Silane-azodicarbonamide mixtures, process for production thereof and use thereof

Abstract

This invention relates to a silane-azodimethylamine mixture comprising 5 to 95% by weight of an azodicarbonyl-functionalized silane of formula I, based on the total amount of azocarbonyl-functionalized silane of formula I, silane of formula II, and azodimethylamine of formula III. , Based on the total amount of azocarbonyl-functionalized silanes of Formula I, silanes of Formula II, and azodimethylamine compounds of Formula III, 0 to 90% by weight of silane of Formula II, and Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, 1 to 80% by weight of the azodimethylamine compound of Formula III, . The silane-azodimethylamine mixture is prepared by mixing 5 to 95% by weight of an azocarbonyl-functionalized silane of formula I, 0 to 90% by weight of a silane of formula II, and 1 to 80% by weight of an azodimethylamine compound of formula III. The present invention also relates to a rubber compound comprising at least one rubber, 5 to 95% by weight of an azocarbonyl-functionalized silane of formula I, 0 to 90% by weight of a silane of formula II, and 1 to 80% by weight of an azodimethylamine compound of formula III.

Description

Technical Field

[0001] This invention relates to a silane-azodimethylamine mixture, its manufacturing method, and its use in rubber mixtures. Prior Technology

[0002] EP 2937351 discloses an azocarbonyl-functionalized silane of formula (R1)3-a(R2)aSi-RI-NH-C(O)-N=NR4. KR20170049245 also discloses an alkyl-substituted azodimethylamine compound of formula R5-NH-C(O)-N=NC(O)-NH-R5, wherein R5 is a straight-chain or branched cyclic alkyl group. One known disadvantage of silanes in rubber compounds is their low modulus of 300%. Summary of the Invention

[0003] One object of the present invention is to provide a rubber compound containing a silane-azodimethylamine mixture, which shows an improvement in modulus of 300% relative to known rubber compounds. The present invention provides a silane-azodimethylamine mixture comprising, based on the total amount of an azocarbonyl-functionalized silane of formula I, a silane of formula II, and an azodimethylamine compound of formula III, 5 to 95% by weight, more preferably 5 to 50% by weight, and particularly preferably 20 to 40% by weight of an azocarbonyl-functionalized silane of formula I. Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, 0 to 90% by weight, preferably 20 to 60% by weight, and most preferably 30 to 60% by weight of the silane of Formula II, and Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, the content is 1 to 80% by weight, preferably 5 to 50% by weight, and most preferably 15 to 40% by weight of the azodimethylamine compound of Formula III. Wherein R1 is the same or different and represents C1 to C10-alkoxy (preferably methoxy or ethoxy), phenoxy, or alkyl polyether group -O- (R6-O) rR7, wherein R6 is the same or different and represents branched, saturated or unsaturated aliphatic, aromatic, or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group (preferably -CH2-CH2-), r is an integer from 1 to 30, preferably from 3 to 10, and R7 represents unsubstituted or substituted branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl, preferably representing C13H27 alkyl. R2 may be the same or different and represents -OH, C6 to C20-aryl (preferably phenyl), C1 to C10-alkyl (preferably methyl or ethyl), C2 to C20-alkenyl, C7 to C20-aralkyl, or halogen (preferably Cl). a can be between 0 and 3, with 0 being the best. y is between 0 and 3, with 3 being preferred. R 3 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30-alkyl group, preferably C1 to C20, particularly preferably C1 to C10, very preferably C2-C7-alkyl group, especially preferably CH 2CH 2 and CH 2CH 2CH 2. R 4 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, preferably phenyl, halophenyl (e.g., chlorophenyl, bromophenyl, or iodophenyl), tolyl, alkoxyphenyl (e.g., methoxyphenyl), o-, m-, or p-nitrophenyl, or a substituted or unsubstituted alkyl group (preferably methyl, ethyl, propyl, butyl, isobutyl, tributyl, nitromethyl, nitroethyl, nitropropyl, nitrobutyl, or nitroisobutyl). x is the average sulfur chain distribution, where x is 2 to 10, preferably 2 to 4. R 5 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic or cyclic monovalent C1 to C30-alkyl group (preferably C1-C20-, especially C1-C10-, very preferably C2-C8-alkyl group, particularly preferably CH(CH 3) 2, CH 2CH(CH 3) 2, C(CH 3) 3, CH 2C(CH 3) 3, CH 2CH 2CH(CH 3) 2, CH 2CH(CH 3) CH 2CH 3、CH 2CH(CH 2CH 3) 2、 CH 2CH 2CH(CH 2CH 2CH 3)CH 2CH 2CH 2CH 3. CH 2CH(CH 2CH 3)CH 2CH 2CH 2CH 3), or substituted or unsubstituted aryl groups (preferably phenyl). R3 independently represents -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH(CH3)-, -CH2CH(CH3)-, -CH(CH 3)CH 2-, -C(CH 3) 2-, -CH(C 2H 5)-, -CH 2CH 2CH(CH 3)-, -CH(CH 3)CH 2CH 2-, -CH 2CH(CH 3)CH 2-, -CH 2CH 2CH 2CH 2CH 2-, -CH 2CH 2CH 2CH 2CH 2CH 2-, -CH 2CH 2CH 2CH 2CH 2CH 2CH 2-, -CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-、 -CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-、 -CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-, -CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-, -CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2CH 2-, , . The azocarbonyl-functionalized silane of formula I is preferably (CH3CH2O-)3Si-CH2-NH-CO-N=N-phenyl. And it is especially good The silane of formula II is preferred. The azodimethylamine compound of formula III is preferably... And it is especially good The silane-azodimethylamine mixture may preferably contain: Azocarbonyl-functionalized silane of Formula I , Silane of Formula II and Formula III azodimethylamine compound , Where a is 0, y is 3, x is 2 to 4, R1 is ethoxy, R3 is (CH2)3, R4 is phenyl, nitrophenyl or tributyl, and R5 is branched or unbranched alkyl, preferably CH2-CH(C2H5)-(CH2)3-CH3. The silane-azodimethylamine mixture may contain additional additives, or may consist solely of an azocarbonyl-functionalized silane of Formula I, a silane of Formula II, and an azodimethylamine compound of Formula III. Additives may be, for example, solvents such as methanol, ethanol, propanol, butanol, cyclohexanol, N,N-dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane, heptane, octane, decane, toluene, xylene, acetone, acetonitrile, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloromethane, tetrachloroethylene, diethyl ether, methyl terephthalate, methyl ethyl ketone, tetrahydrofuran, dimethyl ether, pyridine, or methyl acetate. Amines of general formula IV Wherein R 8 represents a branched or unbranched, saturated or unsaturated aliphatic or cyclic monovalent C1 to C30-alkyl group (preferably C1-C20-, especially C1-C10-, very preferably C2-C8-alkyl group, particularly preferably CH(CH 3) 2, CH 2CH(CH 3) 2, C(CH 3) 3. CH 2C(CH 3) 3. CH 2CH 2CH(CH 3) 2. CH 2CH(CH 3)CH 2CH 3、CH 2CH(CH 2CH 3) 2、 CH 2CH 2CH(CH 2CH 2CH 3)CH 2CH 2CH 2CH 3. CH 2CH(CH 2CH 3)CH 2CH 2CH 2CH 3), or substituted or unsubstituted aryl groups (preferably phenyl), Or silyl-functionalized amines of general formula V Where R9 is the same or different and represents C1 to C10-alkoxy or alkyl polyether group -O-(R6-O)rR7, where R6 is the same or different and represents branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30-hydrocarbon group, r is an integer from 1 to 30, and R7 represents unsubstituted or substituted branched or unbranched alkyl, alkenyl, aryl or aralkyl. R 10 may be the same or different and represents -OH, C6 to C20-aryl (preferably phenyl), C1 to C10-alkyl, C2 to C20-alkenyl, C7 to C20-aralkyl, or halogen. aa can be 0 to 3. R 11 represents a branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30-alkyl group, preferably C1 to C20-, particularly preferably C1 to C10-, very preferably C2 to C7-alkyl group, especially preferably CH 2CH 2 and CH 2CH 2CH 2. The silane-azodimethylamine mixture according to the present invention may contain oligomers formed by the hydrolysis and condensation of silane of formula I and / or silane of formula II. The silane mixture according to the invention may be in the form of an application to a carrier (e.g., wax, polymer, or carbon black). The silane-azodimethylamine mixture according to the invention may be in the form of an application to silicon dioxide, wherein the bonding may be physical or chemical. The present invention further provides a method for manufacturing a silane-azodimethylamine mixture according to the present invention, wherein the method comprises: mixing 5 to 95% by weight, preferably 5 to 50% by weight, and most preferably 20 to 40% by weight of the azodicarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, based on the total amount of these compounds. Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, 0 to 90% by weight, preferably 20 to 60% by weight, and most preferably 30 to 60% by weight of the silane of Formula II, and Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, the content is 1 to 80% by weight, preferably 5 to 50% by weight, and most preferably 15 to 40% by weight of the azodimethylamine compound of Formula III. . Blending can be carried out at various suitable times, either after the manufacture of individual components or during the manufacture of individual components. Blending of azocarbonyl-functionalized silanes of Formula I with silanes of Formula II can be carried out during the manufacture of azodimethylamine compounds of Formula III. The method according to the invention can be carried out under vented air. The method according to the invention can be carried out under a protective atmosphere, such as argon or nitrogen, preferably nitrogen. Blending can be better carried out by mixing with a stirrer. The method according to the invention can be performed under standard pressure, high pressure, or reduced pressure. Preferably, the method according to the invention can be performed under standard pressure. High voltage can range from 1.1 bar to 100 bar, preferably from 1.1 bar to 50 bar, exceptionally good from 1.1 bar to 10 bar, and very exceptionally good from 1.1 bar to 5 bar. The pressure reduction can be from 1 mbar to 1000 mbar, preferably from 250 mbar to 1000 mbar, and even more preferably from 500 mbar to 1000 mbar. The method according to the present invention can be carried out between 0°C and 100°C, preferably between 10°C and 50°C, and most preferably between 10°C and 35°C. The method according to the invention can be carried out in a solvent, such as methanol, ethanol, propanol, butanol, cyclohexanol, N,N-dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane, heptane, octane, decane, toluene, xylene, acetone, acetonitrile, carbon tetrachloride, chloroform, dichloroethane, 1,2-dichloromethane, tetrachloroethylene, diethyl ether, methyl terephthalate, methyl ethyl ketone, tetrahydrofuran, dimethyl ether, pyridine or methyl acetate, or mixtures of the above solvents. The method according to the invention can preferably be carried out in the absence of a solvent. Volatile minor components can be separated by distillation. Distillation purification can be performed before or after the mixture of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III. Distillation purification is preferably performed after the mixture of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III. Distillation purification can be carried out in batches or via a thin-film evaporator. Distillation purification can be carried out under vented air. The method can be performed under a protective atmosphere, such as argon or nitrogen, preferably nitrogen. Distillation purification can be carried out under standard pressure or reduced pressure. The method according to the invention is preferably carried out under reduced pressure. The pressure reduction can be from 1 mbar to 1000 mbar, preferably from 10 mbar to 200 mbar, and even better from 20 mbar to 1000 mbar. Distillation purification can be carried out between 20°C and 100°C, preferably between 20°C and 80°C, and most preferably between 30°C and 60°C. The present invention further provides a rubber compound comprising: At least one type of rubber, Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, the content is 5 to 95% by weight, preferably 5 to 50% by weight, and most preferably 20 to 40% by weight of the azocarbonyl-functionalized silane of Formula I. Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, 0 to 90% by weight, preferably 20 to 60% by weight, and most preferably 30 to 60% by weight of the silane of Formula II, and Based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, the content is 1 to 80% by weight, preferably 5 to 50% by weight, and most preferably 15 to 40% by weight of the azodimethylamine compound of Formula III. Wherein R1 is the same or different and represents C1 to C10-alkoxy (preferably methoxy or ethoxy), phenoxy, or alkyl polyether group -O- (R6-O) rR7, wherein R6 is the same or different and represents branched, saturated or unsaturated aliphatic, aromatic, or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group (preferably -CH2-CH2-), r is from 1 to 30, preferably an integer from 3 to 10, and R7 represents unsubstituted or substituted branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl, preferably representing C13H27 alkyl. R2 may be the same or different and represents -OH, C6 to C20-aryl (preferably phenyl), C1 to C10-alkyl (preferably methyl or ethyl), C2 to C20-alkenyl, C7 to C20-aralkyl, or halogen (preferably Cl). a can be between 0 and 3, with 0 being the best. y is between 0 and 3, with 3 being preferred. R 3 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30-alkyl group, preferably C1 to C20, particularly preferably C1 to C10, very preferably C2-C7-alkyl group, especially preferably CH 2CH 2 and CH 2CH 2CH 2. R 4 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, preferably phenyl, halophenyl (e.g., chlorophenyl, bromophenyl, or iodophenyl), tolyl, alkoxyphenyl (e.g., methoxyphenyl), ortho, meta, or para-nitrophenyl, or a substituted or unsubstituted alkyl group (preferably methyl, ethyl, propyl, butyl, isobutyl, tributyl, nitromethyl, nitroethyl, nitropropyl, nitrobutyl, or nitroisobutyl). x is the average sulfur chain distribution, where x is 2 to 10, preferably 2 to 4. R 5 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic or cyclic monovalent C1 to C30-alkyl group (preferably C1-C20-, especially C1-C10-, very preferably C2-C8-alkyl group, particularly preferably CH(CH 3) 2, CH 2CH(CH 3) 2, C(CH 3) 3, CH 2C(CH 3) 3, CH 2CH 2CH(CH 3) 2, CH 2CH(CH 3) CH 2CH 3, CH 2CH(CH 2CH 3) 2, CH 2CH 2CH(CH 2CH 2CH 3)CH 2CH 2CH 2CH 3. CH 2CH(CH 2CH 3)CH 2CH 2CH 2CH 3), or substituted or unsubstituted aryl groups (preferably phenyl). The rubber is preferably diene rubber, especially natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, isobutylene / isoprene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene / diene copolymer (EPDM), and partially or fully hydrogenated NBR rubber. The rubber used may be natural rubber and / or synthetic rubber. Preferred synthetic rubber is described, for example, in W. Hofmann, Kautschuktechnologie [Rubber Technology], Genter Verlag, Stuttgart 1980. Rubber may include: - Polybutadiene (BR) - Polyisoprene (IR), - Styrene / butadiene copolymers, such as emulsion polymerized SBR (E-SBR) or solution polymerized SBR (S-SBR), preferably have a styrene content of 1% to 60% by weight, more preferably 5% to 50% by weight (SBR). - Chloroprene (CR), - Isobutylene / isoprene copolymer (IIR) - Butadiene / acrylonitrile copolymer having an acrylonitrile content of 5% to 60% by weight, preferably 10% to 50% by weight (NBR). - Partially hydrogenated or fully hydrogenated NBR rubber (HNBR) - Ethylene / propylene / diene copolymer (EPDM) - The aforementioned rubber also possesses functional groups, such as carboxyl, silyl, or epoxy groups, for example, epoxidized NR, carboxyl-functionalized NBR or amine (NR 2), silyl (-SiOH)-, epoxy-, mercapto-, hydroxyl-, or siloxy (-Si-OR)-functionalized SBR. And mixtures of these rubbers. The aforementioned rubbers may also be silicone coupling rubbers or tin coupling rubbers. In a preferred embodiment, the rubber may be vulcanizable. For manufacturing automotive tire tread patterns, anionic polymeric S-SBR rubber (solution polymeric SBR) with a glass transition temperature above -50°C and mixtures thereof with butadiene rubber are particularly suitable. S-SBR rubber in which the butadiene portion has more than 20% by weight of a vinyl portion is especially suitable. S-SBR rubber in which the butadiene portion has more than 50% by weight of a vinyl portion is very particularly suitable. A mixture of the above-mentioned rubbers having an S-SBR content of more than 50% by weight, preferably more than 60% by weight, can preferably be used. The rubber may be a functionalized rubber, wherein the functional groups may be amines and / or amides and / or carbamates and / or urea and / or aminosiloxanes and / or siloxanes and / or silicones and / or alkylsilyls (e.g., N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane or methyltriphenoxysilane) and / or halogenated silicones and / or sulfurized silicones and / or thiols and / or hydroxyl groups and / or ethoxy groups and / or epoxy groups and / or carboxyl groups and / or tin (e.g., tin tetrachloride or dibutyltin dichloride) and / or silicones and / or hexachlorodisiloxanes and / or thiocarboxyl groups and / or nitriles and / or nitrogen oxides and / or amide groups and / or Imino group and / or carbamate and / or urea and / or dimethylimidazolium ketone and / or 2-methyl-2-thiazoline and / or 2-benzothiazoline acetonitrile and / or 2-thiophene carboxynitrile and / or 2-(N-methyl-N-3-trimethoxysilylpropyl)thiazoline and / or carbodiimide and / or N-substituted amino aldehyde and / or N-substituted amino ketone and / or N-substituted amino thioaldehyde and / or N-substituted amino thioketone and / or diphenyl ketone and / or amino-containing thiodiphenyl ketone and / or isocyanate and / or isothiocyanate and / or hydrazine and / or sulfonylurea and / or sulfinyl and / or acezoline and / or ester group. [] The rubber compound according to the present invention contains at least one filler. Fillers that can be used in rubber compounds according to the present invention include the following fillers: - Carbon black: Carbon black can be produced by lampblacking, furnace blackening, gas blackening, or thermal methods and has a BET surface area ranging from 20 to 200 m² / g. Carbon black can also contain heteroatoms, such as Si. -Amorphous silica, such as prepared by means of precipitation from silicate solution or flame hydrolysis of silica fluoride, has a specific surface area (BET surface area) from 5 to 1000 m 2 / g, preferably from 20 to 400 m 2 / g and a primary particle size from 10 to 400 nm. Silicon dioxide may also be arbitrarily in the oxide form of mixed oxides having other metal oxides, such as Al, Mg, Ca, Ba, Zn and titanium. -Synthesized silicates, such as aluminum silicate, alkaline earth metal silicates (such as magnesium silicate or calcium silicate), which have a BET surface area from 20 to 400 m 2 / g and a primary particle size from 10 to 400 nm. - Synthetic or natural alumina and synthetic or natural alumina hydroxide. - Natural silicates, such as kaolin and other natural silica. - Fiberglass and fiberglass products (mats, jig wires) or glass microbeads. Preferably amorphous silica prepared from silicate solution can be used, which has a BET surface area ranging from 20 to 400 m 2 / g, more preferably 100 m 2 / g to 250 m 2 / g, and quantities from 5 to 150 parts by weight as a benchmark of 100 parts of rubber in various cases. Very preferably, precipitated silica can be used as a filler. The above fillers may be used alone or as a mixture. Rubber mixtures according to the invention may contain from 5 to 150 parts by weight of filler and 0.1 to 30 parts by weight, preferably from 2 to 25 parts by weight, and extra-preferably from 5 to 20 parts by weight of the silane-azodimethylamide mixture according to the invention, wherein The silane-azodimethylamide mixture according to the present invention can be used as an adhesive agent between an inorganic material and an organic polymer such as glass beads, glass fragments, glass surfaces, glass fibers, or oxide fillers (preferably silica, such as precipitated silica and molded silica), or as a crosslinker for oxide surface modifiers. The silane-azodimethylamide mixture according to the present invention may be used as a coupling agent in a filler rubber mixture (e.g., tire splines, industrial rubber products, or soles). The rubber mixture according to the present invention may contain additional rubber additives, such as reaction accelerators, aging stabilizers, heat stabilizers, light stabilizers, anti-ozone agents, processing aids, plasticizers, resins, tackifiers, foaming agents, dyes, pigments, waxes, elongation agents, organic acids, retardants, metal oxides, and activators, such as diphenylguanidine, triethanolamine, polyethylene glycol, alkoxy-terminated polyethylene glycol alkyl-O-(CH2-CH2-O)yI-H, wherein yI = 2 to 25, preferably yI = 2 to 15, more preferably yI = 3 to 10, most preferably yI = 3 to 6, or hexanetriol familiar to the rubber industry. Rubber additives can be used in a commonly used amount, particularly determined by factors including the intended use. The commonly used amount can be, for example, from 0.1% to 50% by weight based on the rubber. The crosslinking agent used can be a peroxide, sulfur, or a sulfur donor. The rubber mixture according to the invention may additionally contain a vulcanization accelerator. Suitable examples of vulcanization accelerators include mercaptobenzothiazole, sulfinamide, methyl thiocarbamate, dithioamine formate, thiourea, and thiocarbonates. The vulcanization accelerator and sulfur can be used in an amount from 0.1% to 10% by weight, preferably from 0.1% to 5% by weight, based on 100 parts by weight of rubber. The rubber compound according to the invention can be vulcanized at a temperature of 100°C to 200°C, preferably 120°C to 180°C, at a pressure of 10 to 200 bar. The blending of rubber with fillers, and optionally rubber additives with silane-azodimethylamine mixtures, can be carried out in known mixing units (e.g., rollers, closed mixers, and mixing extruders). The rubber compound according to the present invention can be used to manufacture molded articles, such as tires (especially pneumatic tires or tire treads), cable sheaths, hoses, drive belts, conveyor belts, overlock rollers, shoe soles, sealing rings and damping elements. The advantage of the silane-azodimethylamine mixture according to the present invention is that it results in a more balanced stress value and resilience measurement of the rubber mixture. Implementation

[0004] [Example] [Substances Used] [] Example 1: Si 69™ (bis-[3-(triethoxysilyl)-propyl]-tetrasulfide) from Evonik Operations GmbH was used as Example 1. Example 2: 2-Phenylacetyl-N-(3-(triethoxysilyl)propyl)azomethylamine, manufactured according to Example 7 of EP 2 937 351, was used as Example 2. Example 3: [manufacture] [N,N-] [pair] [(2-)] [Ethylhexyl] [)] [Azodimethylamine] [] 2-Ethylhexylamine and pentane were cooled to 0°C in a 2 L flask equipped with a stirrer and reflux condenser. Diisopropyl diazonium carboxylate (DIAD) was slowly added while maintaining the temperature at 0°C. The mixture was stirred at this temperature for 30 minutes, and then stirred at 20°C for 2 to 3 hours. The crude N,N-bis(2-ethylhexyl)azodimethylamine was obtained as a solution in pentane and isopropanol. The reaction conversion was monitored by HPLC. The solvent was removed under vacuum, yielding a product as a deep red solid with a purity >= 70% (determined by 1H-NMR analysis). [Example] [4] [:manufacture] [Si 69™] [and] [2-] [Phenyl] [-N-(3-(] [Triethoxysilyl] [)] [Propyl] [)] [Azomethamine and] [N,N-] [pair] [(2-)] [Ethylhexyl] [)] [Azodimethylamine blends] [] In a 2 L flask equipped with a stirrer and a reflux condenser, 2-ethylhexylamine (291 g, 2.25 mol) and pentane (122 g, 1.69 mol) were cooled to 5 °C. While maintaining the temperature at 5 °C, diisopropyl didiazocarboxylate (DIAD) (227 g, 1.16 mol) was slowly added. The mixture was stirred at 0 °C for 30 minutes, and then at 20 °C for 2 to 3 hours. Subsequently, the resulting N,N-bis(2-ethylhexyl)azodimethylamine solution was partitioned, and a quarter of this solution (126.0 g, 60% in iPrOH / pentane, 0.28 mol) was mixed with Si 69™ (95 g, 0.18 mol) and 2-phenyl-N-(3-(triethoxysilyl)propyl)azodimethylamine (128 g, 0.36 mol). The reaction solution was stirred at 20°C for 5 minutes. Pentane was distilled off at 40°C and 500 mbar, and then pentane and iPrOH were removed by distillation under a vacuum of 20 mbar with stirring at 40 to 60°C. The distillation mixture was analyzed by NMR and GC. Si 69:30% (1H-NMR, DMSO-d6) 2-Phenylacetyl-N-(3-(triethoxysilyl)propyl)azomethamine: 40% (1H-NMR, DMSO-d6) N,N-bis(2-ethylhexyl)azodimethylamine: 30% (1H-NMR, DMSO-d6) Isopropanol: 0.3% (GC) [Example] [5] [:] [Natural rubber blend] [(NR)] Table 1 lists the materials used. The formulations for the rubber blends are detailed in Table 2. The unit phr refers to parts by weight based on 100 parts of raw rubber used. Table 3 describes the preparation of the mixture. Elastomer mixtures were prepared using a GK 1.5 E closed mixer from Harburg Freudenberger Maschinenbau GmbH. Test methods for the mixtures and their vulcanization products were performed according to Table 4. [, , ] [] [surface] [3. NR] [Mixture of Mixtures] [Phase 1] GK 1.5 E, kneader filler factor 0.65; 65 rpm; kneader temperature: 65℃ minutes: seconds Desired mixing temperature: 140-150℃ 00:00 – 00:30 Add the polymer; turn off the plunger and mix for 30 seconds. 00:30 – 01:30 Add 1 / 2 of the silica, silane / silane; close the plunger and mix for 60 seconds. 01:30 – 01:30 Raise the plunger to allow air in and clean the plunger. 01:30 – 02:30 Add half the silicon dioxide, leaving the components from the first stage; close the plunger and mix for 60 seconds. 02:30 – 02:30 Raise the plunger to allow air in and clean the plunger. 02:30 – 04:00 Close the plunger and mix for 90 seconds; adjust the mixer speed as needed to maintain the temperature at 140°C-150°C. 04:00 – 04:00 Raise the plunger to allow air in. 04:00 – 05:00 Close the plunger and mix for 60 seconds; adjust the mixer speed as needed while maintaining the temperature at 140°C-150°C. 5:00 Discharge the mixture and check the weight. A rolled sheet is formed on a laboratory rolling mill (two-roll calender) with a 4 mm roll gap for 45 seconds and then discharged. Storage: 24 h / RT [Phase Two] GK 1.5 E, kneader filler factor 0.62; 80 rpm; kneader temperature: 80℃ Desired mixing temperature: 140-150℃ 00:00 – 01:00 Add the mixture from the first stage; shut off the plunger and mix for 60 seconds. 01:00 – 03:00 Mix for 120 seconds, adjusting the mixer speed as needed to maintain the temperature between 140°C and 150°C. 3:00 Discharge the mixture and check the weight. A rolled sheet is formed on a laboratory rolling mill (two-roll calender) with a 4 mm roll gap for 45 seconds and then discharged. Storage: 4-24 h / RT [Phase Three] GK 1.5 E, kneader filler factor 0.59; 55 rpm; kneader temperature: 50℃ Desired mixing temperature: 90-110℃ 00:00 – 02:00 Add the mixture from stage two, the accelerator, and sulfur; shut off the plunger and mix for 120 seconds. 02:00 The mixture is discharged and rolled into sheets at a 3-4 mm roll gap on a laboratory rolling mill (two-roll calender) for 20 seconds. Storage: 12 h / RT [surface] [4.] [List of Physical Experiments Used] method standard Tested at 23℃: Standard test piece S1; Emission speed: 500 mm / min. Used to determine 300% stress value / MPa. DIN 53 504 Resilience; 60℃ / % ASTM D 2632 Resilience; 60℃–23℃ / % ASTM D 2632 It is evident from Table 5 that the sulfidation products of mixtures 1 to 11 of the present invention, which contain the silane-azodimethylamine mixture of the present invention, show a significantly improved stress value of 300% compared with the comparative mixtures 1 to 3. In terms of composition, mixture 4 of the present invention is the same as 11 and Examples 1 to 3. Mixture 4 of the present invention is produced by adding individual components of Examples 1 to 3 to a closed mixer during mixing, while in the case of mixture 11 of the present invention, the premixes of Examples 1 to 3 are added. Similar results are obtained whether the silane-azodimethylamine mixture is produced as a premix or during mixing. [Example] [6] [Natural rubber blend] [(NR)] Table 1 lists the materials used. The formulations for the rubber compounds are detailed in Table 6. The unit phr refers to parts by weight based on 100 parts of raw rubber used. Table 3 describes the preparation of the mixture. Elastomer mixtures were prepared using a GK 1.5 E closed mixer from Harburg Freudenberger Maschinenbau GmbH. Test methods for the mixtures and their vulcanization products were performed according to Table 7. Vulcanization products were prepared in a pressure vulcanizing machine at 150°C for 30 minutes. [surface] [7.] [List of Physical Experiments Used] method standard Tested at 23℃: Standard test piece S1; Emission speed: 500 mm / min for determining 300% stress value / MPa DIN 53 504 ML(1+4) at 100℃ DIN 53523-3 [surface] [8.] [Results of the physical experiment] [unit] [Compared mixtures] [4] [The mixture of the present invention]

[12] [The mixture of the present invention]

[13] [300%] [Stress value] MPa 10.2 11.7 10.7 [M, L , (1+4) ] [At]

[0100] [℃] [, , ] [Third Mixing Phase] 52 42 37 As is evident from Table 8, the sulfidation products of mixtures 12 and 13 of the present invention, which contain the silane-azodimethylamine mixture of the present invention, show a significantly improved 300% stress value compared to mixture 4. The Mooney viscosity is also significantly lower.

Claims

1. A silane-azodimethylamine mixture comprising, based on the total amount of azocarbonyl-functionalized silane of formula I, silane of formula II, and azodimethylamine of formula III, 5 to 95% by weight of azocarbonyl-functionalized silane of formula I, silane of formula II, and azodimethylamine of formula III, 0 to 90% by weight of silane of formula II, silane of formula I, silane of formula II, and azodimethylamine of formula III, and 1 to 80% by weight of azodimethylamine of formula III, wherein R1 is the same or different and represents C1 to C10-alkoxy, phenoxy, or alkyl polyether-O-(R6-O)rR 7, where R6 is the same or different and represents a branched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group; r is an integer from 1 to 30 and R7 represents an unsubstituted or substituted branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group; R2 is the same or different and represents -OH, C6 to C20-aryl, C1 to C10-alkyl, C2 to C20-alkenyl, C7 to C20-aralkyl or halogen; a is 0 to 3; y is 0 to 3; R3 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group; R4 represents a substituted or unsubstituted aryl or substituted or unsubstituted alkyl group; x is the average sulfur chain distribution, where x is 2 to 10; R 5 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic or cyclic monovalent C1 to C30-hydrocarbon group or a substituted or unsubstituted aryl group.

2. The silane-azodimethylamine mixture of claim 1, wherein the azocarbonyl-functionalized silane of formula I is (CH 3CH 2O-) 3Si-(CH 2) 3-NH-CO-N=N-phenyl, (CH 3O-) 3Si-(CH 2) 3-NH-CO-N=N-phenyl, or (CH 3CH 2O-) 3Si-(CH 2) 3-NH-CO-N=N-(p-nitrophenyl).

3. The silane-azodimethylamine mixture of claim 1, wherein the silane of formula II is [(EtO)3Si(CH2)3]2S, [(EtO)3Si(CH2)3]2S2, [(EtO)3Si(CH2)3]2S3 or [(EtO)3Si(CH2)3]2S4.

4. The silane-azodimethylamine mixture of claim 1, wherein the azodimethylamine compound of formula III is CH3(CH2)5-NH-C(=O)-N=NC(=O)-NH-(CH2)5-CH3, CH3(CH2)7-NH-C(=O)-N=NC(=O)-NH-(CH2)7-CH3, CH3(CH2)3-CH(C2H5)-CH2-NH-C(=O)-N=NC(=O)-NH-CH2-CH(C2H5)-(CH2)3-CH3, or CH3-(CH2)3-CH(C3H7)-CH2-CH2-NH-C(=O)-N=NC(=O)-NH-CH2-CH 2-CH(C 3H 7)-(CH 2) 3-CH 3.

5. The silane-azodimethylamine mixture of claim 1, wherein a is 0, y is 3, x is 2 to 4, R1 is ethoxy, R3 is (CH2)3, R4 is phenyl, nitrophenyl or tert-butyl, and R5 is branched or unbranched alkyl.

6. A method for manufacturing a silane-azodimethylamine mixture as claimed in claim 1, wherein the method comprises: mixing 5 to 95% by weight of an azocarbonyl-functionalized silane of formula I, a silane of formula II, and an azodimethylamine compound of formula III, based on the total amount of the azocarbonyl-functionalized silane of formula I, the silane of formula II, and the azodimethylamine compound of formula III; 0 to 90% by weight of a silane of formula II, based on the total amount of the azocarbonyl-functionalized silane of formula I, the silane of formula II, and the azodimethylamine compound of formula III; and 1 to 80% by weight of an azodimethylamine compound of formula III, based on the total amount of the azocarbonyl-functionalized silane of formula I, the silane of formula II, and the azodimethylamine compound of formula III.

7. The method for manufacturing a silane-azodimethylamine mixture as claimed in claim 6, wherein the azodimethylamine compound of formula III is added with the azocarbonyl-functionalized silane of formula I and the silane of formula II during the manufacturing of the azodimethylamine compound of formula III.

8. A rubber compound comprising at least one rubber, 5 to 95% by weight of an azocarbonyl-functionalized silane of Formula I, a silane of Formula II, and an azodimethylamine compound of Formula III, based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, 0 to 90% by weight of a silane of Formula II, based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, and 1 to 80% by weight of an azodimethylamine compound of Formula III, based on the total amount of the azocarbonyl-functionalized silane of Formula I, the silane of Formula II, and the azodimethylamine compound of Formula III, wherein R1 is the same or different and represents C1 to C10-alkoxy, phenoxy, or alkyl polyether-O-(R6-O)rR7, wherein R 6 is the same or different and represents a branched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group; r is an integer from 1 to 30; and R7 represents an unsubstituted or substituted branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group; R2 is the same or different and represents -OH, C6 to C20-aryl, C1 to C10-alkyl, C2 to C20-alkenyl, C7 to C20-aralkyl or halogen; a is 0 to 3; y is 0 to 3; R3 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic, aromatic or mixed aliphatic / aromatic divalent C1 to C30 hydrocarbon group; R4 represents a substituted or unsubstituted aryl or substituted or unsubstituted alkyl group; x is the average sulfur chain distribution, where x is 2 to 10; R 5 is the same or different and represents a branched or unbranched, saturated or unsaturated aliphatic or cyclic monovalent C1 to C30-hydrocarbon group or a substituted or unsubstituted aryl group.

9. The rubber mixture of claim 8, wherein the azocarbonyl-functionalized silane of formula I is (CH 3CH 2O-) 3Si-(CH 2) 3-NH-CO-N=N-phenyl, (CH 3O-) 3Si-(CH 2) 3-NH-CO-N=N-phenyl, or (CH 3CH 2O-) 3Si-(CH 2) 3-NH-CO-N=N-(p-nitrophenyl).

10. The rubber mixture of claim 8, wherein the silane of formula II is [(EtO)3Si(CH2)3]2S, [(EtO)3Si(CH2)3]2S2, [(EtO)3Si(CH2)3]2S3 or [(EtO)3Si(CH2)3]2S4.

11. The rubber mixture of claim 8, wherein the azodimethylamine compound of formula III is CH3(CH2)5-NH-C(=O)-N=NC(=O)-NH-(CH2)5-CH3, CH3(CH2)7-NH-C(=O)-N=NC(=O)-NH-(CH2)7-CH3, CH3(CH2)3-CH(C2H5)-CH2-NH-C(=O)-N=NC(=O)-NH-CH2-CH(C2H5)-(CH2)3-CH3 or CH3-(CH2)3-CH(C3H7)-CH2-CH2-NH-C(=O)-N=NC(=O)-NH-CH2-CH2-CH(C3H5)-NH-C2H5 ... 7)-(CH 2) 3-CH 3.

12. The rubber mixture of claim 8, wherein a is 0, y is 3, x is 2 to 4, R1 is ethoxy, R3 is (CH2)3, R4 is phenyl, nitrophenyl or tert-butyl, and R5 is branched or unbranched alkyl.

13. Use of the rubber compound of claim 8 for manufacturing tires, cable sheaths, hoses, drive belts, conveyor belts, overlock rollers, shoe soles, sealing rings and damping elements.