Gurable rubbery mixture and method of producing the same

BACKGROUND OF THE INVENTION The present invention relates to rubber compositions containing silicate builders which have a beneficial effect on the production and properties of vulcanizates. These additives belong chemically to the group of organosilicate compounds containing sulfur in the molecule. These additives to improve the stiffening properties of the silicate fillers and increase the crosslinking yield when cured will be referred to hereinafter as stiffening agents.

It is known that carbon black in general and especially developed special types of carbon black do not act as mere fillers of rubber vulcanizates, but in some sense act as a reinforcing agent (active filler). The effect of carbon black on polymer reinforcement and the determination of the interaction of rubber and filler are described, for example, in the journal "Kautschuk und Gummi" [1966, no. 8, pp. 470-474], or "Kunststoffe" (1970, no. 1, p. 7 to 14).

In his activity since. carbon blacks are known silicate fillers, such as highly disperse silicas, silicates, or commercially. First, the stiffening effect of the various silicate fillers varies with respect to a completely different surface. Secondly, the active silicic acid affects the vulcanization process, especially when the sulfur and vulcanization vulcanization is carried out. Thus, no sulfur vulcanization has the effect of reducing the crosslinking ability of the silicate fillers. ·

In recent years, it has been tried that by incorporating chemicals into the starting mixture, the activity of silicate fillers is substantially improved.

It is known that when mercaptoalkoxysdane is used as a bonding agent between a silicate material such as glass, asbestos, clay, or silica and organic resins such as butadiene styrene resin, natural rubber, polyester resin, polystyrene, or a styrene anhydride blend; maleic acid, wherein the silanes were randomly deposited on the substrate and bound with the resin. (DOS No. 2,038,715).

Furthermore, organosilicon sulfides are described as having a single sulfide sulfur atom between two hydrocarbon residues and have been recommended for use as a cohesive agent or as intermediates for compounds that can be used as water repellents or anti-oxidants. Said organosilicon compounds may, however, also have sulfur-containing end groups such as a thiocyanato group, a xanthogenic group, a thioether group, a thioester group, or the like. (DOS No 1 191 227)

Similar end groups also include organo-organooxysilanes, for example 3-thiocyanatopropyltrimethoxysilane, or 3-thiocyanatopropyltriethoxysilane, which according to Belgian patent specification 770 097 find excellent use in crosslinked or vulcanized mixtures consisting of organic polymers, inorganic substances and corresponding or vulcanizing agents or systems. The two publications mentioned above show that the silanes contain only one carbon atom bound to the silicon atom, or in addition an additional silicon atom can be bound to the oxygen or amino nitrogen.

Also known are γ-mercaptopropyltrimethoxy and γ-mercaptopropyltriethoxysilanes, as well as β-mercaptoethyltriethoxysilane and other sulfur-free silanes which, after partial hydrolysis and application to the silicic acid surface, or silicate filler particles, can serve to improve the strength of the compositions. properties of reinforced rubber. Furthermore, the circumferential frictional surfaces of tires made of a rubber compound containing silicic acid as a filler and silane as a binder are known (Belgian Patent No. 760,999). Very different silanes with a common formula have been presented, but the introduction of the tables and the examples show that only γ-mercaptopropyltrimethoxysilane can be selected as the only binder tested.

The invention thus relates to one group of sulfur-containing organosilanes per molecule, which in many respects differ from the various known silanes in their advantages of use and are particularly useful as reinforcing agents, as will be described, demonstrated and demonstrated below. The novel additives cause unexpected, valued and technically surprising properties in the silicate builders, the rubber compositions and the vulcanizates obtained, and thus the rubber compositions comprise rubber, a crosslinking system, sulfur-containing organcsilanes, fillers and finally other conventional excipients. The invention is thus characterized in that the rubber compositions comprise as reinforcing agent one or more organosanes of the general formula I

<td>Z — alk — S_n—Alk—</td><td>-OF</td><td>AND,</td>

<td>where</td><td></td><td></td>

<td>Z is from the group</td><td></td><td></td>

<td>Ri</td><td>Ri</td><td>Rž</td>

<td> /</td><td> /</td><td> /</td>

<td>—Si — Ri -</td><td>Si — Rž</td><td>—Si — Rz,</td>

<td> \ .</td><td> \</td><td> \</td>

<td>Rž</td><td>Rž</td><td>Rž</td>

up to 8 carbon atoms or a straight or branched alkyl mercapto group having 1 to 8 carbon atoms, and wherein R 1 and R a are the same or different, alk being a divalent or unsaturated, straight or branched hydrocarbon radical having 1 to 18, in particular with 1 to 6, preferably 2 to 3 carbon atoms and n is a number from 2 to 6, in particular between 2 and 4, as well as one or more silicate builders, optionally in admixture with carbon black.

The rubber mixtures also contain at least one organosilane, in particular, one or two, preferably one, of the aforementioned general formula (I), in which Z represents a compound from the group consisting of:

Rz / - —Sl — R, \ Rz in which denotes

R 2 is C 1 -C 8 alkoxy, preferably 1 to 4 carbon atoms, and an alk saturated hydrocarbon radical having 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms.

Thus, the selected novel compounds have two or more sulfur atoms in the center of the nearly symmetrically built molecule and two separate, to some extent terminal silane groups. This structure of the molecule was believed to result in the excellent properties of the new curing agent.

The 3-mercapto-propyitrimethoxysilane selected above increases significantly the tensile strength, the fracture strength, the abrasion resistance, the compressive strength and the Shore hardness in the rubber compositions containing the silicic acid filler.

On the other hand, it is undesirable to influence the vulcanization time and defo - elasticity of the unvulcanized mixtures. Vulcanization times are drastically shortened. In the production of such mixtures in a kneading machine, often vulcanization occurs prematurely, which makes it impossible to further process the mixture.

The defo-elasticity is increased, which means an increase in the elastic fractions in the raw mixture and the difficulty of further processing such as spraying.

These new reinforcing agents contained in rubber compositions, on the other hand, exhibit significant technical advantages relative to the properties of the raw compositions and vulcanizates as compared to the prior art. Thus, in particular, the raw mixtures give a hitherto unknown processing certainty a strong reduction in stiffness and only a slight increase in Defo 'elasticity.

All these advantageous properties or effects for the first time open the way for the industrial use of these mixtures. The properties of the obtained vulcanizates are excellent and are commensurate with those corresponding to which

R 1 is C 1 -C 4 alkyl or phenyl,

R 2 is an alkoxy group having 1 to 8, preferably up to 4 carbon atoms, a cycloalkyl group having 5 carbon blacks of filled vulcanizates, or these, as will be shown below, even surpassing them. These improvements in the properties of raw mixtures and vulcanizates open up the field for the first time. For silicate fillers, nail as reinforcing fillers have so far been used only carbon black.

The term "silicate filler" is a broad term and refers to rubber-acceptable or workable rubber fillers which are proven to be suitable for the silicates group, or which also contain silicates chemically bound, including mixtures of two or more silicates fillers. For. silicate fillers are especially considered:

High. a silica (silica) dispersion having a specific surface area in the range of from 5 to 1000, preferably from 20 to 100. '400 m²g / g, determined according to the known BET measurement method with nitrogen gas and with a particle size of 10.10 ~ 9 m to 400.10 &amp; lt; 9 &amp; gt ;, which can be produced, for example, by precipitation from silicate solutions, hydrolysis or oxidation reaction at high temperature, also called flame hydrolysis, from volatile halide horseradish. or in an electric arc. These silicas may optionally act as mixed oxide, or. as a mixture of silica with oxides of aluminum, magnesium, calcium, barium, zinc, zirconium or optionally. also titanium.

Synthetic silicates, for example aluminum silicate or alkaline earth metal silicates, such as magnesium silicate or calcium silicate with a specific surface area of ​​20 to 400 m²/ gas primary particle size from 10.10 ~⁹ do 400.10⁹meters.

Natural silicates, such as kaolin and asbestos, or natural silicic acid.

Glass fibers and glass fiber products such as meshes, ropes, fabrics, staple fibers and the like, including microspheres.

Known silicate builders can be incorporated in amounts. from about 10 to about 250 parts by weight based on. 100 parts by weight of rubber polymers.

as filler combinations, for example, silicic acid (kaolin or silicic acid) can be glass fibers (asbestos, or components of reinforcing fillers with known types of carbon black for rubber, for example silicic acid) ISAF-carbon black, or silicic acid (glass fiber cord) HAF —- soot.

Typical examples of silicate builders useful in the present invention are, for example, Degussa-produced and marketed silicas or silicates under the trade names Aerosil, Ultrasil, Silteg, Durosil, Extrusil, Calsil and the like.

Furthermore, various additives, as is known and widely used in the rubber industry, can be admixed to the rubber compositions.

Numerous advantages are obtained when the additive according to the invention is not added to the rubber mixtures as such, but first when a mixture consisting of at least one silicate filler and at least one organosilane of the aforementioned general formula I is prepared and then mixed, possibly later, into rubber blends, optionally into the other components of the rubber blends in the usual manner and using conventional mixing equipment, then mixed uniformly. ·

In the preparation of the mixture, a still viscous, practically dry product is then formed when the silicate filler is admixed in the same or even in a larger quantity to the liquid nrganosilane. Thus, it is also possible to add only one portion of the necessary fillers in the manufacture of the rubber fillers, which contains all the necessary amounts of silanes directly in the premixing.

Examples of organosilanes of formula I above are:

Bis- [trialkoxysilyl-alkyl- [1)] -polysulfides such as [2-trimetexes, -trietoxy, -tri- (methylethoxy) -, -tripropoxy-, -tributoxy-, etc., up to -trioctyloxysllyl-ethyl) -sulfuccinides, namely di-, tri-, tetra-, penta-, and hexasulfides, further bis- [3-trimethoxy-, -triethoxy-, -tri- (methylethoxy) -, -tributoxy-, -tripropoxy-, and the like up to -trioctyl-oxypropyl) -polysulfides, further di-, tri-, tetra-, and the like up to hexasulfides, hereinafter. other suitable bis- [3-trialkoxysilyl-isobutyl) -polysulfides, suitable bis- [4-trialkoxysilyl-butyl) -polysulfides and the like up to bis- [6-trialkoxysilylhexyl] -polysulfides. Of these selected, relatively simple-built organosilanes of the formula I, Ins- [3-trimethoxy-, -triethoxy-, and -tripropoxysilyl-propyl) -polysulfides, namely di-, tri-, and tetrasulfides, are preferred. These and other organosilanes of the above general formula (I) useful with good results can be prepared, for example, according to the procedure described in, for example, DOS No. 2,141,159, DOS No. 2,141,160 and 2,212,239.

The novel thickners used according to the invention can be admixed to the rubber mixtures in an amount of from 0.1 parts by weight, preferably in the range of 0.5 to 25 parts by weight, based on 100 parts by weight of the starting rubber.

In use, organosilanes may be used. directly added to the rubber mixtures or to the components of these mixtures. It is not desirable to hydrolyze the useful organosilanes prior to mixing.

However, the disclosed organosilicate compounds may also be admixed, particularly with the possibility of careful dosing and handling, in part to the required filler, whereby liquid organosilanes may be converted into a powdered product and thus rendered more suitable for use. Optionally, it is also possible to deposit the organosilanes on the surface of the filler particles. and to use them in this form, but this is not associated with any major advantage. The two or three options described above may also be combined.

The rubber mixtures may be made from one or more kinds, optionally oil-adjusted, natural or synthetic rubbers. These include, in particular, natural rubbers, synthetic rubbers, in particular diene elastomers, such as butadiene, isoprene, butadiene and styrene, butadiene and acrylonitrile, or 2-chlorobutadlene, butyl rubber and halogenated butyl rubber; furthermore, known diene rubbers such as terpolymers of ethylene, propylene and optionally unconjugated dienes, transpolypentamer, carboxyl rubber, or epoxy rubber and the like known elastoniers remain. Also suitable for use are chemical derivatives of natural rubber and modified natural rubbers within the meaning of the invention.

Silicone fillers and organosilane additives, optionally known reaction accelerators, as well as one or more compounds of the group may be attached to the organic polymer rubber blends; anti-aging agents, heat stabilizers, light retardants, tackifiers, blowing agents, dyes, pigments, waxes, ozone stabilizers, processing aids, plasticizers, fillers such as wood flour, organic acids such as acid stearic acid, benzoic acid, salicilic acid, and further: · lead oxide or zinc oxide, · activators such as triethanolamine, polyethylene glycol, or hexanitrol, where all substances are known in the rubber technology and industry. In the vulcanization, the rubber mixtures are admixed with general crosslinking agents such as, in particular, peroxides, sulfur or, in particular, magnesium oxide, or optionally vulcanization accelerators, or mixtures thereof.

The production of rubber compounds as well as molding and vulcanization are based on the current needs of the rubber industry.

Industrial applications for the rubber compounds described are, for example:

Technical rubber goods such as cable sheaths, drive belts, V-belts, conveyor belts, passenger and truck tire treads, tire carcasses and tire sidewalls, off-road tires, shoe soles, sealing rings, damping components and many others. New rubber compositions have also proven to be useful as a.fibre mixtures for glass fibers and the like.

The following describes examples of instructions for rubber compositions with test results for vulcanizates and uses, or comparisons of these results without limiting the invention in any way. In the following, many different expressions are repeated so that uniform abbreviations can be used.

List of abbreviations used

<td>Abbreviation</td><td>Importance</td><td>measured</td>

<td>DH</td><td>Defo - hardness</td><td>G</td>

<td>DE</td><td>Defo - flexibility</td><td></td>

<td>t5</td><td>Mooney - Scorch</td><td>min.</td>

<td>t3 5</td><td>M-ooney - Cure</td><td>min.</td>

<td>ML 4</td><td>Mooney plasticity at 100 ° C, standard rotor, test duration: 4 min.</td><td></td>

<td>spec. in.</td><td>specific gravity</td><td>g / cm³</td>

<td>VZ</td><td>vulcanization time</td><td>min.</td>

<td>VT</td><td>vulcanization temperature</td><td>Noc: 2 ° C</td>

<td>ZF</td><td>tensile strength</td><td>kp / cm³</td>

<td>M 300</td><td>value of voltage at 300% elongation</td><td>kp / cm³</td>

<td>BD</td><td>ductility</td><td> %</td>

<td>bl. D</td><td>residual elongation after rupture</td><td> %</td>

<td>E</td><td>elasticity</td><td> %</td>

<td>SH</td><td>A - Shore hardness</td><td> —</td>

<td>EF</td><td>• resistance to further tearing</td><td>kp / cm</td>

<td>AND</td><td>Abrasion (also "DIN Abrasion")</td><td>mm3</td>

<td>AT</td><td>temperature increase (according to Goodrich flexometer)</td><td>Noc: 2 ° C</td>

Test standards

Physical tests were carried out at room temperature according to the following standards:

<td>tensile strength, ductility</td><td></td><td></td><td></td>

<td>voltage value to 6 mm</td><td></td><td></td><td></td>

<td>solid circle</td><td>DIN</td><td> 53</td><td> 504</td>

<td>resistance to further tearing</td><td>DIN</td><td> 53</td><td> 507</td>

<td>compression elasticity</td><td>DIN</td><td> 53</td><td> 512</td>

<td>A - Shore hardness</td><td>DIN</td><td> 53</td><td> 505</td>

<td>specific gravity</td><td>DIN</td><td> 53</td><td> 550</td>

Mooney - test DIN 53 524

Goodrich flexometer (Heat build-np.AT) ASTM D 623-62 Abrasion DIN 53 516

The vulcanizates were always produced in a steam-heated transfer press at the indicated vulcanization temperature.

- In the examples, the amounts of the constituents of the mixtures are always given in parts by weight.

Example. 1

<td>Starting materials</td><td>mixture 1</td><td>mixture 2</td><td>mixture 3</td>

<td>Natural rubber</td><td> 100</td><td> 100</td><td> 100</td>

<td>21.00 Ribbed Smoked Sheets I pentachlorothiophenyl-zinc</td><td> 0,25</td><td> 0,25</td><td> 0,25</td>

<td>salt (Rcnacit IV Farbepfabrik BAYER, Leverkusen) finely divided, precipitated silica</td><td> 40</td><td> 40</td><td> 40</td>

<td>(ULTRASIL VN 3, DEGUSSA) Zinc oxide</td><td> 3</td><td> 3</td><td> 3</td>

<td>stearic acid</td><td> 2</td><td> 2</td><td> 2</td>

<td>3-mercaptopropyltrimethoxy- Sílan</td><td></td><td> 2</td><td></td>

<td>bis- (3-trimethoxysilyl-propyl) -trisulfide</td><td></td><td></td><td> 2</td>

<td>dibenzothiazyldisulfide</td><td> 0,8</td><td> 0,8</td><td> 0,8</td>

<td>diphenylguanidine</td><td> 2,25</td><td> 2,25</td><td> 2,25</td>

<td>sulfur</td><td> 2,5</td><td> 2,5</td><td> 2,5</td>

Mixing method

Mixed in a kneading machine at a flow temperature of 80 ° C.

Additions or operations finished after natural rubber 0 min.

1/2 quantity of silicic acid 1 min. and stearic acid

1/2 quantity of silicic acid, zinc oxide and organosilane 2.5 min.

Additions or operations finished · after cleaning, ventilation 4 'min.

termination 4.5 min.

The mixture was allowed to lie for 24 hours. Then the mixture was finally stirred in a kneading machine at 80 ° C. (Stirring time 1.5 min.).

Properties of unvulcanized mixture

<td></td><td>mixture 1</td><td>mixture 2</td><td>mixture 3</td>

<td>DH / DE</td><td> 675/20</td><td>vulcanized</td><td> 650/20</td>

<td>t5</td><td> 6,4</td><td> —</td><td> 5,0</td>

<td>t3 5</td><td> 7,5</td><td> — ’</td><td> 5,8</td>

<td>ML 4</td><td> 57</td><td>232 (rising)</td><td> 54</td>

<td>spec. in.</td><td> 1,13</td><td> 1,13</td><td> 1,13</td>

Properties of vulcanized mixture

Vulcanization temperature: 150 ° C

<td>mixture</td><td>vz</td><td>ZF</td><td>M 300</td><td>BD</td><td>bl.D</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 10</td><td> 256</td><td> 62</td><td> 622</td><td> 41</td><td> 50</td><td> 62</td><td> 39</td><td> 165</td>

<td></td><td> 20</td><td> 250</td><td> 58</td><td> 630</td><td> 43</td><td> 47</td><td> 64</td><td> 31</td><td> 165</td>

<td></td><td> 40</td><td> 229</td><td> 48</td><td> 640</td><td> 37</td><td> 46</td><td> 62</td><td> 35</td><td> 165</td>

<td></td><td> 60</td><td> 227</td><td> 42</td><td> 678</td><td> 33</td><td> 45</td><td> 62</td><td> 35</td><td> 165</td>

<td> 2</td><td></td><td></td><td>falls away</td><td>considering</td><td colspan="2">to premature</td><td colspan="2">vulcanizing</td><td></td>

<td> 3</td><td> 10</td><td> 274</td><td> 95</td><td> 558</td><td> 41</td><td> 47</td><td> 63</td><td> ' 27 '</td><td> 140</td>

<td></td><td> 20</td><td> 257</td><td> 94</td><td> 548</td><td> 36</td><td> 48</td><td> 64</td><td> 29</td><td> 140</td>

<td></td><td> 40</td><td> 262</td><td> 84</td><td> 580</td><td> 35</td><td> 48</td><td> 61</td><td> 25·</td><td> 140</td>

<td></td><td> 60</td><td> 242</td><td> 76</td><td> 582</td><td> 28</td><td> 47</td><td> 61</td><td> 27</td><td> 140</td>

Example 2

<td>Starting materials</td><td>mixture 1</td><td>mixture 2</td><td>mixture 3</td>

<td>cis-1,4-polyisoprene rubber</td><td> 100</td><td> 100</td><td> 100</td>

<td>fine-grained, precipitated silica (ULTRASIL VN3, DEGUSSA)</td><td> 50</td><td> 50</td><td> 50</td>

<td>plasticizer (naphthenic hydrocarbon)</td><td> 3</td><td> 3</td><td> 3</td>

<td>Zinc oxide (active)</td><td> 2</td><td> 2</td><td> 2</td>

<td>anti-aging agent (mixture of aralkylated phenols)</td><td> 1</td><td> 1</td><td> 1</td>

<td>mixture of equal parts of fine-grained, precipitated silica and hexanitrole (activator, DEGUSSA)</td><td> 4</td><td> 4</td><td> 4</td>

<td>benzoic acid</td><td> 0,8</td><td> 0,8</td><td> 0,8</td>

<td>3-mercaptopropyltrimethoxysilane</td><td> —</td><td> 1,5</td><td> —</td>

<td>bis- [3-triethoxysilylpropyl] -tetrasulfide</td><td> —</td><td> —</td><td> 1,5</td>

<td>dibenzůthiazyldisulfid</td><td> 0,8</td><td> 0,8</td><td> 0,8</td>

<td>diphenylguanidine</td><td> 1,6</td><td> 1,6</td><td> 1,6</td>

<td>sulfur</td><td> 2,5</td><td> 2,5</td><td> 2,5</td>

<td>Mixing method</td><td></td><td colspan="2">Allowances or operations ended after</td>

<td colspan="2">Mixed in a kneading machine at 80 ° C.</td><td>plasticizer,</td><td>zinc oxide</td>

and organosilane 2.5 min.

<td>Additions or actions</td><td colspan="2">finished after</td><td>cleaning, ventilation 4 11 Insuring 4 5</td><td>min. min</td>

<td>cis-1,4-polyisoprene rubber 1/2 quantity of silicic acid,</td><td> 0</td><td>min.</td><td colspan="2">This mixture was after twenty-four hours</td>

<td>stearic acid 1/2 quantity of silicic acid,</td><td> 1</td><td>min.</td><td>The agitation at 80 ° C was finally stirred in the melter (stirring time 1.5 min:).</td><td>hne-</td>

Properties of unvulcanized mixture mixture 1 mixture 2 mixture 3

DH / DE 1500./6,0 vulcanization 1375 / 7.0 t5 9.2 —6.5 t3 5 11.6 —8.4

ML 4 100 154 (rises) 91 Special v 1.13 1,141,14

Properties of vulcanized mixture · vulcanization temperature: 134 ° C

<td>mixture</td><td>VZ</td><td>THAT</td><td>M 300</td><td>BD</td><td>bl.D</td><td colspan="2">E SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 10</td><td> 136</td><td> 21</td><td> 707</td><td> 17</td><td> 33</td><td> 48</td><td> 20</td><td> 196</td>

<td></td><td> 20</td><td> 198</td><td> 27</td><td> 742</td><td> 24</td><td> 36</td><td> 59</td><td> 30</td><td> 196</td>

<td></td><td> 30</td><td> 215</td><td> 31</td><td> 733</td><td> 30</td><td> 36</td><td> 61</td><td> 28</td><td> 196</td>

<td></td><td> 40</td><td> 220</td><td> 34</td><td> 723</td><td> 34</td><td> 38</td><td> 61</td><td>Ž3</td><td> 196</td>

<td> 2</td><td></td><td colspan="2">not applicable due to</td><td colspan="3">premature vulcanization</td><td></td><td></td><td></td>

<td> 3</td><td> 10</td><td> 199</td><td> 47</td><td> 632</td><td> 23</td><td> 40</td><td> 63</td><td> 40</td><td> 158</td>

<td></td><td> 20</td><td> 242</td><td> 63</td><td> 640</td><td> 31</td><td> 42</td><td> 68</td><td> 44</td><td> 158</td>

<td></td><td> 30</td><td> 266</td><td> 79</td><td> 628</td><td> 36</td><td> 43</td><td> 71</td><td> 41</td><td> 158</td>

<td></td><td> 40</td><td> 272</td><td> 87</td><td> 620</td><td> 41</td><td> 44</td><td> 72</td><td> 43</td><td> 158</td>

In Examples 1 and 2, rubber mixtures based on natural rubber or synthetic cis-1,4-polyisoprene are used which contain a finely divided silicic acid precipitated as a silicate filler. Bis- [3-trimethoxysilyl-propyl] -trisulfide and bis- [3-triethoxysilyl-propyl] -1-tetrasulfide were used as reinforcing agents for the rubber mixtures, and 3-mercaptopropyltrimethoxysilane was used as a comparator in the prior art. As the properties of the unvulcanized composition have already shown, the production of the composition in a kneading machine suitable for practice only results in the further processing of the raw mixture when the rubber composition according to the invention is formulated, whereas the comparative mixtures cannot be further processed due to premature vulcanization.

Polysulfide organosilanes shorten the vulcanization times ts and ts 5 in the mixture only slightly and have no negative effect on the Mooney plasticity (ML 4) or the DH / DE ratio compared to the mixture without the organosilane additive.

The properties of the vulcanizates of the new rubber compositions are improved compared to the composition without organosilane, slightly tensile strength and clearly the stress value (M 300), thereby achieving the reinforcing effect according to the invention and proven by documented numbers.

Finally, the mixture 3 in Example 2 exhibits an extremely high resistance to further tearing.

Example 3

<img file="CS198130B2_D0001.tif" />

Starting materials mixture 1 mixture 2 mixture 3

<td>styrene-butadiene rubber Buna Hiils 1502</td><td> 100</td><td> 100</td><td> 100</td>

<td>precipitated aluminum silicate (SILTEG AS 7, DEGUSSA)</td><td> 40</td><td> 40</td><td> 40</td>

<td>Zinc oxide (active)</td><td> 3</td><td> 3</td><td> 3</td>

<td>stearic acid</td><td> 1</td><td> 1</td><td> 1</td>

<td>Coumarone resin (B 1/2 85 °)</td><td> 5</td><td> 5</td><td> 5</td>

<td>a mixture of equal parts of fine-grained, precipitated silica</td><td> 5</td><td> 5</td><td> 5</td>

and hexanitrole (DEGUSSA Activator)

Starting materials mixture 1 mixture 2 mixture 3

<td>anti-aging agent (mixture of aralkylated phenols)</td><td> 1</td><td> 1</td><td> 1</td>

<td>3-mercaptopropyltrimethoxysilane</td><td> —</td><td> 1,5</td><td> —</td>

<td>bis- (triethoxysilyl propyl) -tetrasulfide</td><td> —</td><td> —</td><td> 1,5</td>

<td>benzothiazole-2-cyclohexylsulphenamide</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>

<td>diphenylguanidine</td><td> 0,8</td><td> 0,8</td><td> 0,8</td>

<td>sulfur</td><td> 2,0</td><td> 2,0</td><td> 2,0</td>

Mixing method

Additions or actions completed after

Mixed in a kneading machine at 80 ° C.

Additions or operations finished after polymer (SBR) 0

1/2 amount of aluminum silicate, stearic acid and anti-aging agent1

1/2 amount of aluminum silicate, plasticizer, zinc oxide, organosilane, others ct2,5 cleaning, ventilation4 termination4,5

Accelerator and sulfur were added to the cylinder (mixing time 1.5 min.).

Properties of unvulcanized mixture mixture 1 mixture 2 mixture 3

<td>t5</td><td> 4,9</td><td> __</td><td> 3,1</td>

<td>t3 5</td><td> 5.9</td><td> —</td><td> 4,3</td>

<td>ML 4</td><td> 78</td><td>196 (rising)</td><td> 82</td>

<td>spec. in.</td><td> 1,16</td><td> 1,16</td><td> 1,16</td>

Properties of vulcanized mixture vulcanization temperature: 150 ° C

<td>mixture</td><td>VZ</td><td>ZF</td><td>M 300</td><td>BD</td><td>bl.D</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 8</td><td> 127</td><td> 39</td><td> 610</td><td> 19</td><td> 47</td><td> 58</td><td> 5</td><td> 160</td>

<td></td><td> 10</td><td> 140</td><td> 40</td><td> 630</td><td> 21</td><td> 47</td><td> 58</td><td> 4</td><td> 160</td>

<td></td><td> 15</td><td> 146</td><td> 41</td><td> 690</td><td> 18</td><td> 47</td><td> 58</td><td> 5</td><td> 160</td>

<td></td><td> 20</td><td> 121</td><td> 41</td><td> 583</td><td> 16</td><td> 47</td><td> 58</td><td> 4</td><td> 160</td>

<td> 2</td><td></td><td>falls away</td><td>considering</td><td colspan="2">to the previous one</td><td colspan="2">vulcanizing</td><td></td><td></td>

<td> 3</td><td> 8</td><td> 142</td><td> 78</td><td> 560</td><td> 15</td><td> 50</td><td> 59</td><td> 6</td><td> 132 ,</td>

<td></td><td> 10</td><td> 140</td><td> 69</td><td> 528</td><td> 13</td><td> 50</td><td> 59</td><td> 5</td><td> 132</td>

<td></td><td> 15</td><td> 130</td><td> 71</td><td> 465</td><td> 11</td><td> 51</td><td> 60</td><td> 4</td><td> 132</td>

<td></td><td> 20</td><td> 121</td><td> 72</td><td> 500</td><td> 13</td><td> 51</td><td> 60</td><td> 5</td><td> 132</td>

Example 4

<td>starting materials</td><td>mixture 1</td><td>mixture 2</td><td>mixture 3</td>

<td>styrene-butadiene rubber</td><td></td><td></td><td></td>

<td>(Buna Hols 1502)</td><td> 100</td><td> 100</td><td> 100</td>

<td>fine-grained, precipitated</td><td></td><td></td><td></td>

<td>Silicic acid (ULTRA-</td><td></td><td></td><td></td>

<td>SIL VN 3, DEGUSSA)</td><td> 50</td><td> 50</td><td> 50</td>

<td>zinc oxide</td><td></td><td></td><td></td>

<td>(active)</td><td> 1</td><td> 1</td><td> 1</td>

<td>stearic acid</td><td> 2</td><td> 2</td><td> 2</td>

<td>anti-aging agent</td><td></td><td></td><td></td>

<td>(mixture of aralkylated phenols)</td><td> 1</td><td> 1</td><td> 1</td>

<td>polyethylene glycol</td><td></td><td></td><td></td>

<td>(PEG 4000)</td><td> 2</td><td> '2</td><td> 2</td>

<td>3'inerkaptopropyltri-</td><td></td><td></td><td></td>

<td>inetoxysilane</td><td> —</td><td> —</td><td> — ‘</td>

<td>bis- f 3-trimethoxysilyl-</td><td></td><td></td><td></td>

<td>propyl disulfide</td><td> —</td><td> —</td><td> 2</td>

<td>dibenzothiazyldisulfide</td><td> 1</td><td> 1</td><td> 1</td>

<td>diphenylguanidine</td><td> 2</td><td> 2</td><td> 2</td>

<td>sulfur</td><td> 2</td><td> 2</td><td> 2</td>

<td>Mixing method</td><td></td><td colspan="2">Additions "eventually finished" after</td>

<td colspan="2">The mixture is mixed in a kneading machine at a temperature</td><td colspan="2">zinc oxide, organosilane,</td>

<td>80 ° C</td><td></td><td>other chemicals</td><td>..... 2.5 min.</td>

<td></td><td></td><td>cleaning, ventilation</td><td>4 min.</td>

<td>Additions or actions</td><td>finished after</td><td>end</td><td>4.5 min.</td>

<td>polymer</td><td>0 min</td><td colspan="2">&gt; After stirring for 24 hours, the mixture was</td>

<td>1/2 quantity of silicic acid,</td><td></td><td>mixed in the mixing</td><td>machine (mixing time</td>

<td>stearic acid, composition</td><td></td><td>1.5 min).</td><td></td>

<td>anti aging</td><td>1 min</td><td></td><td></td>

<td>1/2 quantity of silicic acid,</td><td></td><td colspan="2">Properties of unvulcanized mixture</td>

<td></td><td>mixture 1</td><td>mixture 2</td><td>mixture 3</td>

<td>DH / DE</td><td> 2250/19,5</td><td>vulcanized</td><td> 2050/31,0</td>

<td>t5</td><td> 8,1</td><td> —</td><td> 7,8</td>

<td>t3 5</td><td> 10,0</td><td> —</td><td> 9,6 ·</td>

<td>ML 4</td><td> 143</td><td>242 (rising)</td><td> 116</td>

<td>spec. in.</td><td> 1,16</td><td> 1,16</td><td> 1,17</td>

Properties of vulcanized mixture vulcanization temperature: 150 ° C

<td>mixture</td><td>vz</td><td>ZF</td><td>M 300</td><td>BD</td><td>bl.D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 5</td><td> 170</td><td> 40</td><td> 660</td><td> 40</td><td> 33</td><td> 71</td><td> 17</td><td> 126</td>

<td></td><td> 10</td><td> 174</td><td> 42</td><td> 640</td><td> 34</td><td> 33</td><td> 72</td><td> 14</td><td> 126</td>

<td></td><td> 15</td><td> 178</td><td> 41</td><td> 625</td><td> 31</td><td> 33</td><td> 71</td><td> 13</td><td> 126</td>

<td></td><td> 20</td><td> 196</td><td> 42</td><td> 647</td><td> 32</td><td> 33</td><td> 71</td><td> 14</td><td> 126</td>

it is not necessary due to the previous vulcanization

<td>mixture VZ</td><td>ZF</td><td>M 300</td><td>BD</td><td>E</td><td>SH EF</td><td>AND</td><td>bl.D.</td>

<td> 3 5</td><td> 208</td><td> 63</td><td> 592</td><td> 32</td><td> 70 17</td><td> 89</td><td> 33</td>

<td> 10</td><td> 222</td><td> 77</td><td> 548</td><td> 32</td><td> 71 13</td><td> 89</td><td> 29</td>

<td> 15</td><td> 222</td><td> 85</td><td> 523</td><td> 32</td><td> 70 14</td><td> 89</td><td> 24</td>

<td> 20</td><td> 216</td><td> 85</td><td> 513</td><td> 32</td><td> 71 13 .</td><td> 89</td><td> 21</td>

<td>Example 5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>starting materials</td><td></td><td>mixture</td><td> 1</td><td>mixture</td><td> 2</td><td>mixture 3</td><td></td>

<td colspan="2">styrene-butadiene rubber</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>(Buna Hiils 1500)</td><td></td><td> 100</td><td></td><td> 100</td><td></td><td> 100</td><td></td>

<td>colloidal kaolin</td><td></td><td> 75</td><td></td><td>7á</td><td></td><td> 75</td><td></td>

<td>zinc oxide</td><td></td><td> 4</td><td></td><td> 4</td><td></td><td> 4</td><td></td>

<td>stearic acid</td><td></td><td> 2</td><td></td><td> 2</td><td></td><td> 2</td><td></td>

<td>3-mercaptopropyltri- methoxysilane</td><td></td><td> —</td><td></td><td> 2,5</td><td></td><td> —</td><td></td>

<td>bis- (3-triethoxysilyl-propyl) -tetrasulfide</td><td></td><td></td><td></td><td></td><td></td><td> .2,5</td><td></td>

<td>dibenzothiazyldisulfide</td><td></td><td> 1,2</td><td></td><td> 1,2</td><td></td><td> 1,2.....</td><td></td>

<td>diphenylguanidine</td><td></td><td> 1,2</td><td></td><td> 1,2</td><td></td><td> 1,2</td><td></td>

<td>sulfur</td><td></td><td> 2,75</td><td></td><td colspan="2"> 2,75</td><td> 2,75</td><td></td>

<td>Mixing method</td><td></td><td></td><td></td><td>Additions,</td><td colspan="3">eventually finished after</td>

<td colspan="2">Mixed- - in a 'mixing' machine</td><td>at temperature</td><td>80 ° C</td><td>end</td><td></td><td></td><td>4.5 - min.</td>

<td colspan="2">Additions or actions</td><td colspan="2">finished after</td><td colspan="3">The mixture is left to stand for 24 hours</td><td>finally</td>

<td></td><td></td><td></td><td></td><td rowspan="2">stirred</td><td rowspan="2">at 80</td><td rowspan="2">% (time</td><td rowspan="2">stirring</td>

<td></td><td></td><td></td><td></td>

<td>rubber</td><td></td><td> 0</td><td>min.</td><td>1.5 min).</td><td></td><td></td><td></td>

1/2 amount of kaolin, oxide

<td>zinc, organosilane</td><td></td><td>2.5 min.</td><td>Properties</td><td>unvulcanized - mixtures</td>

<td>cleaning, ventilation</td><td></td><td>4 min.</td><td></td><td></td>

<td></td><td>mixture 1</td><td></td><td>mixture 2</td><td>mixture 3</td>

<td>DH / DE</td><td> 1750/27</td><td></td><td> 2550/32,5</td><td> 1450/23,5</td>

<td>ts</td><td> 34,0</td><td></td><td> 6,6</td><td> 29,2</td>

<td>t3 5</td><td> 41,3</td><td></td><td> 11,6</td><td> 38,2</td>

<td>ML - - 4 -......</td><td> 63</td><td></td><td> 80</td><td> 61</td>

<td>spec. in.</td><td> 1,32</td><td></td><td> 1,32</td><td> 1,32</td>

Properties of vulcanized mixture

<td colspan="3">vulcanization temperature: 150%</td><td rowspan="2">M 300</td><td rowspan="2">BD</td>

<td>mixture</td><td>VZ</td><td>ZF</td>

<td> 1</td><td> 15</td><td> 101</td><td> 50</td><td> 635</td>

<td></td><td> 30</td><td> 99</td><td> 66</td><td> 483</td>

<td></td><td> 45</td><td> 96</td><td> 65</td><td> 490</td>

<td></td><td> 60</td><td> 94</td><td> 64</td><td> 480</td>

<td> 2</td><td> 15</td><td> 154</td><td> 137</td><td> 335</td>

<td></td><td> 30</td><td> 146</td><td> 138</td><td> 307</td>

<td></td><td> 45</td><td> 145</td><td> 138</td><td> 305</td>

<td></td><td> 60</td><td> 147</td><td> 143</td><td> 303</td>

<td>bl.D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 53</td><td> 45</td><td> 64</td><td> 13</td><td> 268</td>

<td> 36</td><td> 42</td><td> 67</td><td> 6</td><td> 268</td>

<td> 34</td><td> 40</td><td> 66</td><td> 6</td><td> 268</td>

<td> 34</td><td> 40</td><td> 67</td><td> 9</td><td> 268</td>

<td> 18</td><td> 45</td><td> 67</td><td> 8</td><td> 210</td>

<td> 13</td><td> 44</td><td> 68</td><td> 5</td><td> 210</td>

<td> 10</td><td> 43</td><td> 68</td><td> 5</td><td> 210</td>

<td> 11</td><td> 42</td><td> 67</td><td> 5</td><td> 210</td>

2.1 mixture VZ ZF M 300 BD bl.D. E

SH E'F A

M 200

<td> 3</td><td> 15</td><td> 125</td><td> 77</td><td> 440</td>

<td></td><td> 30</td><td> 125</td><td> 101</td><td> 287</td>

<td></td><td> 45</td><td> 125</td><td> 102</td><td> 262</td>

<td></td><td> 60</td><td> 129</td><td> 104</td><td> 293</td>

<td> 22</td><td> 42</td><td> 66</td><td> 8</td><td> 223</td>

<td> 14</td><td> 41</td><td> 69</td><td> 5</td><td> 223</td>

<td> 10</td><td> 40</td><td> 69</td><td> 5</td><td> 223</td>

<td> 14</td><td> 39</td><td> 69</td><td> 4</td><td> 223</td>

In Examples 3 to 5, rubber blends based on blended butadiene-styrene polymers containing synthetic aluminum silicate or natural silicate (colloidal kaolin) as silicate filler are used. Suitable organosilane additives include bis- (3-triethoxysilyl-propyl) -tetrasulfide and bis- (3-trimethoxysilyl-propyl) -disulfide; these were compared to 3-mercaptopropyltrimethoxysilane (prior art) in otherwise identical mixtures.

According to Examples 3 and 4, a ductile mixture with 3-mercaptopropyltrimethoxysilane with conditions suitable for practice without premature vulcanization was not possible, while this is suitable for rubber mixtures with polysulfide organosilanes without problems.

The properties of the new rubber blend vulcanizates are substantially improved compared to the same blends without the silane additive: tensile strength and stress value are increased, the residual elongation after rupture is reduced, and abrasion is improved.

Example 5 shows that these effects also work with relatively inactive silicate fillers such as colloidal kaolin.

Example 5 also demonstrates, with respect to the properties of the unvulcanized compositions, a marked progress of the present invention over the prior art: 3-mercaptopropyltrimethoxysilane increases DH / / DE and ML4 values ​​as part of the mixture and greatly reduces the vulcanization portion t5. In the case of the new rubber mixtures, on the other hand, the DH / DE and ML 4 values ​​are changed in a positive sense, while the vulcanization portion t5 is not substantially altered with respect to the reference mixture.

The following Examples 6-9 show that the new rubber mixtures can be produced with the same good result also on the basis of a mixed polymer of butadiene-acrylonitrile, butyl rubber, polychloroprene rubber, or ethylene-propylene terpolymers.

EXAMPLE 6 Starting Material Mixture 1 Butadiene-Acrylonitrile Rubber (Perbutan N 3310 Farbenfabriken Bayer AG) 100 Heat-treated Silicic Acid (Aerosil 130 V)

DEGUSSA) 40 Zinc oxide4 Bis- (3-triethoxysilylpropyl) -Tetrasulfide-dibenzothiazyl disulfide1,5 Diphenylguanidine 1,5 Mixture 2

100

1,5

1,5

1.5 sulfur

2,75

2,75

Mixing method

Mixed in a mixer at 80 ° C

Additions or operations finished after butadiene-acrylonitrile-rubber 0 min.

1/2 quantity of silicic acid, stearic acid 1 min.

1/2 quantity of silicic acid,

Additions or operations finished after zinc oxide, organosilane 2.5min.

cleaning, ventilation 4min.

ending 4,5min.

After standing for 24 hours, the mixture is finally stirred in a mixer at 80 ° C.

mixture 2

Properties of the unvulcanized mixture mixture 1

DH / DE t5 tJ 5

ML 4 spec. in.

2550/26

10,6

13,4

132

1,21

1950/31

7.8

9.8

105

1,20

<td colspan="3">Properties of vulcanized mixture</td><td rowspan="3">BĎ</td><td rowspan="3">bl.D.</td><td rowspan="3">E</td><td rowspan="3">SH</td><td rowspan="3">EF</td><td rowspan="3">AND</td>

<td colspan="2">vulcanization temperature: 150 ° C</td><td rowspan="2">M 200</td>

<td>mixture VZ</td><td>ZF</td>

<td> 1 60</td><td> 182</td><td> 99</td><td> 303</td><td> 3</td><td> 18</td><td> 76</td><td> 12</td><td> 107</td>

<td> 80</td><td> 178</td><td> 110</td><td> 285</td><td> 3</td><td> 17</td><td> 77</td><td> 10</td><td> 107</td>

<td> 100</td><td> 161</td><td> 106</td><td> 265</td><td> 2</td><td> 17</td><td> 76</td><td> 12</td><td> 107</td>

<td> 120</td><td> 158</td><td> 109</td><td> 262</td><td> 1</td><td> 17</td><td> 79</td><td> 13</td><td> 107</td>

<td> 2 60</td><td> 200</td><td> 179</td><td> 218</td><td> 1</td><td> 16</td><td> 78</td><td> 7</td><td> 58</td>

<td> 80</td><td> 210</td><td> 189</td><td> 215</td><td> 1</td><td> 16</td><td> 78</td><td> 9</td><td> 58</td>

<td> 100</td><td> 226</td><td> 187</td><td> 215</td><td> 1</td><td> 16</td><td> 77</td><td> 9</td><td> 58</td>

<td> 120</td><td> 228</td><td> 204</td><td> 225</td><td> 2</td><td> 16</td><td> 78</td><td> 8</td><td> 58</td>

<td>Example 7</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>starting materials</td><td></td><td>mixture</td><td> 1</td><td></td><td></td><td>mixture 2</td><td></td><td></td>

<td>butyl rubber</td><td> 100</td><td> 100</td>

<td>fine-grained, precipitated silica (ULTRASIL VN 3 DEGUSSA)</td><td> 50</td><td> 50</td>

<td>zinc oxide</td><td> 5</td><td> 5</td>

<td>stearic acid</td><td> 1</td><td> 1</td>

<td>plasticizer (petroleum oil)</td><td> 5</td><td> 5</td>

<td>bis- (3-triethoxysilylpropyl) -tetrasulfide</td><td> —</td><td> 1,5</td>

<td>2-mercaptobenzothiazole</td><td> 1</td><td> 1</td>

<td>tetramethylthiuram disulfide</td><td> 0,5</td><td> 0,5</td>

<td>sulfur</td><td> 1,5</td><td> 1,5</td>

Mixing procedure

Mixed in a mixer at 60 ° C

Additions or operations terminated after butyl rubber

1/2 quantity of silicic acid, stearic acid2

1/2 quantity of silicic acid, zinc oxide, organosilane, plasticizer 4min.

cleaning, ventilation 6min.

ending 7min.

Mixing was carried out on a roller at a roller temperature of 50 ° C

<td>allowances or actions</td><td>finished after</td>

<td>addition of the starting mixture</td><td>0 min</td>

<td>twice right and left</td><td></td>

<td>pruned</td><td>1 min</td>

<td>accelerator and sulfur</td><td>1 min.</td>

<td>twice right and left</td><td></td>

<td>pruned</td><td>4 min.</td>

<td>pull out the coating mixture</td><td>5 min.</td>

Properties * of unvulcanized mixture mixture 1 mixture 2

DH / DE t5

Í3 5

ML 4 spec. in.

4300/3

1,2

135

1,15

3200/5

2,9

17,6

112

1,15

Properties, vulcanized mixtures vulcanization temperature: 160 ° C

<td>mixture</td><td>VZ</td><td>ZF</td><td>M 300</td><td>BD</td><td>bl.D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 10</td><td> 85</td><td> 19</td><td> 893</td><td> 100</td><td> 12</td><td> 64</td><td> 15</td><td> 270</td>

<td></td><td> 20</td><td> 103</td><td> 23</td><td> 850</td><td> 100</td><td> 13</td><td> 67</td><td> 16</td><td> 270</td>

<td></td><td> 40</td><td> 117</td><td> 27</td><td> 818</td><td> 100</td><td> 13</td><td> 68</td><td> 23</td><td> 270</td>

<td></td><td> 60</td><td> 116</td><td> 28</td><td> 795</td><td> 96</td><td> 13</td><td> 70</td><td> 25</td><td> 270</td>

<td></td><td> 80</td><td> 112</td><td> 28</td><td> 778</td><td> 93</td><td> 13</td><td> 70</td><td> 26</td><td> 270</td>

<td> 2</td><td> 10</td><td> 108</td><td> 27</td><td> 805</td><td> 97</td><td> 11</td><td> 63</td><td> 17</td><td> 227</td>

<td></td><td> 20</td><td> 133</td><td> ' 34</td><td> 773</td><td> 78</td><td> 11</td><td> 64</td><td> 22</td><td> 227</td>

<td></td><td> 40</td><td> 145</td><td> 40</td><td> 738</td><td> 68</td><td> 12</td><td> 67</td><td> 23</td><td> 227</td>

<td></td><td> 60</td><td> 148</td><td> 43</td><td> 708</td><td> 64</td><td> 12</td><td> 69</td><td> 28</td><td> 227</td>

<td></td><td> 80</td><td> 151</td><td> 45</td><td> 693</td><td> 63</td><td> 12</td><td> 69</td><td> 27</td><td> 227</td>

<td>Example 8</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Starting materials</td><td></td><td></td><td></td><td>mixture</td><td> 1</td><td></td><td></td><td>mixture 2</td><td></td>

polychlorobutadiene rubber (Baypren 210, Farbenfabrik

Bayer AG, Leverkusen] 100 di-o-tolylguanidine0,5 magnesium oxide4 stearic acid1 mixture of liquid and soft paraffin (vaseline) 1 phenyl-β-naphthylamine (anti-aging agent) 2 fine-grained, precipitated silica (ULTRASIL VN 2,

DEGUSSA) 50 plasticizer (naphthenic hydrocarbons) 10 bis- (3-triethoxysilyl-propyl) -tetrasulfide-

2-mercaptoimidazoline 0.55 zinc oxide5

100

0,5

1,5

0,75

Mixing method

Mixed in a kneading machine at 60 ° C.

Supplements, resp. operations finished after polychlorobutadiene, guanidine derivative 0 min.

anti-aging agent, magnesium oxide, stearic acid, vaseline, o quantity of silicic acid 1 min.

3 / quantity of silicic acid,

V2 amount of plasticizer, organosilane 2.5 min.

Supplements, resp. operations finished after

Vs amount of silicic acid,

V2 amount of plasticizer, cleaning, ventilation 4 min.

termination and heating on a water bath 5 minutes 5 min.

After lying for 24 hours, the mixture was now mixed in a kneader with 2-mercaptoimidazoline and zinc oxide at 60 ° C and then heated on a water bath for 5 minutes.

Properties of the unvulcanized mixture mixture 1 mixture 2

DH / DE ts 6,25,5 t3 5 10,810,1

ML 4 9184 spec. 1,421.42

Properties of vulcanized mixture

Vulcanization temperature: 150 ° C

<td>mixture</td><td>VZ</td><td>ZF</td><td>M 300</td><td>BD</td><td>bl.D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 10</td><td> 156</td><td> 47</td><td> 810</td><td> 28</td><td> 34</td><td> 57</td><td> 37</td><td> 161</td>

<td></td><td> 20</td><td> 167</td><td> 52</td><td> 790</td><td> 18</td><td> 33</td><td> 61</td><td> 31</td><td> 161</td>

<td></td><td> 30</td><td> 171</td><td> 53</td><td> 742</td><td> 17</td><td> 33</td><td> 62</td><td> 23</td><td> 161</td>

<td></td><td> 40</td><td> 171</td><td> 53</td><td> 735</td><td> 15</td><td> 33</td><td> 62</td><td> 19</td><td> 161</td>

<td> 2</td><td> 10</td><td> 196</td><td> 75</td><td> 673</td><td> 17</td><td> 37</td><td> 60</td><td> 29</td><td> 105</td>

<td></td><td> 20</td><td> 208</td><td> 105</td><td> 555</td><td> 10</td><td> 36</td><td> 63</td><td> 14</td><td> 105</td>

<td></td><td> 30</td><td> 214</td><td> 113</td><td> 532</td><td> 10</td><td> 35</td><td> 64</td><td> 11</td><td> 105</td>

<td></td><td> 40</td><td> 216</td><td> 119</td><td> 513</td><td> 10</td><td> 35</td><td> 65</td><td> 14</td><td> 105</td>

Example 9

Starting materials Mixture 1 Mixture 2 Terpolymeric ethylene-propylene-rubber (Keltan 70) 100 Fine-grained, precipitated silica (EXTRUSIL, DEGUSSA) 100 Naphthenic hydrocarbon, as a plasticizer50 Titanium dioxide10 Zinc oxide5 Stearic acid1 Bis- (3-triethoxysilylpropyl) -ethylsilylpropylsilylpropylsilylpropylsilylpropyl- tetramethylthiuram disulfide0,8 dimethyldiphenylthiuram disulfide1,5 tellurdiethyldithiocarbamate0,8 dipentamethylenethiuram tetrasulfide0,8 sulfur2,0

100

100

0,8

1,5

0,8

0,8

2,0

Mixing method

Mixing is carried out in a kneading machine at a temperature of 80 ° C.

Additions or operations completed after ethylene-propylene-terpolymer 0 min.

У2 amount of silicic acid, stearic acid 1 min.

amount of silicic acid, zinc oxide,

<td>Supplements, resp. tasks</td><td>finished after</td>

<td>organosilane, other chemicals cleaning, ventilation termination</td><td>2.5 min. 4 min. 5 min.</td>

This mixture was finally stirred in a kneading machine at 80 for 24 hours ^dC (stirring time 1.5 min).

Properties of unvulcanized mixture

DH / DE t 35 t 35

ML 4 spec. in.

mixture 2

400/19,5

19,2

50,4

1.16 mixture 1

550/17,5

8,5

16,4

1,16

Properties of vulcanized mixture

<td colspan="5">Vulcanization temperature: 160 ° C</td>

<td>mixture</td><td>VZ</td><td>ZF</td><td>M 300</td><td>BD</td>

<td> 1</td><td> 10</td><td> 67</td><td> 23</td><td> 825</td>

<td></td><td> 20</td><td> 62</td><td> 29</td><td> 627</td>

<td></td><td> 30</td><td> 55</td><td> 32</td><td> 550</td>

<td> 2</td><td> 10</td><td> 77</td><td> 42</td><td> 725</td>

<td></td><td> 20</td><td> 91</td><td> 74</td><td> 392</td>

<td></td><td> 30</td><td> 98</td><td> 98</td><td> 300</td>

198

<td> 130</td><td colspan="3"> 30</td>

<td>bl.D.</td><td>E</td><td>SH</td><td>EF</td>

<td> 43</td><td> 40</td><td> 53</td><td> 7</td>

<td> 25</td><td> 42</td><td> 57</td><td> 3</td>

<td> 21</td><td> 42</td><td> 59</td><td> 2</td>

<td> 26</td><td> 41</td><td> 54</td><td> 8</td>

<td> 7</td><td> 43</td><td> 60</td><td> 3</td>

<td> 5</td><td> 44</td><td> 63</td><td> 2</td>

In case 6, a compound of the present invention based on nitrile rubber was used which, as a silicate filler, contained flame-hydrolyzed pure silicic acid (AEROSIL 130 V, DEGUSSA) and bis- (3-triethoxysilyl-propyl 1 H -tetrasulfide) as an organosilane reinforcing agent.

The Mooney viscosity of the composition of this Example 6 is significantly reduced compared to the composition without the organosilane additive, which means less energy consumption and thus lower costs for further processing of the raw composition. The vulcanization time ts is only insignificantly shortened. The vulcanizates of blend 2 are characterized by significant improvements in the respective tensile strength, stress value and DIN wear compared to blend 1 without the organosilane additive.

In accordance with Example 7, the compound rubber blend based on butyl rubber contained precipitated silica (ULTRASIL VN 3, DEGUSSA) as a silicate filler and bis- (3-triethoxysilyl-propyl) -tetrasulfide as an organosilane reinforcing agent.

These additions of accelerators to the comparative mixture, which in itself is already very rapidly accelerated, do not lead to premature vulcanization but to a surprising extension of the vulcanization time t5. The tensile strength, the stress value and the residual elongation of the vulcanizate were clearly improved compared to the vulcanizate of the comparative mixture.

Example 8 discloses a rubber blend based on polychloroprene rubber precipitated with silicic acid (ULTRASIL VN 3, DEGUSSA) as a silicate builder, and again bis-3-triethoxysilyl] -p^,(1) -tetrasulfide as an organosilane builder. The vulcanization reaction of mixture 2 is virtually unchanged compared to the mixture without organosilane, the respective Mooney viscosity of mixture 2 being somewhat better. The properties of the vulcanizates of the compound rubber compositions according to the invention are clearly improved compared to the composition without the organosilane additive: the tensile strength value is higher than 40 kp / cm 2 and the stress value (300 ° / o) partially higher than 60 kp / cm². The last means an improvement of 100 percent or more, based on the zero mixture No. 1.

Example 9 relates to rubber mixtures based on ethylene-propylene terpolymers with further precipitated silica (EXTRUSIL, DEGUSSA) as a silicate filler and with bis- (3-ethoxy-silyl-propyl) -tetrasulfide as an organosilane. Here too, a surprising increase in the vulcanization time ts is found; ML 4 was reduced by 10 Mooney units, both values ​​compared to the mixture without the organosilane additive. Compared to the zero blend 1, the properties of the compound blend vulcanizate according to the invention, the respective tensile strength, the stress value, and the residual elongation after overload are clearly improved.

Example 10

Blends for passenger car tire treads. ·

<td>Starting materials</td><td>mixture 1</td><td>mixture 2</td>

<td>styrene-butadiene rubber (Buna Hols 1712)</td><td> 96,5</td><td> 96,5</td>

<td>cis-1,4-polybutadiene</td><td></td><td></td>

<td>Buna CB 10</td><td> 30</td><td> 30</td>

<td>fine-grained, precipitated silica (ULTRASIL VN 3 DEGUSSA)</td><td> 75</td><td> 70</td>

<td>bis- (methoxysilyl-propyl) -tetrasulfide</td><td> 5</td><td></td>

<td>mixture of equal parts of precipitated silica (ULTRASIL VN 3) and bis- [3-triethoxysilyl-propyl) -tetrasulfide</td><td></td><td> 10</td>

<td>zinc oxide</td><td> 4</td><td> 4</td>

<td>stearic acid</td><td> 1,2</td><td> 1,2</td>

Starting materials mixture 1 mixture 2 plasticizer (naphthenic hydrocarbon) anti-aging agent bitches Ι-β-naphtha lamin anti-aging agent

N-isopropyl-N'-phenyl-p-phenylenediamine benzthiazoyl-2-cyclohexylsulfenamide diphenylguanidine sulfur

<td> 15</td><td> 15</td>

<td> 1,5</td><td> 1,5</td>

<td> 1,5</td><td> 1,5</td>

<td> 1,2</td><td> 1,2</td>

<td> 3,5</td><td> 3,5</td>

<td> 1,6</td><td> 1,6</td>

UP-sidc-down mixing method

Mixed in a kneading machine at 80 ° C.

Supplements, resp. operations finished after

1. filler, chemicals, polymers 0 mni.

cleaning 3 min.

Additions and / or actions completed after 3.5 min.

bedtime 2 4 hours

2. final mixing in a kneading machine at 80 ° C.

Accelerator and sulfur are mixed in the kneading machine.

mixing time 1.5 min.

Properties of unvulcanized mixture.

mixture 1 mixture 2

<td>t5</td><td> 20,0</td><td> 18,1</td>

<td>Í3 5</td><td> 26,5</td><td> 28,0</td>

<td>ML 2</td><td> 67</td><td> 67</td>

<td>spec. in.</td><td> 1,19</td><td> 1,19</td>

Properties of vulcanized mixture.

Vulcanization temperature: 160 ° C.

<td>mixture</td><td>VZ</td><td>ZF ..</td><td>M 300</td><td>BD</td><td>bl.D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

<td> 1</td><td> 20</td><td> 190</td><td> 66</td><td> 592</td><td> 26</td><td> 38</td><td> 62</td><td> 23</td><td> 91</td>

<td> 2</td><td> 20</td><td> 196</td><td> 63</td><td> 627</td><td> 26</td><td> 38</td><td> 62</td><td> 27</td><td> 90</td>

<td>Example</td><td> 11</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">Tread compound</td><td colspan="2">Earth-Mover</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">starting materials</td><td></td><td></td><td colspan="2">mixture 1</td><td></td><td></td><td>mixture 2</td><td></td>

100

100 ALIGN! natural rubber [Ribbed Smoked Sheets L], pentachlorothiophenyl-Zn (Renacit IV, Farbenfabriken Bayer, Leverkušen) carbon black ISAF-LM (CORAX 6 LM DEGUSSA) blend of 10 parts of bis- (3-triethoxysilyl-propyl) -tetrasu0u and 100 parts precipitated silicic acid (ULTRASIL VN 3 DEGUSSA) zinc oxide stearic acid

0,25

0,25

2,5

2,5

<td>starting materials</td><td>mixture 1</td><td>mixture 2</td>

<td>anti-aging agent phenyl-β-naphthylamine</td><td> 1</td><td> 1</td>

<td>anti-aging agent phenynyl [beta] -naphthyl</td><td> 1</td><td> 1</td>

<td>an anti-aging agent for N-isopropyl-N-methyl-propyl-diamine</td><td> 0,8</td><td> 0,8</td>

<td>gum-okozerít (protector 3888 Lüneburger Wa ^ sbleíche GmbH)</td><td> 0,8</td><td> 0,8</td>

<td>a plasticizer (Naphthenic hydrocarbon)</td><td> 2</td><td> 2</td>

<td>bis- (3-triethylsilyl-propyl) -tetrasplide</td><td> 0,6</td><td> 0,6</td>

<td>diphenylgenidine</td><td> —</td><td> 2</td>

<td>sulfur</td><td> 1,2</td><td> 1,2</td>

Mixing method: "Up-side-down"

Supplements, resp. operations finished after

Mixed in a kneading machine at 80 ° C.

<td>Supplements, resp. tasks</td><td>finished after</td>

<td>1. sstupn:</td><td></td>

<td>filler, chemicals, polymer</td><td>0 min.</td>

<td>cleaning</td><td>3 min.</td>

<td>end</td><td>3,5 min.</td>

<td>lying time</td><td>2-4 hours</td>

<td></td><td>mixture 1</td>

<td>Mooney Scorch</td><td> 25,4</td>

<td>Mooney Cure t3 4</td><td> 28,1</td>

<td>Mooney Win-Echo ML 4</td><td> 88</td>

<td>spec. in.</td><td> 1,15</td>

2. degree:

final mixing in a kneading machine at 80 ° C were mixed with accelerator and sulfur in a kneading machine at home mixing 1.5 min.

Properties unvulcanized mixtures.

mixture 2

19,9

25,3

1,18

Properties vulcanized by the mixture

Vulcanization temperature: 145 ° C.

mix ZZ M300 BD E SH EF AT (0.250 “)

60 249 139 490 33S 68 31 102 87

60 257 119 547 41 77 42 104 64

According to Example 10, the tire tread for passenger car tires has been clarified and applied, and according to Example 11, the tread pattern for Eearth-Mover. For both prescriptions, bis- (3-triethoxysilyl-proeyl) -tetrasulfide is used as a stiffener, for personal car treads also in mixtures with silicic acid in a ratio of 1: 1 and for Earth-Mover in the form of mixtures with fine-grained silicic acid in ratio of 1: 1. 10.

Example 10 shows that there is no difference between the application of the reinforcing agents in pure form and the application of the reinforcing agents in the form of mixtures with precipitated highly disperse silicic acid within the error limits of the rubber-processing methods used.

The properties of the vulcanized and vulcanized compositions show to those skilled in the art that, by using the reinforcing agents of the invention, the silicic acid-reinforced tread compound of passenger car tires is imparted in many respects to the properties of the corresponding carbon black compositions.

Thus, it is for the first time possible, using functional polyol-reinforcing additives, to produce treads for silicic acid-reinforced passenger car tires without altering the conventional mixing and vulcanization method. in the rubber industry, which are at least equal in all technically usable characteristics with the corresponding mixture of carbon black.

In Example 11, the reinforcing agents of the invention were opposed in a silica-reinforced Earth-Mover blend and a conventional soot-reinforced Earth-Mover blend.

In Example 11, it is shown that the silicic acid reinforcing agents of the invention impart properties at a predetermined point to the rubber composition at a point which exceeds the properties of the carbon black-reinforced mixture, in particular resistance to further tearing and heat generation (Heat-buildup.Goodrich-Flexometer test). )

Compared to Comparative Composition 1, it has been found that while using the reinforcing agents of the invention, while Mooney-Scorch and Mooney-Cure have been somewhat shortened, they are still within the range applicable to industrial practice. The viscosity of the raw blend decreases by even 11 Mooney units compared to the comparator blend, which is remarkable as an absolutely desired effect that leads to a reduction in the cost price for tire manufacturers.

With respect to the properties of the vulcanizates which essentially correspond to those of the comparative mixture, the two properties of the mixture according to the invention are particularly outstanding: a distinct increase in resistance to further tearing and a reduced heat generation. Resistance to further tear (tear strength) is increased by 35% compared to a carbon black-reinforced comparative mixture, heat generation is reduced by 31% from 87 ° C to 64 ° C. When assessing the value of the Goodrich flexometer test, it should be taken into account that it was measured with a stroke of 0.250 inches, while ASTM prescribes a stroke of 0.175 inches. It is particularly notable that the DIN-value of the soot mixture and the silica mixture is practically the same.

Thus, it was again confirmed that by using the organosilane additives according to the invention it is for the first time easier to make suitable mixtures with silicic acid and then to vulcanize them, which in aggregate are the same as the corresponding carbon black-filled mixtures and even surpass them in the critical characteristics.

In addition to the foregoing, and in particular in the examples of the preferred reinforcing agents of the formula II

R²

<img file="CS198130B2_D0002.tif" />

/ —S_n—Alk — Si — R² \

R² \

R²—Si — alk /

R² (П) with the following meanings

R²:

—ОСНз;

—ОСНг — СНз;

—ОСНг — СНг — СНз;

СНз /

—ОСН \

СНз alk:

—СНг — СНг—;

—СНг — сн—;

and

СНз — СНг — СНг — СНг—;

* —СНг — СН — СНг;

СНз * —СНг — СНг — СН—;

AND

СНз — СНг — СНг — СНг — СНг—;

—СНг — СНг — СН — СНг—

СНз — СНг — СНг — СНг — СН—

AND

2 to 4 can also be used according to the invention preferably those silanes which instead of the group (see also Z according to the general formula I)

R² /

—Si — R² \

R² they also contain groups

R¹

From —Si — R² \

R² or

Ri /

—Si — R¹, \

R² where

R¹ denotes alkyl (branched or unbranched) having 1 to 4 carbon atoms, phenyl, or cyclohexyl.