Rubber mixtures containing reinforcing additives

<td rowspan="2">POLAND REPUBLIC CHINA</td><td>PATENT DESCRIPTION</td><td colspan="2"> 87778</td>

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

<td></td><td>Additional patent to patent no</td><td colspan="2">MKP C08c 11/66 C08d 9/00</td>

<td></td><td>Reported: 13.11.1973 (P. 166509)</td><td></td><td></td>

<td> **</td><td>Priority: 13/11/1972 Republic</td><td></td><td></td>

<td>OFFICE</td><td>Federal German</td><td colspan="2">Int. Cl.^{and 2 * *} C08K5 / 36 C08K 5/54</td>

<td>PATENT</td><td>The application was announced on December 2, 1974</td><td></td><td>READING ROOM</td>

<td>FUL</td><td>Patent description published: 30.11.1977</td><td></td><td>official hUę ę L «*« |</td>

Inventor: Patent holder: Deutsche Gold- und Silber- Scheideanstalt vormals Roessler, Frankfurt (Federal Republic of Germany)

Rubber compounds and method of producing rubber mixtures and

The invention relates to rubber mixtures containing reinforcing additives for silicate fillers which in an unexpectedly pronounced manner favorably influence the production of rubber mixtures and the properties of vulcanizates. ^{5 * * * *}

These additives belong chemically to the group of organosilicon compounds containing sulfur in the molecule. Additives give silicate fillers better reinforcing properties and increase the crosslinking efficiency of^{10 * * * *} vulcanization time; they will then be called reinforcing additives.

It is known that soot in general, and especially specially developed soot species, occur in rubber vulcanizates not only as a winner. ¹⁵canine fillers, but in a certain way act as a reinforcing filler (active filler). The effect of sulfur on the strengthening of the polymer and the importance of the interaction between the rubber and the filler is described, for example, in the journal Kautschuk und Gummi, Kunststoffe, 1966, No. 8, pp. 470-474 and 1970, No. 1, pp. 7-14.

In terms of activity, silicate fillers, such as finely divided silica, silicates and the like are very different from soot. This difference is revealed in two ways. Firstly, the strengthening effect of silicate fillers differs from soot due to the completely differently shaped surface. Secondly, active silica 30 affects the vulcanization process, in particular if vulcanization is caused by sulfur and accelerator additives. To date, there is no sulfur vulcanization which silicate fillers would not act in such a way as to reduce crosslinking.

In recent years, attempts have been made to improve the activity of silicate fillers by mixing chemicals into the starting mixtures.

Thus, it is known that mercaptomethylalkoxysilanes are used as adhesion promoters between silicate materials such as glass, clay, asbestos or silicon dioxide and organic resins, such as styrene butadiene copolymers, natural rubber, polyester resins, polystyrene and styrene maleic anhydride copolymers. what these silanes are applied to by means of any method on the substrate and thus combined with resins (publications of the Patent Office of the Federal Republic of Germany No. 2038715).

Furthermore, compounds known as organosilicon sulphides containing a sulphide silicon atom between two hydrocarbon residues are known, which have been recommended for use as adhesion promoters or as intermediates for the preparation of compounds which can be used as hydrophobizing agents or oxidation inhibitors. Said organosilicon compounds may also contain sulfur-containing end groups such as thiocyanate, xanthate, thioether, thionic acid ester group and the like (German Patent Office Publication No. DOS No. 1911227).

Similar end groups also have organoxysilanes, for example 3-thiocyanatopropyltrimethoxysilane or 3-thiocyanatotrioxysilane, which according to Belgian patent 770097 finds excellent use in cross-linking or vulcanizing mixtures composed of organic polymers, inorganic substances and suitable cross-linking or vulcanizing agents or systems.

The silicates disclosed in both of the last-mentioned descriptions have only one silicon atom bonded to carbon or another silicon atom bonded through an oxygen atom or an amino nitrogen atom.

In addition, γ-mercaptopropyltrimethoxysilanes and γ-mercaptopropyltriethoxysilanes, as well as β-mercaptoethyltriethoxysilane and other sulfur-free silanes are known, which after partial hydrolysis and application of silica or silicate filler particles to serve to facilitate the improvement of the properties of rubber blends rubber (U.S. Patent No. 3,350,345).

In addition, tire treads made of a rubber compound containing silica as a filler and silane as a coupling agent are known (Belgian Patent 760999). In addition, numerous silanes are represented by general formulas, however, from the introduction, tables and examples it can be concluded that the only coupling agent tested is γ-mercaptopropyltrimethoxysilane.

The present invention relates to a group of sulfur-containing organosilanes in a molecule that stand out in numerous respects from the numerous known silanes due to the benefits * associated with their use and are particularly suitable as reinforcing additives, as will be described and proved below. The new additives cause in rubber mixtures and vulcanizates containing silicate fillers unpredictable, valuable and technically excellent properties, wherein the rubber mixtures contain at least one rubber, one crosslinking system, one sulfur-containing organosilane, fillers and preferably other commonly used rubber auxiliaries. The invention is characterized in that the rubber compounds contain as a reinforcing additive one or more organosilanes of the general formula Z — Alk — Sn — Alk — Z, in which Z is a group of formulas 1, 2 and 3 in which R¹ is an alkyl group having 1-4 carbon atoms or a phenyl residue and R² means an alkoxy group containing 1-8, preferably 1-4 carbon atoms, a cycloalkoxy group containing 5-8 carbon atoms or a chain or branched alkylomercaptyl group containing 1-8 carbon atoms, whereby R1 and R2 can be the same in each case or different meanings, Alk is a divalent, optionally unsaturated, chain or branched, optionally cyclic hydrocarbon residue containing 1-18, in particular 1-6, preferably 2 or 3 carbon atoms and n is a number from 2.0 to 6.0, preferably from 2.0 to 4.0 as well as one or more silicate fillers, optionally in a mixture with sulfur.

The rubber mixtures preferably contain at least one organosilane, in particular one or two, preferably one organosilane of the above general formula Z-Akl-S "- -Alk-Z, wherein Z is a moiety of formula 3, wherein the R moiety² means an alkoxy group containing 1-8 carbon atoms, preferably 1-4 carbon atoms and -Alk is a divalent, chain, saturated hydrocarbon residue containing 1-6, preferably 2 or 3 carbon atoms.

In addition to the above-mentioned, and in particular to the examples mentioned, recommended reinforcing agents of general formula 4 with the following meanings:

R2: —OCH_S; -OCH-CH ,; OCH₂-CH-CH ,; and —OCH (CH,) - CH3

Alk: —CH2 — CH₂-; CH-CH-; CH, -CH-CH2-;

AND

CH, —CHa — CH — CH_and—;

AND

CH, —CH2 — CH2 ^ —CH—; —C Η, —CH2 — CH, —CH - ^ -;

AND

CH3 —CHa — CHO — CH — CHa—;

AND

CH3 and —CH, —CH, —CHa — CH—;

AND

CH, n = 2-4, silanes may also advantageously be used which instead of a moiety (see also the meaning of Z according to the general formula Z — Alk — Sn — Alk — Z) of formula 3 also have moieties of formula 2 or 1 in which R1 is a branched or unbranched alkyl group having 1-4 carbon atoms, a phenyl or cyclohexyl group.

Selected new jsilanes have, therefore, in the middle of a molecule built approximately symmetrically 2 or more sulfur atoms and two separate, to some extent, end silane groups. It should be assumed that this structure of the molecule determines the excellent properties of new vulcanization amplifiers.

The aforementioned 3-mercaptopropyltrimethoxysilane in rubber mixtures containing silica as a filler clearly increases the value of the modulus at tensile strength.

. β anger for bursting,. abrasion resistance, resilience and hardness according to Shore * a.

However, it adversely affects the times of vulcanization and elastic relaxation according to Defo mixtures. uncured. The vulcanization times are very short. When preparing such mixtures, even premature curing, which prevents further processing of the mixtures, often occurs in a closed mixer.

Defo elastic rests are much larger, 'co. means an increase in the proportion of flexible pupils in the raw mixture and makes further processing difficult, for example during extrusion.

Rubber compounds containing new reinforcing additives, on the other hand, stand out due to clear technical 'advantages' over the properties of raw mixtures or vulcanizates known from the prior art. In particular, the raw mixes show processing reliability, previously unknown, significantly reduced stiffening and only a slight increase in elastic stress according to Defo. These beneficial properties or phenomena enable the industrial application of such mixtures for the first time. The properties of the obtained vulcanizates are excellent and are comparable with the properties of the corresponding vulcanizates filled with soot and even, as it will be shown, exceed them. These improvements in the properties of raw mixtures and vulcanizates are opening for the first time for silicate fillers those fields of application that until now have been reserved exclusively for carbon black as a reinforcing filler.

The term "silicate filler" is a broad term and refers to fillers miscible with rubbers or capable of being incorporated into rubber mixtures, which fillers consist of silicates, contain silicates or also contain silicates chemically bonded in the widest sense of the word, including mixtures of two or several silicate fillers. In particular, silicate fillers include;

Fine silica (silicon dioxide). with specific surfaces in the range from about 5 to 1000, preferably 20-400 m / g (marked. known method according to BET using nitrogen gas) and with primary particle sizes · in the range of about 10-400 millimicrons that can be prepared, for example, by precipitation from silicate solutions, by high-temperature hydrolysis and simultaneous oxidation, also called flame hydrolysis of volatile silicon halides or by electric arc method. These silicas may also be in the form of mixed oxides or mixtures of oxides with the oxides of the following metals: aluminum, magnesium, calcium, barium, zinc, zirconium and / or titanium.

Synthetic silicates, e.g., alkaline earth aluminosilicate or silicates, such as magnesium or calcium silicate, with specific surfaces of about 20-400 m '/ g and primary particle sizes of about 10-400 millimicrons. Natural silicates, e.g. kaolins and asbestos, as well as natural silicas.

β Glass fibers and glass fiber products, such as fabric mats, nets and the like, as well as glass microspheres. ' Said silicate fillers can be used in an amount of from about 10, and optionally even below, to i * about 250 parts by weight per 10 ° parts by weight of the rubber polymer. '

As filler mixtures, for example, mixtures of silica with kaolin or silica with glass fibers and asbestos can be used, as well as mixtures of silicate-containing reinforcing fillers with known rubber soot, for example silica - ISAF carbon black or silica - glass fiber cord - HAF carbon black .

* · Typical examples of silicate fillers that can be used according to the invention are, for example, silicas or silicates produced and sold by Degussa under the trade names Aerosil, Ultrasil, Silteg, * Durosil, Extrusil, Calsil and others.

In addition, various additives known and widely used in the rubber industry can be added to the rubber compounds. ·

The introduction of the additive according to the invention not to the rubber mixture itself has a number of advantages, but the preparation of a mixture consisting of at least one silicate filler and at least one órganosilane having the general formula Z-Alk-S given above_n—

3 »—Alk — Z and the addition of such a mixture later to the rubber compound or to other components of the rubber compound in the usual manner and using ordinary mixers with the following thorough distribution.

«· During the production of the masterbatch, even a loose, practically dry product is formed if an equal or even greater amount of liquid organosilane is added to the silicate filler. So you can use it for. producing the rubber compound only part of the total filler needed, which already contains the necessary amount of silane as the masterbatch.

Examples of organosilanes of the general formula Z-Alk-S given above_n—Alk —— Z are many di- [trialkoxysilylalkyl] sulfides, such as di- {2-trimethoxy-, -triethoxyoxy-, tri- (methylethoxy) -, tripropoxy-, tri-butoxy- etc. namely, disulphides, trisulphides, tetra sulphides, pentasulphides and hexasulphides, in addition, di-I3-tri-methoxy-, -triethoxyoxy-, -threes- {methylethoxy) -, - tripropoxy-, tri-butoxy-, etc. to -thioctyoxyoxypropyl], namely, again, disulfides, trisulfides, tetra sulfides, etc. up to hexasulfides, in addition, the corresponding di- {3-trialkoxysilylisobutyl] sulfides], and the corresponding di- [4-trialkoxysilylbutyl] sulfides, etc., up to di- [... O-trójalkoksysililoheksyluj.

Of the selected, relatively simple · · built organosilanes of the general formula

Z-Alk-Sn-Alk-Z are di- [3-trimethoxy-, ^ - triethoxyoxy- and-tri-propoxy-silylpropyl] sulfides, namely disulfides, trisulfides and tetra sulfides. These and others with good results used organosilanes of the general formula Z-Alk-Sn-Alk-Z can be prepared, for example, by methods in German Patent Office publications No. 2141159, 2141160, 2212239. All these methods are also described in Belgian Patent No. 787691.

The new silanes used according to the invention can be used in rubber compounds in. amounts from 0.1-50 parts by weight, preferably within 0.5-25 parts by weight based on 100 parts by weight of rubber.

When used, the described organosilanes can be added directly to the rubber mixtures or to the components of these mixtures. It is not necessary and it is not preferred to hydrolyze the organosilanes before use.

The organosilicon compounds described can, however, also be added, in particular for reasons of ease of dosing and handling, to a part of the filler used, whereby liquid organosilanes are converted into a powder product and used in such form. It is also possible, but without special benefits, to apply the organosilanes evenly to the surface of the filler particles and use as such. You can also use a total of 3 or only 2 of the given methods of use.

Rubber mixtures can be made using one or more, possibly with the addition of oils, natural or synthetic caustics, czuków. These include, in particular, natural rubbers, synthetic rubbers, preferably diene elastomers, e.g. from butadiene, isoprene, from butadiene and styrene, from butadiene and acrylonitrile or from 2-chlorobutadiene, in addition butyl rubber and halogenated butyl rubber, such as chlorinated or brominated butyl rubber, in addition, there are the known ethene ethene rubber, e.g. and, for example, unconjugated dienes, in addition trans-polypentenamer, carboxyl or epoxy rubbers, and other known elastomers. Chemical derivatives of natural rubber and modified natural rubbers are also included in the applications of the invention.

Rubber compounds of organic polymers, crosslinking system, silicate fillers and organosilane additives may also contain known reaction accelerators, as well as one or several compounds from the group of anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, softeners, adhesion promoters, foaming agents, dyes, pigments, waxes, inactive fillers, for example wood flour, organic acids, such as stearic, benzoic or salicylic acid, in addition lead oxide or zinc oxide, activators such as triethanolamine, polyethylene glycol or hexanotriol, which are all known in the art and rubber industry. For vulcanization, rubber compounds are generally added. crosslinking agents, in particular peroxides, sulfur or, in a special case, magnesium oxide, as well as optionally a vulcanization accelerator or a mixture of these accelerators.

The production of rubber mixtures as well as their formation and vulcanization takes place by methods known in the rubber industry.

The fields of industrial application of the described rubber compounds are, for example, the following: technical rubber articles, such as cable coatings, hoses, drive belts, V-belts, conveyor belts, roller linings, car tire treads, in particular passenger cars and trucks, as well as tire skeletons tire shunts for these cars, off-road tires, shoe gel materials, sealing rings, vibration damping components and much more. The new rubber compounds are also good as fiberglass adhesives and the like.

Below are some examples of recipes for new ones. rubber compounds with the results of vulcanizate tests and the assessment or comparison of these results which do not limit the invention. The examples repeat various terms, so you can use abbreviations.

List of abbreviations used

<td>Shortcut</td><td>Importance</td><td>measurement in:</td>

<td>DH</td><td>Defo hardness</td><td>g</td>

<td>DE</td><td>Flexible relaxation according to Defo</td><td></td>

<td></td><td>Mooney cure time</td><td>min.</td>

<td>^t35</td><td>Vulcanization time according to Mooney * a</td><td>min.</td>

<td>ml₄</td><td>Plasticity according to Mooney at 100 ° C, standard rotor, test time: 4 minutes</td><td></td>

<td colspan="2">c. incl. Specific gravity</td><td>g / cm '</td>

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

<td>VT</td><td>Vulcanization temperature</td><td>° C</td>

<td>ZF</td><td>Tear resistance</td><td>kp / cm²</td>

<td colspan="2">M 300M &lt;300 °%</td><td>kp / cm²</td>

<td>BD</td><td>Elongation at bursting</td><td> %</td>

<td>bl. D.</td><td>Permanent elongation after bursting</td><td>•/about</td>

<td>E</td><td>rebound</td><td> %</td>

<td>SH</td><td>Shore hardness, scale A</td><td> —</td>

<td>EF</td><td>Tear resistance</td><td>kp / cm</td>

<td>AND</td><td>Abrasion (also DIN abrasion)</td><td>mm '</td>

<td>T</td><td>Temperature rise (see Goodrich flexometer)</td><td>° C</td>

Standards for tests

Physical tests were carried out at room temperature in accordance with the following standards:

Tear resistance, elongation at break and module on rings 6 mm thick DIN 53 504

Tear resistance DIN 53 507

Impact resistance DIN 53 512

Shore hardness DIN 53 505

Specific weight DIN 53 550

Test according to Mooney * a DIN 53 · 524

Flexometer according to Goodrich (determination of heat generation - T) ASTM D 623-62 Abrasiveness DIN 53 516

Vulcanizates were always prepared in multi-stage press at given vulcanization temperatures.

In the examples, the amounts of the components of the mixture were always given in parts by weight.

Mix VZ ZF M 300 · BD bl. D. E SH EF A

Example 1

Recipe: Mie- Mie- Mie-

<td></td><td>the chances</td><td>the chances</td><td>the chances</td>

<td></td><td>ka 1</td><td>ka 2</td><td>ka 3</td>

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

<td>(Ribbed Smoked Sheets I)</td><td> 100</td><td> 100</td><td> 100</td>

<td>Zinc pentachlorothio</td><td></td><td></td><td></td>

<td>phenyl (Renaoit IV from Far-</td><td></td><td></td><td></td>

<td>benfabriken Bayer, Leverkusen)</td><td> 0,25</td><td> 0,25</td><td> 0,25</td>

<td>Small molecule, precipitated</td><td></td><td></td><td></td>

<td>silica (Ultrasil VN company</td><td> 3</td><td></td><td></td>

<td>Degussa)</td><td> 40</td><td> 40</td><td> 40</td>

<td>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-mercaptopropyl-trójmetoksy-</td><td></td><td></td><td></td>

<td>silane</td><td> — ‘</td><td> 2</td><td> —</td>

<td>Bis [3-trimethic trisulphide</td><td></td><td></td><td></td>

<td>ksysililopropylu]</td><td> —</td><td> —</td><td> 2</td>

<td>Dibenzothiazyl disulphide</td><td> 0,8</td><td> 0,3</td><td> 0,8</td>

<td>Dwufenyloguanidyna</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>

<td>Mixing method</td><td></td><td></td><td></td>

<td colspan="2">Pre-mixing in a mixer at</td><td colspan="2">temperatures</td>

80 °.

Add or operation Finished after:

Natural rubber 0 min.

1/2 amount of silica, stearic acid 1 min.

1/2 amount of silica, zinc oxide, organosilane. 2.5 min

Cleaning, airing 4 min.

Emptying 4.5 min.

This mix is ​​left for 24 hours. Then the mixing was completed in the mixer at 80 ° C, mixing time 1.5 min. Properties of unvulcanized mixtures

Mix 1 Mix 2 Mix 3

<td>DH / DE</td><td> 675/20</td><td>podwulka- lows</td><td> 650/20</td>

<td>t #</td><td> 6,4</td><td> —</td><td> 5,0</td>

<td>t_M</td><td> 7,5</td><td> —</td><td> 5,8</td>

<td>ML4</td><td> 57</td><td>232 (increasing)</td><td> 54</td>

<td>c. on</td><td> 1,13</td><td> 1,13</td><td> 1,13</td>

<td>properties</td><td>blends</td><td>vulcanized</td><td></td>

<td colspan="3">Vulcanization temperature: 150 ° C</td><td></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> 20</td><td> 250</td><td> 58</td><td> 630</td><td> 43</td><td> 47</td><td> 64</td><td> 31</td>

<td> 40</td><td> 220</td><td> 48</td><td> 640</td><td> 37</td><td> 46</td><td> 62</td><td> 35 165</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>

the vulcanization was premature

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

Example II

Mie- Mie- Mie-

<td>Recipe:</td><td>shan- shan- ka 1 ka 2 ka 3</td>

<td colspan="2">Cis-1, 4-polyisoprenic rubber</td>

<td>new</td><td> 100 100 100</td>

<td colspan="2">Fine particle precipitated silica (Ultrasil VN3</td>

<td>Degussa companies)</td><td> 50 50 50</td>

<td colspan="2">Plasticizer (hydrocarbon</td>

<td>tenowy)</td><td> 3 3 3</td>

<td>Active zinc oxide</td><td> 2 2 2</td>

<td colspan="2">Anti-aging agent (mixture of arylalkylated</td>

<td>phenols)</td><td> 1 11</td>

<td></td><td>Mie- Mie- Mie-</td>

<td>Recipe</td><td>shan- shan-</td>

<td></td><td>ka 1 ka.2 ka3</td>

<td colspan="2">A mixture of equal amounts of low molecular weight precipitated silica and hexanetriol</td>

<td>(activator of Degussa company)</td><td> 4 4 4</td>

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

<td colspan="2">3-merkaptopropylotrójmetoksy-</td>

<td>silane</td><td> - 1,5 —</td>

<td>Tetrasulphide di- [3-tri-</td><td></td>

<td>toksysililopropylu]</td><td> _ _ 1,5</td>

<td>Dibenzothiazyl disulphide</td><td> 0,8 0,8 0,8</td>

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

<td>Sulfur</td><td> 2,5 2,5 2,5</td>

<td colspan="2">Mixing method</td>

<td colspan="2">Pre-mixing in a mixer at a temperature of</td>

<td colspan="2">80 °</td>

<td>Addition or operation</td><td></td>

<td>Cis-1 rubber, polyisoprene</td><td>Ukoń- czono after</td>

<td>1/2 amount of silica, stea acid</td><td>0 min</td>

<td>rynowy</td><td>1 min</td>

<td colspan="2">1/2 amount of silica, softener,</td>

<td>zinc oxide, organosilane</td><td>2.5 min</td>

<td>Cleaning, airing</td><td>4 min</td>

<td>Discharge</td><td>4.5 min</td>

<td colspan="2">The mix was finished after 24 hours in</td>

<td>mixer at 80 ° C</td><td>!, mixing time</td>

<td colspan="2">1.5 min</td>

<td colspan="2">Properties of unvulcanized mixtures</td>

<td colspan="2">Mix 1 Mix 2 Mix 3</td>

DH / DE 1500 / 6.0 Podwilka- 1375 / 7.0.

lows

Mix 1 Mix 2 Mix 3

<td>ts</td><td> 9,2</td><td> —</td><td> 6,5</td><td></td>

<td> 1»</td><td> 11,6</td><td>154 (increased</td><td> 8,4</td><td></td>

<td>ML 4</td><td> 100</td><td>sta)</td><td> 91</td><td> 8</td>

<td>c. on</td><td> 1,13</td><td> 1,14</td><td> 1,14</td><td></td>

<td colspan="4">Properties of vulcanized mixtures</td>

<td colspan="2">Vulcanization temperature: 134 ° C</td><td rowspan="2">SH EF A</td><td rowspan="2"> 10</td>

<td>Mix VZ ZF M 300 BD bl. D.</td><td>E</td>

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

<td> 20 198 27. 742 24</td><td> 36</td><td> 59 30 196</td><td> 15</td>

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

<td> 40 220 34 723 34</td><td> 38</td><td> 61 23</td><td></td>

<td colspan="3">2 fell out because of premature</td><td></td>

<td colspan="3">scorching</td><td> 20</td>

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

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

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

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

<td></td><td></td><td></td><td> 25</td>

In examples I and II, rubber mixtures based on natural or synthetic cis-1,4-polyisoprene rubber were used, which contain ³⁰as silicate filler precipitated, low molecular weight silica (Ultrasil VN 3 from Degussa). As a reinforcing additive for the rubber mixtures, di [3-trimethoxysilylpropyl] disulfide or di- [3-triethoxysilylpropyl] disulfide was used, with 3-mercaptopropyltrimethoxysilane according to the state of the art being used as a reference substance.

As can already be seen from the properties of non-vulcanized mixtures, the production of mixtures in accordance with practice in a closed mixer leads to raw mixtures suitable for further processing only in the case of rubber mixtures having the composition according to the invention, while the comparative mixtures could not be further processed due to premature curing. '

Polysulphide organosilanes shorten the vulcanization times in mixtures, vol₈ it ^ 'only slightly and does not adversely affect the plastic ^INaccording to Mooney (ML 4) as well as the DH / DE ratio if compared with suitable mixtures without the addition of organosilane.

The properties of the vulcanizates of the new rubber mixtures are, compared to the comparative compound without silane, slightly higher in terms of tear strength, and in terms of the 300 'modulus clearly better, thanks to which the reinforcing effect obtained by the method according to the invention has been proven numerically. These important advantages are caused by the use of organosilanes.

Mixture 3 of Example 2 also exhibits extremely high tear resistance.

<td>Example III</td><td>measured</td><td>measured</td><td>measured</td>

<td>Recipe:</td><td>the chances</td><td>the chances</td><td>the chances</td>

<td>Styrene-butadiene rubber</td><td>ka 1</td><td>ka 2</td><td>ka 3</td>

<td>new (Buna Hiils 1502) Aluminum silicate, precipitated</td><td> 100</td><td> 100</td><td> 100</td>

<td>- (Silteg AS 7 from Degussa)</td><td> 40</td><td> 40</td><td> 40</td>

<td>Active zinc oxide</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 (Bl / 2 850) Mixture of equal parts of low molecular weight precipitated silica and hexanetriose</td><td> 5</td><td> 5</td><td> 5</td>

<td>lu (activator from Degussa) Anti-aging agent (mixture of arylalkylated</td><td> 5</td><td> 5</td><td> 6</td>

<td>phenols) 3-merkaptopropylotrójmetoksy-</td><td> 1</td><td> 1</td><td> 1</td>

<td>silane Bis [3-triethyl tetra sulfide]</td><td></td><td> 1,5</td><td></td>

<td>ksysiililopropylu] Benzothiazyl-2-cyclohexyl-</td><td></td><td> —</td><td> 1,5</td>

<td>sulfonamide</td><td> 0,4</td><td> 0,4</td><td> 0,4</td>

<td>Dwufenyloguanidyna</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:

Pre-mixing in a mixer at 80 °

Addition or operation

Polymer (SBR rubber)

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

1/2 amount of aluminum silicate, plasticizer, zinc oxide, organosilane, other chemicals

Cleaning, ventilation. Discharge

Accelerator and sulfur will be added by mixing 1.5 min)

Finished after minutes

C

2.5 4

4.5 rollers (time

Properties of non-vulcanized mixtures

Mix 1 Mix 2 Mix 3

<td>ts</td><td> • 4,9</td><td> —</td><td> 3,1</td>

<td>^t35</td><td> 5,9</td><td>196 (increased</td><td> 4,3</td>

<td>ML 4</td><td> 78</td><td>sta)</td><td> 82</td>

<td>c. on</td><td> 1,16</td><td> 1,16</td><td> 1,16</td>

Properties of vulcanized mixtures

Vulcanization temperature; 150 ° C

Mix VZ ZF M 300 BD bl. D. E SH EF A

<td> 55</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></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></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> 5 160</td>

<td></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>eo</td><td> 2</td><td></td><td colspan="3">fell out of</td><td colspan="4">premature</td>

scorching

<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></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> 6</td>

<td></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> 4 132</td>

<td>in</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>Example IV</td><td colspan="2">Mie- Mie-</td><td>measured</td>

<td>Recipe:</td><td>the chances</td><td>the chances</td><td>the chances</td>

<td>Styrene-butadiene rubber</td><td>ka 1</td><td>ka 2</td><td>ka 3</td>

<td>new (Buna Huls 1502) Low molecular weight precipitated silica (Ultras: 'VN?</td><td> 100</td><td> 100</td><td> 100</td>

<td>Degussa companies)</td><td> 50</td><td> 50</td><td> 50</td>

<td>Active zinc oxide</td><td> 1</td><td> 1</td><td> 1</td>

<td>Stearic acid Anti-aging agent (arylalkylated mixtures</td><td> 2</td><td> 2</td><td> 2</td>

<td>phenols)</td><td> 1</td><td> 1</td><td> 1</td>

<td>Polyethylene glycol (PEG 4000) 3-mercaptopropyltrimethoxy</td><td> 2</td><td> 2</td><td> 2</td>

<td>silane Two- [3-trimethyl disulphide</td><td></td><td> 2</td><td></td>

<td>ksysililopropylu]</td><td> —</td><td> —</td><td> 2</td>

<td>Dibenzothiazyl disulfide,</td><td> 1</td><td> 1</td><td> 1</td>

<td>Dwufenyloguanidyna</td><td> 2</td><td> 2</td><td> 2</td>

<td>Sulfur</td><td> 2</td><td> 2</td><td> 2</td>

Mixing method:

Pre-mixing in a mixer at 80 °

Addition or operation Completed after a few minutes

Polymer (SBR) 0

1/2 amount of silica, stearic acid, anti-aging agent 1

1/2 amount of silica, zinc oxide, organosilane, other chemicals 2.5

Cleaning, airing 4

Discharge 4.5

After storage for 24 hours, the mix was finished in a mixer at 80 ° C (mixing time 1.5 minutes).

Properties of non-vulcanized mixtures

Mix 1 Mix 2 Mix 3

<td>DH / DE</td><td> 2250/19,5</td><td>podwulka- lows</td><td> 2050/31,0</td>

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

<td>t_M</td><td> 10,0</td><td>242 (increased</td><td> 9,6</td>

<td>ML 4</td><td> 143</td><td>sta)</td><td> 116</td>

<td>c. on</td><td> 1,16</td><td> 1,16</td><td> 1,16</td>

Properties of vulcanized mixtures. Vulcanization temperature: 150 ° C

<td colspan="9">Mix VZ ZF M 300 BD bl. D. E SH EF A</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></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></td><td> 15</td><td> 178</td><td> 41</td><td> 625</td><td> 31</td><td> 33</td><td> 71</td><td> 13 126</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> 2</td><td></td><td colspan="3">fell out of</td><td colspan="4">premature</td>

under vulcanization

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

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

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

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

η

Example V

<td></td><td>measured</td><td>Mie- Mie-</td>

<td>Recipe:</td><td>the chances</td><td>shan-</td>

<td></td><td>ka 1</td><td>ka 2 ka 3</td>

<td>Styrene-butadiene rubber</td><td></td><td></td>

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

<td>Colloidal Kaolin</td><td> 75</td><td> 75 75</td>

<td>Zinc oxide</td><td> 4</td><td> 4 4</td>

<td>Stearic acid</td><td> 2</td><td> 2 2</td>

<td>3-merkaptopropylotrójmetoksy-</td><td></td><td></td>

<td>silane</td><td> ' —</td><td> 2,5 —</td>

<td>Bis [3-triethyl tetra sulfide]</td><td></td><td></td>

<td>ksysililopropylu]</td><td> —</td><td> — 2,5</td>

<td>Dibenzothiazyl disulphide</td><td> 1,2</td><td> 1,2 1,2</td>

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

<td>Sulfur</td><td> 2,75</td><td> 2,75 2,75</td>

<td>Mixing method</td><td></td><td></td>

<td>Pre-mixing in a mixer</td><td colspan="2">in temperature</td>

<td> 80°</td><td></td><td></td>

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

<td>Addition or operation</td><td></td><td>after minutes</td>

<td>Rubber</td><td></td><td> 0</td>

<td>1/2 amount of kaolin, zinc oxide,</td><td></td><td></td>

<td>organosilane</td><td></td><td> 2,5</td>

<td>Cleaning, airing</td><td></td><td> 4</td>

<td>Discharge</td><td></td><td> 4,5</td>

After 24 hours storage, the mix was finished in a mixer at 80 ° C, mixing time 1.5 min.

Properties of non-vulcanized mixtures

Mieszań- Mieszań- Mix___ka 1 ka 2 ka 3

<td>DH / DE</td><td></td><td colspan="2"> 1750/27</td><td colspan="3"> 2550/32,5</td><td colspan="2"> 1450/23,5</td>

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

<td>here</td><td></td><td></td><td></td><td> 41,3</td><td></td><td>Π.6</td><td></td><td> 38,2</td>

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

<td>c. on</td><td></td><td></td><td></td><td> 1,32</td><td></td><td> 1,32</td><td></td><td> 1,32</td>

<td>properties</td><td colspan="3">blends</td><td colspan="4">vulcanised</td><td></td>

<td colspan="6">Vulcanization temperature: 150 ° C</td><td></td><td></td><td></td>

<td>Blend</td><td colspan="6">VZ ZF M 300 BD bl. D. E</td><td>SH</td><td>EF A</td>

<td> 1</td><td> 15</td><td> 101</td><td> 50</td><td> 635</td><td> 53</td><td> 45</td><td> 64</td><td> 13</td>

<td></td><td> 30</td><td> 99</td><td> 66</td><td> 483</td><td> 36</td><td> 42</td><td> 67</td><td> 6</td>

<td></td><td> 45</td><td> 96</td><td> 65</td><td> 490</td><td> 34</td><td> 40</td><td> 66</td><td> 6 258</td>

<td></td><td> 60</td><td> 94</td><td> 64</td><td> 480</td><td> 34</td><td> 40</td><td> 67’</td><td> 9</td>

<td> 2</td><td> 15</td><td> 154</td><td> 137</td><td> 335</td><td> 18</td><td> 45</td><td> 67</td><td> 8</td>

<td></td><td> 30</td><td> 146</td><td> 138</td><td> 307</td><td> 13</td><td> 44</td><td> 68</td><td> 5</td>

<td></td><td> 45</td><td> 145</td><td> 138</td><td> 305</td><td> 10</td><td> 43</td><td> 68</td><td> 5 210</td>

<td></td><td> 60</td><td> 147</td><td> 143</td><td> 303</td><td> 11</td><td> 42</td><td> 67</td><td> 5</td>

<td colspan="9"> 210</td>

<td> 3</td><td> 15</td><td> 125</td><td> 77</td><td> 440</td><td> 22</td><td> 42</td><td> 66</td><td> 8</td>

<td></td><td> 30</td><td> 125</td><td> 101</td><td> 287</td><td> 14</td><td> 41</td><td> 69</td><td> 5</td>

<td></td><td> 45</td><td> 125</td><td> 102</td><td> 262</td><td> 10</td><td> 40</td><td> 69</td><td> 5 223</td>

<td></td><td> 60</td><td> 129</td><td> 104</td><td> 293</td><td>* 14 and</td><td> 39</td><td> 69</td><td> 4</td>

In examples III-V, rubber mixtures based on styrene-butadiene copolymers were used, which contained as silicate fillers synthetic aluminum silicate, or precipitated / silica or natural silicate (colloidal kaolin). Di-3-triethoxyoxysilylpropyl tetra sulfide or di-3-tri-tri disulfide was used as organosilane strengthening additives.

16 methoxysilylpropyl and compared with 3-mercaptopropyltrimethoxysilane (Prior art) in equivalent mixtures.

According to examples III and IV, 3-mercaptopropyltrimethoxysilane could not be obtained under the conditions in practice for blends in mixers without premature curing, while it is possible without. difficulties in the case of rubber mixtures with polysulphide. organosilanes.

The properties of vulcanizates of the new rubber compounds have clearly improved compared to the previous reference compound without the addition of silane: tear strength and modulus increased, permanent deformation after rupture ¹⁵decreased and DIN abrasion improved.

Example V shows that this effect 'also occurs when using such a relatively inactive silicate filler as colloidal ²⁰kaolin.

Example V also shows, as far as the properties of non-vulcanized mixtures are concerned, a clear advance of the present invention relative to the state of the art: 3-mercaptopropyltrimethoxysilane is higher, as components of the mixture, DH / DE and ML 4 values ​​and reduces the time of scarification very much₆. However, in the case of new rubber compounds, the DH / DE and Ml 4 values ​​change in a positive sense, while the curing time 1₅ differs only slightly from the time of the comparative mix.

Examples 6 to 9 show that new rubber compounds based on acrylonitrile butadiene copolymers, butyl rubber, chloroprene rubber, or ethylene propylene terpolymers can be prepared with equally good results.

<td>Example VI</td><td></td><td></td><td>sililopropylu]</td><td> - 1,5</td>

<td></td><td>Mie- Mie-</td><td> 40</td><td>2-mercaptobenzothiazole</td><td> 1 1</td>

<td>Recipe:</td><td>shan-</td><td></td><td>Tetramethylurane disulphide</td><td> 0,5 0,5</td>

<td></td><td>• ka 1 ka 2</td><td></td><td>Sulfur</td><td> 1,5 1,5</td>

<td>Acrylonitrile butadiene rubber</td><td></td><td></td><td>Mixing method</td><td></td>

<td>lowy (Perbunan N 3310 from Far-</td><td> 100 100</td><td></td><td colspan="2">Pre-mixing in a mixer at a temperature</td>

<td>benfabriken Bayer AG)</td><td></td><td> 45</td><td>60 ° C</td><td></td>

<td>Pyrogenic silica (Aerosil</td><td></td><td></td><td></td><td></td>

<td>130 V from Degussa)</td><td> 40 40</td><td></td><td></td><td>completed</td>

<td>Zinc oxide</td><td> 4 4</td><td></td><td>Addition or operation</td><td>after min</td>

<td>Di- [3-triethoxyoxy tetra sulfide</td><td></td><td></td><td>Butyl rubber</td><td> 0</td>

<td>sililopropylu]</td><td> — 1,5</td><td> 50</td><td>1/2 amount of silica, stearic acid</td><td> 2</td>

<td>Dibenzothiazyl disulphide</td><td> 1,5 1,5</td><td></td><td>1/2 amount of silica, zinc oxide</td><td></td>

<td>Dwufenyloguanidyna</td><td> 1,5 1,5</td><td></td><td>organosilane, softener</td><td> 4</td>

<td>Sulfur</td><td> 2,75 2,75</td><td></td><td>Cleaning, airing</td><td> 6</td>

<td>Mixing method</td><td></td><td></td><td>Discharge</td><td> 7</td>

<td>Pre-mixing in a mixer at</td><td>temperature</td><td> 55</td><td>The final mixing took place on</td><td>rolling mill in</td>

<td>80 ° C</td><td></td><td></td><td>roller temperature 50 ° C.</td><td></td>

<td>Addition or operation '</td><td>Completed after</td><td></td><td></td><td></td>

<td colspan="2">Acrylonitrile butadiene rubber 0 min.</td><td></td><td></td><td>completed</td>

<td colspan="2">1/2 amount of silica, stearic acid 1 min.</td><td> 00</td><td>Addition or operation</td><td>after min</td>

<td>1/2 amount of silica, zinc oxide,</td><td></td><td></td><td>Loading imposition</td><td> 0</td>

<td>organosilane</td><td>2.5 min</td><td></td><td>Double cut right and left</td><td> 1</td>

<td>Addition and operation</td><td>Completed after</td><td></td><td>Accelerator and sulfur</td><td> 2</td>

<td>Cleaning, airing</td><td>4 min</td><td></td><td>Double cut right and left</td><td> 4</td>

<td>Discharge</td><td>4.5 minutes.</td><td>JO</td><td>Skin photo. mix</td><td> 5</td>

After storage for 24 hours, the mix was finished in a mixer at 80 ° C, mixing time 1.5 min.

Properties of non-vulcanized mixtures

<td></td><td>Mixture 1</td><td>Mixture 2</td>

<td>Dh / de</td><td> 2350/26</td><td> 1950/31</td>

<td>ts</td><td> 10,6</td><td> 7,8</td>

<td>t "</td><td> 13,4</td><td> 9.8</td>

<td>ML 4</td><td> 132</td><td> 105</td>

<td>c. on</td><td> 1.21</td><td> 1,20</td>

<td>properties</td><td colspan="2">vulcanized mixtures</td>

Vulcanization temperature: 150 ° C

<td>Blend</td><td>vz:</td><td colspan="2">ZF M 300</td><td colspan="2">BD bl. D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

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

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

<td></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></td>

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

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

<td></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></td>

Example VII

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

<td>Recipe:</td><td>the chances</td><td>the chances</td>

<td></td><td>ka 1</td><td>ka - 2</td>

<td>Butyl rubber</td><td> 100</td><td> 100</td>

<td>Low molecular weight precipitated silica</td><td></td><td></td>

<td>muon (Ultrasil VN 3 by De-</td><td></td><td></td>

<td>Gussa)</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>Softener (petroleum oil)</td><td> , 5</td><td> 5</td>

<td>Di- [3-triethoxyoxy tetra sulfide</td><td></td><td></td>

Properties of non-vulcanized mixtures

Mix - Mix 1 ka 2

DH / DE 4300/3 3200/5 vol₅ 1.2 2.9 t «40 17.6

ML 4 135 112

owner: 1.15 1.15

Properties of vulcanized mixtures. Vulcanization temperature: 160 ° C io

Properties of non-vulcanized mixtures

<td>DH / DE</td><td>Mixture 1</td><td>Mixture 2</td>

<td>⁵ AT</td><td> 6,2</td><td> 5,5</td>

<td>t »5</td><td> 10,8</td><td> 10,1</td>

<td>ML 4</td><td> 91</td><td> 84</td>

<td>c. on</td><td> 1,42</td><td> 1,42</td>

<td>properties</td><td colspan="2">vulcanized mixtures</td>

<td>Blend</td><td colspan="5">VZ ZF M 300 BD bl. D.</td><td>E</td><td colspan="2">SH 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></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></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></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></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></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></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></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></td>

<td>Blend</td><td>VZ</td><td>ZF M 300 BD sheet D.</td><td>E</td><td>SH</td><td>EF</td><td>AND</td>

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

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

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

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

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

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

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

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

Example IX

Example VIII

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

<td>Recipe:</td><td>the chances</td><td>the chances</td>

<td></td><td>ka 1</td><td>ka 2</td>

<td>Chlorobutadiene rubber</td><td> 100</td><td> 100</td>

<td>(Baypren 210 from Farbenfabrik</td><td></td><td></td>

<td>Bayer AG. Leverkusen)</td><td></td><td></td>

<td>Two-for-toliloguanidyna</td><td> 0,5</td><td> 0,5</td>

<td>Magnesium oxide</td><td> 4</td><td> 4</td>

<td>Stearic acid</td><td> 1</td><td> 1</td>

<td>A mixture of liquid and soft materials</td><td></td><td></td>

<td>rafin (petroleum jelly)</td><td> 1</td><td> 1</td>

<td>Phenyl-P-naphthylamine (agent</td><td></td><td></td>

<td>anti-aging)</td><td> 2</td><td> 2</td>

<td>Low molecular weight precipitated silica</td><td></td><td></td>

<td>muon Ultrasil VN 2 from Degussa)</td><td> 50</td><td> 50</td>

<td>Plasticizer (naphthenic hydrocarbons)</td><td> 10</td><td> 10</td>

<td>Di- [3-triethoxyoxysil- tetra sulfide</td><td></td><td></td>

<td>lopropylu]</td><td> —</td><td> 1,5</td>

<td>2-merkaptaimidazolina</td><td> 0,75</td><td>0,7E</td>

<td>Zinc oxide</td><td> 5</td><td> 5</td>

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

<td>Recipe:</td><td>the chances</td><td>the chances</td>

<td></td><td>ka 1</td><td>ka 2</td>

<td>Rubber ethylene terpolymer</td><td></td><td></td>

<td>-propylene (Keltan 70 ho-</td><td></td><td></td>

<td>Dutch Staatsminen)</td><td> 100</td><td> 100</td>

<td>Low molecular weight precipitated silica</td><td></td><td></td>

<td>muon (Extrusil from Degussa).</td><td> 100</td><td> 100</td>

<td>Naphthenic hydrocarbon as softener</td><td></td><td></td>

<td>Chach</td><td> 50</td><td> 50</td>

<td>Titanium dioxide</td><td> 10</td><td> 10</td>

<td>Zinc oxide</td><td> 5</td><td> 5</td>

<td>Stearic acid</td><td> 1</td><td> 1</td>

<td>Di- [3-triethoxyoxy tetra sulfide</td><td></td><td></td>

<td>lilopropylu]</td><td> — ’</td><td> 5</td>

<td>Tetramethylthiuram disulfide</td><td> 0,3</td><td> 0.8</td>

<td>Dimethyldiphenyl disulfide</td><td></td><td></td>

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

<td>Tellurium diethyldiocarbamate</td><td> 0,8</td><td> 0,8</td>

<td>Dipentamethylene tetra sulfide</td><td></td><td></td>

<td>thiuram</td><td> 0,8</td><td> 0.8</td>

<td>Sulfur</td><td> 2,0</td><td> 2.0</td>

Mixing method ⁴⁵ Pre-mixing in a mixer at 80 ° C

completed

Mixing method

Pre-mixing in a mixer at 60 ° C

completed

Add or skip operation.

Polychlorobutadiene, guanidine derivative 0 Anti-aging agent, magnesium oxide, stearic acid, petrolatum, 1/3 of silica and

1/3 the amount of silica, 1/2 the amount of plasticizer, organosilane 2.5

1/3 the amount of silica, 1/2 the amount of softener Cleaning, airing 4

Mixing discharge and 5 min. cooling in a water bath 5

After storage for 24 hours, 2-mercaptoimidazoline and zinc oxide were added to the blend at 60 ° C and cooled after 5 min. in a water bath.

Addition or operation after min

Ethylene propylene terpolymer 0

5 ° 1/2 amount of silica, stearic acid 1

1/2 amount of silica, zinc oxide, organosilane, other chemicals 2.5

Cleaning, airing 4

Discharge 5

After storage for 24 hours, the mix was finished in a mixer at 80 ° C, mixing time 1.5 min.

Properties of non-vulcanized mixtures

<td> 00</td><td>Mixture 1</td><td>Mixture 2</td>

<td>DH / DE</td><td> 550/17,5</td><td> 400/19,5</td>

<td>t₆</td><td> 8,5</td><td> 19,2</td>

<td>t85</td><td> 16,4</td><td> 50,4</td>

<td>ML 4</td><td> 50</td><td> 40</td>

<td>C. On</td><td> 1,16</td><td> 1,16</td>

Properties of vulcanized mixtures. Vulcanization temperature: 160 ° C

<td>Blend</td><td colspan="6">VZ ZF M 300 BD bl. D. E</td><td colspan="2">SH EF A</td>

<td> 1</td><td> 10</td><td> 61</td><td> 23</td><td> 825</td><td> 43</td><td> 40</td><td> 53</td><td> 1</td>

<td></td><td> 20</td><td> 62</td><td> 29</td><td> 621</td><td> 25</td><td> 42</td><td> 51</td><td> 3</td>

<td></td><td> 30</td><td> 55</td><td> 32</td><td> 550</td><td> 21</td><td> 42</td><td> 59</td><td> 2</td>

<td> 2</td><td> 10</td><td> 11</td><td> 42</td><td> 125</td><td> 26</td><td> 41</td><td> 54</td><td> 8</td>

<td></td><td> 20</td><td> 91</td><td> 14</td><td> 392</td><td> 1</td><td> 43</td><td> 60</td><td> 3</td>

<td></td><td> 30</td><td> 98</td><td> 98</td><td> 300</td><td> 5</td><td> 44</td><td> 63</td><td> 2</td>

<td colspan="3">In example VI</td><td colspan="5">a blend was used</td><td>a rubber</td>

composition according to the invention based on nitrile rubber, which contained as silicate filler pure silica, produced by flame hydrolysis (Aerosil 130 V from the company Degussa) and di- [3-triethoxysilylpropyl] tetra sulfide as an organosilane reinforcing additive.

The viscosity according to Mooney of blend 2 of this example VI clearly decreased compared to the comparative blend without the addition of organosilane, which means less energy consumption and thus lower costs for further processing of the raw blend. Vulcanization time t₆ shortened only slightly. Vulcanizates from mix 2 are distinguished by a marked improvement in tear strength, modulus and abrasion according to DIN, compared to mix 1 without the addition of organosilane.

According to example VII, the rubber compound according to the invention based on butyl rubber contains precipitated silica (Ultrasil VN 3 from Degussa) as a silicate filler. and di- [3-triethoxysilylpropyl] sulfisulfide as an organosilane reinforcing additive.

This addition of organosilane to the already highly accelerated reference mix does not cause premature curing, but surprisingly extends the curing time t₅. The tensile strengths, modules and permanent deformations of vulcanizates are clearly better than those of the comparative compound vulcanizate.

Example VIII describes a rubber compound based on chloroprene rubber with precipitated silica (Ultrasil VN 3 from Degussa) as a silicate filler and again with di-3-triethoxysilylpropyl tetra sulfide as an organosilane reinforcing additive. The compound 2 vulcanization property is virtually unchanged compared to the comparative compound, while in Mooney's viscosity mix 2 is slightly better. The properties of vulcanizates from the rubber compound according to the invention are clearly better compared to the comparative compound: the tensile strength is more than 40 kg / cm * higher and a 300% module with sometimes more than 60 kg / cm * higher. The latter means an improvement of 100% and above in comparison with mix zero 1.

Example 9 relates to a rubber compound based on ethylene-propylene terpolymer with other precipitated silica (Extrusil from Degussa) as a silicate filler and di-3-triethoxysilylpropyl chper sulfide as an organosilane. Also in this case, an unexpected extension of the time of scorching t was found; ML 4 decreased by 10 units according to Mooney * both. values ​​compared to the reference mixture without the addition of organosilane. The properties of vulcanizates with mixtures 2 of the composition according to the invention are, compared to compound zero 1, much better in terms of breaking strength, modulus and permanent deformation after bursting.

Example X

Car tire tread compound

Mie-MeeHeceptura: cannabis 1 ka 2

Styrene-butadiene rubber with the addition of oil (Buna Hiils 1712) 96, and 96.5 cis-l, 4-polybutadiene (Buna CB 10) 0 (3) 0

Low molecular weight precipitated silica (Ultrasil VN 3 from Degussa) 15 70

Di- [3-Triethoxystltlopropyl] tetra sulfide 6 -

Mixture of equal parts of precipitated silica (Ultrasil VN 3) and di- [3-triethoxysilylpropyl tetra sulfide] - 16

Zinc oxide 4 4

Stearic acid 1.2 1.2

Plasticizer (naphthenic hydrocarbon) 15 15

Anti-aging agent phenyl-β-naphthylamine 1.5 1.5

Anti-aging agent N-isopropyl-N'-phenyl-p-phenylenediamine 1, 1.5

Benzothiazolyl-2-cyclohexylsulfenamide 1.2 1.2

Diphenylguanidine 3.5 3.5

Sulfur 1.6 1.6

Mixing method: "Up-side-down"

Pre-mixing in a mixer at 80 ° C

Addition or operation Completed after

1. Stage:

Fillers, chemicals, polymers 0 min. Cleaning 3 min.

3.5 πΰη discharge.

Storage time 224 hours

2. Stage:

Finishing in a mixer at 80 ° C

The accelerator and sulfur are added to the mixer.

Mixing time 1.5 min.

Properties of non-vulcanised mixtures

Mix - Mix 1 ka 2

<td>these</td><td>_in 20,0</td><td> 18,1</td>

<td>t "</td><td> ’ 26,5</td><td> 26,0</td>

<td>ML 4</td><td> 61</td><td> 61</td>

<td>c. on</td><td> 1,19</td><td> 1,19</td>

Properties of vulcanized mixtures. Tempie vulcanization ratio: 160 ° C

<td colspan="2">Mix VZ ZF M 300 BD bl. D.</td><td rowspan="2">E 38</td><td>SH EF A</td>

<td> 1 20 190 66 592</td><td> 26</td><td> 64 23 91</td>

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

<td colspan="4">Example XI Bulldozer tire tread compound Mie- Mie- Recipe: shan- ka 1 ka 2 Natural rubber (Ribbed Smoked Sheets I) 100 100 Pentachlorothiophenyl zinc salt 0.25 0.25</td>

(Renacit IV from Farbenfabriken Ba-

<td colspan="3">yer, Leverkusen)</td>

<td>Soot ISAF-LM (Corax 6 from Degussa</td><td> 60</td><td></td>

<td>A mixture of 10 parts of di- [3-triethoxysilylpropyl] sulfisulfide and 100 parts of precipitated silica (Ultrasil VN 3 from Degussa)</td><td> 5</td><td> 5</td>

<td>Zinc oxide Stearic acid</td><td> 2,5</td><td> 2,5</td>

<td>Anti-aging agent phenyl-α-naphthylamine</td><td> 1</td><td> 1</td>

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

<td>Anti-aging agent N-isopropyl-N-phenyl-p-femlenediamine.</td><td> 0,8</td><td> 0,8</td>

Ozokerite for rubber (Protector 3888

<td>my · Luneburger Wachsbleiche, GmibH)</td><td> 0,8</td><td> 0,8</td>

<td>Softener (naphthene hydrocarbon)</td><td> 2</td><td> 2</td>

<td>Di- [2-ethylamino-4- disulfide</td><td></td><td></td>

<td>-dwuetyloamino-6-trójazynylu]</td><td> 0,6</td><td> 0,6</td>

<td>Dwufenyloguanidyna</td><td> —</td><td> 2</td>

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

<td>Mixing method: "Up-side-down"</td><td></td><td></td>

Pre-mixing in a mixer at 80 ° C

Addition or operation Completed after

1. Stage:

Filler, chemicals, polymer 0 min.

Cleaning. 3 min

3.5 mm discharge.

Storage time 244 hours

2. Stage:

Finishing in a mixer at 80 ° C

The accelerator and sulfur are added to the mixer

Mixing time 1.5 min.

Properties of non-vulcanized mixtures. Mooney's vulcanization time

<td>these</td><td> 25,4</td><td> 19,9</td>

<td>Vulcanization time t_ss</td><td> 28,1</td><td> 25,3</td>

<td>Mooney viscosity ML 4</td><td> 88</td><td> 77</td>

<td>c. on</td><td> _ 1,15</td><td> 1,18</td>

Properties of vulcanized mixtures

Vulcanization temperature: 145 ° C

Mix VZ ZF M 300 BD E SH EF AT (0.250)

60 249 139 490 36 68 31 102 87

60 257 119 545 15 76 -2 104 64

In Example X, the formula for treads of passenger car tires was disclosed and used in practice, and in Example XI the formula for tread tires for bulldozers. In both formulas, di- [3-triethoxysilylpropyl] tetra sulfide was used as a reinforcing additive, for car tire treads also in the form of a mixture with silica in a 1: 1 ratio for tire tread for bulldozers in the form of a mixture with low molecular weight silica in a ratio of 1:10 .

Example X shows that, within the error limits of the rubber testing methods used, there are no differences between the use of the reinforcing additive in pure form and its use as a mixture with precipitated, fine particle silica.

The properties of unvulcanized and vulcanized mixtures indicate to the skilled person that by using the reinforcing additives of the invention for tire treads of passenger cars reinforced with silica, properties are obtained that largely correspond to those of the respective mixtures with carbon black.

So for the first time it turned out to be possible thanks to the use of polysulphide organosilane reinforcing additives to produce mixtures for treads of passenger cars reinforced with silica without changing the hitherto used rubber industry * mixing method, which in terms of all properties are at least equivalent to appropriate reinforced mixtures soot. '

Example 11 compares the reinforcing additives of the present invention in a tread compound for silica reinforced bulldozer tires with a conventional compound for tread tires of a sulfur reinforced bulldozer.

In Example XI it was shown that, thanks to the use of the inventive additives, silica reinforced rubber compounds are given a number of basic properties that exceed those of carbon black reinforced compounds, e.g. in relation to tear resistance and heat generation (Goodrich flexometer test). '

Compared with Comparative Mixture 1, it should be noted that the use of the reinforcement additive according to the invention slightly reduced the Mooney vulcanization time and the Mooney vulcanization time, however these times are still within the range suitable for the application. The viscosity of the raw mix decreases compared to the comparative mix by as much as 11 units according to Mooney, which should be considered a desirable phenomenon because it reduces the production costs of tire production.

As for the vulcanizate properties, which generally correspond to the properties of the comparative mix, the most important are two properties of the mix according to the invention: clearly greater tear resistance and reduced heat generation. The tear resistance compared to the carbon black reinforced comparative compound increased by 35 ° / · and heat production decreased by 31 · / · from 87 ° to 64 ° C. When assessing absolute values, a Goodrich flexometer test should be noted that it was measured at a 1/4 inch stroke, when the ASTM method recommends a 0.175 inch stroke. It should also be noted that the abrasion according to DIN of the blend with carbon black and the blend with silica are practically the same.

Thus, it was again confirmed that by using the organosilane reinforcing additives according to the invention, it was possible for the first time to easily prepare and then vulcanize mixtures for practical use with pure silica filling, which are comparable in terms of properties with the corresponding mixtures filled with soot, and even exceed them in some important respects.