Polymers containing modified pigments and methods of preparing the same
Abstract
A method of preparing a polymer composition comprising at least one polymer and at least one modified pigment having at least one organic group attached, wherein said method comprises introducing at least one suspension containing at least one modified pigment having attached at least one organic group to a water-based polymer solution to form mixtures; wherein said water-based polymer solution has not been dehydrated; and dehydrate said mixture to form the polymer composition.
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16 claims: 1 independent, 15 dependent
- 1ES 2 333 100 T3 REIVINDICACIONES 1. Un método de preparación de una composición polimérica que comprende al menos un polímero y al menos un pigmento modificado que tiene unido al menos un grupo orgánico, en el que dicho método comprende introducir al menos una suspensión que contiene al menos un pigmento modificado que tiene unido al menos un grupo orgánico a una solución polimérica basada en agua para formar mezclas;en el que dicha solución polimérica basada en agua no se ha deshidratado;y deshidratar dicha mezcla para formar la composición polimérica.
- 2El método de la reivindicación 1, en el que dicha solución polimérica basada en agua es una solución de polímeros en emulsión.
- 3El método de la reivindicación 1, en el que dicha solución polimérica basada en agua es una solución polimérica en suspensión.
- 4El método de la reivindicación 1, en el que dicha solución polimérica basada en agua es una solución polimérica por radicales libres.
- 5El método de la reivindicación 1, en el que dicha suspensión se produce por micropulverización del pigmento modificado en agua.
- 6El método de la reivindicación 1, en el que dicha suspensión se produce por micropulverización del pigmento modificado en un disolvente.
- 7El método de la reivindicación 1, en el que dicha suspensión se produce por micropulverización del pigmento modificado en un proceso seco y después añadiendo pigmento molido a un líquido en una mezcladora separada.
- 8El método de la reivindicación 1, en el que dicho pigmento modificado es negro de humo modificado, fibra de carbono modificada, carbono activado modificado, grafito modificado, grafito activado modificado, tela de carbono modificada, carbono vítreo modificado o combinaciones de los mismos.
- 9El método de la reivindicación 1, en el que dicho pigmento modificado es negro de humo modificado.
- 10El método de la reivindicación 1, en el que dicho pigmento modificado es un producto de carbono modificado.
- 11El método de la reivindicación 10, en el que dicho producto de carbono modificado es un agregado que comprende una fase de carbono y una fase de una especie que contiene silicio.
- 12El método de la reivindicación 10, en el que dicho producto de carbono modificado es un agregado que comprende una fase de carbono y una fase de especie que contiene metal o es un negro de humo recubierto con sílice.
- 13El método de la reivindicación 10, en el que dicho producto de carbono modificado es un producto de carbono que tienen grupos sulfuro aromáticos unidos.
- 14El método de la reivindicación 1, en el que dicho pigmento modificado es negro de humo que tiene unido al menos un grupo orgánico.
- 15El método de la reivindicación 14, en el que dicho grupo orgánico comprende un grupo aromático o un grupo alquilo C 1 -C 100 o ambos.
- 16El método de la reivindicación 1, en el que dicho polímero es SBR en solución, goma natural, SBR en solución funcionalizado, SBR en emulsión, polibutadieno, poliisopreno o mezclas de los mismos.
Independent claims16
74 paragraphs in 8 sections, as filed
IS 2 333 100 T3
DESCRIPTION
Polymers containing modified pigments and methods of their preparation.
Background of the invention
The present invention relates to polymeric compositions and, more particularly, it relates to polymeric compositions containing modified pigments and to methods of preparing the same.
US Patent Nos. 5,559,169 and 5,851,280 describe polymeric compositions containing modified carbon products that are useful in various applications such as plastics, tires, and other polymeric articles.
US Patent No. 5,985,953 describes a process for the manufacture of a silica filled masterbatch of natural and synthetic rubber and thermoplastic polymers. The process comprises the preparation of a compatibilized silica suspension and its introduction into a latex mixture.
European Patent Publication No. 0.955.343 describes a process for the production of a modified carbon black by granulating a water-dispersed silica with a carbon black. Also disclosed is a rubber composition that includes a modified carbon black in which a suspension of the modified carbon black is mixed with a latex mixture.
In preparing the polymer compositions containing the modified carbon products or modified pigments, it would be beneficial if improved methods could be envisaged for incorporating the modified pigments into the polymer compositions. Typically, modified pigments such as modified carbon black are formed in an aqueous solution and this resulting suspension is dried, resulting in a dry modified carbon black. This dry modified carbon black can then be incorporated into polymeric compositions and other compositions such as inks and coatings. Thus, a substantial cost is incurred in drying the modified carbon black and redispersing the product in the polymer. Additionally, the modification process generally results in the production of by-products such as salts that are not easily removed from the product.
The described invention allows for a substantially improved and more economical process. The separate drying step of the carbon black can be eliminated. Additionally, the salt associated with the product can be more easily removed. Additionally, the resulting elastomeric compound containing the carbon black and the polymer will not require a separate redispersion step. Also, the elastomeric compound will have a good dispersion of carbon black and therefore will result in improved properties.
Summary of the invention
A feature of the present invention is to provide processes for incorporating modified pigments into polymer compositions.
Another feature of the present invention is to provide methods of introducing modified pigments into polymer compositions that result in economic savings as well as reducing the amount of time required to prepare polymer compositions containing modified pigments.
Another feature of the present invention is to provide products with better dispersion of the components.
Another feature of the present invention is to provide products with improved performance.
Another feature of the present invention is to provide products with substantially no associated by-products.
Additional features and advantages of the present invention will be set forth in part in the description that follows and in part will be apparent from the description, or may be learned by practice of the present invention. The objects and other advantages of the present invention will be realized and obtained by the elements and combinations indicated particularly in the written description and in the appended claims.
In order to achieve these and other advantages and in accordance with the purposes of the present invention, as it is carried out and widely described herein, the present invention relates to a method of preparing a polymeric composition comprising at least one polymer and to the minus a modified pigment. The method involves introducing at least one suspension containing at least one modified pigment to a polymer solution to form a mixture. The modification of the charge is preferably carried out in an aqueous medium. At this stage, the polymer solution has not dehydrated. After introducing the suspension, the mixture is then dehydrated to form the polymer composition. The polymer solution can be a polymer emulsion, a polymer suspension, or a polymer prepared by free radical polymerization. In addition, polymers prepared by solvent-based polymerizations can also benefit from the methods of the present invention.
IS 2 333 100 T3
The present invention also relates to a method of preparing the polymer composition by introducing at least one suspension containing at least one modified pigment in a solution of the precursor of an emulsion polymer. The polymerization of the precursor is then initiated to form a polymeric product. This product is then dehydrated to form the polymer composition of the present invention.
In another method of preparing the polymeric composition, the method involves attaching at least one organic group on a pigment in the presence of a polymeric emulsion to form a polymeric product. This product is then dehydrated to form the polymer composition of the present invention.
Furthermore, the present invention relates to a method of forming a polymer composition by attaching at least one organic group on a pigment in the presence of an inactivated and unwashed solution of a polymer prepared by solution or suspension polymerization and a solvent. The mixture can then be washed and dehydrated to form the polymer composition of the present invention.
In another method of the present invention, a polymer composition is formed by introducing at least one suspension containing at least one carbon black or modified pigment into an inactivated solution of a polymer prepared by solution or suspension polymerization to form a mixture. This mixture is then washed and dehydrated to form the polymer composition of the present invention.
In another method, the filler or pigment can be treated in the aqueous phase with an emulsion or mixture of water and an organic solvent. The modified filler or pigment is transferred to the organic solvent after treatment. This organic solvent solution can be mixed with the already formed polymer solution or with the polymer precursor solution. After polymer formation, the resulting product can be washed and dehydrated.
Finally, the present invention relates to a method of preparing a polymer composition by introducing a modified pigment having at least one organic group attached to a solution containing at least one living polymer. The living polymer can then be terminated by any technique including the option of at least one organic group having a group capable of terminating the living polymer and thereby forming a polymer composition of the present invention.
It should be understood that both the above general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention, as claimed.
Detailed description of the present invention
The present invention relates to methods of preparing polymer compositions containing modified pigments, in which the modified pigment has at least one organic group attached. The present invention further relates to the products resulting from these methods, as well as the intermediate mixtures or compositions formed during the methods of the present invention.
The modified pigment is a pigment that has at least one organic group attached to it. Examples of the pigment include, but are not limited to, any colored pigment, carbon black, carbon fibers, activated carbon, graphite, activated graphite, carbon cloth, glassy carbon, and the like. Preferably, the modified pigment is a modified carbon product such as modified carbon black. The organic group that is attached to the pigment can be any variety of organic groups such as those described in US Patent Nos. 5,955,232, 5,922,118, 5,575,845, 5,630,868, 5,900,029, 5,895. 522, 5,885,335, 5,851,280, 5,837,045, 5,803,959, 5,672,198, 5,571,311, 5,630,868; 5,707,432, 5,803,959, 5,554,739, 5,698,016 and 5,713,988, and in PCT Publication Nos. WO 96/18688, WO 97/47697, WO 99/31175, WO 99/41304, WO 97 / 47692 and WO 97/47699; all of which are included in their entirety by reference in this document.
Also, for the purposes of the present invention, a modified carbon product includes an aggregate comprising a carbon phase and a silicon-containing species phase. A description of this aggregate, as well as a means of preparing this aggregate are described in PCT Publication No. WO 96/37547 as well as in United States Patents No. 5,830,930, 6,008,272, 5,977,213, 5,948 .835, 5,919,841, 5,904,762, 5,877,238 and 5,869,550. This modified carbon product can be used as is or it can have an organic group attached to it. All such patents, publications, and patent applications are incorporated herein in their entirety by reference.
The modified carbon product, for the purposes of the present invention, can also be an aggregate comprising a carbon phase and a metal-containing species phase where the metal-containing species phase can be a variety of different metals such as magnesium, calcium, titanium, vanadium, cobalt, nickel, zirconium, tin, antimony, chromium, neodymium, lead, tellurium, barium, cesium, iron, molybdenum, aluminum and zinc and mixtures thereof. The aggregate comprising the carbon phase and a metal-containing species phase is described in US Patent Nos. 6,017,480 and 6,150,453 and in PCT Publication No. WO 98/42778 which are also incorporated herein. throughout this document by reference. This carbon product can be used as is or it can have an organic group attached to it.
IS 2 333 100 T3
Also, for the purposes of the present invention, a modified carbon product includes a silica-coated carbon black, such as that described in PCT Publication No. WO 96/37547, Published November 28, 1996, and US Pat. United States No. 5,916,934 which are also incorporated herein in their entirety by reference. This modified carbon product can be used as is or it can have an organic group attached to it.
Depending on the polymer composition, different organic groups are preferred. For example, if the polymeric composition is used in the formation of a tire or a component of a tire, preferably, the organic groups are aromatic sulfides or thiols or the organic groups consisting of amines, ionic groups, hydroxyl groups, groups containing sulfur such as polysulfides, sulfenamide groups, esters, ketones, or halogen-containing groups. Another group is phenylsulfatoethylsulfone which can be used to prepare a stabilized filler dispersion of the filler or pigment in water and then subsequently used to provide an improved polymer-filler interaction once in contact with the polymer.
Modified pigments, especially modified carbon products having aromatic sulfide groups are particularly useful in elastomer or rubber compositions. These aromatic sulfides can be represented by the formulas Ar (CH<sub>2</sub>)<sub>what</sub>S<sub>k</sub> (CH<sub>2</sub>)<sub>r</sub>Ar 'or A- (CH<sub>2</sub>)<sub>what</sub>S<sub>k</sub> (CH<sub>2</sub>) Ar ", where Ar and Ar 'are independently substituted or unsubstituted amylene or heteroarylene groups, Ar" is an aryl or heteroaryl group, k is 1 to 8 and q and r are 0-4. Substituted aryl groups would include substituted alkylaryl groups. Arylene groups can include phenylene groups, particularly p-phenylene groups or benzothiazolylene groups. Aryl groups can include phenyl, naphthyl benzothiazolyl. The number of sulfurs present, defined by k, preferably ranges from 2 to 4. The modified carbon products may have an organic aromatic sulfide group attached, of formula (C<sub>6</sub>H<sub>4</sub>) -S<sub>k</sub>- (C<sub>6</sub>H<sub>4</sub>) -, where k is an integer from 1 to 8 and more preferably where k ranges from 2 to 4. Aromatic sulfide groups can be bis-para- (C<sub>6</sub>H<sub>4</sub>) -S<sub>2</sub>- (C<sub>6</sub>H<sub>4</sub>) - and for- (C<sub>6</sub>H<sub>4</sub>) -S<sub>2</sub>- (C<sub>6</sub>H<sub>5</sub>). The diazonium salts of these aromatic sulfide groups can conveniently be prepared from their corresponding primary amines, H<sub>2</sub>N-Ar-S<sub>k</sub>-Ar'-NH<sub>2</sub> or H<sub>2</sub>N-Ar-S<sub>k</sub>-Ar ”. Groups include dithiodi-4,1-phenylene, tetrathiodi-4,1-phenylene, phenyldithiophenylene, dithiodi-4,1- (3-chlorophenylene), - (d-CHj-SS - ^^ HNS), - (4- C6H4) -SS- (4-C6H4) -OH, -6- (2-C<sub>7</sub>H<sub>3</sub>NS) -SH, - (4-C6H4) -CH2CH2-SS-CH2-CH2- (4-C6H4) -, - (4-C6H4) -CH2CH2-SSS-CH2CH2- (4-C6H4) -, - (2 -C6H4) -SS- (2-C6 H4) -, - (3-C6H4) -SS- (3-C<sub>6</sub>H4) -, -6- (C6H<sub>3</sub>N2S), -6- (2-C7H<sub>3</sub>NS) -S-NRR 'where RR' is -CH2CH2OCH2CH2, - (4-C6H4) SSSS- (4-C6-H4) -, - (4-C6H4) -CH = CH2, - (4-C6H4) -S -SO3H, - (4-C6H4) -SO2NH- (4-C6H4) -S-, S- (4-C<sub>6</sub>H4) -NHSQr (4C6H4) -, -6- (2-C7H3NS) -SS-2- (6-C7H3NS) -, - (4-C6H4) -S-CH2-4-C6H4) -, - (4- C6H4) -SO2-S- (4-C6H4) -, - (4-C6H4) -CH2S-CH2- (4-C6H4) -, - (3-C6H4) -CH2-S-CH2- (3-C6H4) -, - (4-C6H4) - (CH2-S-CH2- (4-C6H4) -, - (3-C6H4) -CH2- (3-C6H4) -, - (4-C6H4) -SS-CH2- (4-C6H4) -S-NRR 'where RR' is -CH2CH2OCH2CH2-, - (4-C6H4) -SO2NH-CH2CH2-SS-CH2CH<sub>2</sub>-NhSo<sub>2</sub>- (4-C<sub>6</sub>H<sub>4</sub>) -, - (4-C<sub>6</sub>H<sub>4</sub>) -2- (1,3-dithianyl) and - (4-C<sub>6</sub>H<sub>4</sub>) -S- (1,4-piperizindiyl) -S- (4-C<sub>6</sub>H<sub>4</sub>)-.
Another set of organic groups that can be attached to the pigment are organic groups that have an aminophenyl, such as (C6H4) -NH2, (C6H4) -CH2- (C6H4) -NH2, (C6H4) -SO2- (C6H4) -NH2. Organic groups also include aromatic sulfides represented by the formulas Ar-S<sub>n</sub>-Ar 'or Ar- S<sub>n</sub>-Ar ", where Ar and Ar 'are independently arylene groups, Ar" is an aryl and n is 1 to 8.
Preferably, the organic group comprises an aromatic group and / or a C alkyl group.<sub>1</sub>-C<sub>100</sub> (and more preferably a C<sub>1</sub>-C<sub>12</sub>) directly attached to the pigment, with or without an ionic, ionizable or polar group to improve dispersion in aqueous media. For dispersions in organic solvents such as toluene, the attached group is preferably nonpolar or nonionic.
More than one type of organic group can be attached to the pigment or two or more types of modified pigments with different organic groups attached can be used. Using two or more different types of organic groups allows for a combination of properties. If two different types of organic groups are joined, for example a benzenesulfonic acid group and a vinyl aromatic group, the sulfonic acid group promotes dispersibility and the vinyl aromatic group serves as the radical graft site. The proportion of the different organic groups can be the same or different. Preferably, only a minimal treatment level of the ionic, ionizable or polar group is used to impart stability to the dispersion. For example, groups such as ionic species (eg sulfates, phosphates, alkali salts of organic acids or quaternary ammonium salts), non-ionic species (eg hydroxyl, organic acids) or surface active stabilizers (eg SDMS, SDS , Antarox) can be used to provide stable pigment dispersions in aqueous media. Dispersion of the modified pigment in organic liquids can be facilitated in a similar manner by employing treatments that are more compatible with these less polar environments. The levels of organic group treatment for the purposes of radical graft sites may depend on the uses of the material. For example, the attachment of epoxy groups would facilitate grafting to hydroxyl bearing polymeric matrices such as polyurethane or polycarbonates or amine matrices such as nylon. Other examples include the attachment of radical sensitive vinyl groups such as styrenics or acrylates to facilitate crosslinking type reactions in radical polymerizations. These linked groups would ultimately affect the properties of the materials containing these modified pigments. Properties that would be affected include, but are not limited to, impact behavior, modulus response, and dispersibility in plastics.
Also, a combination of different modified pigments can be used. For example, a modified pigment having one type of organic group attached to it can be used in combination with another modified pigment having a different organic group attached to it. Also, a modified pigment such as an aggregate that
ES 2 333 100 T3 comprises a carbon phase and a silicon-containing species phase can be used in combination with a modified carbon product having an organic group attached and so on.
At least one organic group can be attached to a pigment by various mechanisms such as those described in the patents and publications described above. Preferably, the organic group is linked chemically such as by covalent and / or ionic bonds.
One process for attaching an organic group to the pigment involves the reaction of at least one diazonium salt with a pigment in the absence of an externally applied current sufficient to reduce the diazonium salt. That is, the reaction between the diazonium salt and the pigment proceeds without an external source of electrons sufficient to reduce the diazonium salt. Mixtures of different diazonium salts can be used in the process of the invention. This process can be carried out under various reaction conditions and in any type of reaction medium, including both protic and aprotic solvent systems or suspensions.
In another process, at least one diazonium salt reacts with a pigment in a protic reaction medium. Mixtures of different diazonium salts can be used in this process of the invention. This process can also be carried out under various reaction conditions. In both processes, the diazonium salt can be formed in situ.
The processes can be carried out in any reaction medium that allows the reaction between the diazonium salt and the pigment to proceed. The reaction medium can be a solvent-based system. The solvent can be a protic solvent, an aprotic solvent, or a mixture of solvents. Protic solvents are solvents, such as water or methanol, that contain hydrogen linked to oxygen or nitrogen and are thus sufficiently acidic to form hydrogen bonds. Aprotic solvents are solvents that do not contain an acidic hydrogen as defined above. Aprotic solvents include, for example, solvents such as hexanes, tetrahydrofuran (THF), acetonitrile, and benzonitrile. For a discussion of protic and aprotic solvents see Morrison and Boyd, Organic Chemistry, 5<sup>to</sup> Ed., Pp. 228-231, (Allyn and Bacon, Inc. 1987). The reaction between a diazonium salt and a carbon product can take place with any type of carbon product, for example, in fluffy or granulated form.
The polymer with which at least one modified pigment is combined can be any polymer including natural products and synthetic products. The polymer can be any type of polymer, such as a random polymer, an alternate polymer, a graft polymer, a block polymer, a star-type polymer, and a comb-type polymer. The polymer can also be one or more polyblends. The polymer can be a polymeric interpenetrating network (iPN); a polymeric interpenetrating network (SIN) or an elastomeric interpenetration network (ESI). The polymer can be thermoplastic or thermoset.
Examples of polymers include, but are not limited to, olefin-containing, diene-containing, and butene-containing polymers and copolymers. Particular examples include elastomers such as solution SBR, natural rubber, emulsion SBR, polybutadiene, polyisoprene, NBR, EPDM, EPM, isobutene elastomers and their functionalized or modified derivatives or mixtures thereof.
Other examples of polymers include, but are not limited to, linear and non-linear polymers, such as polyethylene, polyvinyl chloride, polyisobutylene, polystyrene, polycaprolactam (nylon), polyisoprene, and the like. Other general classes of polymers include polyamides, polycarbonates, polyelectrolytes, polyesters, polyethers, (polyhydroxy) benzenes, polyimides, sulfur-containing polymers (such as polysulfides, (polyphenylene) sulfides and polysulfones, polyolefins, polymethylbenzenes, polystyrene and copolymers including ABS), acetal polymers, acrylic polymers, acrylonitrile polymers and copolymers, halogen-containing polyolefins (such as polyvinyl chloride and vinylidene chloride), fluoropolymers, ionomeric polymers, polymers containing ketone groups, liquid crystal polymers, polyamide-imides, polymers containing olefinic double bonds (such as polybutadiene, polydicyclopentadiene), olefin copolymers, polyphenylene oxides, polyurethanes, thermoplastic elastomers, silicone polymers, alkyds, epoxy, unsaturated polyester, vinyl ester, urea-melamine or phenol-formaldehyde resins and the like. Preferably, the polymer is an acrylic polymer, a methacrylic polymer, or a styrenic polymer but would be highly dependent on the intended application. For example, reinforcement applications would generally involve the formation of a rubber product that could bind to the modified carbon product in such a way that the rubber product is preferably non-extractable, for example non-solvent extractable. This can be accomplished by using a modified carbon product that has styrenic groups attached to the surface. During a radical polymerization in aqueous media, the propagation chains would graft to these sites on the surface of the modified carbon product and generate a rubbery coated particle.
The polymers that are used in the methods of the present invention are preferably formed from polymerization environments in aqueous medium such as emulsion polymerizations and suspension polymerizations and in general free radical polymerizations. Also, solvent-based polymerizations can be used. Accordingly, although emulsion polymerization and solution polymerization are discussed in detail below, these methods can be adapted to free radical polymerizations in general including, but not limited to, suspension polymerizations and solvent-based polymerizations.
IS 2 333 100 T3
Many of the polymers identified above can be prepared by emulsion polymerization techniques and / or solution polymerization techniques. For example, a styrene-butadiene rubber can be prepared by emulsion polymerization techniques. Those skilled in the art will have a full appreciation of the various polymerization techniques that can be used in the formation of the polymers described above.
Various methods can be used to prepare a polymer composition containing at least one polymer and at least one modified pigment. Generally, conventional ingredients used to expedite polymerization can be used in conventional amounts in these methods, such as an initiator, surface active agents, inhibiting or inactivating agents, crosslinking agents, and the like.
In one embodiment, the polymer composition containing at least one polymer and at least one modified pigment is prepared by introducing at least one suspension containing at least one modified pigment into a polymer emulsion that has not been dehydrated. The introduction of the suspension into the polymeric emulsion can be considered a mixture for the purposes of the present invention. This mixture is then dehydrated to form the polymer composition of the present invention. Dehydration for the purposes of the present invention includes the removal of the aqueous or solvent phase, which may be the continuous phase, to recover the polymer formed.
Conventional techniques can be used to achieve dehydration of the mixture including decantation, filtration, and the like.
In another method of the present invention, a polymer composition can be formed by introducing at least one suspension containing at least one modified pigment to a polymer emulsion precursor. The polymer emulsion precursor are the components that after polymerization will result in a polymer emulsion. Once the suspension is introduced into the polymeric emulsion precursor, polymerization can begin to form a polymeric product. This polymeric product can then be dehydrated to recover the polymeric composition of the present invention.
Apart from the above processes, the polymer composition can be prepared by forming the modified pigment in the presence of the polymer emulsion. In particular, the process involves attaching at least one organic group on a pigment in the presence of a polymeric emulsion to form a product. This product is then dehydrated as described above. In said process, the reactants related to the formation of a modified pigment as described in the patents and publications mentioned above are used in the presence of a polymeric emulsion to carry out the reaction that will result in the binding of at least one organic group on the pigment. After this reaction has been completed to form the modified pigment, the modified pigment in the presence of the polymer emulsion is subjected to a dehydration process to result in the polymer composition of the present invention.
Generally, any salt or by-product formed as a result of the filler or pigment treatment is removed by the process of washing and dehydrating the polymeric product.
In another embodiment of the present invention, a polymer composition is formed by introducing at least one suspension containing at least one modified pigment into an inactivated solution of a polymer, for example, prepared by solution or suspension polymerization to form a mixture. Basically, in this process, a solution polymer system is used in which before washing the polymer solution, but after inactivating the polymer solution, the suspension containing at least one modified pigment is introduced. Once introduced, the suspension present with the polymer solution that is inactivated is then washed using conventional techniques known to those skilled in the art for the recovery of any polymer from solution polymerization.
In yet another embodiment of the present invention, a polymer composition is formed by attaching at least one organic group on a pigment in the presence of an inactivated or unwashed solution of a polymer, for example, prepared by solution or suspension polymerizations and a solvent. . As one of the aforementioned embodiments, in this embodiment, the modified pigment is actually formed in the polymer solution and in the presence of the components used in the solution polymerization. In this case, the modification would occur in a biphasic mixture of organic solvent and water. The treated pigment or filler is transferred to the solvent phase. In this way, reactants that are used to form a modified pigment as described in the above-mentioned patents and publications are introduced into the polymer in solution and the reaction is initiated to form the modified pigment. Once the modified pigment is formed in the presence of an inactivated and unwashed solution polymer, the solution polymer containing the modified pigment is then washed using conventional techniques to recover the polymer composition of the present invention.
Finally, in another embodiment of the present invention, a polymer composition is formed in which a modified dry pigment or filler having attached at least one organic group is introduced into a solution containing at least one living polymer. Preferably, the modified pigment having at least one organic group attached has a component on the organic group that is a terminating group capable of terminating polymerization. Examples of such groups are esters, ketones, amines, and thiols.
IS 2 333 100 T3
The suspension containing the modified pigment can be prepared in various ways. The suspension can be prepared by adding agglomerates of carbon black or other pigment (granules) to the water. Preferably, the pigment particles in the suspension are free of agglomerates so that they will easily disperse in the polymer. One method of producing a non-agglomerate modified pigment suspension is to prepare a paste containing micropruff solids. A device such as a ball mill is used to micro-spray the pigment in the presence of a liquid such as water or a solvent. Alternatively, a device such as a ball mill can be used to deagglomerate the pigment without any liquid and then add the micro-powdered pigment downstream in a mixer.
The methods of the present invention can be incorporated into the inventions described in WO 99/16600, WO 97/36724 and US Provisional Application No. 60 / 129,791; all incorporated in their entirety by reference herein.
The intermediates described above are considered part of the present invention and are unique in the way that the modified pigment is incorporated into the polymer. Thus, the presence of the suspension containing the modified pigment in the presence of the polymer solution in a water-based or solvent-based system is considered part of the present invention and new mixtures or compositions are considered.
The polymer compositions of the present invention can be used in numerous ways and in a number of applications including, but not limited to, the following reinforcing applications, rubber articles, plastic articles, and the like.
For example, the modified pigment products of this invention can be used as colorants in a plastic material. The modified pigment products of the invention can also be used to impart conductivity to a plastic material. The modified pigment products of the invention can give a higher dispersion speed or improve the quality of the dispersion on the corresponding untreated pigment. These improvements offer an economic advantage in the manufacture of plastics and in the value of the finished products, respectively. Using the modified pigment products of the invention can improve the impact resistance of plastic. Thus, the invention relates to an improved plastic composition comprising a plastic and the modified pigment product.
As with conventional pigments, modified pigment products can be used with a variety of plastics, including but not limited to plastics made from thermoplastic resins, thermosetting resins, or modified materials, for example composites. Typical classes of thermoplastic resin include: (1) acrylonitrile-butadiene-styrene (ABS) resins; (2) acetals; (3) acrylics; (4) cellulosics; (5) chlorinated polyethers; (6) fluorocarbons such as polytetrafluoroethylene (TFE), polychlorotrifluoroethylene (CTFE) and fluorinated ethylenepropylene (FEP), (7) nylons (polyamides) (8) polycarbonates; (9) polyethylenes (including copolymers); (10) polypropylenes (including copolymers); (11) polystyrenes; (12) vinyls (polyvinyl chloride); (13) thermoplastic polyesters such as polyethylene terephthalate or polybutylene terephthalate; (14) polyphenylene ether alloys and mixtures and alloys of the above with rubber modifiers. Typical thermosetting resins include: (1) alkyds, (2) allylics; (3) amines (melamine and urea); (4) epoxies; (5) phenolics, (6) polyesters; (7) silicones; and (8) urethanes.
In accordance with the invention, the thermoplastic composition includes, but is not limited to, any plastic materials, articles, goods, surfaces, fabrics, sheets, films, and the like. For example, plastic materials include automotive parts, house enclosures, pool liners, roofing materials, packaging materials, synthetic fibers, food and storage containers, light absorbing applications (e.g. barcodes), and any variety of other household or industrial items.
From the foregoing it will be understood that the present invention can be used in the preparation of polymeric foams comprising a modified pigment. In preferred embodiments the load is preferably located in the windows of the foam cells.
The modified pigment products of the present invention can also be used as with conventional pigments, in the combination and preparation of rubber and elastomer compositions. Accordingly, the present invention relates to the preparation of a rubber or elastomeric composition containing at least one rubber or elastomer and at least one modified pigment using the methods of the present invention.
Carbon blacks, for example, are useful in the preparation of rubber vulcanizates such as tires. Generally, in the production of tires it is desirable to use carbon blacks that produce tires with satisfactory abrasion resistance and hysteresis performance. The wear properties of a tire tread are related to abrasion resistance. The higher the abrasion resistance, the greater the number of kilometers the tire will last without wearing out. The hysteresis of a rubber compound refers to the difference between the energy applied to deform a rubber compound and the energy released when the rubber compound returns to its initial undeformed state. Tires with lower hysteresis values reduce rolling resistance and are therefore capable of reducing the fuel consumption of the vehicle using the tire. Thus, it is particularly desirable to have carbon black products capable of conferring greater abrasion resistance and less hysteresis on tires.
IS 2 333 100 T3
The modified pigment products and preferably the modified carbon black products of this invention are useful in rubbers. Carbon black products comprising an aromatic sulfide group are preferred for this use. The carbon black or other pigment products of the invention can be used in rubber compositions that are sulfur cured, peroxide cured, or chemically crosslinked.
The modified pigment products of the invention can be used with any of the polymers described above, including synthetic rubbers such as copolymers of about 10 to about 70 percent by weight styrene and from about 90 to about 30 percent by weight. weight of butadiene, such as a copolymer of 19 parts of styrene and 81 parts of butadiene, a copolymer of 30 parts of styrene and 70 parts of butadiene, a copolymer of 43 parts of styrene and 57 parts of butadiene and a copolymer of 50 parts of styrene and 50 parts of butadiene; the polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene and the like and copolymers of said dienes conjugated with a monomer containing an ethylenic group copolymerizable therewith such as styrene, methyl styrene, chlorostyrene, acrylonitrile, 2-vinylpyrile, 2-vinylpyrile -methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl substituted acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, alphamethylene carboxylic acids and the esters and amides thereof, such as acrylic acid and dialkyl acrylic acid amide; Also suitable for use herein are copolymers of dienes, ethylene, and other higher alpha olefins such as propylene, butene-1, and pentene-1. They can also be used with natural rubber.
The rubber composition of the present invention, therefore, may contain at least one elastomer, curing agents, reinforcing fillers, a coupling agent, and optionally various processing aids, oil diluents, and antidegradants. In addition to the examples mentioned above, the elastomer can be, but is not limited to, polymers (eg homopolymers, copolymers and terpolymers) made from 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl -1,3-butadiene, acrylonitrile, ethylene, propylene, and the like. These elastomers are preferred to have a glass transition temperature (T<sub>g</sub>) measured by DSC between -120 ° C and 0 ° C. Examples of such elastomers include poly (butadiene), poly (styrene-co-butadiene), poly (isoprene), styrene-butadiene rubber (SBR), natural rubber, and their oil diluent derivatives. Mixtures of any of the above can also be used.
Elastomeric compositions described in the present invention and which can be prepared include, but are not limited to, vulcanized compositions (VR), thermoplastic vulcanizates (TPV), thermoplastic elastomers (TPE), and thermoplastic polyolefins (TPO). TPV, TPE, and TPO materials are further rated for their ability to be extruded and molded multiple times without losing performance characteristics.
The elastomeric composition can include one or more curing agents such as, for example, sulfur, sulfur donors, activators, accelerators, peroxides, and other additive systems used to effect vulcanization of the elastomer composition.
The resulting elastomeric compounds containing the modified pigment, and preferably modified carbon black of the present invention and optionally containing one or more coupling agents can be used for various elastomeric products including tires and components thereof such as a compound of the tread, a tread compound, a sidewall compound, a wire mesh compound, an inner liner compound, bead, vertex, any compound used in the carcass and other components for vehicle tires, industrial products, seals, timing tapes, power transmission tapes, and other rubber items.
Advantageously, the modified pigment products and especially the modified carbon black products of the present invention can confer improved abrasion resistance and / or reduced hysteresis to rubber or elastomeric compositions containing them.
The modified pigment products of this invention can also be used to color fibers or fabrics. The preferred modified pigment products for this use are dispersible modified pigment products. Accordingly, the invention relates to fiber and fabric compositions comprising a fiber or fabric and a modified pigment product. Suitable fibers that can be used include natural and synthetic fibers such as cotton, wool, silk, linen, polyester, and nylon. Suitable fabrics that can be used include natural and synthetic fibers such as cotton, wool, silk, linen, polyester, and nylon. Preferably, natural fibers and fabrics comprising cotton, wool, silk and linen are used.
The modified pigment products of the present invention can be colored by means known in the art for coloring fibers and fabrics, for example with direct and acid dyes. Also, the modified pigments can be incorporated into the fibers by centrifugation techniques such as wet centrifugation, dry centrifugation and melt centrifugation techniques. For a general discussion of coloring with dyes, see Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 8 pp. 280-350 "Dyes, Application and Evaluation" (John Wiles and Sons, 1979), which is incorporated herein by reference. The use of a solvent or water dispersible modified pigment product discussed above provides a method of coloring these materials with a photoresist dye.
IS 2 333 100 T3
The present invention also relates to toner compositions comprising toner resin particles and the modified pigment particles of the present invention in which the toner resin particle can be formed using the methods described herein. Conventional additives may be used as described in U.S. Patent Nos. 5,278,018, 5,510,221, 5,275,900, 5,571,654, and 5,484,575, and EPO 270-066A1 and these patents are incorporated herein by reference.
Contents8
19 members in 8 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 17825700 | United States of America | P | |
| 17825700 | United States of America | P | |
| 01946876178257P | – | – | – |
| US20000178257P | – | – | – |
Members19
| Document | Office | Kind | |
|---|---|---|---|
| WO0155245A2 | World Intellectual Property Organization (WIPO) | A2 | |
| AU2974001A | Australia | A | |
| WO0155245A3 | World Intellectual Property Organization (WIPO) | A3 | |
| US2002006984A1 | United States of America | A1 | |
| US2002027110A1 | United States of America | A1 | |
| EP1185579A2 | European Patent Office (EPO) | A2 | |
| US6534569B2 | United States of America | B2 | |
| JP2003523470A | Japan | A | |
| EP1185579B1 | European Patent Office (EPO) | B1 | |
| AT442398T | Austria | T | |
| ATE442398T1 | Austria | T1 | |
| DE60139843D1 | Germany | D1 | |
| ES2333100T3This record | Spain | T3 | |
| JP2013028815A | Japan | A | |
| JP2015129305A | Japan | A | |
| JP5767187B2 | Japan | B2 | |
| JP2017039948A | Japan | A | |
| JP6228150B2 | Japan | B2 | |
| JP6291012B2 | Japan | B2 |
Numbers
- Publication, DOCDB
- 2333100
- Publication, EPODOC
- ES2333100T
- Application
- 1946876
- Application, DOCDB
- 01946876
- Application, EPODOC
- ES20010946876T
Titles2
- Spanish
- POLIMEROS QUE CONTIENEN PIGMENTOS MODIFICADOS Y METODOS DE PREPARACION DE LOS MISMOS.
- English
- POLYMERS CONTAINING MODIFIED PIGMENTS AND METHODS OF PREPARATION OF THE SAME.
Classification
- CPC, 1
- C08J3/215
- IPC, 9
- C08J3 215
- C08J3 22
- C08K9 00
- C08L7 00
- C08L9 00
- C09C1 44
- C09C3 04
- C09C3 06
- C09C3 08