EP3387060A1

EP3387060A1 - Rubber mixtures

Info

Publication number: EP3387060A1
Application number: EP16802056.8A
Authority: EP
Inventors: Caren RÖBEN; Sascha Erhardt
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2015-12-07
Filing date: 2016-11-28
Publication date: 2018-10-17
Also published as: CN108291054B; JP6828051B2; ZA201804383B; BR112018011508B1; IL259779B; US10781302B2; CA3007487A1; UA124194C2; US20180346696A1; BR112018011508A2; CA3007487C; KR20180090279A; CN108291054A; MX2018006672A; DE102015224436A1; IL259779A; MY187475A; RU2018123802A; RU2018123802A3; WO2017097625A1

Abstract

The invention relates to rubber mixtures, said rubber mixtures containing at least one rubber, with the exception of silicone rubber, and at least one silatrane of general formula (I): G-Si(-O-CX1X2-CX1X3-)3N. The rubber mixture is produced by mixing at least one rubber and a silatrane of formula (I). The silatrane of formula (l) can be used as a secondary accelerator in rubber mixtures.

Description

rubber compounds

The present invention relates to rubber mixtures, a process for their preparation and their use.

From US 4,048,206 is the synthesis of compounds of the general formula X'-Z'-Si (OR ') 3N, wherein X' = halogen, HS, Z '= bivalent hydrocarbon and R' = -CH 2 -CH 2 - or -CH (CH3) - CH2- may be known.

Further, from J. Gen. Chem. USSR (EN) 45 (6), 1975, 1366 (Voronkov et al.) Describe the synthesis of NCS-CH ₂ -Si (O-CH ₂ -CH 2) ₃ N and NCS-CH ₂ -CH ₂ -CH ₂ -Si (0 -CH ₂ -CH ₂ ) 3N by transesterification of the corresponding methoxysilanes with triethanolamine with the release of methanol. From Syntesis and Reactivity in Inorganic and Metal-Organic Chemistry (1987), 17 (10), 1003-9, alkyl silatrans are known.

Furthermore, EP 2 206 742 discloses silatran-containing particles which are used as coupling agents between silica and rubber.

From EP 0919558 are silane derivatives of the formula R ^"'Si ^(0-CR'R" -CR ^'R') 3 N, where at least one R ^"is an alkenyloxyalkyl group. These silane derivatives can in

Silicone compounds are used.

Furthermore, EP 1 045 006, EP 1 045 002 and EP 0 919 558 disclose silatranes for

Silicone rubber applications are known.

The use of diphenylguanidine as a secondary accelerator in silica-filled rubber blends is known from various references (for example, H.-D.

Luginsland, A Review on the chemistry and reinforcement of the silica-silane filing system for rubber applications, Shaker, Aachen, 2002, p. 49).

Disadvantage of the known accelerator diphenylguanidine or guanidine derivatives is the

Release of toxic aniline or toxic aniline derivatives during mixing. The object of the invention is to prepare rubber mixtures with accelerators which release no toxic aniline or its derivatives. The invention relates to rubber mixtures which are characterized in that they comprise at least one rubber, with the exception of silicone rubber, and at least one silatran of the general formula (I),

G-Si (-O-CX X ² -CX X ³ -) ₃ N (I), where G is a monovalent unbranched or branched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic (C ² -C 5) -, preferably (C2-C6) -, particularly preferably (C3-C6) -, very particularly preferably (C3) -, hydrocarbon chain is,

X ¹ , X ² and X ^{3 are} each independently hydrogen (-H), straight-chain unsubstituted or branched unsubstituted (C 1 -C 10) -alkyl, preferably straight-chain unsubstituted or branched unsubstituted (C 1 -C 6) -alkyl, particularly preferably methyl or Ethyl, mean.

The rubber may preferably be a diene rubber.

G may preferably be CH3CH2CH2-. X ¹ , X ² and X ³ may preferably be H. Preferably, the silatran of the general formula (I) can be CH ₃ CH ₂ CH ₂ -Si (-O-CH ₂ -CH ₂ -) 3N. Silatrans of the general formula (I) may be mixtures of silatrans of the general formula (I).

Silatrans of the general formula (I) may contain partially hydrolyzed silatrane compounds of the general formula (I).

Silatrans of the general formula (I) can be: CH ₃ -CH 2 -si (-O-CH ₂ -CH ₂ -) ₃ N,

CH ₃ -CH 2 -CH 2 Si (-0-CH2-CH ₂ -) 3 N,

CH ₃ -CH (CH3) -CH2-Si (-0-CH2-CH ₂ -) 3 N,

CH ₃ -CH 2 Si (-0-CH (CH ₃₎ -CH 2) 3 N,

CH ₃ -CH 2 -CH 2 Si (-0-CH (CH ₃₎ -CH 2) 3 N or

CH ₃ -CH (CH3) -CH2-Si (-0-CH (CH ₃₎ -CH 2) 3N.

The silatrans of the formula (I) can be prepared by reacting at least one compound of the general formula (I)

G-Si (-O-Alk) ₃ (II) where G has the abovementioned meaning and Alk is, independently of one another, (C 1 -C 10) -alkyl, preferably methyl, ethyl or propyl,

with compounds of general formula III,

(HO-CX X ² -CX X ³ -) ₃ N (III) where X ¹ , X ² , and X ^{3 have} the meanings given above,

reacted with elimination of alk-OH and alk-OH is separated from the reaction mixture.

The reaction can be catalyzed or uncatalyzed. The alk-OH can from the

Reaction mixture are separated continuously or discontinuously.

Examples of compounds of the general formula III may be: triethanolamine,

Triisopropanolamine and [HO-CH (phenyl) CH ₂ ] 3N.

A low water content of the compounds of the formula III used can have a favorable effect on the composition and the product properties of the compounds. The compounds of the formula III may preferably have a water content of less than 1% by weight, particularly preferably less than 0.2% by weight. The reaction can be carried out in typical organic solvents having a boiling point of less than 200 ° C., preferably less than 100 ° C.

The reaction can be carried out in the absence of organic solvents.

As a catalyst in the process for the preparation of silatrans of the formula (I), metal-free or metal-containing catalysts can be used. As metal-containing catalysts, metal compounds of the 3.-7. Group, the 13.-14. Group and / or the Lanthanidengruppe be used.

As metal-containing catalysts transition metal compounds can be used.

The metal-containing catalysts may be metal compounds such as metal chlorides, metal oxides, metal oxychlorides, metal sulfides, metal sulfochlorides, metal alcoholates, metal thiolates, metal oxyalcoholates, metal amides, metal imides, or multiple bonded ligand transition metal compounds.

For example, titanium alkoxides can be used as metal-containing catalysts. In particular, titanates, such as, for example, tetra-n-butyl orthotitanate, tetraethyl orthotitanate, tetra-n-propyl orthotitanate or tetraisopropyl orthotitanate, can be used as catalysts.

As metal-free catalysts, organic acids can be used. Examples of suitable organic acids are trifluoroacetic acid, trifluoromethanesulfonic acid or p-toluenesulfonic acid, trialkylammonium compounds R 3 NH ⁺ X ^" or organic bases such as, for example, trialkylamines NR 3.

The preparation process can be carried out at atmospheric pressure or reduced pressure, preferably between 1 and 600 mbar, more preferably between 5 and 200 mbar. The production process can be carried out in the temperature range between 20 ° C and 200 ° C, preferably between 35 ° C and 150 ° C.

The reaction mixture may be added before or during the reaction substances that promote the transport of water from the product by forming azeotropic mixtures. The corresponding substances can be cyclic or straight-chain aliphatics, aromatics, mixed aromatic-aliphatic compounds, ethers, alcohols or acids. For example, hexane, cyclohexane, benzene, toluene, ethanol, propanol, iso-propanol, butanol, ethylene glycol, tetrahydrofuran, dioxane, formic acid, acetic acid, ethyl acetate or Dimetyhlformamid can be used.

To avoid condensation reactions, it may be advantageous to carry out the reaction in an anhydrous environment, ideally in an inert gas atmosphere.

The silatranes of formula (I) can be used as accelerators in filled rubber compounds, for example tire treads.

The silatrans of the general formula (I) can be used in amounts of 0.1 to 8 parts by weight, preferably 0.2 to 6 parts by weight, more preferably 0.8 to 4 parts by weight, based on 100 wt. - Parts of the rubber used to be used.

Another object of the invention is a process for the preparation of the rubber mixtures according to the invention, which is characterized in that at least one rubber and a silatrane of the formula (I) is mixed.

The rubber mixture may contain at least one filler. The addition of the silatrans of the general formula (I), as well as the addition of the fillers can be carried out at melt temperatures of 100 to 200 ° C. However, it can also be carried out at lower temperatures of 40 to 100 ° C, for example together with other rubber auxiliaries.

The silatranes of the formula (I) can be added to the mixing process both in pure form and supported on an inert organic or inorganic carrier, as well as pre-reacted with an organic or inorganic carrier. Preferred support materials may be precipitated or pyrogenic silicas, waxes, thermoplastics, natural or synthetic silicates, natural or synthetic oxides, preferably alumina, or carbon blacks.

Furthermore, the silatrans can also be pre-reacted with the filler to be used

Mixing process to be added.

As fillers, the following fillers can be used for the rubber mixtures according to the invention:

Carbon black: The carbon blacks to be used in this case can be prepared by the flame black, furnace, gas black or thermal black process. The carbon blacks may have a BET surface area of 20 to 200 m ² / g. Optionally, the carbon blacks may also be doped, such as with Si.

Amorphous silicas, preferably precipitated silicas or fumed silicas. The amorphous silicas may have a specific surface area of 5 to 1000 m ² / g, preferably 20 to 400 m ² / g (BET surface area) and a primary particle size of 10 to 400 nm. If appropriate, the silicas may also be used as mixed oxides with others

Metal oxides, such as Al, Mg, Ca, Ba, Zn and titanium oxides are present.

Synthetic silicates, such as aluminum silicate or alkaline earth silicates, for example

Magnesium silicate or calcium silicate. The synthetic silicates with BET surface areas of 20 to 400 m ² / g and primary particle diameters of 10 to 400 nm. - Synthetic or natural aluminas and hydroxides.

Natural silicates, such as kaolin and other naturally occurring silicas.

Glass fiber and glass fiber products (mats, strands) or glass microspheres.

Preference is given to using amorphous silicas, particularly preferably precipitated silicas or silicates, particularly preferably precipitated silicas having a BET surface area of from 20 to 400 m ² / g in amounts of from 5 to 180 parts by weight, based in each case on 100 parts of rubber. The fillers mentioned can be used alone or in a mixture. In a particularly preferred embodiment of the process, 10 to 180 parts by weight of fillers, preferably precipitated silica, optionally together with 0 to 100 parts by weight of carbon black, and 0, 1 to 8 parts by weight of silatrans of the general formula I, respectively based on 100 parts by weight of rubber, be used for the preparation of the mixtures.

For the preparation of the rubber mixtures according to the invention are in addition to

Natural rubber also synthetic rubbers. Preferred synthetic rubbers are described, for example, in W. Hofmann, Kautschuktechnologie, Genter Verlag, Stuttgart 1980. They include, among others, polybutadiene (BR),

Polyisoprene (IR),

Styrene / butadiene copolymers, for example emulsion SBR (E-SBR) or solution SBR (L-SBR), preferably with a styrene content of 1 to 60 wt .-%, particularly preferably 2 to 50 wt .-%, based on the total polymer, - chloroprene (CR),

Isobutylene / isoprene copolymers (NR),

Butadiene / acrylonitrile copolymers, preferably having an acrylonitrile content of 5 to 60% by weight, preferably 10 to 50% by weight, based on the total polymer (NBR), partially hydrogenated or fully hydrogenated NBR rubber (HNBR), ethylene / Propylene / diene copolymers (EPDM) or rubbers mentioned above, which additionally have functional groups, such as Carboxy, silanol or epoxy groups, for example epoxidized NR, carboxy-functionalized NBR or silanol (-SiOH) or siloxy-functionalized (-Si-OR), amino-epoxy, mercapto, hydroxy-functionalized SBR, and mixtures these rubbers. For the production of automobile tire treads are in particular anionically polymerized L-SBR rubbers (solution SBR) with a

Glass transition temperature above -50 ° C and mixtures thereof with diene rubbers of interest. The rubber vulcanizates of the invention may comprise further rubber auxiliaries, such as reaction accelerators, anti-aging agents, heat stabilizers, light stabilizers,

Antiozonants, processing aids, plasticizers, resins, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators such as diphenylguanidine, triethanolamine, polyethylene glycol, alkoxy-terminated polyethylene glycol, alkyl-O- (CH 2 -CH 2 -O) yi -H with y ¹ = 2-25, preferably y '= 2-15, more preferably y' = 3-10, most preferably y -3-6, or hexanetriol, which are known to the rubber industry.

The rubber auxiliaries may be present in known amounts, inter alia, after the

Intended use, be used. Usual amounts may be, for example, amounts of 0, 1 to 50 wt .-%, based on rubber. As crosslinkers, peroxides, sulfur or sulfur-donating substances can be used. The invention

Rubber compounds may also contain vulcanization accelerators. Examples of suitable vulcanization accelerators may be mercaptobenzothiazoles, sulfenamides, thiurams, dithiocarbamates, thioureas and thiocarbonates. The vulcanization accelerators and sulfur can be used in amounts of 0.1 to 10 wt .-%, preferably 0, 1 to 5 wt .-%, based on 100 parts by weight of rubber.

The vulcanization of the rubber mixtures according to the invention can be carried out at temperatures of 100 to 200 ° C, preferably 120 to 180 ° C, optionally under pressure of 10 to 200 bar. The blending of the rubbers with the filler, optionally rubber auxiliaries and the silatrane can be carried out in known mixing units, such as rollers, internal mixers and mixing extruders.

The rubber mixtures according to the invention can be used for the production of moldings, for example for the production of pneumatic tires, tire treads, cable sheaths, hoses,

Driving belts, conveyor belts, roller coverings, tires, shoe soles, sealing rings and

Damping elements used.

The rubber mixtures according to the invention can be carried out without the addition of guanidines. In a preferred embodiment, the rubber mixture may be free from

Guanidine derivatives, preferably diphenylguanidine.

The silatrans of the general formula (I) can be used as a secondary accelerator. As a result, the use of guanidine accelerator can be omitted partially or completely. Another object of the invention is the use of silatrans of the general formula (i),

G-Si (-O-CX X ² -CX X ³ -) ₃ N (I),

where G is a monovalent unbranched or branched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic (C2-Cs) -, preferably (C2-C6) -, particularly preferably (C3-C6) -, very particularly preferably (C3) -, hydrocarbon chain is,

X ¹ , X ² and X ^{3 are} each independently hydrogen (-H), straight-chain unsubstituted or branched unsubstituted (C 1 -C 10) -alkyl, preferably straight-chain unsubstituted or branched unsubstituted (C 1 -C 6) -alkyl, particularly preferably methyl or Ethyl, mean, in

Rubber compounds as secondary accelerator.

The rubber mixtures of the invention have the advantage that they in the

Compounding and / or vulcanization over the known guanidine accelerators release no toxic aniline or its derivatives, have in rubber mixtures without DPG longer incubation times (t10, t20), increased crosslink density and a lower Mooney viscosity.

Examples

The following raw materials are used for the examples: triethanolamine from BASF SE, isobutyltriethoxysilane, hexadecyltrimethoxysilane, octyltriethoxysilane and propyltriethoxysilane from Evonik Industries AG, sodium hydroxide and phenyltrimethoxysilane from Sigma-Aldrich, ethanol and methanol from Sasol Solvents Germany GmbH, trimethoxymethylsilane from the company Merck, as well as n-hexane and n-pentane from VWR.

Comparative Example 1: (1-Methyl-2,8,9-trioxa-5-aza-1-silicabicyclo [3.3.3] undecane; 1 -

Methylsilatran)

193.94 g of triethanolamine, 177.09 g of trimethoxymethylsilane, 500 ml of methanol and 0.52 g of sodium hydroxide are placed under stirring in a round-bottomed flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen. The reaction mixture is heated at 36 ° C for 18h, whereby the product precipitates as a solid. On a rotary evaporator is the

Concentrated under vacuum at 40 ° C and then separated by means of a pressure filtration of residual methanol and dried under vacuum. There are obtained 241, 52 g of 1-methylsilatran as a white, finely crystalline solid with a yield of 98%. The product has a melting range of 146-171 ° C and according to H-NMR analysis contains 94.2 wt .-% 1 -Methylsilatran.

Example 1: (1-Propyl-2,8,9-trioxa-5-aza-1-silicyclo [3.3.3] undecane; 1-propylsilatran)

183.5 g of triethanolamine, 253.81 g of propyltriethoxysilane, 500 ml of ethanol and 4.8 g of sodium hydroxide are placed under stirring in a round bottom flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen. The reaction mixture is heated to 68 ° C for 12 h. After cooling to room temperature, the reflux condenser is replaced by a

Replacement of the distillation bridge. Subsequently, at 78 ° C and atmospheric pressure, so much ethanol is removed that the mixture is still stirrable. The product is completely precipitated with pentane and separated by a pressure filtration of residual ethanol and pentane. The filter cake is dried under vacuum. There are obtained 267.33 g of 1-propylsilatran as a white, crystalline solid with a yield of 78%.

The product has a melting point of 85 ° C and according to analysis by H-NMR

Spectroscopy a purity> 99 wt .-%.

Example 2: (1-octyl-2,8,9-trioxa-5-aza-1-silicabicyclo [3.3.3] undecane; 1-octylsilatran)

134.3 g of triethanolamine, 256.5 g of octyltriethoxysilane, 400 ml of ethanol and 3.56 g of sodium hydroxide are placed under stirring in a round-bottomed flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen. The reaction mixture is heated to 80 ° C for 24 h. After cooling to room temperature, the reaction mixture on

Rotary evaporator concentrated at 40 ° C under reduced pressure. By adding pentane, the product is completely precipitated and separated by a pressure filtration of residual ethanol and pentane. The filter cake is dried under vacuum. There are obtained 186.8 g of 1-octylsilatran as beige powder with a yield of 71%.

The product has a melting point of 69 ° C and according to H-NMR analysis contains 98.4 wt .-% 1-Octylsilatran.

Comparative Example 2: (1-hexadecyl-2,8,9-trioxa-5-aza-1-silicabicyclo [3.3.3] undecane; 1-hexadecylsilatran)

90.0 g of triethanolamine, 208.0 g of hexadecyltriethoxysilane, 900 ml of methanol and 2.39 g of sodium hydroxide are placed under stirring in a round bottom flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen atmosphere. The reaction mixture is for Heated to 36 ° C for 16 h. After cooling to room temperature, the reaction mixture is concentrated on a rotary evaporator at 40 ° C under reduced pressure. By addition of n-hexane, the product is completely precipitated and separated by a pressure filtration of residual methanol and hexane. The filter cake is dried under vacuum. There are obtained 159.8 g of 1-hexadecylsilatran as a white, finely crystalline solid with a yield of 66%.

The product has a melting point of 79 ° C and contains according to H-NMR analysis 99.8 wt .-% 1-Hexadecylsilatran.

Example 3: (1-Isobutyl-2,8,9-trioxa-5-aza-1-silicabicyclo [3.3.3] undecane; isobutylsilatran)

203 g of triethanolamine, 300.0 g of isobutyltriethoxysilane, 500 ml of ethanol and 5.68 g of sodium hydroxide are placed under stirring in a round bottom flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen atmosphere. The reaction mixture is heated to boiling temperature for 16 h. After cooling to room temperature, the reaction mixture is concentrated on a rotary evaporator at 40 ° C under reduced pressure. For complete removal of ethanol, the product is melted and dried at 70 ° C under vacuum. There are obtained 314.6 g of 1 -Isobutylsilatran as a yellow solid with a yield of 100%.

The product has a melting point of 55 ° C and according to H-NMR analysis contains 96.0 wt .-% of 1-isobutylsilatran.

Example 4: (1-Phenyl-2,8,9-trioxa-5-aza-1-silicabicyclo [3.3.3] undecane; 1-phenylsilatran)

134.3 g of triethanolamine, 178.5 g of phenyltrimethoxysilane, 900 ml of methanol and 3.62 g of sodium hydroxide are placed under stirring in a round-bottomed flask with attached stirring apparatus (KPG stirrer) and reflux condenser under nitrogen. The reaction mixture is heated to 36 ° C for 4 hours. After cooling to room temperature, the reaction mixture is slurried with n-hexane and filtered. The filter cake is dried under vacuum. There are obtained 208.0 g of 1-phenylsilatran as a white, coarse crystalline solid in a yield of 92%.

The product has a melting point of 205 ° C and according to H-NMR analysis contains 94.4 wt .-% 1-phenylsilatran. Example 5: Rubber Engineering Studies

The recipe used for the rubber compounds is given in Table 1 below. The unit phr means by weight, based on 100 parts of the used

Raw rubber. The silatrans become equimolar, i. used with the same amount of substance. The following secondary accelerators are examined:

In comparison mixture 1: Λ /, Λ / '- diphenylguanidine (DPG-80).

In comparison mixture 2: mixture without secondary accelerator.

In comparison mixture 3: Silatran according to Comparative Example 1.

In inventive mixture 4: Silatran according to Example 1. In mixture 5 according to the invention: Silatran according to Example 2.

In comparison mixture 6: Silatran according to Comparative Example 2.

In inventive mixture 7: Silatran according to Example 3.

In inventive mixture 8: Silatran according to Example 4.

Table 1

Comparative Comparison Comparison Mix 4 Mix 5 Comparison Mix 7 Mix 8 Mix 1 Mix 2 Mix 3 Mix 6

(phr) (phr) (phr) (phr) (phr) (phr) (phr) (phr)

1st stage

Buna VSL 4526-2 ^a 96.3 96.3 96.3 96.3 96.3 96.3 96.3 96.3

Buna CB 24 ^b 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0

ULTRASIL ^® GR 7000 ^C 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0

Si 266 ^® · ^d 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8

^Corax® N 330 ^e 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0

ZnO ^f 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Fatty acid ⁹ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Vivatec 500 ^h 8.8 8.8 8.8 8.8 8.8 8.8 8.8 8.8

Protector G 3108 '2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Vulkanox ^® 4020 / LÖ 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Vulkanox ^® HS / LG ^k 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5

Rhenogran DPG-80 ^® ¹ '2.5

Comparative Example 1 1, 7

Example 1 2.0

Example 2 2.6

Comparative Example 2 3.7

Example 3 2, 1

Example 4 2.3

2nd stage

Batch level 1

3rd stage

Batch level 2

Perkacit TBzTD ^m) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Vulkacit ^® CZ / EG-C ^n> 1, 6 1, 6 1, 6 1, 6 1, 6 1, 6 1, 6 1, 6

Sulfur ⁰ '2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0

Substances used: a) Buna VSL 4526-2: Solution polymerized SBR copolymer from Lanxess AG (styrene content = 26% by weight, vinyl content = 44.5% by weight, TDAE oil content = 27.3% by weight, Mooney viscosity (ML 1 + 4/100 ° C) = 50 ME). b) Buna CB 24: Solution polymerized high cis-1,4-polybutadiene (neodymium catalyst) from Lanxess AG (cis-1,4 content = at least 96%, Mooney viscosity (ML 1 + 4/100 ° C ) 44 ME). c) Silica: ULTRASIL ^® 7000 GR from Evonik Industries AG (readily dispersible precipitated silica, BET surface area = 170 m ² / g, CTAB surface area = 160 m ² / g). d) Si 266 ^®: Bis (triethoxysilylpropyl) from Evonik Industries AG disulfide. e) ^Corax® N 330: carbon black from Orion Engineered Carbons GmbH. f) ZnO: zinc oxide ZnO RS RAL 844 C from Arnsperger Chemikalien GmbH. g) fatty acid mixture (Ci6 / Cis), EDENOR ST1, Caldic Germany Chemie BV h) Vivatec 500: TDAE oil from H & R AG. i) Protector G3108: Ozone protection wax from refined hydrocarbons

(Solidification point ^"57 ° C) from Paramelt BV j) Vulkanox ^® 4020 / LG: Λ / - (1, 3-dimethylbutyl) - / V-phenyl-p-phenylene diamine (6PPD) Rhein Chemie Rheinau GmbH. k) Vulkanox ^® HS / LG: polymeric 2,2,4-trimethyl-1, 2-dihydroquinoline (TMQ), Rhein Chemie Rheinau GmbH. I) ^® Rhenogran DPG-80: 80% Λ /, Λ / '- diphenylguanidine (DPG) elastomeric to 20% carrier and dispersing agent of Rhein Chemie Rheinau GmbH. m) Perkacit TBzTD: Tetrabenzylthiuram disulfide (TBzTD) based on Weber & Schaer (manufacturer: Dalian Richon). n) Vulkacit ^® CZ / EG-C: A / Rhein Chemie Rheinau GmbH cyclohexyl-2-benzothiazole. o) Sulfur: Milling sulfur 80/90 ° from Solvay & CPC Barium Strontium GmbH & Co. KG. The mixtures are prepared in three stages in a 1.5 L internal mixer (E type) at a batch temperature of 155 ° C. according to the mixing instructions described in Table 2.

The general process for preparing rubber mixtures and their vulcanizates is described in the book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994.

Table 2

Level 2

settings

Mixing unit as in step 1 up

Filling level 0.62

Speed 95 min ^"1

Flow temp. 90 ° C

mixing process

0 to 1, 0 min Break up batch stage 1

1, 0 to 3.0 min Mix at 155 ° C, adjust temperature if necessary via speed variation

Throw out the batch for 3.0 min and form a coat for 45 s on a laboratory mixer

(Laboratory mill: diameter 250 mm, length 190 mm, nip 4 mm, flow temperature 60 ° C)

3 h storage at room temperature

The vulcanization takes place at a temperature of 165 ° C in a typical

Vulcanization press with a holding pressure of 120 bar after t.95%. The t.95% time is determined by means of Moving The Rheometer (rotorless Vulkameter) according to ISO 6502 (paragraph 3.2 "rotorless curemeter") at 165 ° C. The rubber test is carried out according to the test methods given in Table 3.

Table 3

Physical testing standard / conditions

Mooney Viscosity ML 1 +4 at 100 ° C ISO 289-1

Mooney viscosity / ME

Moving The Rheometer (MDR) at 145 ° C, 1.67 Hz, ISO 6502, paragraph 3.2 "rotorless 0.5 ° = 7% curemeter"

tw / min

Rubber Process Analyzer (RPA) at 165 ° C, 1.67 Hz, ISO 6502, section 3.2 "rotorless 3 ° = 42% curemeter"

Δ torque (M _max -M _man ) / dNm

DIN abrasion, 10 N ISO 4649

Abrasion / mm ³

Ball Rebound 23 ° C DIN EN ISO 8307

Rebound resilience /% fall height 500 mm, steel ball d = 19 mm, 28 g

Table 4 gives the rubber technical data for the raw mixtures and vulcanizates.

Table 4

Compared with comparative mixture 2, the operation of the secondary accelerator is in all other mixtures in increased crosslinking yields (A torque (M _ma x Mmin), improved processing (Mooney viscosity) and increased

Processing safety (tio and t2o values). The crosslinking yield of

mixtures according to the invention 4, 5, 7 and 8 and the comparison mixture 6 is also improved compared to the comparison mixture 1, which the

Standard secondary accelerator DPG contains and compared to the comparison mixture 3. The processing (Mooney viscosities) and the processing safety (tio and t.20 values) of the inventive mixtures 4, 5, 7 and 8 and the comparative mixture 6 im

Comparison with comparative mixture 3, which contains the silatran according to Comparative Example 1, is improved even further.

The comparative mixture 6, however, has weaknesses in the abrasion (DIN abrasion) compared to the mixtures according to the invention 4, 5, 7 and 8.

The mixtures according to the invention 4, 5, 7 and 8 have opposite to all

Comparative blends Benefits in wet adhesion (ball rebound at 23 ° C) compared to the comparative blends 1, 2, 3 and 6 on.

Claims

claims

Rubber mixtures, characterized in that these at least one

Rubber, other than silicone rubber, and at least one silatran of the general formula (I),

G-Si (-O-CX X ² -CX X ³ -) ₃ N (I), where G is a monovalent unbranched or branched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic (C ² -C 8) hydrocarbon chain is

X ¹ , X ² and X ^{3 are} each independently hydrogen (-H), straight-chain

unsubstituted or branched unsubstituted (C1-C10) - alkyl- mean.

Rubber mixtures according to claim 1, characterized in that the silatran of the general formula (I) is CH ₃ -CH ₂ -CH ₂ -Si (-O-CH ₂ -CH ₂ -) 3N.

Rubber mixtures according to claim 1, characterized in that they contain filler and optionally further rubber auxiliaries.

Rubber mixtures according to Claim 1, characterized in that they contain the silatran of the general formula (I) in amounts of from 0.1 to 8 parts by weight, based on 100 parts by weight of the rubber used.

Process for the preparation of the rubber mixtures according to claim 1, characterized in that at least one rubber, except

Silicone rubber, and at least one silatran of formula (I) mixes.

Use of rubber mixtures according to claim 1 for the production of moldings.

Use of rubber compounds according to claim 1 for the production of pneumatic tires, tire treads, rubber-containing tire components, cable sheaths, hoses, drive belts, conveyor belts, roller coverings, tires, shoe soles, sealing rings and damping elements.

Use of alkyl silanes of the general formula (I),

G-Si (-O-CX X ² -CX X ³ -) ₃ N (I), where G is a monovalent unbranched or branched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic (C 2 -C 8) -hydrocarbon chain,

X ¹ , X ² and X ^{3 are} each independently hydrogen (-H), straight-chain unsubstituted or branched unsubstituted (C ¹ -C 10) -alkyl-, in

Rubber compounds as secondary accelerator.