BRPI0810968B1 - Process for the production of rubber blends, rubber blends, process for the production of vulcanized and vulcanized - Google Patents

Description

(54) Title: PROCESS FOR THE PRODUCTION OF RUBBER MIXTURES, RUBBER MIXTURES, PROCESS FOR THE PRODUCTION OF VULCANIZED AND VULCANIZED (51) lnt.CI .: C08K 3/36; C08K 5/54; C08K 9/00; C08L 21/00 (30) Unionist Priority: 27/04/2007 DE 102007020451.7 (73) Holder (s): ARLANXEO DEUTSCHLAND GMBH (72) Inventor (s): WERNER OBRECHT (85) National Phase Start Date: 27 / 10/2009

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PROCESS FOR THE PRODUCTION OF RUBBER MIXTURES, RUBBER MIXTURES, PROCESS FOR THE PRODUCTION OF VULCANIZED AND VULCANIZED [001] The present invention relates to the production of rubber mixtures, containing microgel, which can be obtained according to this process, covers processes for the production of vulcanized, as well as vulcanized according to the vulcanization process, especially in the form of tires, tire parts or technical rubber articles. By the processes according to the invention, the physical and mechanical properties of non-vulcanized and vulcanized rubber mixtures, silicic acid and microgels, especially microgels containing rubbers, will be improved by the fact that the transformation is carried out sequentially, in several separate stages, with the use of organosilicon compositions with sulfur content.

[002] For the production of tire rolling faces with a good combination of wet slip resistance and friction wear properties, as required for motor vehicle rolling faces, the use of rubber mixtures, containing silicic acid. In order to achieve the desired combination of properties, good dispersion of silicic acid is important, making the coupling in the rubber matrix during vulcanization. For this, in the production of the mixture, organic silanes containing sulfur are used (eg DE-A-24 47 614; US-A4,709,065; EP-A-0 501 227; EP-A-99 074; DE -A-3 813 678 as well as EP-A-447 066).

[003] In these patents, when preparing the mixture, silicic acid is used in combination with organic silanes, containing sulfur. Silanes are integrated into the mixture in the same mixing step as silicic acid, in order to

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2/39 hydrophobic silicic acid and to achieve good dispersion in the mixture. In addition, with sulfur-containing organosilicon, a good coupling of silicic acid in the rubber matrix is achieved during vulcanization.

[004] In these patents there is again a teaching to combine silicic acid with microgels in addition to the sequential integration of silanes.

[005] Also the use of microgels in rubber compounds is known, being, for example, described in the following patents and applications: EP-A-405 216, EP-A-0 575 851, DEA-197 01 489, EP- A-1 149 866, EP-A-1 149 867, EP-A-1 152 030, EP-A-1 298 166, EP-A-1 245 630 and EP-A-1 291 369.

[006] EP-A-405 216 teaches the production and use of polychloroprene-based gels. EP-AO 575 851 teaches the production and use of polybutadiene based gels and EP-A-0 854 171 teaches the production of gels with active vulcanization groups. According to the teaching of this patent, the use of gels is advantageous to achieve a good resistance to wet shutdown / rolling resistance. An indication for this combination of properties is the difference in rebound elasticities at 70 ° C and 23 ° C (^ (R70-R23)). However, the mechanical properties of the vulcanized products produced with these gels are not satisfactory.

[007]

An improvement in the mechanical properties of rubber compounds, containing microgels, is achieved by the use of silanes (EP-A-1 063 259 / U8-A6,399,706). The compounds are based on NR and contain only gel without other fillers. The production of compounds is done in a two stage process. According to the teaching of this patent, in dosages of 75 phr gel (without silica) were

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3/39 found differences very high rebound elasticity of between 70 ° C and 23 ° C (maximum values of 43% and 45% in ^the third. Number of mixtures). However, the mechanical properties of vulcanized products are not sufficient, especially the product (V300 x Eb) from the tension value at 300% elongation (V300) and elongation at break (Eb).

[008] By combining silica, microgel and carbon black in rubber-containing compounds (EP-A-1 401 951 / US-A2003 / 092827) other improvements are achieved, especially in the mechanical properties of vulcanized products, expressed as product V300 x Eb . The best values are found in the addition of 1 phr of the microgel (V300 x E _b = 510 6). With an additional increase in the microgel portion, the V300 x Eb product starts to get worse. In the presence of silica, the highest values for the differences in rebound elasticities Δ (R70R23) = represent 30% (mixture series A) as well as 36% (mixture series B). The greatest difference in rebound elasticities A (r ₇ o-R23) = 38% is found in compound no. 8, free of silica, in mixing series B.

[009] According to the teachings of EP-A-1 149 866, EP-A-1867, EP-A-1 152 030, EP-A-1 298 166, EP-Al 245 630, EP-A-1 291 369 rubber compounds containing silicic acid are produced in combination with gel. In these patents, there is no teaching for the sequential addition of silanes. In addition, the aforementioned patents are missing from the module 300 (V300). In this way, it is not possible to make a comparison of the mechanical properties of vulcanized products, produced according to the teaching of these patents, with other additional data, available in the patent literature, etc., on the basis of the product (V300 x Eb).

[010] To provide further enhancement of

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4/39 properties of rubber compounds, containing silicic acid and rubber gels, further improvements in the properties of vulcanized products are necessary, especially the product of the stress value at 300% elongation and elongation at break (V300 x £ b) without differences in rebound elasticities A (R.7o-R.23) are impaired.

[011] It has now been verified that this objective can be achieved with rubber compounds, especially on the basis of SBR and BR5, which contain, as fillers, at least one oxidic filling material with hydroxyl content, such as, especially , silicic acid and rubber gel, when the production of the mixture is carried out in several stages, and the addition of organic silane, with sulfur content, is divided into at least two mixing stages.

[012] Therefore, an object of the invention is a process for the production of rubber mixtures that involves mixing the following components:

[013] a) one or more rubber components, [014] b) one or more fillers, containing hydroxyl groups, [015] c) one or more microgels, containing hydroxyl groups, [016] d) one or more compositions, of organosilicon, containing sulfur, [017] e) possibly one or more means of vulcanization, [018] f) possibly one or more rubber additives, characterized by the fact that the organosilicon compound, with sulfur content, is added in combination with at least two separate portions, the first portion comprising at least 30% by weight of the total amount of

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5/39 silicon-organic compound, containing sulfur.

RUBBER COMPONENTS A) [019] The rubber components a), according to the invention, preferably comprise those based on dienes, as especially rubbers, containing double bonds, which practically contain no portion of gel and which are according to DIN / ISO 1629 as R-Kautschuke. These rubbers have double bonds in their main chain. Preferably used rubber components are, for example,

example, those in base [020] NR:] [021] SBR: [022] BR:] isoprene [023] SIBR [024] NBR: [025] IIR: isobutene / isoprene) [026] HNBR [027] CR:: [028] XSBR carboxylated [029] XNBR carboxylated [030] ENR: [031] ESBR

Butyl rubber (Rubber of

Styrene / Butadiene Rubber

Butadiene rubber / acrylonitrile

Espoxidized styrene / butadiene rubber and mixtures thereof.

[032] Rubber components, containing double bonds, according to the invention also include those which, according to DIN / ISO 1629, are M-Kautschuke and which, in addition to the saturated main chain, have double bonds and chains

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6/39 collateral. This includes, for example, EPDM.

[033] Preferred rubber components, according to the invention, are: NR, BR, IR, SBR, IIR and EPDM.

[034] Especially preferred are natural rubber (NR) and synthetic polyisoprene (IR), as well as styrene / diolefin rubbers, especially styrene / diene, especially styrene / butadiene rubbers, as well as mixtures of these rubbers.

[035] The term styrene / diolefin (especially butadiene rubbers) is also understood as the SBR solution: rubbers abbreviated L-SBR also as emulsion rubbers SBR, abbreviated E-SBR. The term L-SBR means polymers with rubber content, produced in a solution process based on vinyl aromatics and conjugated dienes (HL Hsieh, RP Quirk, Mareei Dekker Inc. New York-Basel 1996; I. Franta Elastomers and

Rubber Compounding Materials; Elsevier 1989, p. 73-74, 92-94;

Houben-Weyl, Methoden der Organischen Chemie, Thieme Verlag,

Stuttgart, 1987, Band E 20, Seiten 114 bis 134; Ullmann's

Encyclopedia of Industrial Chemistry, Vol A 23, Rubber 3.

Synthetic, VCH Verlagsgeselíschaft mbH, D-69451 Weinheim, 1993, S. 239-364 as well as (FR 2 295 972)) suitable vinyl are styrene, the aromatic monomers of m- and -p methylstyrene, technical mixtures of methylstyrene, p-tert . Butylstyrene, [alpha] -methylstyrene, p-methoxystyrene, vinylnaphthalin, divinylbenzol, trivinylbenzol and divinylnaphthalin. Styrene is preferred. The vinyl aromatum content integrated by polymerization is preferably between 5 and 50% by weight, preferably between 10 and 40% by weight. Suitable diolefins are 1,3-Butadiene, Isoprene, 1,3-Pentadiene, 2,3-dimethylbutadiene 1-phenyl-1,3-butadiene and 1,3-Hexadiene. Are

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Preferred 1,3-Butadiene and isoprene. The content of dienes integrated by polymerization is between 50 to 95% by weight, preferably between 60 to 90% by weight. The content of vinyl groups in the integrated diene by polymerization is between 10 and 90%, the content of double bonds on the basis of 1,4-trans, is between 20 and 80% and the content of double bonds on the basis of 1,4-cis, is complementary to the sum of vinyl groups and double bonds on the basis of 1.4 trans. The vinyl content of L-SBR is preferably> 20%.

[036] Commonly, polymerized monomers and different diene configurations are statistically distributed in polymers. Also rubbers with block-shaped structure, designated as integral rubber, must be framed under the definition of L-SBR (A) (K.-H. Nordsiek, K.-H. Kiepert, GAK Kautschuk Gummi Kunststoffe 33 (1980) , No. 4, 251255).

[037] Under L-SBR, branched rubbers and modified end groups must be included. For example, documents FR 2 053 786 and JP-A-56- 104 906 are cited here. As a branching agent, silicon tetrachloride or tin tetrachloride will preferably be employed.

[038] The production of the rubber component a) for the rubber mixtures according to the invention, is carried out especially by anionic solution polymerization, that is, by means of a catalyst based on alkali or alkaline earth metals, in a organic solvent.

[039] The rubbers / vinyl aroma / diolefin, polymerized in solution, have, advantageously, values

Mooney between 20 and 150 Mooney units, preferably 30 to

100 Mooney units, especially E-SBR types with high molecular index with Mooney values> 80 ME can contain oils

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8/39 in quantities of 30 to 100 parts by weight, referred to 100 parts by weight of rubber. L-SBR rubbers, oil-free, have glass temperatures of -80 ° to + 20 ° C, determined by means of differential thermoanalysis (DSC).

[040] Under the expression E-SBR is comprised of polymers, containing rubber, which are produced in an emulsion process based on vinyl aromas, conjugated dienes and, possibly, other monomers. Ullmannm's Encyclopedia of Industrial Chemistry, Vol A 23, Rubber 3. Synthetic, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, p. 247-251). Vinyl flavorings are styrene, p-methylstyrene and alpha-methyl styrene. Dienes are especially butadiene and isoprene. Other monomers are especially acrylonitrile.

[041] The vinyl flavor content is between 10 and 60% by weight. The glass temperature is between -50 and + 200 ° C (determined by means of DSC) and the Mooney values are between 20 and 150 Mooney units. Especially the E-SBR types, with high molecular content, with Mooney values> 80 ME, can contain oils in quantities of 30 to 100 parts by weight referred to 100 parts by weight of rubber. L-SBR rubbers, free from +20 '

C, covers, oil, have glass temperatures of -80 ° determined by differential thermoanalysis (DSC).

[042] Polybutadiene (BR) especially, two classes of types of polybutadiene. The first class has a minimum 1.4-cis content of 90% and will be produced with the aid of Ziegler / Natta catalysts based on transition metals. Preferably, catalyst systems based on Ti-, Ni-, Co- and Nd- are used (Houben-Weyl, Methoden der Organischen Chemie, Thieme Verlag, Stuttgart, 1987, Band E 20, pages 114 to 134; Ullmann's Encyclopedia of Industrial Chemistry, Vol A 23, Rubber 3. Synthetic, VCH

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Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, S. 239-364). The glass temperature of this polybutadiene is preferably <90 ° C (determined using DSC).

[043] The second class of polybutadiene is produced with Li catalysts, with a vinyl content of

10%

80%.

The glass temperatures of these polybutadiene rubbers are in the range of -90 to + 20 ° C (determined using DSC).

[044] Polyisoprene (IR) has a minimum 1.4-cis content of 70%. Both synthetic 1,4-cis- (IR) polyisoprene is used, as well as natural rubber (NR). In synthetic form, IR is produced both by means of lithium catalysts and also with the aid of Ziegler / Natta catalysts (Houben-Weyl, Methoden der Organischen Chemie, Thieme Verlag, Stuttgart, 1987, Band E 20, pages 114 to 134 ; Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23, Synthetic, VCH Verlagsgesellschaft mbH, D-69451

Rubber 3 Weinheim, natural rubber [045] known as

1993, S. 239-364). Preferably it is used

It also fits into the IR polyisoprene, 3,4-polyisoprene, with glassy temperatures in the range of -20 to + 30 ° C.

[046] Preferably, according to the invention, the rubber component will be chosen from the group consisting of: styrene / butadiene rubbers, polybutadiene and polyisoprene, and these rubbers can also be stretched with mineral oils.

[047] The relationship of the other components to the rubber components a) is commonly expressed in the relative indication of phr quantity (parts per hundred parts of rubber (ie component a)). Commonly, to 100 parts by weight

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10/39 of the rubber components a) 5 to 100 parts by weight of the oxidizing filler containing hydroxyl groups are used b) (corresponding to 5 to 100 phr), 1 to 30 phr, preferably 5 to 25 phr of the microgels c), 0.1 phr to 15 phr, preferably 0.2 phr to 10 phr of the organosilicon composition, containing sulfur d), preferably bis- (triethoxysilylpropyl) or bis- (triethoxysilylpropyl) disulfide, 0.1 to 15 phr, preferably 0.1-10 phr of the vulcanization media e) as well as 0.1 to 200 phr of the rubber additives f). Preferably, the mixtures according to the invention contain carbon black in quantities of 1 to 100 phr.

[048] Oxidic filling substance, containing hydroxyl groups b). As a filling substance b), containing hydroxyl groups, preferably a filling substance with silicon, oxidic content and containing as silicic acid especially. Hydrophilic silicic acids have hydroxyl groups, especially on the surface.

[049] Silicic acid or Silica (Ullmann ^T s

Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, Silica, S.635-645), is especially used as pyrogenic silicic acid (ibid. S. 635-642) or as precipitated silicic acid (ibid. 642 -645), hydroxyl groups, especially such as, according to the invention, precipitated silicic acid will be preferred. The precipitated silicic acids have a specific surface of 5 to 1000 m ² / g, determined according to BET, preferably a specific surface of 20 to 400 m ² / g. They are obtained by treating sodium silicates with inorganic acids, with sulfuric acid being preferably used. Silicic acids may also occasionally be present as oxides mixed with other oxides

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11/39 metallic, such as AI-, Mg-, Ca-, Ba-, Zn-, Zr-, Ti-.

[050] Preferably, silicic acids, according to the invention, are used with specific surfaces of 5 to 1000 m ² / g, more preferred 20 to 400 m ² / g, always determined according to BET.

[051] The oxidic filling substance, used according to the invention, containing hydroxyl groups b), will preferably be used in quantities of 20 to 150 phr, preferably 30 to 120 phr, referred to 100 phr (parts per 100 parts of rubber), being whereas the oxidic filling substance, containing hdiroxyl groups b), preferably represents at least 50% of the solid substance portion, referring to the total quantity of the filling substances employed.

MICROGELS C) [052] The microgels that can be used in the vulcanizable composition according to the invention, have glass temperatures in the range of -75 ° C to + 120 ° C (determined by means of DSC).

[053] The microgel used in the vulcanizable composition, according to the invention, is normally a crosslinked microgel based on homopolymers or copolymers. In the microgels used, according to the invention, therefore, these are generally crosslinked homopolymers or copolymers. The terms homopolymers and copolymers are sufficiently known to the skilled person, being explained, for example, by Volknert, Polymer Chemistry, Springer 1973.

[054] The glass transition temperatures of the microgels are usually 1 ° to 10 ° C higher than the glass transition temperatures of the corresponding non-re-linked homo- or copolymers, with the temperatures of

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12/39 glass transition of the microgels, in a first approximation, increase proportionally to the degree of crosslinking. In weakly cross-linked microgels, the glass transition temperatures are situated only 1 ° C higher than in the corresponding homo- or copolymers. In the case of intensely cross-linked microgels, the glass transition temperatures can be up to 10 ° C higher than the glass transition temperatures of the corresponding non-cross-linked homo- or copolymers. The glass transition temperatures of non-crosslinked based copolymers can, in particular, also be calculated using the following equations (see eg: U. Eisele, Einführung in die Polymerphysik, Springer-Verlag):

[055] Tg Copolymer WÍ * TC [1 + W2 * TC [2 + W3 * Tg ₃ + [056] Tg Copolymer: temperature transition glassy in ° C [057] Wi: Weight portion of homopolymer 1 [058] Tgl : transition temperatures glassy of homopolymer 1 in ° C [059] W ₂ : weight portions of homopolymer 2 [060] Tg ₂ : transition temperatures glassy of homopolymer 2 in ° C [061] W ₃ : weight portion of homopolymer 3 [062] Tg ₃ : transition temperatures glassy of homopolymer 3 in ° C [063] Tg copolymer = (Wl / Tgi) + (W ₂ / Tg ₂ ) + (W ₃ / Tg ₃ ) + [064] Tg copolymer: temperatures of transition glassy copolymer in K [065] Wi: weight portion of the homopolymer in 1

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[066] Tg _x : temperature of glass transition in homopolymers 1 in K [067] W ₂ : weight portion of homopolymer 2 [068] Tg ₂ : temperature of glass transition of homopolymer 2 in K [069] W3: weight share of homopolymer 3 [070] Tg3: temperature glass transition of homopolymer 3 in K [071] Good results are achieved in these calculations when if it starts from the following temperatures in

glass transition of the respective homopolymers:

[072] Polybutadiene: -80 ° C, polyisoprene: -65 ° C, polychloroprene: -39 ° C, polystyrene: + 100 ° C, polyacrylonitrile: + 100 ° C, poly-alpha-methylstyrene: + 115 ° C , poly (2-hydroxyethyl methacrylate): + 75 ° C and Poly (2-methacrylate-hydroxypropyl): + 80 ° C. Other glass transition temperatures are published in J. Brandrup, Ε. H. Immergut, Polymer Handbook, Wiley & Sons 1975.

[073] The microgels used in the vulcanizable composition according to the invention, conveniently present and toluene at 23 ° C, insoluble portions (gel content) of at least 70% by weight, preferably at least 80% by weight and especially preferred at least 90% by weight. This toluene-insoluble portion will be determined in the toluene at a temperature of 23 ° C. In this case, 250 mg of the microgel are swelled in 25 ml of Toluene for 24 hours under vibration, at 23 ° C. After centrifugation at 20,000 rpm it will be separated and dry the insoluble portion. The gel content results from the dry residue quotient and weighing, and is indicated in weight percentages.

[074] The microgels used in the composition

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Vulcanisable 14/39, according to the invention, commonly present in toluene, at 230 ° C, a swelling index (IQ) below 80, preferably below 60 and especially below 40. Especially preferred , the microgel swelling index is in the range of 1 to 30, especially in the range of 1 to 20. The QI swelling index will be calculated from the weight of Toluene at 23 ° C for microgel, containing solvent and swelled for 24 hours ( after centrifugation at 20,000 rpm) and the weight of the dry microgel, using the following formula:

[075] IQ = Wet weight of microgel / Dry weight of microgel.

[076] To determine the swelling index, 250 mg of the microgel are allowed to swell in 25 ml of toluene for 24 h, by shaking. The gel will be removed by centrifugation and weighed and then at 70 ° C it will be dried and weighed again until weight constancy.

[077] In the vulcanizable composition, according to the invention, the microgels employed preferably have glass transition temperatures Tg in the range of -90 ° C to + 150 ° C, especially preferred in the range of -80 ° C to +120 ° C.

[078] The microgels employed, moreover, commonly have a glass transition width (ATg) greater than 5 ° C, preferably greater than 10 ° C, especially preferred of 20 ° C. Microgels that have such a glass transition width , normally are not fully crosslinked in a homogeneous way, unlike totally homogeneous microgels that are obtained, for example, through ray crosslinking. This results in the modification of the module from the matrix phase to the dispersed phase is not direct.

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Therefore, in the event of a sudden request, no rupture effects are produced between the matrix and the dispersed phase, with which mechanical properties, swelling behavior and buckling behavior are advantageously influenced.

[079] The determination of the glass transition temperatures (Tg) and the glass transition width (ATg) of the microgels is verified by means of differential scanning calorimetry (DSC). For the determination of Tg and ATg, two cooling / heating cycles are performed. Tg and ATg will be determined in the second heating cycle. For determinations 10 - 12 mg of the chosen microgel will be placed in a Perkin-Elmer DSC (standard aluminum pan) test vessel. The first DSC cycle will be performed, and the test is initially cooled with liquid nitrogen to -100 ° C and then heated with a speed of 20K / min to + 150 ° C. The second DSC cycle will start by immediately cooling the test, as soon as a test temperature of + 150 ° C has been reached. Cooling takes place at a speed of approximately 320 K / min. In the second heating cycle, the test, as in the first cycle, will once again be heated to + 150 ° C. The heating speed in the second cycle will again be 20K / min. Tg and ATg will be graphically determined on the DSC curve of the second heating process. For this purpose, three lines are applied to the DSC curve. AI ^a . line will be applied to the section of the DSC curve below Tg, at 2 ^a . line will be applied at the branch of the curve that crosses Tg, with a turning point, and at 3 ^a . straight on the rod of the DCS curve above Tg. In this way, three lines with two points of intersection are obtained. Both points of intersection are marked by a characteristic temperature. The transition temperature

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16/39 glass Tg is obtained as an average of these two temperatures and the width of the glass transition ATg is obtained from the difference of the two temperatures.

[080] The microgels contained in the composition according to the invention are mainly known and can be produced in a known manner (see, for example, EP-A-0 405 216, EP-A-0 854 171, DE-A 42 20 563, GB-PS 1078400, DE-A-197 01 489, DE-A-197 01 488, DE-A-198 34 804, DE-A-198 34 803, DEA-198 34 802, EP-A- 1 063 259, DE-A-199 39 865, DE-A-199 42 620, DE-A-199 42 614, DE-A-100 21 070, DE-A-100 38 488, DE-A100 39 749, DE-A-100 52 287, DE-A-100 56 311 and DE-A-100 61 174).

[081] The microgels used according to the invention, especially cross-linked rubber particles based on the following rubbers:

BR Polybutadiene, APR Copolymers of Butadiene Cl-4 alkyl esters / acrylic acid GO Polyisoprene, SBR Statistical styrene-butadiene copolymers with a styrene content of> 0 to <100% by weight, X-SBR Carboxylated styrene-butadiene copolymers FKM Fluorine Rubber, B.C Acrylate rubber NBR Polybutadiene-acrylonitrile copolymerized with acrylic content of 5-60, preferably 10-50% in Weight X- NBR Carboxylated nitrile rubbers CR Polychloroprene IIR Isobutylene / isoprene copolymerisers with a

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isoprene of 0.5-10% by weight HNBR nitrile rubbers, partial and hydrogenated totally EPDM Copolymers of ethylene-propylene EAM Ethylene / acrylate polymers EVM Acetate / vinyl copolymers Q Silicone rubbers AU Polymerized polyurethanes I Polymerized polymer ENR Epoxidized natural rubber or mixtures thereof.

[082] The production of non-cross-linked microgel starting products is conveniently carried out according to the following methods [083] 1. Emulsion cross-linking copolymerization (direct polymerization) using higher functional monomers.

[084] 2. Crosslinking of non-crosslinking latices, for example through treatment with crosslinking agents, such as, for example, dicumyl peroxide.

[085] 3. Redispersion in polymers, inaccessible by emulsion polymerization The leave of solutions correspondents of these polymers in solvents organic and

crosslinking of secondary latices, obtained in this way, according to method 2.

[086] 4. Functionalization of microgels, obtained according to methods 1 to 3, with suitable methods or by buffering with suitable monomers.

[087] Preferably, microgels (B) will be those that can be obtained according to methods 1 and 2.

Especially preferred are those that are produced by

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18/39 copolymerization according to method 1 in emulsion, and in crosslinking polymerization, suitable monomers are integrated in the polymerization with basic functional monomers, especially hydrofunctional.

[088] In the production of microgels, used according to the invention, by means of emulsion polymerization, the following monomers, which are polymerized by radicals, are used, for example: Butadiene, styrene, acrylonitrile, isoprene, acrylic and methacrylic acid ester , tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, 2-chlorobutadiene, 2,3-dichlorobutadiene as well as double-bonded carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc., hydroxy, double bonding, such as, for example, hydroxyethylmethacrylate, hydroxyethylacrylate, hydroxypropylmethacrylate, hydroxypropylacrylate, hydroxybutylmethacrylate, hydroxybutylacrylate, (meth) aminofunctionalized acrylates, achroylin, N-vinyl-2-pyrrolidone and N-alourethyl, N-alourethyl and N-alourethyl, N-alourethyl and N-alourethyl, and amino- (met), such as 2-terc.-butylaminoethyleneacrylate and 2terc.butylaminoethylmethacrylamide, etc.

[089] The crosslinking of the rubber gel can be achieved directly, during the emulsion polymerization, as by copolymerization with crosslinking, multifunctional compositions, or by subsequent crosslinking, as described below. Direct crosslinking during emulsion polymerization is preferred, as mentioned above. Preferred comonomers, of higher functionality, that is, multifunctional, are compositions with at least two, preferably 2 to 4 copolymerizable C = C double bonds, such as diisopropenyl-benzol, divinylbenzol, trivinylbenzol,

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19/39 divinyleter, divinylsulfone, dialysis phthalate, trial cyanurate, 2-polybutadiene, Ν, N'-m-phenylenomaleimide: 2.4toluene bis (maleimide) and / or trialyltrimelite. In addition, 4-valent C2 to CIO alcohol methacrylates, such as butandiol, hexandiol, bisphenol-A, sorbitol with glycerin units, aliphatic polyesters, as well as acid considered to be the cryolates and polyvalents, preferably 2 ethylene glycol, propandiol-1,2 , polyethylene glycol with 2 to 20, preferably 2 oxyethylene, neopentylglycol, trimethylpropane, pentaerythrite, maleic di- and polyols unsaturated, fumaric acid, and / or itaconic acid.

[090] Examples ethylene glycol (meth) acrylate, propylene glycol (met) acrylate, 1,4-butandioldi (met) acrylate, 1,6-hexandiol (meth) acrylate, trimethylolpropandi (meth) acerylate, hexandioldi (meth) acrylate, trimethylolpropandi ( met) acrylate, trimethylolpropantri (met) acrylate, etc.

[091] Monomers of higher functionality can be used alone and in combination. Quantitative portions of these monomers are located, for example, around 0.01 to 10% by weight, based on the total mass of the microgels.

include:

[092] Examples for direct crosslinking in polymerization are described, by way of example, in the following documents: EP-A-1 664 158, EP-A-1 149 866, EP-A-1 149 867, EPA-1 298 166, EP-A-1 291 369, EP-A-1 245 630.

[093] Cross-linking to rubber microgels during emulsion polymerization may also be carried out by continuing the polymerization to large volumes or in the process of feeding monomers through polymerization with large internal volumes. Another possibility is

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20/39 also in carrying out the emulsion polymerization in the absence of regulators.

[094] For the crosslinking of basic micro-gel products, crosslinked or weakly crosslinked, in connection with the emulsion polymerization, it will be better to use the latices that are obtained in the emulsion polymerization. Natural rubber latices can also be cross-linked in this way.

[095] Suitable chemical agents are, for example, organic peroxides, such as dicumiperoxide, tbutylcumylperoxide, Bis- (t-butyl-peroxy-isopropyl) benzol, butyl dit-peroxide, 2,5-dimethylhexane-didroperoxide, 2,5-dimethylhexine- 3,2,5-dihydroproperoxide; dibenzoyl peroxide, Bis- (2,4-dichlorobenzoyl) peroxide, t-butylperbenzoate as well as organic azo compositions, such as Azo-bis-isobutyronitrile and Azobis-cyclohexanitrile, as well as di- and Ppolimercapto compositions, such as dimercaptoethane, 1,6-dimercaptohexane , 1,3,5 trimercaptotriazine and mercaptotherminated polysulfide rubbers, as mercapto-terminated reaction products of bis-chlorethylformal with sodium polysulfide.

[096] The ideal temperature for carrying out post-cross-linking depends, of course, on the reactivity of the cross-linking agent and can be carried out at a temperature from room temperature to approximately 180 ° C, possibly under increased pressure (see, in this case, Houben -Weyl, Methoden der organischen Chemie, 4. Auflage, Band 14/2, p. 848). Especially preferred crosslinking agents are peroxides.

[097] The crosslinking of rubber, containing C = C double bonds for microgels can also be done in the dispersion. For example, emulsion with simultaneous partial hydration, possibly complete of the double bond C = C by hydrazine, as described in US 5,302,696 or US 5,442,009

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21/39 or, possibly, other hydrating agents, for example, organometallic hydride complexes.

[098] Before, during or after the post-crosslinking, an increase of particles can eventually be achieved by agglomeration.

[099] The microgels used according to the invention are modified by hydroxyl groups, especially on their surface. The hydroxyl group content of the microgels will be determined by reaction with acetane hydride and titration of acetic acid, then released, with KOH according to DIN 53240 as the hydroxyl number with the dimension of mg KOH / g polymer. The hydroxyl number of microgels is preferably between 0.1100, even more preferred 1 to 100 mg KOH / g microgel, even

most preferred 3 to 70 mg KOH / grams microgel, even more preferred from 5 to 50 mg KOH / grams in microgel. [0100] THE integration From hydroxyl groups in microgels, used in a deal with The invention, if you can,

especially by employing hydroxy bonds containing double bonds, such as, for example, hydroxyalkyl (meth) acrylates such as 2hydroxyethiol (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3hydroxybutyl ( met) acrylate and 4-hydroxybutyl (met) acrylate, etc .; Polyalkyleneoxyglycol mono (meth) acrylates (with 2 to 23 alkyleneoxy units) such as polyethylene glycol, polypropylene glycol, etc .; unsaturated amides, containing hydroxy groups, such as N-Hydroxymethyl (meth) acrylamide, N- (2hydroxyethyl) (meth) acrylamide and N, N-Bis (2hydroxyethyl) (meth) acrylamide, etc .; vinilaromatic compositions, containing hydroxy groups such as o-hydroxystyrene, mhydroxystyrene, p-hydroxystyrene, o-hydroxy-alpha-etilstirol, m-hydroxy-alpha-methylstyrene, p-hydroxy-alpha-methylstyrene and

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22/39 p-vinylbenzyl alcohol etc .; compositions, compounds, etc. (Met) alcohol-allyl-.

[0101] The expression (meth) acrylate always includes acrylates and methacrylates in this application.

[0102] In addition, hydroxy groups can also be obtained by further modification of microgels, containing no hydroxyl groups.

[0103] Preferred microgels according to the invention, are those based on styrene, butadiene and hydroalkyl (meth) acrylates, such as ΗΕΜΆ, which are directly cross-linked by the addition of polyfunctional aniline compositions, such as especially polyacrylates, such as trimethylolpropanotriacrylate.

ORGANOSILICE COMPOSITIONS, CONTAINING SULFUR D) [0104] Organosilicon compositions d) generally always contain at least one of the following structural elements:

[0105] - an organosilicon structural element, especially an alkoxysilyl group, preferably a trialcoxysilyl group, [0106] - a structural element, containing sulfur, especially a sulfide or polysulfide radical Sx, where x in the middle may be from 1 to 10, preferably from 1 to

6, [0107] - a so-called divalent Q spacer group that unites the organosilicon structural element with the sulfur-containing structural element.

[0108] As organosilicon compositions, containing sulfur, those with the following basic structures are especially considered:

Petition 870180050307, of 06/12/2018, p. 29/54 ^R \

H —- SJ — Q-Sx-fl

23/39 ° \ _R V_, _S j ™ Q_ _{S; (} ._Q_ _S | R ^{j /} [0109] where [0110] x in the middle can be 1 to 10, preferably 1 to 6, [0111] R ¹ , R ² and R ³ mean alkoxy groups, preferably with 1 to 10 carbon atoms, [0112] Q represents a spacer group especially on the basis of aliphatic, aromatic or [0113] heteroaromatic carbon chains, preferably with 1 to 20 carbon atoms 1 to 10 carbon atoms and 1 to 3 hetero atoms, such as oxygen, sulfur, nitrogen, [0114] R ⁴ represents hydrogen, alkyl and / or a radical with the following structures:

The <

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24/39 [0115] where R represents an aliphatic, heteroaliphatic, cycloaliphatic, aromatic or heteroaromatic radical with 1 to 20, preferably 1 to 10, carbon atoms and 1 to 3 hetero atoms, such as oxygen, nitrogen or sulfur.

[0116] Preferred organosilicon compositions, with sulfur content, are Bis (tri-ethoxy-silyl-propylpolysulfans) with the following structural formula:

OEt

CHj— CH - ^ - 00 OEt [0117] with n = 2 to 4. Such products are marketed under the brand name Silan Si 75 (n = 2) and as Silan Si 69 (n = 4) by the company Fa. Degussa.

[0118] Sulfur-containing organosilicon compositions are conveniently employed in overall amounts from 0.2 phr to 12 phr.

[0119] According to the invention, it is essential that organosilicon compositions, containing sulfur, d) are added in at least two separate portions. Separated means that between the addition of the portions there is a temporal distance. It is clear to the specialist what this means in practice, without determining a lower limit for the temporal distance. Preferably, the time distance is at least approximately 1 minute, and even more preferred, at least 20 minutes to 6 or 8 hours, depending on the rubber mixture and mixing apparatus. Preferably, the addition takes place during at least two different mixing stages, with temperatures increased by especially more than 60 ° C, between which a cooling step is especially situated.

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VULCANIZING MEANS E)

25/39 [0120] Vulcanization means, used in accordance with the invention, are especially sulfur or sulfur-releasing means, such as, for example, dithomorpholine (DTDM) or 2- (4morpholino-dithio) benzothiazole (MBSS). Sulfur and sulfur-releasing means are employed in amounts of, for example, 0.1 to 15 parts by weight, preferably 0.1 - 10 parts by weight, based on the total amount of rubber.

RUBBER ADDITIVES F) [0121] They are used according to vulcanization. Examples of sulfenamide vulcanization are, by guanidines, dithiocarbamates, substances part of rubber additives, the invention, suitable accelerator accelerators, for example, mercapto-benzothiazoles, thiurama, thiourea disulfides, thiocarbonates and dithiophosphates, etc. (Ullrnann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, vol A 23 Chemicals and Additives, S. 366-417).

[0122] Conveniently, the vulcanization accelerators are not added in a mixing step at increased temperatures that is carried out to activate the oxidic filling substance, containing hydroxyl groups, such as silicic acid, that is, microgels, by means of organosilicon compositions. , containing sulfur as they would result in premature vulcanization of the mixture. Therefore, they will be integrated preferentially after the addition of temprature with sulfur content, organosilicon, at temperatures preferably below 100 ° C.

[0123] Vulcanization accelerators will be used preferably in quantities of 0.1 to 15 parts by weight, preferably 0.1-10 parts by weight, referring to the

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26/39 total amount of rubber.

[0124] Rubber mixtures, produced according to the invention, preferably contain at least one vulcanization accelerator. Mixtures often contain several accelerators, possibly in combination with activators.

[0125] Rubber mixtures produced according to the invention preferably contain other rubber additives already known.

[0126] This also includes, in particular, other fillers, such as carbon black, which is preferably used in rubber mixtures produced according to the invention.

[0127] Carbon blacks (E) produced according to the invention, see carbon or carbon black (Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, vol A 5 Carbon Black, S.95-158 ) are preferably obtained according to the process called gas black-, furnace black-, lamp black- and thermal black- being designated according to the new ASTM nomenclature

(ASTM D 1765 and D 2516) as N 110, N 115, N 121, N 125, N 212, N 220, N 231, N 234, N 242, N 293, N 299, s 315, N 326, N 330, N 332, N 339, N 343, N 347, N 351, N 375, N 472, N 539, N 550,

N 582, N 630, N642, N 650, N 660, N 683, N 754, N 762, N 765, N 772, N 774, N 787, N 907, N 908 N 990, N 991 S 3 etc. The carbon blacks used in accordance with the invention preferably have a BET surface between 5 to 200 m ² / g.

[0128] According to the invention, carbon black will preferably be used in amounts from 0 to 120 phr, preferably from 1 to 100 phr, more preferably from 5 to 80 phr.

[0129] According to the invention, the quantity

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27/39 total of oxidic filler, containing hydroxyl groups, b) and carbon black is preferably at 20 to 160 phr, preferably 25 to 140 phr.

filling substances, [0130] Others possibly used, are:

[0131] synthetic silicates, such as aluminum, earth alkali silicate, such as [0132] - magnesium silicate or calcium silicate with BET surfaces of 20-400 m ² / g and primary particles of 5-400 nm silicate of diameters of [0133 ] natural silicates, such as kaolin, and other naturally occurring silicic acids, [0134] - Metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, [0135] -Metallic carbons, such as calcium carbonate , magnesium carbonate, zinc carbonate [0136] - Metal sulphates, such as calcium sulphate, barium sulphate, [0137] -Metallic hydroxides, such as aluminum hydroxide and magnesium hydroxide, [0138] -Glass fibers and glass products glass fibers (straps, strips or glass microspheres) [0139] -Thermoplastics (polyamide, polyester, aramid, polycarbonate, 1,2 syndiotactic polybutadiene and trans-1,4 polybutadiene as well as cellulose and starch, all do not meet the definition of component b).

[0140] Other rubber additives include protective agents against aging, protective means against reversion, protective means against light, protective means against ozone, auxiliary processing means, emollients, mineral oil, tackifier, propellants, dyes, pigments,

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28/39 waxes, resins, thinners, organic acids, vulcanization retarders, vulcanization activators, such as zinc oxide, stearic acid, as well as zinc stearate, metal oxide, as well as other filler activators, such as, for example, triethanolamine, trimethylpropane, polyethylene glycol, hexanthriol, aliphatic trialcoxysilanes or others known in the rubber industry (Ulimann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1993, vol A 23 Chemicals and Additives, S. 366- 417).

[0141] Rubber additives are used in conventional quantities, among other factors according to the purpose of use. Standard quantities for individual rubber additives, with the exception of other filler materials, such as especially carbon black or mineral oil, are, for example, around 0.1 to 50 phr.

[0142] The production of the mixture takes place, at least in the first mixers, components a) + b) + c) are integrated into the mixture, as well as from 30% to 80%, preferably 40 to 60% of the total amount of the sulfur-containing orgnanosilicon composition, d) is added to the mixture, the treatment being carried out at temperatures preferably from 80 to 200, more preferred 120 ° C to 190 ° C, even more preferred from 130 ° C to 180 ° C in thermomechanical form between 1 to 15 minutes, preferably from 2 to 10 min, the total amount of microgel c) being contained in the rubber mixture in whole or in part during the first mixing stage. In the first mixing stage, other rubber additives, such as emollients, vulcanization activators, such as zinc oxide, stearic acid, can be added to the mentioned components, preferably conveniently two-stage means, with at least two stages.

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29/39 vulcanization, such as aging, as well as diphenylguanidine or sulfur, protective means against as an organic base, such as di-o-tolylguanidine, which, preferably, will not be added in the presence of vulcanization means. Conveniently, in the first stage of mixing, no vulcanization accelerators will be added in order to avoid premature vulcanization.

[0143] Conveniently, the rubber mixture obtained in the first mixing stage is cooled to <140 ° C, preferably <100 ° C, before adding the remaining amount of organosilicon composition, containing sulfur, as well as the others. components. It is also possible to store the mixtures at room temperature between the first and the second mixing stage.

[0144] Preferably, in the second mixing stage of the mixture obtained in the first mixing stage, the remaining amount of organosilicon composition, containing sulfur, will be added, being treated in a thermomechanical process at temperatures preferably from 80 to 200, more preferably 120 ° C to 190 ° C ° C, even more preferred 130 ° C to 180 ° C, between 1 to 15 minutes, preferably 2 to 10 min. In the second mixing stage, in addition to the aforementioned components, other rubber additives can be added, such as emollients, vulcanization activators, such as zinc oxide, stearic acid, vulcanization media, such as sulfur, protective media against aging, as well as a base organic as diphenylguanidine or di-o-tolylguanidine, if this has not already been done in the first mixing stage. Conveniently, also in the second mixing stage, vulcanization accelerators will not be added in order to avoid premature vulcanization at high temperatures.

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30/39 [0145] Conveniently, the rubber mixture obtained in the second mixing stage, will be cooled, to temperatures of <100 ° C, preferably <80 ° C before adding other components and especially one or more vulcanization accelerators. It is also possible to store the mixture at room temperature, between the second and third mixing stages.

[0146] In the thermomechanical treatment of the rubber mixture in the first and second mixed stages, premature vulcanization of the mixture must be avoided. For this reason, the thermomechanical treatment will be carried out without additives that would result in a premature vulcanization of the mixture.

[0147] For this reason, the addition of vulcanization accelerators and possibly also sulfur donors, hidden bismercaptanes, as well as sulfur and eventually zinc oxide and stearic acid will have to be added at the end of the second mixing stage, after cooling the mixture. for temperatures of <120 ° C, preferably <100 ° C, especially preferred <80 ° C.

[0148] The addition of accelerators can also be done in a third mixing stage, which is performed at temperatures of <60 ° C, eg in a cylinder.

[0149] Sets suitable for producing the mixture are already known and include, for example, cylinders, internal mixers or also mixer-extruders.

[0150] The vulcanization of rubber mixtures, produced according to the invention, will be carried out preferably at temperatures of 100-250 ° C, preferably 130-180 ° C, possibly under a pressure regime of 1 to 100 bars.

[0151] Rubber mixtures, produced from

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31/39 according to the invention, they are adapted for the production of different tire components, especially for the tire bearing faces, reinforcements, carcasses, side walls, reinforced side walls for spare tires, mixtures of apex, etc., as well as for obtaining technical rubber products, such as damping elements, cylinder linings, conveyor belt linings, belts, spinning looms, seals, golf ball cores, shoe soles, etc. Mixtures for the production of

bearing in tires, reinforcements of tires, carcasses and mixtures apex, tires or tire parts, including also, per example, faces of bearing of tires for summer, Winter and all seasons, good as faces of roundly of tires in vehicles

passenger cars and utilities.

[0152] The invention will be described on the basis of the following examples.

EXAMPLES:

RUBBER GEL [0153] For the present invention an SBR gel with Tg = -15 ° C was used. This gel has an insoluble portion of 94.8% by weight in toiol. The swelling index in toluene is 7.35. The hydroxyl index is 32.8 mg KOH / g Gel.

[0154] The production of the gel was done by copolymerizing a mixture of monomers, whose composition is listed in the following table, and in EP 1 298 166, with the title [1] Production of Rubber Gel, in section [077], revealed polymerization conditions were employed.

Monomers Quantitative installments Butadiene 44.5 Styrene 46.5 Trimethylolpropantrimethacrylate 1.5 Hydroxyethylmethacrylate 7.5

[0155] The continued treatment and preparation of the gelPetição 870180050307, dated 06/12/2018, p. 38/54

32/39 latex, obtained in poilimerização, was made as indicated in EP 1245 630 Production Example 1: Production of Conjugated

Diene-Based Rubber Gel 1, as described in sections [0103] and [0104].

VARIATION IN THE SEQUENCE OF MICROGEL ADDITION AND ORGANOSILICE COMPOSITION, CONTAINING SULFUR [0156] Test 1 represents a comparative example, in which, as a filling substance, essentially silicic acid (80 phr) in addition to carbon black (5 phr) is used without microgel. The activation of silicic acid is carried out with Bis (tri-ethoxy-silylpropyl-monosulfan) (Si 75 from Degussa Hüls AG), and the entire amount of silanes is added in the 1st mixing stage.

[0157] Test 2 is a comparative example, in which the rubber mixture, in addition to silicic acid (80 phr) also contains microgel (20 phr), as well as a little carbon black (5 phr). The activation of silicic acid and microgel occurs with Bis (tri-ethoxy-silylpropyl-monosulfan) (Si 75 from Degussa Hüls AG), and the total amount of organosilanes, containing sulfur, is used in the first mixing stage.

[0158] Tests 6 and 7 are comparative tests not according to the invention, in which, in the first mixing stage, only 20% of the total amount of organosilanes with sulfur content, 80% of the total amount of organosilane with added content were added sulfur (= organosilicon composition, containing sulfur) were added in the second mixing stage.

[0159] Tests 3, 4 and 5 of this study are examples according to the invention, in which, in the first mixing stage, 75% (tests 5 and 4) and 50% were added

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33/39 (test 5) of the total amount of sulfur-containing organosilanes. The total amount of organosilanes, containing sulfur, in these examples was added in the second mixing stage. In test 4, the microgel was also added only in the 2nd. mixing stage.

1. MIXING STAGE

Compound no. 1 2 3 4 5 6 7 SBR Solution ¹¹ 110 110 110 110 110 110 110 Polybutadiene ²¹ 20 20 20 20 20 20 20 Microgel ³¹ 20 20 20 20 Salicylic acid ⁴¹ 80 80 80 80 80 80 80 Mineral oil ⁵¹ 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Zinc Oxide ⁶¹ 2, 5 2, 5 2.5 2.5 2.5 2, 5 2.5 Stearic acid ⁷¹ 1 1 1 1 1 1 1 TMQ ⁸¹ 1 1 1 1 1 1 1 6 PPD ⁹¹ 1 1 1 1 1 1 1 Ozone Wax ¹⁰¹ 1.4 1.4 1.4 1.4 1.4 1.4 1.4 SY75 ¹¹¹ 6.4 6.4 4.8 4.8 3.2 1.3 1.3 Maximum temperature 150 150 150 150 150 150 150 Time in temp.max. 6 6 6 6 6 6 6 Cooling and storage at 23 ° C [h] 24 24 24 24 24 24 24

[0160] 1) Buna® VSL 5025-1 HM from the company Lanxess

Deutschland GmbH (with 37.5 phr diluted mineral oil) [0161] 2) Buna® CB 25 (Neodym-Polybutadien) from Lanxess Deutschland GmbH

[0162] 3) Microgel [0163] 4) Vulkasil S gives Lanxess company Deutschland GmbH [0164] 5) Enerthene 1849-1 [0165] 6) Zinkweiss (oxide in zinc) Rotsiegel da company Firma Grillo Zinkoxid GmbH [0166] 7) Edenor C 18 98- 100 Cognis company

Deutschland GmbH [0167] 8) 2,2,4-Trimethyl-1,2-dihydrochinonlin, polymerisiert (Vulkanox® HS / LG from Lanxess Deutschland

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34/39

GmbH) [0168] 9) N-1,3 -Dimethylbutyl-N'-phenyi-pphenylendiamin (Vulkanox® 4020 / LG from Lanxess Deutschland GmbH) [0169] 10) Antilux® 654 from RheinChemie

GmbH [0170] 11) Bis (tri-ethoxy-silylpropyl monosulfan) (Si 75 from Degussa Hüls AG)

2nd stage mixer Compound no. 1 2 3 4 5 6 7 Microgel - 20 - 20 Si75 - - 1, 6 1, 6 3.2 5.1 5.1 Maximum temperature 150 150 150 150 150 150 150 Time in temp.max. 6 6 6 6 6 6 6 Cooling and storage at 23 ° C [h] 24 24 24 24 24 24 24

3rd. INTERNSHIP

Compound no. 1 2 3 4 5 6 7 Carbon black ¹²⁾ 5 5 5 5 5 5 5 Sulfur ¹³¹ 1.9 1.9 1.9 1.9 1.9 1.9 1.9 CBS ¹⁴¹ 1.9 1.9 1.9 1.9 1.9 1.9 1.9 DPG ¹⁵¹ 2.3 The 2, 3 2.3 2, 3 2.3 2, 3 Maximum temperature [° C] <50 <50 <50 <50 <50 <50 <50

[0171] 12) Corax N 234 from Degussa Hülsa

AG [0172] 13) Soluble sulfur (ground sulfur

90/95 ° Chancel® by Firma Solvay Barium Strontium) [0173] 14) N-Ciclohexil-2-benzothiazilsulfenamide (Vulkanox® CZ / C by Lanxess company

Deutschland GmbH) [0174] 15) Diphenylguanidine (Vulkacit® D / C da

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35/39 company Lanxess Deutschland GmbH).

[0175] Mooney's viscosity and Mooney's relaxation after 10 and 30 sec were determined in the non-vulcanized rubber mixture. It was evidenced that tests 3 and 5, according to the invention, presented lower Mooney viscosities (ML1 + 1 and ML1 + 4 always at 100 ° C), as well as lower Mooney relaxations after 10 and 30 sec. than comparative tests 1 and 2. This means that mixtures, produced according to the invention, can be processed more easily than comparative tests 1 and 2.

MIXING TEST

Compound no. 1 2 3 4 5 6 7 ML1 + 1 (100 ° C) [ME] 133, 9 116, 3 114, 6 130 109.7 103.5 114.2 ML 1 + 4 (100 ° C) [ME] 98.8 99, 4 97, 3 110.5 92 89.5 97.2 Relaxation / 10sec. [% 31.6 30, 3 29.3 33.2 28.8 27.7 29.4 Mooney Relaxation / 30sec. [%] 24.5 23, 3 22.5 27.2 22.2 20.9 23.3

[0176] The vulcanization behavior of the mixtures is examined on the rheometer at 160 ° C according to DIN 53 52 9, with the aid of the Monsanto MDR 2000E rheometer. In this way, characteristic data were determined, such as F _a , F _ma x, F _m ax.-F _a , uncle, t50, t90 and t95.

[0177] According to DIN 53 529, Part 3, they mean: [0178] F _a : Vulcanic indication at least of the crosslinking isotherms [0179] [0180] Fmax: Maximum of the volcanic indication [0181] Fmax - F _a : Differences in the indications volcametric between maximum and minimum

VOLCAMETRIC TEST

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Compound no. 1 2 3 4 5 6 7 F _to [dNm] 3.59 A, 12 4.66 6, 11 4.31 4.26 5, 33 Fmax [dNm] 20, 15 18.2 18, 19, 17, 17, 18, Fmax ~ Fa [Óm] 16, 56 13, 13, 13, 13, 13, 13, uncle [sec] 91 118 122 112 126 125 113 t ₅ o [sec] 188 211 213 204 217 211 202 t ₉₀ [sec] 685 615 630 665 660 589 578 t ₉₅ [sec] 985 878 896 940 935 883 849 tgo ^_ uncle [sec] 497 404 417 461 443 378 376

[0182] In examples 3, 4 and 5 depending on the invention, the influences of the dosage of gel and silanes do not have significant effects with respect to the vulcanization process, vulcanization speed and degrees of crosslinking.

[0183] The test specimens, necessary for the characterization of vulcanization, were obtained by vulcanization by pressing the mixtures with a hydraulic pressure of 120 bar at 160 ° C. The heating times for the different compounds are shown in the following table:

Time vulcanization Compound No. 1 2 3 4 5 6 7 Temperature [° C] 160 160 160 160 160 160 160 time [min.] 21 21 21 21 21 21 21

[0184] The vulcanization properties of the tests

3, 4 and 5, according to the invention, and comparative tests 1, 2, 6 and 7 not according to the present invention, have been gathered in the following table:

Vulcanization properties Compound No. 1 2 3 4 5 6 7 Shore A hardness a 23 ° C DIN 53505 64.9 62.4 62.3 62.7 62.1 61.1 61.3 Shore A hardness at 70 ° C DIN 53505 58.5 58 59 60 59 59 61

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37/39

Elasticity ricochet / 0 ° C DIN 53512 [%] [%] 9 9 9 9 9 9 9 Elasticity ricochet / 23 ° C DIN 53512 [%] [%] 26 23 23 20 23 24 22 Elasticity ricochet / 70 ° C DIN 53512 [%] [%] 58 61 62 62 63 62 62 Elasticity / 100 ° C 56 69 69 69 69 70 69 Delta R70-R23 32 38 39 42 40 38 40 Set of 5, 6 5, 01 6, 01 5.23 5.68 5.59 4.53 Set of 14.42 14.41 14.32 14.28 15.23 15.74 14.78 ol0 DIN 53504 [MPa] 0.6 0.5 0.6 0.6 0.5 0.5 0.5 o 25 DIN 53504 [MPa] 1.0 0.9 0.9 1.0 0.9 0.9 0.9 50 DIN 53504 [MPa] 1.5 1.4 1.4 1.5 1.4 1.3 1.4 o 100 DIN 53504 [MPa] 2.6 2.7 2.8 3 2.8 2.6 2.7 o 300 DIN 53504 [MPa] 13, 8 16.2 16.4 16.2 16.8 15, 4 15, 0 resistance DIN53504 [MPa] 21.4 20.1 20.4 20.2 20.2 20 19, 9 Dilation DIN53504 [MPa] 413 355 351 368 344 368 378 o 300 x sb 5699 5751 6388 5962 5779 5667 5670 Wear DIN53516 [mm ³ ] 117 116 115 113 115 121 116

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Set of compression / 23 ° C [%] 5, 6 5, 01 6, 01 5.23 5.68 5.59 4.53 Set of compression / 70 ° C [%] 14.42 14.41 14.32 14.28 15.23 15.74 14.78 DIN 53504 [MPa] 0, 6 0.5 0, 6 0.6 0.5 0.5 0.5 o 25 DIN 53504 [MPa] 1.0 0.9 0.9 1.0 0.9 0.9 0.9 50 DIN 53504 [MPa] 1.5 1.4 1.4 1.5 1.4 1.3 1.4 o 100 DIN 53504 [MPa] 2, 6 2.7 2.8 3 2.8 2, 6 2.7 o 300 DIN 53504 [MPa] 13.8 16.2 16.4 16.2 16.8 15, 4 15, 0 resistance DIN53504 [MPa] 21.4 20.1 20.4 20.2 20.2 20 19, 9 Dilation DIN53504 [MPa] 413 355 351 368 344 368 378 The 300 X Sb 5699 5751 6388 5962 5779 5667 5670 Wear DIN53516 [mm ³ ] 117 116 115 113 115 121 116

Dynamic properties / Eplexor-1 Test * (Rate heating: lK / min) Compound No. 1 2 3 4 5 6 7 E '(0 ° C) / 10Hz [MPa] 44.09 46.11 47.15 60.96 43, 98 46, 99 55.56 E (0 ^u C) / 10Hz [MPa] 15.86 21.04 21.63 31.36 20.09 20.97 29, 14 tan δ (0 ° C) / 10 Hz 0.36 0.456 0.459 0.515 0.457 0.447 0.525 E '(60 ^u C) / 10Hz [MPa] 10.57 7.01 7.03 6.73 6, 66 7.01 6.28 E (60 ^u C) / 10Hz [MPa] 1.15 0.66 0.68 0.59 0.62 0.68 0.56 tan δ (60 ° C) / 10 Hz 0.109 0.095 0.096 0.088 0.093 0.098 0.09 tan õ (0 ° C) -tan δ (60 ° C) 0.251 0.361 0.363 0.427 0.364 0.349 0.435

[0185] Eplexor 500 N (Gabo-Testanlagen GmbH,

Ahlden, Deutschland) [0186] Vulcanized products 3, 4 and 5, produced according to the invention, compared to comparative products 1 and 2 present products greater than 0300 x Sb without loss in differences in rebound elasticities A (R70R23) , that is, the vulcanized ones, produced according to the

Petition 870180050307, of 06/12/2018, p. 45/54

39/39 invention, have improved mechanical properties without loss in the wet slip resistance / rolling resistance reaction.

[0187] Improvements in the wet slip resistance / rolling resistance ratio are confirmed by dynamic measurements (Eplexor Test). In vulcanized 3, 4 and 5 greater differences are found for tan δ (0 ° C) - tan δ (60 ° C) than in comparative tests 1 and 2.

[0188] By sequential silanization, according to the invention, in the vulcanized products an improved product is obtained with a tension value at 300% elongation and elongation at break (0300 x Sb,) without losses in the difference in rebound elasticities A (R70 -R23).

Petition 870180050307, of 06/12/2018, p. 46/54

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Claims (24)

1. PROCESS FOR THE PRODUCTION OF RUBBER MIXTURES, covering the mixture of the following components: a) one or more rubber components, b) one or more oxidic fillers, containing hydroxyl groups, c) one or more micreogels, containing hydroxyl groups, d) one or more organosilicon compositions, containing sulfur, e) possibly one or more means of vulcanization, f) evidently one or more rubber additives, characterized by the organosilicon composition, containing sulfur d), be added in at least two separate portions, the first portion comprising at least 30% by weight of the total amount of the organosilicon composition, containing sulfur. 2. featured mixers. PROCESS, according to covering claim 1, minus two stages PROCESS, according to claim 1 or 2, characterized by the addition of the organosilicon composition d) to be made in at least two different mixing stages. 4. PROCESS, according to any one of claims 1 to 3, characterized by covering: (i) a first mixing stage, where one or more rubber components are mixed a), Petition 870180050307, of 06/12/2018, p. 47/54 one or more oxy-filling substances, containing hydroxyl b), one or more microgels c), containing hydroxyl groups, one or more organosilicon compositions, containing sulfur d), possibly one or more means of vulcanization e), as well as possibly one or more rubber additives f), at temperatures above 60 ° C, with at least 30% by weight of the total amount of organosilicon compositions containing sulfur being added d), (ii) eventual cooling of the mixture, obtained in the first mixing stage, (iii) another mixing stage, where at least another portion of the total amount of organosilicon compositions, containing sulfur, as well as possibly one or more of the components a), b), c), e) and f) , are added and mixed at temperatures above 60 ° C. PROCESS, according to claim 4, characterized in that in step (iii) the other mixing stage is a second mixing stage. 6. PROCESS, according to claim 4 or 5, characterized in that in the sequential mixer stage all the remaining amount of the organosilicon composition, containing sulfur d) is added. 7. PROCESS according to any one of claims 1 to 6, characterized in that component c) is added in at least two separate portions. PROCESS, according to any one of claims 2 to 7, characterized in that a portion of the total amount of component c) is added in a first mixing stage and at least another portion of the Petition 870180050307, of 06/12/2018, p. 48/54 3/5 total amount of component c) be added in another mixing stage. 9. PROCESS according to claim 8, characterized in that the other mixing stage is the second mixing stage. PROCESS, according to claim 8 or 9, characterized in that in the other mixing stage all remaining component c) is added. PROCESS, according to claim 9, characterized in that the other mixing stage is the second mixing stage. 12. PROCESS, according to any one of claims 1 to 11, characterized in that the mixing takes place in the mentioned mixing stages, at temperatures above 60 ° C. 13. PROCESS, according to claim 12, characterized by the mixing occurring in the mentioned mixing stages at temperatures above 100 ° C. 14. PROCESS according to any one of claims 1 to 13, characterized in that the mixtures are cooled between the mixing stages. 15. PROCESS, according to any one of claims 1 to 14, characterized in that 30 to 80% by weight of the organosilicon composition, containing sulfur d) are added in a first mixing stage, referring to the total amount of the composition of organosilicon, with sulfur content. 16. PROCESS, according to claim 15, characterized in that 40 to 70% by weight of the organosilicon composition are added in a first stage mixer, Petition 870180050307, of 06/12/2018, p. 49/54 Α / 5 containing sulfur d), referring to the total amount of the organosilicon composition, with sulfur content. 17. PROCESS, according to any one of claims 1 to 16, characterized by covering: (i) a first mixing stage, in which one or more rubber components a), one or more of the filling substances with hydroxyl content b), one or more microgels, containing hydroxyl groups c), one or more organosilicon compositions, containing sulfur d), possibly one or more vulcanization media e), as well as possibly one or more rubber additives f), are mixed at temperatures above 60 ° C, with at least 30% by weight of the total amount being added of organosilicon compositions, containing sulfur d), (ii) possible cooling of the mixture, obtained in the first mixing stage, (iii) another mixing stage, where at least one another installment of the total amount of compositions in organosilicon, containing sulfur as well as eventually one or several of components a), b), ç) , e) and f) are added, being mixed at temperatures above 60 ° C, (iv) cooling the mixture obtained in step (iii), (v) another mixing stage, in which one or more vulcanization accelerators (f), as well as possibly one or more media vulcanization e), are added and mixed. 18. PROCESS, according to claim 17, characterized in that in step (iii) the other mixing stage is a second mixing stage; and put in step (v) the other Petition 870180050307, of 06/12/2018, p. 50/54 5/5 mixing stage is a third mixing stage, in which one or more vulcanization accelerators f), as well as possibly one or more vulcanization means e), are added and mixed at temperatures below 60 ° C. 19. PROCESS, according to claim 17 or 18, characterized in that a portion of the components c) is added in the first mixing stage (i) and the remaining portion of the components c) in the other mixing stage (iü) 20. POCESS according to claim 1, characterized in that at least two organosilicon compositions containing sulfur are added. 21. RUBBER MIXTURES, characterized by being obtained according to the process as defined in any one of claims 1 to 20. 22. PROCESSES FOR THE PRODUCTION OF VULCANIZED PRODUCTS, characterized by covering the vulcanization of rubber mixtures as defined in claim 21. 23. VULCANIZED, characterized by being obtained by vulcanizing rubber mixtures as defined in claim 21. 24. VULCANIZED, according to claim 23, characterized in that they are in the form of tires, tire parts or technical rubber articles. Petition 870180050307, of 06/12/2018, p. 51/54