> 61,3</td><td> 306</td><td> 1675</td><td> 3886</td><td> 563</td>
<td>counter 160</td><td> 50,5</td><td> 62,6</td><td> 331</td><td> 1752</td><td> 3884</td><td> 549</td>
<td>by Wynal. 9</td><td> 77,8</td><td> 60,9</td><td> 277</td><td> 1563</td><td> 4176</td><td> 593</td>
1psi = 6.89476x103Pa
189 105
Table 29 (continued)
<td>sample no</td><td>resilience</td><td>crack growth rate, cm / million cycles</td><td>abrasion, g</td><td>tg δ @ 0 ° C</td><td>tan δ @ 60 ° C</td>
<td>counter 145</td><td> 57,8</td><td> 2,84</td><td> 0,0952</td><td> 0,225</td><td> 0,129</td>
<td>cont. 146</td><td> 58,1</td><td> 2,52</td><td> 0,0887</td><td> 0,217</td><td> 0,126</td>
<td>counter 147</td><td> 57,6</td><td> 2,03</td><td> 0,0946</td><td> 0,205</td><td> 0,125</td>
<td>counter 148</td><td> 56,3</td><td> 1,63</td><td> 0,0927</td><td> 0,221</td><td> 0,129</td>
<td>counter 149</td><td> 57,2</td><td> 3,39</td><td> 0,0827</td><td> 0,234</td><td> 0,142</td>
<td>counter 150</td><td> 56,8</td><td> 2.77</td><td> 0,0866</td><td> 0,234</td><td> 0,150</td>
<td>counter 151</td><td> 55,6</td><td> 2,61</td><td> 0,0933</td><td> 0,241</td><td> 0,149</td>
<td>counter 152</td><td> 54,5</td><td> 2,79</td><td> 0,0857</td><td> 0,249</td><td> 0,155</td>
<td>counter 153</td><td> 55,4</td><td> 3,12</td><td> 0,0911</td><td> 0,258</td><td> 0,170</td>
<td>counter 154</td><td> 56,0</td><td> 3,35</td><td> 0,0858</td><td> 0,241</td><td> 0,147</td>
<td>counter 155</td><td> 55,4</td><td> 2,63</td><td> 0,0811</td><td> 0,254</td><td> 0,152</td>
<td>counter 156</td><td> 54,9</td><td> 3,55</td><td> 0,0906</td><td> 0,261</td><td> 0,153</td>
<td>counter 157</td><td> 55,5</td><td> 3,02</td><td> 0,0931</td><td> 0,254</td><td> 0,149</td>
<td>counter 158</td><td> 55,4</td><td> 3,81</td><td> 0,0914</td><td> 0,249</td><td> 0,150</td>
<td>counter 159</td><td> 54,9</td><td> 3,23</td><td> 0,0933</td><td> 0,240</td><td> 0,158</td>
<td>counter 160</td><td> 55,2</td><td> 3,19</td><td> 0,0942</td><td> 0,245</td><td> 0,163</td>
<td>by Wynal. 9</td><td> 58,4</td><td> 0,77</td><td> 0,0939</td><td> 0,225</td><td> 0,136</td>
Figure 17 shows the dispersion and Mzol quality of samples according to the invention and controls described above and containing REGAL® 660 carbon black. Selected samples of the invention and controls shown in Fig. 17 contained oil as stated above. The data in Fig. 17 clearly shows that the macrodispersion quality of the novel elastomer composites of the invention containing the Regal® 660 carbon black over a wide range of Mzzol values is significantly better than the quality of the control samples. The macrodispersion values of the elastomer composites of the invention containing REGAL® 660 carbon black as shown in Fig. 17 are described by the following equations:
D,% & lt; 1% (15) when MWzol & lt; 0.6 x 106; and log D <log (l) + 2.5 x [MWzol - (0.6 x 106)] x 106 (16) when 0.6 x 10<sup>r</sup><Mzol <1.1 x 106.
None of the controls achieved a macrodispersion quality of 1.0% or better at any MWzol even after dry blending sufficient to degrade the MWzol below 0.6 x 106. In contrast, the elastomer composites of the invention containing Regal® 660 carbon black and having a MWzol greater than 0. 6 x 106 <sub>has</sub>j<sub>and</sub> excellent macrodispersion such as D% less than 0.2%. The properties of the blends and the characteristics of the inventive sample 10 and the control samples shown in Fig. 17 containing Regal® 660 carbon black are given in Table 30, below. It can be seen that the inventive sample 10 has extremely good crack growth resistance as indicated by the very low crack growth rate value of only 0.69 cm / million cycles. Thus, the sample according to the invention is significantly superior to the corresponding control samples. It is assumed that this is mainly due to the better Mzol value and the better macrodispersion of the carbon black in the sample of the invention as discussed above.
189 105
Table 30. Properties of NR compositions blends containing 55 parts by weight of REGAL® 660 carbon black per 100 parts by weight
<td>Sample No.</td><td>Mooney ML (1 + 4) @ 100C</td><td>Hardness</td><td>E100 (psi)</td><td>E300 (psi)</td><td>Stretching (psi)</td><td>EB,%</td>
<td>counter 177</td><td></td><td> 61,0</td><td> 213</td><td> 942</td><td></td><td> 702</td>
<td>counter 178</td><td> 87,6</td><td> 63,2</td><td> 232</td><td> 943</td><td> 4002</td><td> 694</td>
<td>counter 179</td><td> 87,1</td><td> 64,9</td><td> 285</td><td> 1134</td><td> 4016</td><td> 644</td>
<td>counter 180</td><td> 85,6</td><td> 64,0</td><td> 271</td><td> 1198</td><td> 4058</td><td> 618</td>
<td>counter 181</td><td> 80,1</td><td> 61,0</td><td> 206</td><td> 945</td><td> 4098</td><td> 661</td>
<td>counter 182</td><td> 93,4</td><td> 59,0</td><td> 192</td><td> 835</td><td> 3924</td><td> 733</td>
<td>counter 183</td><td> 89,0</td><td> 61,0</td><td> 215</td><td> 920</td><td> 4134</td><td> 698</td>
<td>counter 184</td><td> 83,4</td><td> 62,4</td><td> 223</td><td> 996</td><td> 4236</td><td> 694</td>
<td>counter 185</td><td> 70,1</td><td> 60,0</td><td> 178</td><td> 794</td><td> 3768</td><td> 717</td>
<td>counter 186</td><td> 69,8</td><td> 60,3</td><td> 196</td><td> 920</td><td> 4051</td><td> 666</td>
<td>counter 187</td><td> 76,7</td><td> 63,5</td><td> 166</td><td> 866</td><td> 4157</td><td> 720</td>
<td>counter 188</td><td> 72,1</td><td> 62,0</td><td> 191</td><td> 883</td><td> 4182</td><td> 704</td>
<td>counter 189</td><td> 54,3</td><td> 61,2</td><td> 222</td><td> 1079</td><td> 4240</td><td> 674</td>
<td>counter 190</td><td> 55,7</td><td> 61,1</td><td> 193</td><td> 942</td><td> 4125</td><td> 692</td>
<td>counter 191</td><td></td><td> 65,0</td><td></td><td></td><td></td><td></td>
<td>counter 192</td><td> 61,1</td><td> 60,4</td><td> 191</td><td> 902</td><td> 4189</td><td> 710</td>
<td>by Wynal. 10</td><td> 88,1</td><td> 62,9</td><td> 249</td><td> 1202</td><td> 4292</td><td> 634</td>
psi = 6.89476x103 Pa
Table 30 (continued)
<td>Sample No.</td><td>Resilience</td><td>Crack growth rate, cm / million cycles</td><td>Abrasion, g</td><td>tg δ @ 0 ° C</td><td>tan δ @ 60 ° C</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 177</td><td> 54,6</td><td></td><td></td><td></td><td> 0,131</td>
<td>counter 178</td><td> 55,6</td><td> 2.34</td><td> 0,1649</td><td> 0,194</td><td> 0,129</td>
<td>counter 179</td><td> 53,7</td><td> 2,78</td><td> 0,1620</td><td> 0,200</td><td> 0,140</td>
<td>counter 180</td><td> 52,9</td><td> 2,98</td><td> 0,1385</td><td> 0,220</td><td> 0,153</td>
<td>counter 181</td><td> 53,0</td><td> 3,41</td><td> 0,1189</td><td> 0,267</td><td> 0,185</td>
<td>counter 182</td><td> 49,9</td><td> 3,11</td><td> 0,1076</td><td> 0,270</td><td> 0,194</td>
<td>counter 183</td><td> 50,1</td><td> 3,15</td><td> 0,1086</td><td> 0,264</td><td> 0,192</td>
<td>counter 184</td><td> 48,0</td><td> 3,11</td><td> 0,1085</td><td> 0,284</td><td> 0,208</td>
<td>counter 185</td><td> 47,5</td><td> 4,59</td><td> 0,0937</td><td> 0,306</td><td> 0,209</td>
<td>counter 186</td><td> 48,5</td><td> 4,06</td><td> 0,1008</td><td> 0,295</td><td> 0,211</td>
189 105
continued from Table 30
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 187</td><td> 47,7</td><td> 3,53</td><td> 0,1041</td><td> 0,297</td><td> 0,198</td>
<td>counter 188</td><td> 47,8</td><td> 3,79</td><td> 0,0985</td><td> 0,285</td><td> 0,205</td>
<td>counter 189</td><td> 47,5</td><td> 3,71</td><td> 0,0957</td><td> 0,306</td><td> 0,203</td>
<td>counter 190</td><td> 46,8</td><td> 4,14</td><td> 0,0962</td><td> 0,300</td><td> 0,200</td>
<td>counter 191</td><td> 47,4</td><td></td><td></td><td></td><td> 0,226</td>
<td>counter 192</td><td> 46,5</td><td> 4,78</td><td> 0,0897</td><td> 0,301</td><td> 0,226</td>
<td>by Wynal. 10</td><td> 48,2</td><td> 0.69</td><td> 0,0942</td><td> 0,271</td><td> 0,178</td>
Figure 18 shows the dispersion quality and Mzol of the samples according to the invention and the control samples described above and containing carbon black. Selected samples of the invention and controls shown in Fig. 18 contained oil as stated above. The data in Fig. 18 clearly shows that the macrodispersion quality of the novel elastomer composites of the invention containing the N234 carbon black over a wide range of Mvol values is significantly better than the quality of the control samples. The macro-dispersion values of the elastomer composites of the invention containing the N234 carbon black as shown in Fig. 18 are described by the following equations:
D,% <0.3% 117) when MWzol <0.35 x 10<sup>6</sup>; and<sub>with</sub> log D <log (0.3) + 2.8 x [MW - (0.35 x 106)] x 10 '<sup>6</sup> (18) when 0.35 x 10<sup>6</sup> <Mzol <1.1 x H.<sup>6</sup>·
None of the control samples achieved low quality and 0.3% hib quality through any Mzol even after dry blending sufficient to degrade the Mzole below 0.35 x 10<sup>6</sup>. In contrast, the elastomer composites of the invention containing carbon black N234 and having a Mzol value greater than 0.35 x 10<sup>6</sup> have an excellent macro-dispersion such as D% not more than 0.3 or even 0.2%. Properties of the blends and characteristics of sample 14 of the invention and the various controls shown in Fig. 18 containing the N234 carbon black are given in Table 31, below. It can be seen that sample 14 of the present invention has good crack growth resistance as indicated by a crack growth rate value of only 2.08 cm / million cycles.
Table 31. Properties of blends of NR compositions containing 55 parts by weight of N234 carbon black per 100 parts by weight
<td>Sample No.</td><td>Moonoy ML (1 + 4) @ 100C</td><td>Hardness</td><td>E100 (psi)</td><td>E300 (psi)</td><td>Stretching (psi)</td><td>EB,%</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>
<td>counter 273</td><td> 94,5</td><td> 68,0</td><td> 386</td><td> 2077</td><td> 3718</td><td> 511</td>
<td>counter 274</td><td> 121,6</td><td> 69,6</td><td> 464</td><td> 2299</td><td> 3925</td><td> 501</td>
<td>counter 275</td><td> 121,4</td><td> 72,5</td><td> 564</td><td> 2545</td><td> 3994</td><td> 472</td>
<td>counter 276</td><td> 132,2</td><td> 71,9</td><td> 511</td><td> 2259</td><td> 3964</td><td> 520</td>
<td>counter 277</td><td> 79,6</td><td> 68,5</td><td> 468</td><td> 2453</td><td> 3857</td><td> 469</td>
<td>counter 278</td><td> 96,3</td><td> 70,0</td><td> 531</td><td> 2499</td><td> 3874</td><td> 469</td>
<td>counter 279</td><td> 108,6</td><td> 69,0</td><td> 406</td><td> 2131</td><td> 3863</td><td> 533</td>
<td>counter 280</td><td> 120,3</td><td> 71,5</td><td> 476</td><td> 2273</td><td> 3852</td><td> 502</td>
189 105
continued from table 31
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td>
<td>counter 281</td><td> 76,4</td><td> 69,7</td><td> 556</td><td> 2723</td><td> 4027</td><td> 451</td>
<td>counter 282</td><td> 89,8</td><td> 69,8</td><td> 553</td><td> 2574</td><td> 3896</td><td> 465</td>
<td>counter 283</td><td> 93,6</td><td> 69,6</td><td> 506</td><td> 2416</td><td> 3867</td><td> 475</td>
<td>counter 284</td><td> 106,7</td><td> 71,8</td><td> 526</td><td> 2384</td><td> 3788</td><td> 484</td>
<td>counter 285</td><td> 73,3</td><td> 69,3</td><td> 529</td><td> 2586</td><td> 3831</td><td> 444</td>
<td>counter 286</td><td> 79,2</td><td> 69,5</td><td> 531</td><td> 2574</td><td> 3856</td><td> 456</td>
<td>counter 287</td><td> 77,8</td><td> 70,7</td><td> 544</td><td> 2486</td><td> 3834</td><td> 461</td>
<td>counter 288</td><td> 82,8</td><td> 71,2</td><td> 485</td><td> 2295</td><td> 3799</td><td> 499</td>
<td>according to inventory 14</td><td> 82,6</td><td> 71,5</td><td> 500</td><td> 2440</td><td> 3883</td><td> 531</td>
psi = 6.894 76x10<sup>3</sup> Bye
Table 3 1 (continued)
<td>Sample No.</td><td>Resilience</td><td>Crack growth rate, cm / million cycles</td><td>Abrasion, g</td><td>tg δ @ 0 ° C</td><td>tan δ @ 60 ° C</td>
<td>counter 273</td><td> 45,9</td><td> 2,14</td><td> 0,0563</td><td> 0,285</td><td> 0,183</td>
<td>counter 274</td><td> 47,2</td><td> 1,84</td><td> 0,0583</td><td> 0,276</td><td> 0,173</td>
<td>counter 275</td><td> 46,1</td><td> 1,70</td><td> 0,0538</td><td> 0,284</td><td> 0,172</td>
<td>counter 276</td><td> 46,9</td><td> 1,21</td><td> 0,0620</td><td> 0,270</td><td> 0,173</td>
<td>counter 277</td><td> 47,1</td><td> 2,22</td><td> 0,0628</td><td> 0,305</td><td> 0,173</td>
<td>counter 278</td><td> 45,8</td><td> 2,40</td><td> 0,0634</td><td> 0,299</td><td> 0,196</td>
<td>counter 279</td><td> 45,4</td><td> 2,00</td><td> 0,0680</td><td> 0,306</td><td> 0,198</td>
<td>counter 280</td><td> 44,2</td><td> 1,81</td><td> 0,0646</td><td> 0,298</td><td> 0,198</td>
<td>counter 281</td><td> 46,3</td><td> 3,10</td><td> 0,0598</td><td> 0.293</td><td> 0,174</td>
<td>counter 282</td><td> 46,6</td><td> 2,33</td><td> 0,0537</td><td> 0,307</td><td> 0,182</td>
<td>counter 283</td><td> 46,4</td><td> 2,41</td><td> 0,0594</td><td> 0,309</td><td> 0,186</td>
<td>counter 284</td><td> 44,2</td><td> 1,99</td><td> 0,0579</td><td> 0,304</td><td> 0,190</td>
<td>counter 285</td><td> 47,0</td><td> 2,99</td><td> 0,0554</td><td> 0,295</td><td> 0,178</td>
<td>counter 286</td><td> 45,6</td><td> 2,85</td><td> 0,0551</td><td> 0,294</td><td> 0,172</td>
<td>counter 287</td><td> 45,4</td><td> 2,93</td><td> 0,0569</td><td> 0,305</td><td> 0,187</td>
<td>counter 288</td><td> 44,0</td><td> 2,39</td><td> 0.0647</td><td> 0,316</td><td> 0.198</td>
<td>by Wynal. 14</td><td> 45,1</td><td> 2,08</td><td> 0,0698</td><td> 0,310</td><td> 0,198</td>
Figure 19 shows the dispersion and Mzol quality of the inventive and control samples described above containing 55 parts by weight of N110 carbon black per 100 parts by weight. The data of Fig. 19 clearly show that the macrodispersion quality of the novel elastomer composites of the invention containing the N110 carbon black, over a wide range of Mvol values, is significantly better than the quality of the controls. Macrodispersion values
189 The 105 elastomer composites of the invention containing carbon black N110 as shown in Fig. 19 are described by the following equations:
D,% <0.5% (19) when MWjol <0.35 x 10<sup>6</sup>; and log D <log (0.5) + 2.5 x [MW<sub>o</sub>, - (0.6 x10 <sup>6</sup>) 106 10'<sup>6</sup> (200 when 0.35 x 106 <Mzol <1.1 x 1 ^ 0.
None of the control samples achieved a macrodispersion quality of 0.5% at any µl<sub>WITH</sub>ol even after dry blending sufficient to degrade Mw<sub>WITH</sub>ol less than 0.35 x 106. In contrast, the elastomer composites of the invention containing carbon black N110 and having an Mw value<sub>WITH</sub>o1 greater than 0.35 x 106 have excellent macro-dispersion such as D% less than 0.2%.
Figure 20 shows the dispersion quality and Mzol of sample 22 according to the invention and the control samples described above containing 33 parts by weight per 100 parts by weight of N351 carbon black. The data of Fig. 20 clearly show that the macrodispersion quality of the novel elastomer composites of the invention containing the N351 carbon black over a wide range of Mzol values is significantly better than the quality of the controls. The macro-dispersion values of the elastomer composites of the invention containing the N351 carbon black as shown in Fig. 20 are described by the following equations:
D,% <0.3% (211 when Mzol <0.35 x 106 and log D <log (0.3) + 2.0 0) MWzzl - (0.55 x 10)))] x 10 '<sup>6</sup> (22) when 0.55 x 10<sup>6</sup> <Mzol <1.1 1) 00
None of the controls achieved a macrodispersion quality of 1.0% at any Mzol even after dry blending sufficient to degrade the Mzol less than 0.35 x 106. In contrast, the elastomer composites of the invention containing the N351 carbon black and having a MWol greater than 0.35 x 106 have excellent macro-dispersion such as D% less than 0.2%.
Figure 21 shows the dispersion quality and Mzol of sample 23 according to the invention and the controls described above containing Sterling® 6740 carbon black in an amount of 55 parts by weight per 100 parts. The data of Fig. 21 clearly shows that the macrodispersion quality of the novel elastomer composites of the invention containing the Sterling® 6740 carbon black over a wide range of Mzol values is significantly better than the quality of the controls. The macro-dispersion values of the elastomer composites of the invention containing the Sterling® 6740 carbon black as shown in Fig. 21 are described by the following equations:
D,% <0.1% (223 when Mw<sub>WITH</sub>oi <0.3 x 106; and log D <log (0.1) + 2.0 x Mwool - (0.3 x10<sup>6</sup>) - xW '<sup>6</sup> (^^ 2 when 0.3 x 106 <Mw<sub>WITH</sub>oi <1.1 x 106.
None of the controls achieved a macrodispersion quality of 0.1% or even 0.2% at any Mzol even after dry blending sufficient to degrade the Mzol below 0.3 x 106. In contrast, the elastomer composites of the invention containing Sterling® 6740 carbon black and having a value of Mzol over 0.35 x 106 <sub>has</sub>it has an excellent macrodispersion such as D% below 0.2%. The properties of the blends and the performance characteristics of the sample 23 of the invention and the control samples shown in Fig. 21 containing Sterling® 6740 carbon black are given in Table 32, below. It can be seen that sample 23 of the invention has good crack growth resistance as indicated by a crack growth rate value of only 0.91 cm / million cycles. This is believed to be mainly due to the improved Mzol value and macrodispersion of the carbon black in the sample of the invention as discussed above.
189 105
Table 32. Properties of blends of NR compositions containing 55 parts by weight of Sterling® 6740 carbon black per 100 parts by weight
<td>Sample No.</td><td>Mooney ML (1 + 4) @ 100C</td><td>Hardness</td><td>E100 (psi)</td><td>E300 (p<sup>si)</sup></td><td>stretching (psi)</td><td>EB,%</td>
<td>counter 412</td><td> 75,50</td><td> 65,1</td><td> 46,0</td><td> 2308,0</td><td> 3519</td><td> 451</td>
<td>counter 413</td><td> 85,70</td><td> 65,1</td><td> 469,0</td><td> 2314,0</td><td> 3655</td><td> 479</td>
<td>counter 414</td><td> 92,70</td><td> 67,7</td><td> 462,0</td><td> 2243,0</td><td> 3613</td><td> 472</td>
<td>counter 415</td><td> 9,60</td><td> 66,9</td><td> 492,0</td><td> 2260,0</td><td> 3572</td><td> 477</td>
<td>counter 416</td><td> 74,50</td><td> 65,8</td><td> 521,0</td><td> 2468,0</td><td> 3584</td><td> 445</td>
<td>counter 417</td><td> 78,20</td><td> 67,1</td><td> 502,0</td><td> 2372,0</td><td> 3445</td><td> 436</td>
<td>counter 418</td><td> 82,00</td><td> 66,0</td><td> 534,0</td><td> 2418,0</td><td> 3604</td><td> 453</td>
<td>counter 419</td><td> 86,10</td><td> 67,8</td><td> 540,0</td><td> 2330,0</td><td> 3620</td><td> 475</td>
<td>counter 420</td><td> 66,70</td><td> 6,0</td><td> 515,0</td><td> 2382,0</td><td> 3468</td><td> 444</td>
<td>counter 421</td><td> 76,30</td><td> 67,8</td><td> 488,0</td><td> 2310,0</td><td> 3375</td><td> 440</td>
<td>counter 422</td><td> 78,30</td><td> 65,8</td><td> 548,6</td><td> 2440,0</td><td> 3549</td><td> 442</td>
<td>counter 423</td><td> 82,10</td><td> 66,5</td><td> 487,0</td><td> 2219,0</td><td> 3452</td><td> 466</td>
<td>counter 424</td><td> 64,80</td><td> 66,1</td><td> 541,0</td><td> 2448,0</td><td> 3397</td><td> 425</td>
<td>counter 425</td><td> 67,50</td><td> 66,5</td><td> 524,0</td><td> 2374,0</td><td> 3474</td><td> 445</td>
<td>counter 426</td><td> 70,30</td><td> 66,9</td><td> 546,0</td><td> 2351,0</td><td> 3428</td><td> 446</td>
<td>counter 427</td><td> 71,00</td><td> 68,1</td><td> 554,0</td><td> 2340,0</td><td> 3322</td><td> 435</td>
<td>by Wynal. 23</td><td> 110,50</td><td> 64,8</td><td> 453,6</td><td> 2241,0</td><td> 3324</td><td> 443</td>
psi = 6.894 76x10<sup>3</sup>Bye
Table 32 (continued)
<td>Sample No.</td><td>Resilience</td><td>Crack growth rate, cm / million cycles</td><td>Abrasion, g</td><td>tg δ @ 0 ° C</td><td>tan δ @ 60 ° C</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 412</td><td> 59,8</td><td> 5,04</td><td> 0,127</td><td> 0,202</td><td> 0,107</td>
<td>counter 413</td><td> 60,0</td><td> 3,63</td><td> 0,128</td><td> 0,203</td><td> 0,108</td>
<td>counter 414</td><td> 59,3</td><td> 3,96</td><td> 0,126</td><td> 0,208</td><td> 0,114</td>
<td>counter 415</td><td> 58,0</td><td> 4,56</td><td> 0,12</td><td> 0,217</td><td> 0,118</td>
<td>counter 416</td><td> 60,3</td><td> 5,67</td><td> 0,117</td><td> 0,188</td><td> 0,094</td>
<td>counter 417</td><td> 60,0</td><td> 4,67</td><td> 0,112</td><td> 0,202</td><td> 0,104</td>
<td>counter, 418</td><td> 59,3</td><td> 4.23</td><td> 0,125</td><td> 0,204</td><td> 0,105</td>
<td>counter 419</td><td> 57,5</td><td> 3,22</td><td> 0,122</td><td> 0,218</td><td> 0,117</td>
<td>counter 420</td><td> 60,0</td><td> 4,23</td><td> 0,131</td><td> 0,204</td><td> 0,099</td>
<td>counter 421</td><td> 58. 8</td><td> 3,84</td><td> 0,127</td><td> 0.206</td><td> 0,105</td>
<td>counter 422</td><td> 59,8</td><td> 3,98</td><td> 0,126</td><td> 0,210</td><td> 0,106</td>
189 105
cd table
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>counter 423</td><td> 56,8</td><td> 3.83</td><td> 0,120</td><td> 0,213</td><td> 0,117</td>
<td>counter 424</td><td> 58,3</td><td> 4,54</td><td> 0,131</td><td> 0,200</td><td> 0,104</td>
<td>counter 425</td><td> 58,8</td><td> 3,65</td><td> 0,129</td><td> 0.207</td><td> 0,100</td>
<td>counter 42 6</td><td> 58,0</td><td> 3,07</td><td> 0,134</td><td> 0,211</td><td> 0,110</td>
<td>counter 427</td><td> 56,9</td><td> 3,25</td><td> 0,126</td><td> 0,217</td><td> 0,115</td>
<td>by Wynal. 23</td><td> 57,3</td><td> 0,91</td><td> 0,1642</td><td> 0,206</td><td> 0,124</td>
Additional examples: vulcanized samples
A number of the masterbatch samples described above were vulcanized and tested, including both selected samples of the invention as well as corresponding controls. Specifically, the samples were mixed according to step II in table 8 above using the recipe according to table 9 to produce the final blend. The final blend was then cured in the mold in each case using conventional techniques at a temperature of about 150 ° C until substantially complete cure was achieved. The performance properties of the vulcanized samples were determined by measuring their crack growth rate in accordance with the measuring technique specified above, i.e. using a rotary bending machine according to ASTM D 3627-94. The rotary bending machine is produced on an industrial scale and is known. For example, it is reviewed in Proceedings of the International Rubber, Germany, 1995 (Kobe, Japan), Paper N. 277A-6 (pages 472-475). The blends were tested at 100 ° C and 45 ° bend. It is generally recognized by those skilled in the art that the crack growth rate is influenced by the molecular weight of the natural rubber and the quality of the carbon black dispersion, i.e., the Mvol D,%, values of the blends. Higher Mvol values and lower D% values correlate well with a reduction in crack growth rate. Both the crack growth rate as well as other information regarding samples 9, 10 and 16 of the invention are given in Table 33 below. The respective test results for the respective controls are listed in Table 34 below, grouped by carbon black selection. Tan 5 values were also measured for samples 24 to 32 according to the invention and for the corresponding control samples<sub>m</sub>.ks. max. @ 60 ° C. The tan dmax @ 60 ° C values for the inventive samples are given in Table 35 below. The corresponding measurement results for the control samples are given in Table 36 below.
Controls 444 to 450 shown in Table 36 were made by the methods described above for Control Code M2D1 using RSS1 natural rubber. The total amount of carbon black N234 was used in the parts by weight per 100 parts by weight listed in Table 36, together with 5 parts by weight per 100 parts by weight of the diluent oil.
Table 33. Crack Growth Rate (CDR) for the samples of the present invention
<td>Sample No. according to the invention</td><td>soot (CB) / quantity / oil</td><td>MWzoi, K</td><td>crack growth rate (CGR), cm / million cycles</td>
<td> 9</td><td>N326 / 55/0</td><td> 666</td><td> 0,77</td>
<td> 10</td><td>R660 / 55/0</td><td> 678</td><td> 0,69</td>
<td> 16</td><td>N234 / 55/0</td><td> 500</td><td> 0,88</td>
189 105
Table 34. Crack Growth Rate (CDR) for controls
<td rowspan="3">Code</td><td colspan="3">N234 / 55 parts per 100 parts by weight / 0</td>
<td colspan="3">RSS1</td>
<td>Sample No.</td><td>Mwzol, and K.</td><td>CDR, cm / million cycles</td>
<td>M1D1</td><td> 273</td><td> 585</td><td> 2,14</td>
<td>M1D2</td><td> 274</td><td> 669</td><td> 1,84</td>
<td>M1D3</td><td> 275</td><td> 759</td><td> 1,70</td>
<td>M1D4</td><td> 276</td><td> 896</td><td> 1,21</td>
<td>M2D1</td><td> 277</td><td> 580</td><td> 2,22</td>
<td>M2D2</td><td> 278</td><td> 602</td><td> 2,40</td>
<td>M2D3</td><td> 279</td><td> 631</td><td> 2,00</td>
<td>M2D4</td><td> 280</td><td> 667</td><td> 1,81</td>
<td>M3D1</td><td> 281</td><td> 457</td><td> 3,10</td>
<td>M3D2</td><td> 282</td><td> 476</td><td> 2,33</td>
<td>M3D3</td><td> 283</td><td> 493</td><td> 2,41</td>
<td>M3D4</td><td> 384</td><td> 495</td><td> 1,99</td>
<td>M4D1</td><td> 285</td><td> 372</td><td> 2,99</td>
<td>M4D2</td><td> 286</td><td> 382</td><td> 2,85</td>
<td>M4D3</td><td> 287</td><td> 381</td><td> 2,93</td>
<td>M4D4</td><td> 288</td><td> 403</td><td> 2,39</td>
<td rowspan="3">Code</td><td colspan="3">N326 / 55 parts by weight per 100 parts by weight / 0</td>
<td colspan="3">RSS1</td>
<td>Sample No.</td><td>Mwzol, and K.</td><td>CDR, cm / million cycles</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>M1D1</td><td> 145</td><td> 55</td><td> 2,84</td>
<td>M1D2</td><td> 146</td><td> 636</td><td> 2,52</td>
<td>M1D3</td><td> 147</td><td> 650</td><td> 2,03</td>
<td>M1D4</td><td> 148</td><td> 724</td><td> 1,63</td>
<td>M2D1</td><td> 149</td><td> 517</td><td> 3,39</td>
<td>M2D2</td><td> 150</td><td> 572</td><td> 2,77</td>
<td>M2D3</td><td> 151</td><td> 613</td><td> 2,61</td>
<td>M2D4</td><td> 152</td><td> 696</td><td> 2,79</td>
<td>M3D1</td><td> 153</td><td> 489</td><td> 3,12</td>
<td>M3D2</td><td> 154</td><td> 521</td><td> 3,35</td>
189 105
cd table
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td>M3D3</td><td> 155</td><td> 504</td><td> 3,63</td>
<td>M3D4</td><td> 156</td><td> 538</td><td> 3,55</td>
<td>M4D1</td><td> 157</td><td> 415</td><td> 3,02</td>
<td>M4D2</td><td> 158</td><td> 447</td><td> 3,81</td>
<td>M4D3</td><td> 159</td><td> 466</td><td> 3,23</td>
<td>M4D4</td><td> 160</td><td> 469</td><td> 3,19</td>
<td rowspan="3">Code</td><td colspan="3">Regal 660/55 parts by weight per 100 parts by weight / 0</td>
<td colspan="3">RSS1</td>
<td>sample no</td><td>Mwzol, and K.</td><td>CDR, cm / million cycles</td>
<td>M1D1</td><td> 177</td><td> 674</td><td></td>
<td>M1D2</td><td> 178</td><td> 792</td><td> 2,34</td>
<td>M1D3</td><td> 179</td><td> 891</td><td> 2,78</td>
<td>M1D4</td><td> 180</td><td> 676</td><td> 2,98</td>
<td>M2D1</td><td> 181</td><td> 598</td><td> 3,41</td>
<td>M2D2</td><td> 182</td><td> 602</td><td> 3,11</td>
<td>M2D3</td><td> 183</td><td> 697</td><td> 3,15</td>
<td>M2D4</td><td> 184</td><td> 659</td><td> 3,11</td>
<td>M3D1</td><td> 185</td><td> 473</td><td> 4,59</td>
<td>M3D2</td><td> 186</td><td> 506</td><td> 4,06</td>
<td>M3D3</td><td> 187</td><td> 562</td><td> 3,53</td>
<td>M3D4</td><td> 188</td><td> 559</td><td> 3,79</td>
<td>M4D1</td><td> 189</td><td> 401</td><td> 3,71</td>
<td>M4D2</td><td> 190</td><td> 426</td><td> 4,14</td>
<td>M4D3</td><td> 191</td><td> 466</td><td></td>
<td>M4D4</td><td> 192</td><td> 449</td><td> 4,78</td>
Table 35. tan 5 at 60 ° C for the samples of the invention
<td>Sample No. according to the invention</td><td>The amount of N234 and oil, parts per 100 parts resin</td><td>MW<sub>20</sub>i, K.</td><td>tan δ ,,, ^ @ 60 ° C</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td> 24</td><td> 48/5</td><td> 569</td><td> 0,169</td>
<td> 25</td><td> 53/5</td><td> 485</td><td> 0,176</td>
<td> 26</td><td> 58/5</td><td> 447</td><td> 0,191</td>
<td> 27</td><td> 63/5</td><td> 403</td><td> 0,219</td>
189 105
continued from Table 35
<td> 1</td><td> 2</td><td> 3</td><td> 4</td>
<td> 28</td><td> 68/5</td><td> 378</td><td> 0,227</td>
<td> 29</td><td> 49/5</td><td> 618</td><td> 0,159</td>
<td> 30</td><td> 54/5</td><td> 482</td><td> 0,171</td>
<td> 31</td><td> 63/5</td><td> 390</td><td> 0,228</td>
<td> 32</td><td> 65/5</td><td> 325</td><td> 0,224</td>
Table 36. tan 6 at 60 ° C for controls
<td>Sample No.</td><td>MW, K</td><td>D,%</td><td>The amount of N234 and oil, parts by weight per 100 parts by weight</td><td>tan δπ ^ δ- @ 60 ° C</td>
<td> 444</td><td> 428</td><td> 0,25</td><td> 37/5</td><td> 0,154</td>
<td> 445</td><td> 409</td><td> 0,37</td><td> 42/5</td><td> 0,170</td>
<td> 446</td><td> 379</td><td> 0,42</td><td> 46/5</td><td> 0,179</td>
<td> 447</td><td> 361</td><td> 0,58</td><td> 51/5</td><td> 0,195</td>
<td> 448</td><td> 366</td><td> 0,27</td><td> 53/5</td><td> 0,212</td>
<td> 449</td><td> 290</td><td> 0,39</td><td> 58/5</td><td> 0,215</td>
<td> 450</td><td> 296</td><td> 0,64</td><td> 63/5</td><td> 0,245</td>
A comparison of Tables 33 and 34 shows that the samples according to the invention preferably have a lower crack growth rate than the controls. The slower crack growth rate correlates well with good durability and with similar properties for numerous applications, including tire and the like applications. Moreover, the comparison of Tables 35 and 36 shows that the better values of tan<sub>m! 1</sub>k<sub>S.</sub>. are obtained for the samples according to the invention, i.e. values lower than those obtained for the control samples. Thus, better performance properties of the samples of the present invention for many applications are obtained with the samples of the invention, including, for example, tire and the like applications requiring a low hysteresis to obtain a correspondingly low rolling resistance.
The advantageous performance properties of the elastomer composites according to the invention can be illustrated, for example, by the crack growth rate of the inventive sample 16 containing carbon black N234 and the corresponding test results for control samples 273 to 288, graphically represented in Fig. 22. In particular, Fig. 22 clearly shows the correlation between the Mzol and the crack growth rate for the controls as well as the beneficial effect of the excellent macrodispersion of the elastomer composites of the present invention. It should be noted that the Mzol values provided in Figures 22-24 and Tables 33-36 are for masterbatch materials prior to vulcanization. The molecular weight of the vulcanized material is believed to correlate well with the Mvol value of the unvulcanized masterbatch. It can be seen that the crack growth rate of the controls over a wide range of Mwzol, from about 0.25 x 106 to 0.6 x 106, is in good agreement with the rectilinear correlation with Mso. In contrast, inventive sample 16 having a MWol of 0.5 x 10 ° has a clearly better (ie slower) crack growth rate than any of the corresponding controls, as a result of the superior macrodispersion, D,%, of the inventive sample. This is confirmed similarly additionally by Fig. 23, wherein the crack growth rate of the N326 carbon black inclusive sample 9 of the invention is significantly slower than the crack growth rate of any of the respective controls 145 to 160 and clearly below the correlation line. Likewise, in the case of Fig. 24, the perfect macrodispersion of the sample 10 of the invention causes, again,
189 105 that the value of the crack growth rate is well below the correlation line between the crack growth rate and the MWol determined for the respective controls 177 to 192. Figure 25 shows graphically that the tan is better, i.e. lower, for samples 24 through 28. according to the invention of the controls and for samples 29 to 32 according to the invention than the corresponding controls 444 to 450.
The above-discussed better crack growth rate results for the elastomer composites of the present invention not only indicate better fatigue properties, but also favorable fracture properties such as excellent tear resistance and chip formation during cutting. The better histori cal properties of the elastomer composites of the present invention discussed above only demonstrate the favorable low rolling resistance (and correspondingly low fuel consumption) in automotive tire applications, the lacquer also demonstrates a favorable improvement in related performance properties such as reduced heat. One or more of these superior properties, namely fatigue and crack resistance, low historosis, low heat build-up and the like, make the elastomer composites of the present invention well suited for industrial applications such as tire applications and for the manufacture of industrial articles. rubber. With respect to tire applications, variously advantageously, embodiments of the present invention are generally applicable to: tire treads, more generally radial and oblique truck tires, off-road tires (i.e. "OTR" tires for "off-tho-road"), aircraft tires and it supposedly; the lower parts of the tire tread; wire treads; tread sides; the shock-absorbing material; the tires were retreaded; and similar tire applications. The improved performance characteristics have been obtained with the various preferred embodiments of the present invention, which may relate to better tire durability, better tread and cover life, less fuel consumption, and other appeal. With respect to industrial rubber articles, various advantageously embodiments of the present invention are more generally applicable to such applications as: engine mounts, hydraulic beds, bridge bearings and seismic insulators, car cystem tires, mine belts and similar articles. The improved performance properties achieved by the various preferred embodiments of this invention may impart improved fatigue life, durability and other appeal to such article applications.
Figures 26-29 are graphical representations of carbon black morphology, structure (DBPA), and surface area (CTAB), generally corresponding to Figure 8. The carbon black morphology area 261 in Figure 26 includes carbon blacks commercially used for off-road tire biogas (OTR). Arrow 262 indicates the direction in which region 261 may advantageously expand in accordance with the present invention. Performance properties, such as resistance to chip formation on cutting, resistance to rapid crack growth, and tear resistance, usually improve generally in the direction of the trend arrow 262, but have historically been associated with adverse degradation of these and other properties due to reductions in molecular weight. natural rubber and / or worse macrodispersion caused by the use of carbon black with a higher surface area and a lower structure. It is possible to use carbon blacks with a higher surface area and a lower structure as indicated by the tendency arrow 262 for the elastomer composites of the present invention to obtain significantly better oTr materials due to their excellent macro-performance and Moi.
Similarly, the soot morphology area 271 in Figure 27 includes carbon black currently used commercially for truck and bus tire treads (T / B). Arrow 272 indicates the direction in which region 271 can advantageously expand according to the present invention. Performance properties such as chip resistance and toughness generally improve in the direction of the trend arrow 272, however in the past have been associated with unfavorable degradation of these and other properties associated with reductions in the rubber molecular weight and / or poorer macrodispersion caused by use of carbon blacks with a larger surface area and a lower structure. It is possible to use carbon black with a higher surface area indicated by the tendency arrow 272 for elastomer composites according to the present invention in order to obtain better bio-materials T / B due to their excellent manrodispersion and Moisture.
189 105
Likewise, the carbon black morphology regions 281 and 283 in Fig. 28 include currently commercial carbon blacks used for treads of base tires and passenger car (PC) tires, respectively. Trend arrows 282 and 284 indicate the direction in which regions 281 and 283, respectively, may be advantageously extended in accordance with the present invention. Performance such as heat build-up (HBU ) and rolling resistance tend to improve for the base of the tire tread generally in the direction of the trend arrow 282, but have historically been associated with adverse degradation of these and other properties related to with a decrease in the molecular weight of the rubber and / or with a poorer macrodispersion caused by the use of a carbon black with a higher surface area and a lower structure. Likewise, performance properties such as rolling resistance tend to improve for PC treads generally in the direction of the trend arrow 284, however in the past they have been associated with unfavorable degradation of these and other properties related to the reduction of the rubber molecular weight and / or poorer macrodispersion caused by the use of carbon black with a larger surface area and a lower structure. It is possible to use such carbon blacks with higher surface area indicated by arrows 282 and 284 for elastomer composites according to the present invention in order to obtain better materials for the base and treads of PC, respectively, due to their excellent macrodispersion and possibly keeping the high molecular weight of such elastomeric composites. .
Likewise, the carbon black morphology regions 291, 293, and 294 in Figure 29 now include commercial carbon blacks applied to the sidewall, apex, and tire steel belt, respectively. Trend arrows 292 and 295 indicate the direction in which region 291 and 295 may be advantageously extended, respectively, in accordance with the present invention. Performance properties such as heat build-up (HBU) and fatigue life tend to improve for sidewall in the direction of the trend arrow 292, however, in the past, they have been associated with unfavorable degradation of these and other properties due to the reduction of the molecular weight of the rubber and / or poorer macrodispersion caused by the use of carbon black with a lower structure. Likewise, performance properties such as heat build-up, processing, and wire adhesion tend to improve for steel belt of elastomeric materials in the direction of the trend arrow 295, however, in the past, they have been associated with adverse degradation of these and other properties due to the reduction in the molecular weight of the rubber and / or or worse macrodispersion caused by the use of carbon black with a higher surface area and a lower structure. It is possible to use carbon black with higher surface area and / or lower structure, indicated by arrows 292 and 295, for elastomer composites of the present invention to obtain better rubber materials for sidewall belt and steel belt, respectively, due to excellent macrodispersion. and with optionally retaining the high molecular weight of such elastomer composites.
Additional examples: a preferred embodiment of the invention and controls containing other fillers
Additional samples of elastomer composites according to the preferred embodiments of the present invention were prepared, along with corresponding controls.
In the first group, a multiphase granular filler of the type defined above as siliconized carbon black was used.
In particular, Ecoblack® siliconized carbon black commercially manufactured by Cabot Corporation (Billeroca, Massachusetts) was used in samples 33 through 34 of the invention. Ecoblack® filler has morphological properties, i.e. structure and surface area similar to N234 carbon black. Sample 33 used 45 parts by weight of Ecoblack® filler per 100 parts by weight, with no diluent oil. Sample 34 used 68 parts by weight of Ecoblack® filler per 100 parts by weight of resin, with no diluent oil. Typical amounts of filler and diluent oil for various product applications are given in Table 37 for the elastomer composites of the invention containing natural rubber and a mixture of carbon black with silica filler. The silica filler used in the compositions of Table 37 is assumed to replace the usual amount of the carbon black filler.
189 105
Table 37. Typical NR formulations for tire applications
<td>Application</td><td>Type of soot</td><td>The amount of soot per 100 parts</td><td>The amount of oil per 100 parts</td><td>Amount of silica per 100 parts</td>
<td>tread of truck and bus tires</td><td>N110, N115, N121, N134, N220, N299</td><td> 40-60</td><td> 0-20</td><td> 0-10</td>
<td>OTR tread</td><td>N110, N115, N220, N231</td><td> 45-55</td><td> 5-10</td><td> 5-10</td>
<td>steel belt</td><td>N326</td><td> 50-75</td><td> 0-5</td><td> 0-20</td>
<td>the basis of truck and bus tires</td><td>N330, N550</td><td> 40-60</td><td> 0-20</td><td></td>
<td>warp layer</td><td>N326, N330, N550</td><td> 40-60</td><td> 5-30</td><td></td>
<td>side wall</td><td>N330, N351, N550</td><td> 30-60</td><td> 5-30</td><td></td>
<td>top</td><td>N326, N330, N351</td><td> 50-90</td><td> 0-20</td><td></td>
<td>LRR PC tread</td><td>N234, N299, N339, N343, N351</td><td> 40-60</td><td> 0-30</td><td></td>
In the second group of samples, a blend or mixture of silica and carbon black was used. In embodiments of the present invention using a blend of carbon black with silica as fillers, it is usually preferred to use them in a weight ratio of at least 60:40. That is, the carbon black is preferably at least about 60% by weight of the filler in order to achieve good elastomer coagulation and reduce or remove re-agglomeration of the silica in the masterbatch. Specifically, in Examples 35 to 38, as shown in Table 40, the carbon black is used together with HiSil® 233 granular silica filler from PPG Industries (Pittsburgh, Pennsylvania, USA) with a BET surface area of 150 m2 / g, a DBPA surface area of 0.190 inches. / 100 g, pH 7 and a basic particle size of 19nm.
All inventive samples, i.e. additional samples 33-38 of the invention, were prepared according to the methods and equipment used for the samples 133 of the invention as described above. Details of the method and apparatus for each of samples 33-38 of the invention are set forth in Table 38, below. The latex or concentrate used in samples 33-38 was as described with reference to Table 24. As can be seen, the data of Table 38 is consistent with the data of Table 25 above for Samples 1-32 of the invention. The "CRX2000 microfluidizer" carbon black filler listed in Table 38 is the Ecoblack® siliconized carbon black described above.
Table 38. Details of the sample preparation according to the invention
<td rowspan="2">Sample No. according to the invention</td><td colspan="4">Cabot elastomer composite</td><td colspan="2">The tip of the slurry nozzle</td><td rowspan="2">CB suspension concentration, wt.%</td>
<td>Type latex</td><td>Carbon black type number phr</td><td>HISII 233 number phr</td><td>Oil quantity phr</td><td>Diameter, mm</td><td>Length, mm</td>
<td> 33</td><td>field</td><td>CRX2000 46</td><td> 0</td><td> 0</td><td> 0,5</td><td> 12,7</td><td> 14,5</td>
<td> 34</td><td>field</td><td>CRX2000 58</td><td> 0</td><td> 0</td><td> 0,5</td><td> 12,7</td><td> 14,5</td>
<td> 35</td><td>field</td><td>N220 43</td><td> 10</td><td> 5</td><td> 0,6</td><td> 12,7</td><td> 13,9</td>
<td> 36</td><td>field</td><td>N234 41</td><td> 9</td><td> 0</td><td> 0,5</td><td> 12,7</td><td> 13,5</td>
<td> 37</td><td>field</td><td>N234 31</td><td> 20</td><td> 0</td><td> 0,5</td><td> 12,7</td><td> 14,0</td>
<td> 38</td><td>concen- trat</td><td>Sterling 29 6740</td><td> 20</td><td> 0</td><td> 0,5</td><td> 12,7</td><td> 15,5</td>
189 105
<td rowspan="2">Sample No. according to the invention</td><td colspan="8">Coagulum zone (1 inch = 25.4 mm)</td>
<td colspan="2">1 part</td><td colspan="2">2nd part</td><td colspan="2">3rd part</td><td colspan="2">4th part</td>
<td></td><td>diameter, mm</td><td>length, mm</td><td>diameter, mm</td><td>length mm</td><td>diameter, mm</td><td>length mm</td><td>diameter, mm</td><td>length, mm</td>
<td> 33</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
<td> 34</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
<td> 35</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
<td> 36</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
<td> 37</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
<td> 38</td><td> 4,8</td><td> 76,2</td><td> 6,8</td><td> 40,6</td><td> 9,7</td><td> 58,4</td><td> 13,5</td><td> 81,3</td>
Table 38 (continued)
<td>Sample No. according to the invention</td><td colspan="6">Mixing zone (1 lb = 0.454 kg, 1 ft = 0.3 m)</td><td colspan="2">microfluidizer</td>
<td rowspan="2"></td><td>speed flow suspensions kg / h</td><td>speed suspensions, m / s</td><td colspan="2">antioxidant quantity</td><td>speed flow latex, kg / h</td><td>speed latex, m / s</td><td>inlet pressure, psi (kPa)</td><td>pressure output, kPa</td>
<td></td><td></td><td>TNPP</td><td>Santo- -flex</td><td></td><td></td><td></td><td></td>
<td> 33</td><td> 168.7</td><td> 216,4</td><td> 0,3</td><td> 0,4</td><td>half</td><td> 2,3</td><td> 73,8</td><td> 117198</td>
<td> 34</td><td> 168,7</td><td> 216,4</td><td> 0,3</td><td> 0,4</td><td>half</td><td> 1,8</td><td> 57,2</td><td> 117198</td>
<td> 35</td><td> 141,5</td><td> 115,8</td><td> 0,3</td><td> 0,4</td><td>half</td><td> 1,5</td><td> 48,9</td><td> 99963</td>
<td> 36</td><td> 136,0</td><td> 175,6</td><td> 0.3</td><td> 0,4</td><td>half</td><td> 1,3</td><td> 42,7</td><td> 68940</td>
<td> 37</td><td> 130,6</td><td> 167,6</td><td> 0,3</td><td> 0,4</td><td>half</td><td> 1,2</td><td> 40,7</td><td> 65493</td>
<td> 38</td><td> 138,8</td><td> 176,8</td><td> 0,3</td><td> 0,4</td><td>concentrate</td><td> 0,7</td><td> 22,9</td><td> 62046</td>
Table 38 (continued)
<td>Sample No. according to the invention</td><td>Pressure at the tip of the slurry nozzle, psi (kPa)</td><td colspan="2">Dewatering, lump moisture,%</td><td colspan="2">Drying cooling, the product</td><td>Type mixer</td><td>Performance kg / h</td><td>Sample No. according to the invention</td>
<td></td><td></td><td>postal</td><td>end</td><td>tpmn P *</td><td>wiła%</td><td></td><td></td><td></td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 33</td><td> -</td><td> 77,5</td><td> >8,0</td><td> 003,9</td><td> 0,2</td><td>T-block</td><td> 29,9</td><td> 33</td>
<td> 34</td><td> -</td><td> 78,0</td><td> 1,6</td><td> 243,3</td><td> 0,3</td><td>T-block</td><td> 23,6</td><td> 34</td>
<td> 35</td><td> 11375</td><td> 77,9</td><td> >4,0</td><td> 182,2</td><td> 0,4</td><td>T-block</td><td> 24,5</td><td> 35</td>
189 105
continued from Table 38
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 36</td><td> 20682</td><td> 79,2</td><td> 1,0</td><td> 246,1</td><td> 0,5</td><td>T-block</td><td> 17,7</td><td> 36</td>
<td> 37</td><td> 20199</td><td> 78,9</td><td> 12,3</td><td> 223,9</td><td> 0,4</td><td>T-block</td><td> 15,4</td><td> 37</td>
<td> 38</td><td> 17924</td><td> 69,7</td><td> 4,2</td><td> 235</td><td> 0,2</td><td>T-block</td><td> 21,8</td><td> 38</td>
Controls 451-498 were prepared according to the methods and equipment used for Controls 1-450. The processing code (see Table 13, above), the amount of filler, rubber, Mzol, and masterbatch macrodispersion are listed in table 39 below. filler, rubber, Mvol, and macrodispersion values of samples 33-38 of the invention (together with the amount of filler and oil for convenience) are given in Table 40. It can be seen from Table 39 that the composition of Control Samples 451 - 466 corresponds to Samples 33 and 34 of the invention. Likewise, Controls 467-498 correspond to Samples 35-38 of the invention.
Table 39
<td rowspan="3">Code</td><td></td><td>CRX 2000/44/0</td><td></td><td colspan="3">CRX 2000/58/0</td>
<td></td><td>RSS1</td><td></td><td colspan="3">RSS1</td>
<td>sample no</td><td>MWzol, K</td><td>D,%</td><td>Sample No.</td><td>Mwzol, and K.</td><td>D,%</td>
<td>M2</td><td></td><td> 909</td><td></td><td></td><td> 909</td><td></td>
<td>M3</td><td></td><td> 590</td><td></td><td></td><td> 590</td><td></td>
<td>M2D1</td><td> 451</td><td> 461</td><td> 3,48</td><td> 459</td><td> 333</td><td> 8,61</td>
<td>M2D2</td><td> 452</td><td> 474</td><td> 3,68</td><td> 460</td><td> 392</td><td> 5,71</td>
<td>M2D3</td><td> 453</td><td> 489</td><td> 7,17</td><td> 461</td><td> 388</td><td> 9,48</td>
<td>M2D4</td><td> 454</td><td> 515</td><td> 6,28</td><td> 462</td><td> 394</td><td> 8,05</td>
<td>M3D1</td><td> 455</td><td> 393</td><td> 2,89</td><td> 463</td><td> 280</td><td> 2,23</td>
<td>M3D2</td><td> 456</td><td> 422</td><td> 2,87</td><td> 464</td><td> 298</td><td> 2,13</td>
<td>M3D3</td><td> 457</td><td> 435</td><td> 4,15</td><td> 465</td><td> 350</td><td> 4,05</td>
<td>M3D4</td><td> 458</td><td> 449</td><td> 3,23</td><td> 466</td><td> 379</td><td> 7,22</td>
Table 40. Molecular weight of the sol and undispersed surface of samples according to the invention
<td>Sample No. according to the invention</td><td>CB / quantity / oil</td><td>Mwzo K.</td><td>D,%</td>
<td> 33</td><td>CRX 2000/44/0</td><td> 380</td><td> 0,18</td>
<td> 34</td><td>CRX 2000/58/0</td><td> 448</td><td> 0,10</td>
<td> 35</td><td>N220 / Hisil 233/43/10/5</td><td> 500</td><td> 0,14</td>
<td> 36</td><td>N234 / Hisil 233/40/10/0</td><td> 490</td><td> 0,36</td>
<td> 37</td><td>N234 / Hisil 233/30/20/0</td><td> 399</td><td> 0,23</td>
<td> 38</td><td>STERLING 6740 / Hilsil 233/30/20/0</td><td> 354</td><td> 0,39</td>
189 105
Table 41
<td></td><td colspan="3">N220 / Hilsil 233/43/10/5</td><td colspan="3">N234 / Hilsil 233/40/10/0</td>
<td rowspan="2">Code</td><td colspan="3">RSS1</td><td colspan="3">RSS1</td>
<td>No samples</td><td>MW ^ .K</td><td>D,%</td><td>No samples</td><td>MWzol, K</td><td>D,%</td>
<td>M2</td><td></td><td> 803</td><td></td><td></td><td> 909</td><td></td>
<td>M3</td><td></td><td> 601</td><td></td><td></td><td> 590</td><td></td>
<td>M2D1</td><td> 467</td><td> 493</td><td> 1,51</td><td> 475</td><td> 443</td><td> 8,74</td>
<td>M2D2</td><td> 468</td><td> 537</td><td> 2,61</td><td> 476</td><td> 517</td><td> 10,9</td>
<td>M2D3</td><td> 469</td><td> 523</td><td> 2,82</td><td> 477</td><td> 569</td><td> 12,5</td>
<td>M2D4</td><td> 470</td><td> 615</td><td> 2,95</td><td> 478</td><td> 592</td><td> 8,25</td>
<td>M3D1</td><td> 471</td><td> 417</td><td> 0,95</td><td> 479</td><td> 358</td><td> 6,65</td>
<td>M3D2</td><td> 472</td><td> 438</td><td> 1,40</td><td> 480</td><td> 420</td><td> 13,8</td>
<td>M3D3</td><td> 473</td><td> 433</td><td> 2,15</td><td> 481</td><td> 516</td><td> 13,9</td>
<td>M3D4</td><td> 474</td><td> 485</td><td> 2,22</td><td> 482</td><td> 447</td><td> 7,25</td>
<td></td><td colspan="3">N234 / Hilsil 233/30/20/0</td><td colspan="3">Sterling 6740 / HilsiI 233/30/20/0</td>
<td>Code</td><td>No samples</td><td>Mw ^ K</td><td>D,%</td><td>No samples</td><td>MWzol, K</td><td>D,%</td>
<td>M2</td><td></td><td> 909</td><td></td><td></td><td> 909</td><td></td>
<td>M3</td><td></td><td> 590</td><td></td><td></td><td> 590</td><td></td>
<td>M2D1</td><td> 483</td><td> 394</td><td> 4,37</td><td> 491</td><td> 430</td><td> 3,77</td>
<td>M2D2</td><td> 484</td><td> 507</td><td> 5,66</td><td> 492</td><td> 488</td><td> 4,39</td>
<td>M2D3</td><td> 485</td><td> 526</td><td> 4,7</td><td> 493</td><td> 517</td><td> 5,37</td>
<td>M2D4</td><td> 486</td><td> 568</td><td> 5,94</td><td> 494</td><td> 563</td><td> 4,66</td>
<td>M3D1</td><td> 487</td><td> 377</td><td> 8,39</td><td> 495</td><td> 373</td><td> 3,5</td>
<td>M3D2</td><td> 488</td><td> 363</td><td> 4,49</td><td> 496</td><td> 380</td><td> 2,73</td>
<td>M3D3</td><td> 489</td><td> 376</td><td> 5,07</td><td> 497</td><td> 419</td><td> 2,72</td>
<td>M3D4</td><td> 490</td><td> 432</td><td> 5,26</td><td> 498</td><td> 448</td><td> 3,29</td>
The excellent dispersion in the masterbatches of samples 33-38 according to the invention is shown by comparing the macro-dispersion quality and the Mzol values given in Tables 39-41. Samples 33-34 produced with the siliconized Ecoblack® carbon black and the corresponding controls were compared in the semi-log plot of Fig. 30. Fig. 30 found an excellent carbon black dispersion for the inventive samples showing preferred elastomer composites of the present invention. Samples according to the invention are preferably below line 301 in Fig. 30, while all controls have poorer dispersion and are above line 301. Thus, the preferred embodiments in Fig. 30 are below the D,% value, equal to 0.2% even for Mzole values preferably above 0.4 x 106. Fig. thirty clearly show that the macro-dispersion quality of the novel elastomer composites disclosed herein containing siliconized carbon black is significantly better than that obtained with comparable components by mixing methods according to the prior art. The crodispersion values of the inventive elastomer composites shown in Fig. 30 are described by the following equations:
D,% <1.0% (25) when Mzol is less than 0.4 x 10<sup>6</sup>; and log D <log (1.0) + 2.0 x [Mwm - (0.4 x 106)] χ ^ -6 26) when 0.4 x 106 & lt; Mzol <1, ^ 1 (0.
D,%, is taken to be the percentage of undispersed area measured for defects greater than 10 [mu] m and 1% is the grammicmacroDispersionSj of masterbatches according to preferred embodiments of the present invention. That is, none of the dry masticated masterbatches achieved a macrodispersion quality of 1.0% or better at any Mwzol even after dry blending sufficient to degrade the Mwzol below 0.4 x 106. The preferred embodiments shown in Fig. thirty well below the cut-off value. It can be seen that the elastomer composites according to the invention containing siliconized carbon black have an unattainable so far balance between the quality of the macro-dispersion and the value of Mwzol.
Samples 35-38 of the invention containing carbon black in a mixture with silica filler and the respective controls were compared in the semi-log plot of Fig. 31. In particular, Fig. 31 shows the macrodispersion values and the Mwzol values for the inventive samples 35-38 and the corresponding controls 467. - 498. Fig. 31 shows the excellent carbon black dispersion for the inventive samples showing a preferred embodiment of the elastomer composites of the present invention. Samples of the invention are preferably below line 311 in Fig. 31, while all controls have poorer dispersion and are above line 311. Thus, all preferred embodiments in Fig. 31 are below the D,% value of 0.4%. . Data Fig. 31 clearly show that the macrodispersion quality of the novel elastomer composites disclosed herein containing blends of carbon black with silica over a wide range of Mzol values is significantly superior to that obtained with comparable components by prior art blending methods. The macro-dispersion values of the elastomer composites of the invention shown in Fig. 31 are described by the following equations:
D,% & lt; 0.8% (27) when the MW & lt; 1 & gt; is less than 0.5 x 106; and log D <log (0.8) + 2.2 x [MW] i - (0.5 x 106)] x 10<sup>6</sup> (28)
0.5 x 106 <Mso <1.1 x 10 * 6.
D,%, is assumed to be the percentage of undispersed area measured for size defects greater than 10 µm and that 0.8% is the limiting macrodispersion quality of masterbatches according to preferred embodiments of the present invention. This means that none of the dry masticated masterbatches achieved a macrodispersion quality of 0.8% or better with any Mwzol even after dry blending sufficient to degrade the Mwzol below 0.4 x W<sup>6</sup>. The preferred embodiments shown in Fig. 31 are well above the macrodispersion cutoff of 0.8% and even below 0.4%. It can be seen that the elastomer composites of the invention containing blends of carbon black and silica as filler have an unattainable balance between the quality of the macrodispersion and the Mwzol value.
Additional examples.
Blends of elastomer composites according to the present invention were prepared and described and compared with corresponding blends made by known dry / dry blending methods according to the prior art. The elastomer composite blends were prepared with samples of the elastomer composite identified below as "CEC" or "CEC" or "cec masterbatch".
CEC masterbatches were produced as follows using Natural Rubber Field Latex and Vulcan 7H Carbon Black (ASTM Carbon Black N234):
Manufacture of an elastomeric composite (wet mixing step).
An elastomer masterbatch was produced according to the present invention. In particular, an elastomer masterbatch was produced containing standard Malaysia half natural rubber latex with 71 parts by weight to 100 parts by weight of a filler containing
189 105 commercial carbon black N234 from Cabot Corporation. The recipe for the mix (except for minor latex additives) is given in Table 7 below.
Table 7A. Masterbatch recipe
<td>Ingredient</td><td>Parts by weight</td>
<td>rubber</td><td> 100</td>
<td>soot</td><td> 71</td>
<td>Santoflex 134 (antioxidant)</td><td> 0,4</td>
<td>TNPP (Antioxidant)</td><td> 0,4</td>
<td>Together</td><td> 171,7</td>
The apparatus for making elastomer masterbatches was substantially identical to the apparatus described above with reference to the drawings in Figures 1, 3 and 7. The tip of the slurry nozzle (see reference number 167 in Fig. 7) had a diameter of 0.5 mm with a contact surface (see reference 167 in Fig. 7) 5 mm long. The coagulum zone (see No.53 in Fig. 3) included a first portion 4.8mm in diameter and approximately 25.0mm in radial length (partially in the mix head and partially in an extension welded thereto); a second portion 6.8 mm in diameter and 40.6 mm in radial length; a third part 9.6 mm in diameter and 57.3 mm radial in length; and a fourth portion 13.5 mm in diameter and 81.03 mm radial length. Moreover, there were short radial corresponding interconnections between the above-mentioned parts. The preparation of the masterbatch is described in more detail immediately below.
1. Preparation of a soot slurry. The bags of carbon black were mixed with demineralized water in a soot slurry tank equipped with an agitator. The agitator broke the tablets into pieces and a crude slurry was formed containing 15.1% by weight of carbon black. The crude slurry was recirculated using a tubular grinder. During operation, this slurry was pumped continuously by means of an air diaphragm pump into a colloid mill for initial dispersion. The slurry was then fed via a progressive chamber pump to a homogenizer, in this case a Model M210 microfluidizer from Microofluiidics International Corporation to pressurize and shear to form a finely ground slurry. The flow rate of the slurry from the microfluidizer to the mixing sphere was set using the speed of the microfluidizer, with the microfluidizer acting as a pressure positive displacement pump. The flow rate of the slurry was monitored with a Micromotion® mass flow meter. The carbon black slurry was introduced into the microfluidizer at a pressure of about 1723.5 kPa, and the output pressure was set at 51705 kPa to an accumulator set at an output pressure of about 8273 kPa, and thus introduced the slurry as a stream into the mixing zone at a flow rate of about 98 kg / h and a rate of about 152 , 4 m / s).
2. The introduction of latex. The latex was loaded into a reservoir, namely a feed drum with a capacity of 0.21 m<sup>3</sup>. An antioxidant emulsion was introduced into the latex prior to loading. Antioxidants consisting of 0.3 parts by weight per 100 parts by weight of trinonyl-phenyl phosphite (TNPP) and 0.4 parts by weight per 10 parts by weight of Santoplex® 134 (mixtures of alkyl- and aryl-p-phenyldiamine) were introduced. Each of the antioxidants was prepared as a 40 wt% emulsion using 4 parts potassium oleate to 100 parts antioxidant together with potassium hydroxide to adjust the pH of the emulsion to about 10. A peristaltic pump was used to transfer the latex from the feed tank to the mixing zone of the coagulum reactor. The latex flow rate ranged from 87.1 to 89.8 kg / h and about 1.5 m / s and was measured using an Endress + Hauser mass flow meter (Greenwood, Indiana, USA. The desired carbon black content was
189 105 parts by weight per 10 parts by weight were obtained by obtaining the proper ratio of latex introduction rate to carbon black slurry introduction rate.
2. Mixing soot with latex. The carbon black slurry was mixed with the latex by introducing the latex into the carbon black slurry. During this introduction, the carbon black was thoroughly mixed into the latex and the mixture was coagulated. Soft and wet spongy coagulum "lumps" were obtained from the coagulum reactor.
Drainage. The wet lumps discharged from the coagulum reactor contained approximately 0% water. The wet pellets were dehydrated to about 11 to 13% moisture with a dehydration extruder [French Oil Mill Machinery Company; diameter 82.6 mm]. The extruder compresses the wet lumps and squeezes the water from the lumps through a slotted extruder barrel.
5. Drying and cooling. The dehydrated pellets were sent to a second extruder where they were pressed again and heated. The water was chased while the lumps were ejected through the extruder die plate. The product outlet temperature was from about 137.8 ° C to 154.4 ° C and the moisture content was from 3.0% by weight to 4.0% by weight. The hot dry lumps were rapidly cooled (in about 20 seconds) to a temperature of about 37.8 ° C using a forced air vibrating conveyor. The slightly wet lumps were completely dried to a moisture content of less than 0.5% by weight at a temperature of 93.3 ° C to 115.6 ° C in an Aeroglide fume air heater, Raleigh, North Carolina.
Dry mixing step.
In the following examples, both the two "dry blending" steps of the dry / dry method below for comparison and control, and the "dry" blending step of the wet / dry process of the present invention were performed in a Banbury mixer.
Reference in the following procedures and in the following examples to "natural rubber masterbatch" refers to the first-stage dry-blending product. The term mastic natural rubber refers to the product given below "mastic state of natural rubber". The term NR refers to natural rubber. The term CB refers to soot. In all cases, the carbon black is N234. The complete recipes for the wet and dry mixing steps are provided in the recipe table below.
The preceding examples show that excellent properties are obtained for the blends of the elastomer composites according to the present invention.
<td colspan="3">Recipe</td>
<td>Ingredients</td><td></td><td>Parts by weight per 100 parts by weight</td>
<td>rubbers</td><td>masticated RSS1 + Taktene 220, or CEC NR + Taktene 220, or CEC NR + masticated RSS1, or masticated RS1</td><td> 100,0</td>
<td>soot</td><td>V7H</td><td> 50</td>
<td>Oil</td><td>Sundex 790</td><td> 5,0</td>
<td>antioxidant 1</td><td>Santoflex 134</td><td> 0,4</td>
<td>antioxidant 2</td><td>TNPP</td><td> 0,3</td>
<td>zinc oxide</td><td>Azo 65</td><td> 4,0</td>
<td>stearic acid</td><td>Hystrene 5016</td><td> 2,0</td>
<td>accelerant</td><td>Santocure NS</td><td> 1,8</td>
<td>sulfur</td><td></td><td> 1,0</td>
<td colspan="2">Together</td><td> 164,5</td>
189 105
Procedure for the preparation of the CEC NR / BR blends and the NR / BR dry blends
Mixing method
1. Mix a natural rubber masterbatch that has all of the soot in it with the butadiene rubber and the oil. The natural rubber to butadiene rubber ratios were 90/10, 80/20 and 70/30;
2. Mix a natural rubber masterbatch that has all of the soot in it with the butadiene rubber and the oil. The natural rubber to butadiene rubber ratios were 80/20 and 70/30;
3. Blend a natural rubber masterbatch to which 50 parts by weight of carbon black has been added per 100 parts by weight, with a butadiene rubber masterbatch to which 50 parts by weight of carbon black has been added per 100 parts by weight, and oil. The natural rubber to butadiene rubber ratios were 80/20, 70/30, 60/40 and 50/50;
4. Blend a natural rubber masterbatch to which 50 parts by weight of carbon black has been added per 100 parts by weight with a butadiene rubber masterbatch to which 50 parts by weight of carbon black have been added per 100 parts by weight. The natural rubber to butadiene rubber ratios were 80/20, 70/30, 60/40 and 50/50;
5. Mix the CEC masterbatch to which all of the carbon black has been added with the butadiene rubber and the oil. The natural rubber to butadiene rubber ratios were 90/10, 80/20 and 70/30;
6. Mix the CEC masterbatch to which all of the carbon black and oil have been added with the butadiene rubber. The natural rubber to butadiene rubber ratios were 80/20 and 70/30;
7. Blend the CEC masterbatch to which 50 parts by weight of carbon black has been added per 100 parts by weight with the butadiene rubber and the oil. The natural rubber to butadiene rubber ratios were 80/20, 70/30, 60/40 and 50/50;
8. Blend the CEC masterbatch to which 50 parts by weight of carbon black per 100 parts by weight and the total amount of oil have been added, with the butadiene rubber masterbatch to which 50 parts by weight of carbon black have been added per 100 parts by weight. The natural rubber to butadiene rubber ratios were 80/20, 70/30, 60/40 and 50/50.
Methods of proceeding during mixing
Three-step mixing was used on a Banbury for dry mixes and two-step mixing on a Banbury mixer for CEC mixes. Natural rubber was masticated prior to the first dry blending step. Butadiene rubber was used without mastic.
Conditions for masticating natural rubber:
fill factor: O775 rotor speed: 100 rpm temperature of Banbury mixer 30 ° C total energy per batch 950 Wh
Procedure when mixing in a Banbury mixer
Mixing method 1:
Level 1:
fill factor: rotor speed: temperature of the Banbury mixer rotational per mmut 30 ° C
Time
30”
1Ό0
1'3 0
8 'to 13'
The tincture of the introduction of the mastic NR derivation of 40 parts by weight of CB per 100 parts by weight of the sweat of the remaining CB Derivation of the flow of CB o \ ya;
189 105
<td>Sample No.</td><td>Ratio filling</td><td>Time of mixing</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>1-1 (stage 1)</td><td> 0,67</td><td> 8'</td><td> 140,8</td><td> 1,45</td>
<td>1-2 (stage 1)</td><td> 0,66</td><td> 8'</td><td> 148,6</td><td> 1,59</td>
<td>1-3 (stage 1)</td><td> 0,63</td><td> 10'</td><td> 167,3</td><td> 1,89</td>
Stage 2:
fill factor: rotor speed: Banbury mixer temperature
Time
0'
3Ό0
0.70 rpm 30 ° C
The operation of introducing NR masterbatch, BR bale, chemicals and oil, unloading
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>1-1 (stage 2)</td><td> 113,5</td><td> 0,42</td>
<td>1-2 (stage 2)</td><td> 116,2</td><td> 0,45</td>
<td>1-3 (stage 2)</td><td> 116,4</td><td> 0,44</td>
Stage 3:
fill factor: rotor speed: Banbury mixer temperature
Time
0'
3Ό0
0.65 rpm 30 ° C
The act of introducing the mixture from stage 2 and the volcano discharging agents
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 1-1</td><td> 96,5</td><td> 0,42</td>
<td> 1-2</td><td> 89,8</td><td> 0,43</td>
<td> 1-3</td><td> 103,9</td><td> 0,45</td>
Mixing method 2:
Level 1:
fill factor: rotor speed:
Banbury mixer temperature
Time
0''
1Ό0
0.65 rpm 50 rpm once the temperature reached 160 ° C
30 ° C
Action introduce masticated NR introduce 40 parts by weight of CB per 100 parts by weight introduce half of the remaining CB '30 introduce the rest of CB
2'00 oil introduction
9 'to 13' discharge according to the power curve
<td>Sample No.</td><td>Time of mixing</td><td>Discharge temperature ° C</td><td>Energy consumed, kWh</td>
<td>2-1 (stage 1)</td><td> 9'</td><td> 148</td><td> 1,60</td>
<td>2-2 (stage 1)</td><td> 9,5'</td><td> 145</td><td> 1,84</td>
Stage 2:
fill factor: rotor speed: Banbury mixer temperature
Time
3'00''
0.70 rpm 30 ° C
The operation of introducing NR masterbatch, it hurts BR, chemicals and oil discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>2-1 (stage 2)</td><td> 127</td><td> 0,48</td>
<td>2-2 (stage 2)</td><td> 126</td><td> 0,61</td>
Stage 3:
fill factor: rotor speed: Banbury mixer temperature
0.65 rpm 30 ° C
Time The act of introducing the mixture from step 2 and the vulcanizing agents
3'00 discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 2-1</td><td> 99</td><td> 0,42</td>
<td> 2-2</td><td> 107</td><td> 0,44</td>
Mixing method 3:
Level 1:
• item NR fill factor: rotor speed: temperature of the Banbury mixer
Time
0''
1Ό0
9'00
0.65 rpm 30 ° C
Operation introducing mastic NR, introducing 40 parts by weight of CB per 100 parts by weight, introducing the remaining CB, discharging
189 105
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>3-1 to 3-4 (stage 1)</td><td> 142</td><td> 1,51</td>
<td>3-1 to 3-4 (stage 1)</td><td> 143</td><td> 1,48</td>
<td>3-1 to 3-4 (stage 1) '</td><td> 148</td><td> 1,52</td>
o BR masterbatch: fill factor: rotor speed:
Banbury mixer temperature
Time
0'
1Ό0
1'30
7'00
0.75 rpm (60 rpm after reaching 160 ° C)
30 ° C
The operation introducing the BR bale introducing 30 parts by weight of carbon black per 100 parts by weight introducing 1/2 the rest of the carbon black introducing the rest of the carbon black discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>3-1 to 3-4 (stage 1)</td><td> 159</td><td> 1,38</td>
<td>3-1 to 3-4 (stage 1)</td><td> 158</td><td> 1,35</td>
<td>3-1 to 3-4 (stage 1)</td><td> 157</td><td> 1,33</td>
Stage 2:
fill factor: rotor speed and temperature of Banbury mixer
Time
3' 00
0.70 rpm 30 ° C
The activity of introducing the masterbatch from step 1 and chemicals and oil discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>3-1 (stage 2)</td><td> 115</td><td> 0.36</td>
<td>3-2 (stage 2)</td><td> 123</td><td> 0,40</td>
<td>3-3 (stage 2)</td><td> 120</td><td> 0,40</td>
<td>3-4 (stage 2)</td><td> 118</td><td> 0,37</td>
Stage 3:
fill factor: 0.65 rotor speed: 70 rpm temperature of Banbury mixer 30 ° C
Time The act of introducing the mixture from step 2 and the vulcanizing agents
3Ό0 discharge
189 105
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed / kWh</td>
<td> 3-1</td><td> 103</td><td> 0,44</td>
<td> 3-2</td><td> 107</td><td> 0,45</td>
<td> 3-3</td><td> 109</td><td> 0,47</td>
<td> 3-4</td><td> 97</td><td> 0,38</td>
Mixing method 4:
Level 1:
o masterbatch NR: filling factor; rotor speed: temperature of the Banbury mixer
Time
0'
1'00
2'00
9'00’
0655 revolutions per mintta T ^ 0C3
Operation introducing masticated NR introduce 40 parts by weight of CB per 100 parts by weight introduce the remaining CB introduce oil, discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed / kWh</td>
<td>4-1 to 4-4 (step 1)</td><td> 140</td><td> 1,49</td>
<td>4-1 to 4-4 (step 1)</td><td> 138</td><td> 1,49</td>
<td>4-1 to 4-4 (step 1)</td><td> 137</td><td> 1,40</td>
o BR masterbatch: fill factor: rotor speed:
Banbury mixer temperature
Time
0'
1Ό0
1'30'
7'00
0755 revolutions (60 oboots per minute after reaching the temperature of 160 ° C)
30 ° C
The operation introducing the BR bale introducing 30 parts by weight of carbon black per 100 parts by weight introducing 1/2 the rest of the carbon black introducing the rest of the carbon black discharge
<td>Sample No.</td><td>Discharge temperature. ° C</td><td>Energy consumed, kWh</td>
<td>4-1 to 4-4 (step 1)</td><td> 159</td><td> 1,38</td>
<td>4-1 to 4-4 (step 1)</td><td> 158</td><td> 1,35</td>
<td>4-1 to 4-4 (step 1)</td><td> 157</td><td> 1,33</td>
189 105
Stage 2:
fill factor: 0.70 rotor speed: 70 rpm temperature of Banbury mixer 30 ° C
Time Activity ”introduce masterbatch from step 1 and chemicals and oil
3'00 discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>4-1 (stage 2)</td><td> 133</td><td> 0,52</td>
<td>4-2 (stage 2)</td><td> 133</td><td> 0,56</td>
<td>4-3 (stage 2)</td><td> 133</td><td> 0,55</td>
<td>4-4 (stage 2)</td><td> 132</td><td> 0,53</td>
Stage 3:
fill factor: rotor speed: Banbury mixer temperature
0.65 rpm 30 ° C
Time Activity
0 '' introduction of Stage 2 mix and vulcanizing agents
3'00 '' discharge
<td>sample no</td><td>discharge temperature, ° C</td><td>consumed energy, kWh</td>
<td> 4-1</td><td> 107</td><td> 0,48</td>
<td> 4-2</td><td> 108</td><td> 0,48</td>
<td> 4-3</td><td> 109</td><td> 0,47</td>
<td> 4-4</td><td> 111</td><td> 0,46</td>
Mixing method 5:
Level 1:
fill factor: rotor speed:
Banbury mixer temperature
Time
0''
4'
T.
9'
0.75 rpm 30 ° C
The operation of introducing the CEC premix, introducing the BR bale, introducing powders and oil, unloading
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>5-1 to 5-4 (step 1)</td><td> 104,2</td><td> 1,78</td>
<td>5-1 to 5-4 (step 1)</td><td> 107,1</td><td> 1,72</td>
<td>5-1 to 5-4 (step 1)</td><td> 103,9</td><td> 1,79</td>
189 105
Stage 2:
fill factor: rotor speed: Banbury mixer temperature
Time
0'
0.65 rpm 30 ° C
The act of introducing the mixture from step 1 and the discharge vulcanizing agents
3Ό0
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 5-1</td><td> 76,7</td><td> 0,46</td>
<td> 5-2</td><td> 81,0</td><td> 0,46</td>
<td> 5-3</td><td> 83,3</td><td> 0,46</td>
Mixing method 6:
Level 1:
fill factor: 0.75 rotor speed: 70 rpm temperature of Banbury mixer 30 ° C
<td>Time 0 4 ' 7 ' 9 '</td><td colspan="2">Action introduction of CEC masterbatch introduction of BR bale introduction of powders and oil, discharge</td>
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>6-1 (stage 1)</td><td> 114,8</td><td> 1,67</td>
<td>6-1 (stage 1)</td><td> 115,6</td><td> 1,72</td>
Stage 2:
fill factor: 0.65 rotor speed: 70 rpm temperature of Banbury mixer 30 ° C
<td>Time 0 ' vulcanizing 3'00</td><td colspan="2">Action the introduction of the mixture of stage 1 and measures discharge</td>
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 6-1</td><td> 81,6</td><td> 0,47</td>
<td> 6-2</td><td> 81,4</td><td> 0,47</td>
Mixing method 7.
Level 1:
fill factor: rotor speed: Banbury mixer temperature
0.75 rpm 30 ° C
189 105
Time
2'
5'
7'
The operation of introducing the CEC masterbatch introducing the BR masterbatch introducing powders and oil, discharging
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>7-1 (stage 1)</td><td> 117,4</td><td> 1,33</td>
<td>7-2 (stage 1)</td><td> 112,6</td><td> 1,21</td>
<td>7-3 (stage 1)</td><td> 106,0</td><td> 1,14</td>
<td>7-4 (stage 1)</td><td> 105,7</td><td> 1,24</td>
Stage 2:
fill factor: rotor speed: Banbury mixer temperature
0.65 rpm 30 ° C
Time The act of introducing the mixture from step 1 and the vulcanizing agents
3'00 discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 7-1</td><td> 83,6</td><td> 0,48</td>
<td> 7-2</td><td> 83,0</td><td> 0,46</td>
<td> 7-3</td><td> 83,6</td><td> 0,46</td>
<td> 7-4</td><td> 84,4</td><td> 0,46</td>
Mixing method 8 '
Level 1:
fill factor: rotor speed: Banbury mixer temperature
0.75 rpm 30<sup>about</sup>C.
Time
2'
5'
7'
C; ynnoość im ^ t2 <mte ^: ^: ^^ ki1 CEC we introduce pzzednneszki BR introduced jrrc ^^^ lótów discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td>8-1 (stage 1)</td><td> 106,4</td><td> 1,25</td>
<td>8-2 (stage 1)</td><td> 112,4</td><td> 1,27</td>
<td>8-3 (stage 1)</td><td> 103,1</td><td> 1,13</td>
<td>8.4 (stage 1)</td><td> 111,3</td><td> 1,20</td>
Stage 2:
fill factor: rotor speed: Banbury mixer temperature
0.65 rpm 30 ° C
189 105
Time Activity
0 ”introduction of the mixture from step 11 of vulcanizing agents
3 '00 ”discharge
<td>Sample No.</td><td>Discharge temperature, ° C</td><td>Energy consumed, kWh</td>
<td> 8-1</td><td> 78,8</td><td> 0,46</td>
<td> 8-2</td><td> 81,0</td><td> 0,45</td>
<td> 8-3</td><td> 76,4</td><td> 0,44</td>
<td> 8,4</td><td> 79,5</td><td> 0,44</td>
Table 1. Description of samples and code of NR / BR mixtures
<td>No way</td><td>Description</td><td>No samples</td><td>NR / BR</td><td>The amount of soot in NR1</td><td>The amount of soot in BR1</td><td>Oil down</td>
<td> 1</td><td>a mixture, a NR masterbatch to which all the carbon black had been charged, with BR and an oil</td><td> 1-1 1-2 1-3</td><td> 90/10 80/20 70/30</td><td> 55.5 82.5 71,4</td><td> 0 0 0</td><td>m2 no no</td>
<td> 9</td><td>a mixture of the NR masterbatch, into which</td><td> 2-1</td><td> 80/20</td><td> 82,5</td><td> 0</td><td>NO</td>
<td></td><td>all the soot and oil were added from the BR</td><td> 2-2</td><td> 70/30</td><td> 71,4</td><td> 0</td><td>NO</td>
<td></td><td>NR masterbatch mixture to which</td><td> 3-1</td><td> 80/20</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>50 phr of carbon black was introduced, with the masterbatch</td><td> 3-2</td><td> 70/30</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>BR, with 50 phr of carbon black introduced,</td><td> 3-3</td><td> 60/40</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>and oil</td><td> 3-4</td><td> 50/50</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>NR masterbatch mixture to which</td><td> 4-1</td><td> 80/20</td><td> 50</td><td> 50</td><td>NO</td>
<td>AND</td><td>50 phi- carbon black and all the oil</td><td> 4-2</td><td> 70/30</td><td> 50</td><td> 50</td><td>NO</td>
<td></td><td>already, with BR masterbatch, into which</td><td> 4-3</td><td> 60/40</td><td> 50</td><td> 50</td><td>NO</td>
<td></td><td>50 phr of carbon black was used</td><td> 4-4</td><td> 50/50</td><td> 50</td><td> 50</td><td>NO</td>
<td></td><td rowspan="2">CEC masterbatch mixture to which</td><td> 5-1</td><td> 90/10</td><td> 55,5</td><td> 0</td><td>no</td>
<td rowspan="2"> 5</td><td> 5-2</td><td> 80/20</td><td> 2,5</td><td> 0</td><td>no</td>
<td>all the carbon black was introduced, with the BR and the oil</td><td> 5-3</td><td> 70/30</td><td> 71,4</td><td> 0</td><td>no</td>
<td> 6</td><td>CEC masterbatch mixture to which</td><td> 6-1</td><td> 80/20</td><td> 62,5</td><td> 0</td><td>CEC</td>
<td>ABOUT</td><td>all the carbon black and oil were introduced from the BR</td><td> 6-2</td><td> 70/30</td><td> 71,4</td><td> 0</td><td>CEC</td>
<td></td><td>CEC masterbatch mixture to which</td><td> 7-1</td><td> 80/20</td><td> 50</td><td> 50</td><td>no</td>
<td> 7</td><td>50 phr of carbon black was introduced, with the masterbatch</td><td> 7-2</td><td> 70/30</td><td> 50</td><td> 50</td><td>no</td>
<td> /</td><td>BR, with 50 phr of carbon black introduced,</td><td> 7-3</td><td> 60/40</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>and oil</td><td> 7-4</td><td> 50/50</td><td> 50</td><td> 50</td><td>no</td>
<td></td><td>CEC masterbatch mixture to which</td><td> 8-1</td><td> 80/20</td><td> 50</td><td> 50</td><td>CEC</td>
<td rowspan="2"> 8</td><td>50 phr of carbon black and the entire amount of oil added,</td><td> 8-2</td><td> 70/30</td><td> 50</td><td> 50</td><td>CEC</td>
<td>with BR masterbatch into which it was introduced</td><td> 8-3</td><td> 60/40</td><td> 50</td><td> 50</td><td>CEC</td>
<td></td><td>50 phr of carbon black</td><td> 8-4</td><td> 50/50</td><td> 50</td><td> 50</td><td>CEC</td>
- amounts in parts by weight per 100 parts by weight <sup>2</sup>- me = mixture
189 105
Table 2. Properties of vulcanized NR / BR blends
<td>No way</td><td>No</td><td>Mo ^ ey ML</td><td>Indisposition after-</td><td>Part weight</td><td>Bound rubber,</td>
<td>mixing</td><td>samples</td><td>(1 + 4) @ 100 ° C</td><td>top,%</td><td>zolu, K.</td><td> %</td>
<td></td><td> 1-1</td><td> 58</td><td> 1,15</td><td> 296</td><td> 40</td>
<td> 1</td><td> 1-2</td><td> 60</td><td> 1,00</td><td> 277</td><td> 42</td>
<td></td><td> 1-3</td><td> 64</td><td> 2,84</td><td> 243</td><td> 43</td>
<td>about</td><td> 2-1</td><td> 63</td><td> 1,26</td><td> 276</td><td> 41</td>
<td></td><td> 2-2</td><td> 62</td><td> 1,28</td><td> 246</td><td> 41</td>
<td></td><td> 3-1</td><td> 62</td><td> 0,86</td><td> 337</td><td> 37</td>
<td rowspan="2"> 3</td><td> 3-2</td><td> 61</td><td> 0,58</td><td> 338</td><td> 35</td>
<td> 3-3</td><td> 64</td><td> 0,65</td><td> 338</td><td> 36</td>
<td></td><td> 3-4</td><td> 64</td><td> 0,84</td><td> 333</td><td> 34</td>
<td></td><td> 4-1</td><td> 70</td><td> 0,68</td><td> 359</td><td> 37</td>
<td> 4</td><td> 4-2</td><td> 70</td><td> 0,62</td><td> 361</td><td> 37</td>
<td></td><td> 4-3</td><td> 68</td><td> 0,68</td><td> 342</td><td> 37</td>
<td></td><td> 4-4</td><td> 65</td><td> 0,54</td><td> 324</td><td> 35</td>
<td></td><td> 5-1</td><td> 58</td><td></td><td> 334</td><td> 43</td>
<td> 5</td><td> 5-2</td><td> 58</td><td></td><td> 319</td><td> 43</td>
<td></td><td> 5-3</td><td> 58</td><td></td><td> 294</td><td> 41</td>
<td> £</td><td> 6-1</td><td> 50</td><td> 0,32</td><td> 430</td><td> 35</td>
<td> 0</td><td> 6-2</td><td> 59</td><td> 0,40</td><td> 347</td><td> 37</td>
<td></td><td> 7-1</td><td> 65</td><td> 0,51</td><td> 422</td><td> 43</td>
<td></td><td> 7-2</td><td> 65</td><td> 0,46</td><td> 434</td><td> 42</td>
<td> /</td><td> 7-3</td><td> 62</td><td> 0,54</td><td> 428</td><td> 40</td>
<td></td><td> 7-4</td><td> 64</td><td> 0,47</td><td> 404</td><td> 41</td>
<td></td><td> 8-1</td><td> 62</td><td> 0,52</td><td> 401</td><td> 40</td>
<td rowspan="2"> 8</td><td> 8-2</td><td> 64</td><td> 0,52</td><td> 434</td><td> 40</td>
<td> 8-3</td><td> 58</td><td> 0,65</td><td> 407</td><td> 34</td>
<td></td><td> 8-4</td><td> 63</td><td> 0,51</td><td> 359</td><td> 41</td>
Table 3. Physical properties of NR / BR blends
<td>No samples</td><td>Hardness</td><td>E100 MPa</td><td>E300 MPa</td><td>Stretches- no, MPa</td><td>Elongation, %</td><td>Resilience 60 ° C,%</td><td>ReflectionSś 0 ° C,%</td><td>Resilience rt,%</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 1-1</td><td> 65</td><td> 2,9</td><td> 16</td><td> 29</td><td> 500</td><td> 62</td><td> 35</td><td> 52</td>
<td> 1-2</td><td> 64</td><td> 3,1</td><td> 17</td><td> 28</td><td> 462</td><td> 65</td><td> 43</td><td> 55</td>
<td> 1-3</td><td> 65</td><td> 3,2</td><td> 18</td><td> 25</td><td> 404</td><td> 65</td><td> 46</td><td> 56</td>
<td> 2-1</td><td> 69</td><td> 2,9</td><td> 16</td><td> 26</td><td> 459</td><td> 60</td><td> 39</td><td> 50</td>
<td> 2 2</td><td> 69</td><td> 2,9</td><td> 16</td><td> 24</td><td> 434</td><td> 60</td><td>4 1 l</td><td> 51</td>
<td> 3-1</td><td> 65</td><td> 2,4</td><td> 13</td><td> 26</td><td> 510</td><td> 63</td><td> 43</td><td> 53</td>
<td> 3-2</td><td> 66</td><td> 2,4</td><td> 13</td><td> 26</td><td> 514</td><td> 63</td><td> 45</td><td> 54</td>
<td> 3-3</td><td> 66</td><td> 2 5</td><td> 13</td><td> 25</td><td> 486</td><td> 62</td><td> 48</td><td> 54</td>
<td> 3-4</td><td> 67</td><td> 2,5</td><td> 13</td><td> 23</td><td> 465</td><td> 62</td><td> 49</td><td> 57</td>
189 105 c d. Table 3
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td> 4-1</td><td> 68</td><td> 2,6</td><td> 14</td><td> 27</td><td> 502</td><td> 61</td><td> 42</td><td> 52</td>
<td> 4-2</td><td> 69</td><td> 2,6</td><td> 14</td><td> 25</td><td> 472</td><td> 61</td><td> 43</td><td> 53</td>
<td> 4-3</td><td> 68</td><td> 2,6</td><td> 14</td><td> 24</td><td> 467</td><td> 60</td><td> 44</td><td> 53</td>
<td> 4-4</td><td> 68</td><td> 2,7</td><td> 14</td><td> 24</td><td> 459</td><td> 60</td><td> 46</td><td> 53</td>
<td> 5-1</td><td> 65</td><td> 2,9</td><td> 17</td><td> 28</td><td> 452</td><td> 65</td><td> 41</td><td> 54</td>
<td> 5-2</td><td> 64</td><td> 2,8</td><td> 16</td><td> 27</td><td> 452</td><td> 65</td><td> 43</td><td> 55</td>
<td> 5-3</td><td> 64</td><td> 2,9</td><td> 16</td><td> 25</td><td> 432</td><td> 65</td><td> 45</td><td> 56</td>
<td> 6-1</td><td> 66</td><td> 2,5</td><td> 14</td><td> 27</td><td> 505</td><td> 62</td><td> 42</td><td> 54</td>
<td> 6-2</td><td> 65</td><td> 2,9</td><td> 15</td><td> 26</td><td> 482</td><td> 63</td><td> 45</td><td> 55</td>
<td> 7-1</td><td> 68</td><td> 3,0</td><td> 17</td><td> 29</td><td> 472</td><td> 64</td><td> 45</td><td> 55</td>
<td> 7-2</td><td> 65</td><td> 3,0</td><td> 17</td><td> 28</td><td> 459</td><td> 64</td><td> 46</td><td> 5</td>
<td> 7-3</td><td> 67</td><td> 2,9</td><td> 16</td><td> 25</td><td> 429</td><td> 64</td><td> 48</td><td> 58</td>
<td> 7-4</td><td> 67</td><td> 3,0</td><td> 16</td><td> 223</td><td> 397</td><td> 65</td><td> 1</td><td> 59</td>
<td> 8-1</td><td> 67</td><td> 2,8</td><td> 15</td><td> 28</td><td> 480</td><td> 64</td><td> 46</td><td> 56</td>
<td> 8-2</td><td> 67</td><td> 2,8</td><td> 15</td><td> 27</td><td> 476</td><td> 64</td><td> 47</td><td> 56</td>
<td> 8-3</td><td> 66</td><td> 2,8</td><td> 14</td><td> 25</td><td> 465</td><td> 62</td><td> 47</td><td> 55</td>
<td> 8-4</td><td> 65</td><td> 2,8</td><td> 15</td><td> 23</td><td> 400</td><td> 67</td><td> 54</td><td> 60</td>
Table 4. Cracking and dynamic properties of NR / BR mixtures
<td>No samples</td><td>Crack growth rate x 10 '<sup>5</sup>, cm / million cycles</td><td>Tear strength, C die, N / mm</td><td>Abrasion class</td><td>Maximum tan δ @ 60 ° C</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td> 1-1</td><td> 4,32</td><td> 126</td><td> 81</td><td> 0,176</td>
<td> 1-2</td><td> 3,11</td><td> 65</td><td> 83</td><td> 0,147</td>
<td> 1-3</td><td> 1,34</td><td> 54</td><td> 68</td><td> 0,132</td>
<td> 2-1</td><td> 4,37</td><td> 55</td><td> 100</td><td> 0,178</td>
<td> 2-2</td><td> 2,39</td><td> 50</td><td> 99</td><td> 0,164</td>
<td> 3-1</td><td> 4,30</td><td> 101</td><td> 74</td><td> 0,165</td>
<td> 3-2</td><td> 3,86</td><td> 97</td><td> 80</td><td> 0,161</td>
<td> 3-3</td><td> 3,56</td><td> 80</td><td> 85</td><td> 0,153</td>
<td> 3-4</td><td> 2,23</td><td> 73</td><td> 100</td><td> 0,158</td>
<td> 4-1</td><td> 4,47</td><td> 108</td><td> 85</td><td> 0,165</td>
<td> 4-2</td><td> 4,62</td><td> 104</td><td> 96</td><td> 0,173</td>
<td> 4-3</td><td> 3,82</td><td> 70</td><td> 113</td><td> 0,175</td>
<td> 4-4</td><td> 3,73</td><td> 63</td><td> 50</td><td> 0,175</td>
<td> 5-1</td><td> 4,03</td><td> 75</td><td> 114</td><td> 0,176</td>
<td> 5-2</td><td> 3,72</td><td> 65</td><td> 113</td><td> 0,156</td>
<td> 5-3</td><td> 1,99</td><td> 62</td><td> 98</td><td> 0,152</td>
<td> 6-1</td><td> 1,64</td><td> 75</td><td> 101</td><td> 0,186</td>
<td> 6-2</td><td> 0,61</td><td> 61</td><td> 107</td><td> 0,166</td>
<td> 7-1</td><td> 4,59</td><td> 70</td><td> 117</td><td> 0,178</td>
<td> 7-2</td><td> 4,30</td><td> 75</td><td> 132</td><td> 0,166</td>
<td> 7-3</td><td> 4,81</td><td> 58</td><td> 144</td><td> 0,151</td>
<td> 7-4</td><td> 3,43</td><td> 52</td><td> 146</td><td> 0,132</td>
189 105
continued from table 4
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td> 8-1</td><td> 5,08</td><td> 66</td><td> 112</td><td> 0,184</td>
<td> 8-2</td><td> 4,80</td><td> 66</td><td> 134</td><td> 0,181</td>
<td> 8-3</td><td> 5,19</td><td> 58</td><td> 140</td><td> 0,185</td>
<td> 8-4</td><td> 4,43</td><td> 64</td><td> 38</td><td> 0,140</td>
abrasion class - (weight loss of reference sample / weight loss of sample) x 100 (reference sample was sample 2-1)
Procedure for the preparation of the CEC NR / BR blends and the NR / BR dry blends
Mixing method
Dry: mastic RSS1 is mixed with the other ingredients; CEC: Mix the CEC masterbatch that has all of the carbon black introduced with the masticated RSS1 and the oil. The ratios of CEC natural rubber to RSS1 natural rubber were 10/0, 90/10, 80/20 and 70/30.
Methods of proceeding during mixing
A three-stage mixing in a Banbury blender for dry blends and a two-stage blending in a Banbury blender for CEC / RRS1 blends were used. RRS1 natural rubber was masticated prior to the first blending step for the dry blends and CEC / RSS1 blends.
0,75
100 rotations per minute
30 ° C
950 Wh
Mastic conditions RSSł: fill factor: rotor speed: temperature of Banbury mixer total energy per batch
17 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17
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Numbers
- Application
- 33961498
Titles2
- English
- MIXTURE OF ELASTOMERIC COMPOSITES AND METHODS OF OBTAINING THEM
- Polish
- Sposób wytwarzania mieszanki kompozytów elastomerowych
Classification
- CPC, 16
- C08J3/226
- B29B7/76
- B29B15/04
- B29K2021/00
- B29K2105/16
- C08C1/15
- C08J3/215
- C08J2321/00
- C08J2421/00
- C08K3/04
- C08K3/36
- C08L21/00
- B60C1/0016
- B29B7/7495
- B01F25/23
- C08C1/16
- IPC, 13
- B01F5 02
- B29B7 76
- B29B15 04
- B60C1 00
- C08C1 14
- C08C1 15
- C08J3 215
- C08J3 22
- C08K3 00
- C08K3 013
- C08K3 04
- C08K3 36
- C08L21 00