Oligomeric organosilanes, their preparation and use in rubber mixtures

Abstract

The present invention provides a polymerizable compound containing at least structural units (A), (B) and (C) in any linear, branched or cyclic configuration, and an alkyl polyether group -O-(R 5 -O) m -R 6 The oligomeric organosilane according to the present invention is a silane having a molar ratio of mercaptosilane (D), alkylsilane (E), polyol (F), and a compound of the formula HO-(R 5 -O) m -R 6 and a catalyst and reacting them at a temperature of 20 to 180° C. The oligomeric organosilane according to the invention can be used in rubber mixtures. TIFF2025536546000024.tif73150

Description

[Technical Field]

[0001] The present invention relates to oligomeric organosilanes, a process for their preparation, and their use in rubber mixtures.

[0002] It is known that sulfur-containing organosilicon compounds such as 3-mercaptopropyltrimethoxysilane or bis(3-[triethoxysilyl]propyl)tetrasulfane can be used as silane adhesion promoters or reinforcing additives in rubber mixtures with oxide fillers, including for tire treads and other components of automobile tires (German Patent No. 2,141,159; German Patent No. 2,212,239; U.S. Pat. No. 3,978,103; U.S. Pat. No. 4,048,206).

[0003] EP 0 784 072 discloses rubber mixtures based on at least one elastomer containing silica as a filler and reinforcing additive, which are prepared by blending or as an in situ reaction product with at least one functional polyorganosiloxane compound and contain a functional organosilane as a further component. The monomer units used are, in particular, 3-mercaptopropyltrialkoxysilane or bis(trialkoxysilylpropyl)tetrasulfane, which have three and six alkoxy substituents, respectively.

[0004] Furthermore, EP 0964021 discloses oligomeric organosilane polysulfanes that are not polycondensed to form solids and contain structural units A and / or B and / or C in any linear, branched or cyclic arrangement. [ka]

[0005] WO 2006 / 037380, EP 0997489 and EP 1273613 similarly disclose oligomeric organosilanes.

[0006] Furthermore, U.S. Pat. No. 7,368,584 discloses a compound having the chemical structure [G 1 - / SiX α u Z β v Z θ w ) s ] m [(HS) r -G 2 -(SiX α u Z β v Z θ w ) s ] n The present invention discloses a mercapto-functional silane composition comprising at least one mercapto-functional silane having the formula:

[0007] EP 3094686 discloses oligomeric organosilanes containing within the molecule at least two different structural units selected from structural units A, B, C and D linked in any desired linear, branched or cyclic arrangement. [ka]

[0008] Disadvantages of known oligomeric organosilanes are their low tear resistance and / or low storage stability.

[0009] It is an object of the present invention to provide oligomeric organosilanes that have improved tear resistance and / or improved storage stability.

[0010] The present invention provides a method for preparing a silicon-based polyether compound comprising at least the structural units A, B, and C in any linear, branched, or cyclic arrangement, and an alkyl polyether group -O-(R 5 -O)m -R 6 The present invention provides an oligomeric organosilane characterized in that the molar ratio of [ka] (wherein n=1 to 10, preferably 1 to 4, more preferably 3; R 1 and R 3 are the same or different and independently represent -OH, (C1-C4)alkoxy, preferably ethoxy, OSiR 2 R 3 2, OSi((CH2) n SH)R 3 2, and the structural unit C is bonded to the silicon atom of the structural unit A or B via an oxygen atom and terminates with an -OH group, or is bonded to the silicon atom of the structural unit A or B via an oxygen atom and terminates with an Si-O group or an alkyl polyether group -O-(R 5 -O) m -R 6 (In the formula, R 5 are the same or different and are branched or unbranched, saturated or unsaturated aliphatic divalent C1 to C30 hydrocarbon groups, preferably CH2CH2, m has an average value of 1 to 30, preferably 5, and R 6 is unsubstituted or substituted branched or unbranched C1 to C30 alkyl, preferably C 13 H 17 , a C2-C30 alkenyl, a C6-C14 aryl group, or a C7-C40 aralkyl group) R 2 is a branched or unbranched, saturated or unsaturated aliphatic monovalent C1 to C30, preferably C1 to C8, more preferably C8 hydrocarbon group, R 4 are the same or different and are branched or unbranched, saturated or unsaturated C1-C10 alkyl, C1-C10 alkyl-OH, C1-C10 alkyl-NH2 or H; and p=1 to 10.)

[0011] Alkyl polyether group -O-(R 5-O) m -R 6 The molar ratio of may be 0 to 0.30, preferably 0 to 0.10, more preferably 0.01 to 0.09, and most preferably 0.01 to 0.08.

[0012] The molar ratio of structural unit C to silicon can be 0 to 1.7, preferably 0.1 to 1.5. The structural unit C can also be R 1 and / or R 3 The oxygen atom of the Si-O group of the same structural unit may be present in the ring or may be terminated by an OH group.

[0013] The molar ratio of structural units A to B in the oligomeric organosilane according to the invention can be from 10:1 to 1:10, preferably from 3:1 to 1:3, more preferably from 2:1 to 1:2.

[0014] The alkyl polyether group is preferably —O—(CH2CH2—O) m -R 6 , more preferably -O-(CH2CH2-O)5-R 6 , most preferably -O-(CH2CH2-O)5-C 13 H 27 It could be.

[0015] In the oligomeric organosilanes according to the present invention, R 1 =OC2H5 or -O-(R 5 -O) m -R 6 , R 2 =(CH2)7CH3, R 3 =OC2H5 or -O-(R 5 -O) m -R 6 , R 4 =H or CH3, R 5 =CH2CH2, R 6 =C 13 H 27 , n=3, m=5, p=3 may be preferable.

[0016] The structural unit A can be, for example, [-O-(EtO)Si(-(CH2)3-SH)-], [-O-(MeO)Si(-(CH2)3-SH)-], [-O-(EtO)Si(-(CH2)4-SH)-], [-O-(EtO)Si(-(CH2)5-SH)-], [-O-(EtO)Si(-(CH2)6-SH)-], [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)3-SH)-], [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)3-SH)-], [Chem.] [-O-(HO-CH2-CH2-O)Si(-(CH2)3-SH)-], [-O-((EtO)2Si((CH2)3-SH)-O-)Si(-(CH2)3-SH)-], [-O-((C 13 H 27 -(OCH2CH2)5-O)(EtO)Si(-(CH2)3-SH)-O-)Si((CH2)3-SH)-], [-O-((HO-CH2-CH(CH3)-CH2-O)(EtO)Si(-(CH2)3-SH)-O-)Si((CH2)3-SH)-], [-O-((EtO)2Si((CH2)7-CH3)-O-)Si(-(CH2)3-SH)-], [-O-((C 13 H 27 -(OCH2CH2)5-O)(EtO)Si(-(CH2)7-CH3)-O-)Si((CH2)3-SH)- or [-O-((HO-CH2-CH(CH3)-CH2-O)(EtO)Si(-(CH2)7-CH3)-O-)Si((CH2)3-SH)-] may be.

[0017] The structural unit B is, for example, [-O-(MeO)Si(-(CH2)7-CH3)-], [-O-(EtO)Si(-(CH2)2-CH3)-], [-O-(EtO)Si(-(CH2)3-CH3)-], [-O-(EtO)Si(-(CH2)4-CH3)-], [-O-(EtO)Si(-(CH2)5-CH3)-], [-O-(EtO)Si(-(CH2)6-CH3)-], [-O-(EtO)Si(-(CH2)7-CH3)-], [-O-(EtO)Si(-(CH2)2-CH(CH3)2)-]、 [-O-(EtO)Si(-(CH2) 15 -CH3)-], [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)2-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)3-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)4-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)5-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)6-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)7-CH3)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)2-CH(CH3)2)-]、 [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2) 15-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)2-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)3-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)4-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)5-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)6-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)7-CH3)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)2-CH(CH3)2)- [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2) 15 -CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)2-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)3-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)4-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)5-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)6-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)7-CH3)- [-O-(HO-CH2-CH2-O)Si(-(CH2)2-CH(CH3)2)-

Chem.

[0018] In the oligomeric organosilanes according to the invention, the structural unit C may more preferably be [—O—CH 2 —CH(CH) 3 —CH 2 —] or [—O—CH 2 —CH 2 —].

[0019] The oligomeric organosilanes according to the present invention most preferably comprise the structural unit A = [-O-(EtO)Si(-(CH2)3-SH)-] or [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)3-SH)-] or [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)3-SH)-] or [ka] and B = [-O-(EtO)Si(-(CH2)7-CH3)-] or [-O-(C 13 H 27 -(OCH2CH2)5-O)Si(-(CH2)7-CH3)-] or [-O-(HO-CH2-CH(CH3)-CH2-O)Si(-(CH2)7-CH3)-] or [ka] and C=[-O-CH2-CH(CH)3-CH2-] may contain

[0020] The present invention further provides a process for preparing the oligomeric organosilanes according to the present invention, comprising: a mercaptosilane D; an alkylsilane E; a polyol F; [ka] Formula HO-(R 5 -O) m -R 6 and a catalyst, and reacting them at a temperature of 20 to 180°C, preferably 90 to 150°C. (In the formula, R 2 , R 4 , R 5 , R 6 n, m, and p have the same definitions as above, R 7 are the same or different and are —OH, (C1-C4)alkoxy, preferably ethoxy, or an alkyl polyether group —O—(R 5 -O) m -R 6 (In the formula, R 5 are the same or different and are branched or unbranched, saturated or unsaturated aliphatic divalent C1 to C30 hydrocarbon groups, preferably CH2CH2, m has an average value of 1 to 30, preferably 5, and R 6 is unsubstituted or substituted branched or unbranched C1 to C30 alkyl, preferably C 13 H 17 , a C2 to C30 alkenyl, a C6 to C14 aryl group, or a C7 to C40 aralkyl group.

[0021] The reaction can be carried out within 30 minutes to 10 hours, preferably within 30 minutes to 3 hours.

[0022] The reaction can be carried out with stirring.

[0023] The secondary components can be separated by distillation.

[0024] The secondary components can be separated by distillation during or after the reaction. The secondary components can be separated preferably during the reaction.

[0025] The secondary components can be separated by distillation at atmospheric pressure or reduced pressure, preferably at reduced pressure, more preferably at a pressure of 20 to 200 mbara.

[0026] Components D and E may be used in a molar ratio of 1:10 to 10:1, preferably 1:3 to 3:1, more preferably 1:2 to 2:1.

[0027] Components D and F may be used in a molar ratio of 1:1 to 1:10. Preferably, components D and F may be used in a molar ratio of 1:2 to 1:10. More preferably, components D and F may be used in a molar ratio of 1:2 to 1:4. Most preferably, components D and F may be used in a molar ratio of 1:2 to 1:3.

[0028] Component D and the formula HO-(R 5 -O) m -R 6 The alkyl polyether alcohol of the formula HO-(R) may be used in a molar ratio of 1:0.01 to 1:2. Preferably, the component D is used in a molar ratio of 1:0.01 to 1:2. 5 -O) m -R 6 The polyether alcohol may be used in a molar ratio of 1:0.1 to 1:1.

[0029] The catalyst can be added in catalytic or stoichiometric amounts. In this regard, any acidic, basic, or nucleophilic catalyst known to those skilled in the art from the sol-gel chemistry of alkoxysilanes (see, for example, R. Corriu, D. Leclercq, Angew. Chem. 1996, 108, 1524-1540) is also suitable for oligomerization in the context of the present invention. Here, it is not important whether the catalyst is in the same phase as the reaction solution (homogeneous catalysis) or in solid form (heterogeneous catalysis) and is removed after the reaction is completed.

[0030] Preferably, homogeneous catalysis can be carried out using a transition metal complex, such as tetrabutyl orthotitanate, or a transition metal salt. Basic catalysis can be carried out using an organic base, such as triethylamine, tetramethylpiperidine, tributylamine, or pyridine, or an inorganic base, such as NaOH, KOH, Ca(OH), NaCO, KCO, CaCO, CaO, NaHCO, or KHCO, or an alkoxide, such as NaOCH or NaOCH. Acidic catalysis can be carried out using a dilute aqueous solution of a mineral acid, such as HSO or HCl, or an aqueous solution of a Lewis acid.

[0031] Preferably, the catalyst used may be a transition metal complex, KOH, NaOH, ammonium fluoride, H2SO4 or HCl.

[0032] More preferably, the catalyst used may be a transition metal complex.

[0033] Most preferably, the catalyst used may be tetrabutyl orthotitanate.

[0034] The process according to the invention can be carried out in solvent-free form or in the presence of a solvent, preferably in solvent-free form.

[0035] The solvent may be an inert organic solvent or a mixture thereof, for example an aromatic solvent such as chlorobenzene, a halogenated hydrocarbon such as chloroform, methylene chloride, an ether such as diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran or diethyl ether, acetonitrile, a carboxylic acid ester such as ethyl acetate, methyl acetate, isopropyl acetate, or an alcohol such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol or tert-butanol.

[0036] The mercaptosilane of formula D is, for example: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 4-mercaptobutyltriethoxysilane, 5-mercaptopentyltriethoxysilane or 6-Mercaptohexyltriethoxysilane It could be.

[0037] The alkylsilane of formula E is, for example, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, Hexadecyltrimethoxysilane or Hexadecyltriethoxysilane It could be.

[0038] The polyol of formula F is, for example, propane-1,3-diol, propane-1,2,3 triol, 2-methylpropane-1,3-diol or Ethane-1,2-diol It could be.

[0039] The alkyl polyether alcohol is, for example, C 13 H 27 -(OCH2CH2)5-OH It could be.

[0040] The catalyst may remain in the product after the reaction, be deactivated, preferably by neutralization, or be removed, preferably by filtration. More preferably, the catalyst may not be deactivated after the reaction and remain in the product.

[0041] The present invention further provides the use of the oligomeric organosilanes according to the invention in rubber mixtures.

[0042] The present invention further provides rubber mixtures comprising the oligomeric organosilanes according to the invention.

[0043] The rubber mixtures according to the invention can be used for the production of moldings, in particular pneumatic tires or tire treads.

[0044] The rubber mixture according to the invention may comprise rubber, a filler, preferably precipitated silica, optionally further rubber adjuvants, and at least one oligomeric organosilane according to the invention.

[0045] The use of the oligomeric organosilanes according to the invention in rubber blending processes significantly reduces the undesirable release of alcohols due to pre-condensation that has already taken place, e.g., the generation of alcohols during blending operations is reduced compared to the usual mode of operation by simply using bis(3-[triethoxysilyl]propyl)tetrasulfane (TESPT) as an adhesion promoter.

[0046] The rubbers used can be natural and / or synthetic rubbers. Preferred synthetic rubbers are described, for example, in W. Hofmann, H. Gupta, "Handbuch der Kautschuktechnologie" [Handbook of Rubber Technology], Dr. Gupta Verlag, Ratingen 2001, chapter 3, pp. 2-4. They are: Polybutadiene (BR), Polyisoprene (IR), styrene / butadiene copolymers, such as emulsion SBR (E-SBR) or solution SBR (S-SBR), preferably with 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 copolymers with an acrylonitrile content of 5% to 60% by weight, preferably 10% to 50% by weight of (NBR), Partially or fully hydrogenated NBR rubber (HNBR), Ethylene / propylene / diene copolymer (EPDM), the above rubbers, which also have functional groups such as carboxy, silanol or epoxy groups, such as epoxidized NR, carboxy-functionalized NBR or amine (NR2), silanol (—SiOH)-, epoxy-, mercapto-, hydroxy- or siloxy (—Si—OR)-functionalized SBR, and mixtures of these rubbers. The rubbers mentioned may additionally be silicone- or tin-bonded.

[0047] In a preferred embodiment, the rubber may be sulfur vulcanizable. For the production of car tire treads, it is possible to use, in particular, anionic polymerized S-SBR rubbers (solution SBR) having a glass transition temperature above -50°C, and mixtures thereof with diene rubbers. Particularly preferably, S-SBR rubbers having a butadiene content with a vinyl fraction of more than 20% by weight can be used. Very particularly preferably, S-SBR rubbers having a butadiene content with a vinyl fraction of more than 50% by weight can be used.

[0048] It is preferably possible to use mixtures of the abovementioned rubbers having an S-SBR content of more than 50% by weight, preferably more than 60% by weight.

[0049] The rubber may be a functionalized rubber, the functional groups being amine and / or amide and / or urethane and / or urea and / or aminosiloxane and / or siloxane and / or silyl and / or alkylsilyl, for example N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane or methyltriphenoxysilane, and / or silyl halides and / or silane sulfide and / or thiol and / or hydroxyl and / or ethoxy and / or epoxy and / or carboxyl and / or tin, for example tin tetrachloride or dibutyldichlorotin, and / or silanol and / or hexachlorodisiloxane and / or thiocarboxy and / or nitrile and / or nitroxide and / or amide and / or may be imino and / or urethane and / or urea and / or dimethylimidazolidinone and / or 2-methyl-2-thiazoline and / or 2-benzothiazoleacetonitrile and / or 2-thiophenecarbonitrile and / or 2-(N-methyl-N-3-trimethoxysilylpropyl)thiazoline and / or carbodiimide and / or N-substituted aminoaldehyde and / or N-substituted aminoketone and / or N-substituted aminothioaldehyde and / or N-substituted aminothioketone and / or benzophenone and / or thiobenzophenone bearing an amino group and / or isocyanate and / or isothiocyanate and / or hydrazine and / or sulfonyl and / or sulfinyl and / or oxazoline or ester group.

[0050] The rubber mixture according to the invention may contain at least one filler.

[0051] Fillers that can be used in the rubber mixtures according to the invention include the following fillers: Carbon black: Carbon black may be produced by lamp black process, furnace black process, gas black process or thermal process, and has a purity of 20-200m 2 / g The carbon black may also optionally contain heteroatoms such as, for example, Si. For example, 5 to 1000 m 2 / g, preferably 20 to 400m 2 Amorphous silica produced by precipitation from a solution of silicate or by flame hydrolysis of silicon halides, with a specific surface area (BET surface area) of 1000 / g and a primary particle size of 10-400 nm. Silica may also be in the form of mixed oxides, possibly with other metal oxides such as oxides of Al, Mg, Ca, Ba, Zn, and titanium. 20-400m 2 Synthetic silicates such as aluminum silicate, alkaline earth metal silicates such as magnesium silicate or calcium silicate, with a BET surface area of ​​0.15g / g and a primary particle diameter of 10-400nm. · Synthetic or natural aluminum oxide and synthetic or natural aluminum hydroxide. Natural silicates, such as kaolin and other naturally occurring silicas. Glass fibres and glass fibre products (mats, strands) or glass microbeads.

[0052] Preferably, in an amount of 5 to 150 parts by weight per 100 parts of rubber, 20 to 400 m 2 / g, more preferably 100m 2 / g~250m 2 It is possible to use amorphous silica prepared by precipitation from a solution of silicates, having a BET surface area of ​​1000 nm / g.

[0053] It is very particularly preferable to use precipitated silica as filler.

[0054] The above mentioned fillers may be used alone or in mixtures.

[0055] The rubber mixtures according to the invention may contain 5 to 150 parts by weight of filler and 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 2 to 20 parts by weight of the oligomeric organosilane according to the invention, where parts by weight are based on 100 parts by weight of rubber.

[0056] The oligomeric organosilanes according to the invention can be used as adhesion promoters between inorganic materials, such as glass beads, glass flakes, glass surfaces, glass fibers, or oxidative fillers, preferably silica, such as precipitated silica and fumed silica, and organic polymers, such as thermosets, thermoplastics, or elastomers, or as crosslinkers and surface modifiers for oxidative surfaces.

[0057] The oligomeric organosilanes according to the invention may be used as coupling agents in filled rubber mixtures, examples of which are tire treads, industrial rubber articles or footwear soles.

[0058] The rubber mixtures according to the invention may contain further rubber auxiliaries well known in the rubber industry, such as accelerators, ageing stabilizers, 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—CH—O), yI -H(in the formula, y I = 2 to 25, preferably y I = 2 to 15, more preferably y I = 3 to 10, most preferably y I = 3 to 6), or hexanetriol.

[0059] Rubber adjuvants can be used in well-known amounts determined by factors including the end use. Conventional amounts can be, for example, 0.1% to 50% by weight based on the rubber. The crosslinking agent used can be peroxide, sulfur, or a sulfur donor substance. The rubber mixture according to the present invention can further contain a vulcanization accelerator. Examples of suitable vulcanization accelerators are mercaptobenzothiazole, sulfenamide, thiuram, dithiocarbamate, thiourea, and thiocarbonate. The vulcanization accelerator and sulfur can be used in amounts of 0.1% to 10% by weight, preferably 0.1% to 5% by weight, based on 100 parts by weight of rubber.

[0060] The rubber mixtures according to the invention can be vulcanized at temperatures between 100° C. and 200° C., preferably between 120° C. and 180° C., optionally at pressures of 10 to 200 bar. Blending of the rubbers according to the invention with the fillers, optional rubber auxiliaries and oligomeric organosilanes can be carried out in known mixing units such as rollers, internal mixers and mixing extruders.

[0061] The rubber mixtures according to the invention can be used for the production of shaped articles, for example for the production of tires, especially pneumatic tires or tire treads, cable sheaths, hoses, drive belts, conveyor belts, roller covers, footwear soles, sealing rings and damping elements.

[0062] The oligomeric organosilanes and fillers according to the invention are preferably added at a mass temperature of 100-200°C, but can also be added at a lower temperature (40-100°C), for example at a later stage together with further rubber adjuvants.

[0063] The oligomeric organosilanes can be added to the blending operation in pure form or applied to an inert organic or inorganic support. Preferred support materials are silica, natural or synthetic silicates, aluminum oxide, or carbon black.

[0064] The oligomeric organosilanes according to the invention are obtainable by the process according to the invention.

[0065] The oligomeric organosilanes according to the invention have the advantage of improved storage stability and / or improved tear resistance in rubber mixtures.

[0066] GC analysis: Determination of free ethanol / OCTEO / MPTES / 2-methylpropan-2-ol Volatile components are determined by gas chromatography using the internal standard method. For this purpose, calibration of individual components is performed using internal standards such as n-nonane, n-decane, or n-dodecane in appropriate solvents. The gas chromatograph used is an HP6850 or HP7820 equipped with a TCD detector. The separation column used is an HP5 column with the following characteristics: length: 30 m; internal diameter: 0.53 mm, film thickness: 2.65 mm. Alternatively, an HP1 column with the following characteristics is used: length: 30 m; internal diameter: 0.53 mm, film thickness: 1.50 mm. The temperature is 250 °C, and the detector temperature is 280 °C. The temperature program of the column oven is 50 °C - 5 min - 15 °C / min - 275 °C - 15 min. The carrier gas used is helium with a flow rate of approximately 4 ml / min and a split ratio of 1:50 to 1:100. The injected sample volume is 0.4 ml.

[0067] This method can be used to determine other alcohols as well, such as methanol.

[0068] Calculation of sample content:

number

[0069] Gas chromatographic determination of ethanol after hydrolysis: The determination of ethanol after hydrolysis can be carried out by hydrolyzing the silane with sulfuric acid (20% by weight). Water and sodium hydroxide (20% by weight) are then added. The resulting mixture is subjected to steam distillation using an appropriate apparatus. The distillate is collected in a corresponding standard flask, 2-butanol is added as an internal standard, and the mixture is adjusted to the mark with distilled water.

[0070] The gas chromatograph used is a capillary gas chromatograph equipped with an FID and evaluation software, e.g., HP7820 with OpenLab. The separation column has the following characteristics: length: 30 m; internal diameter: 0.32 mm; film thickness: 1.00 mm; stationary phase: Stabiwax (#10654-6850). The injector temperature is 250 °C, and the detector temperature is 280 °C. Column oven: 90 °C - 10 min - 25 °C / min - 240 °C - 0 min. The carrier gas used is helium with a flow rate of approximately 2 ml / min and a split ratio of approximately 1:50. The combustion gas used is a hydrogen / synthetic air mixture. The injected sample volume is 1.0 ml.

[0071] This method is equally applicable to the determination of other hydrolyzable alkoxy groups, such as methoxy groups.

[0072] Calculation of sample content:

number

[0073] NMR analysis: Furthermore, the trialkoxysilane content, as well as the M, D and T structures, can be determined by methods similarly known to those skilled in the art. 29 It can be determined using Si NMR spectroscopy. The solvent used is deuterated chloroform, with tetramethylsilane as the internal standard.

[0074] 29 Si NMR (79.5 MHz): 40-46 ppm (trialkoxysilane); 50-54 ppm (M structure); 57-61 ppm (D structure); 61-65 ppm (T structure). [ka]

[0075] Silicon-containing groups (structural units A and B) and structural unit C, and the bonded alkyl polyether groups (R 1 , R 3 =-O-(R 5 -O) m -R 6 ) is the molar ratio of 13 It can be determined using C NMR spectroscopy, which is also well known to those skilled in the art. The solvent used is deuterated chloroform with tetramethylsilane and chromium acetylacetonate as internal standards.

[0076] The structural unit C can also be R 1 and / or R 3 The oxygen atom of the Si-O group of the same structural unit may be present in the ring or may be terminated by an OH group.

[0077] The oligomeric silane is 13 It was characterized by spectroscopic determination of the following ratios by integration of the C NMR signals: Molar ratio of structural unit C to silicon: [A+B] / [C] Alkyl polyether group -O-(R 5-O) m -R 6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=Polyether alcohol / Si Molar ratio of structural units A and B: [A] / [B] [Example]

[0078] Octyltriethoxysilane (OCTEO) and VP Si 263® (MPTES, 3-mercaptopropyltriethoxysilane) are silanes from Evonik Operations GmbH.

[0079] Marlosol is a type HO-(R manufactured by Sasol 5 -O) m -R 6 Polyether alcohol (wherein R 5 =CH2CH2, R 6 =C 13 H 27 and m=5).

[0080] Comparative Example 1 Corresponds to Example 3 of U.S. Pat. No. 7,369,584 (MPTES:OCTEO:2-MPD=1:2.33:10) 3-Mercaptopropyltriethoxysilane (MPTES) (1.00 equivalents; 0.34 mol; 81.00 g) is initially charged into a round-bottom flask together with octyltriethoxysilane (OCTEO) (2.33 equivalents; 0.79 mol; 219.00 g) and mixed. Concentrated sulfuric acid (0.010 equivalents; 3.60 mmol; 0.30 g) is added to the mixture. A vacuum of 67 mbar is then applied and the mixture is heated to 50°C. Once 50°C has been reached, 2-methylpropane-1,3-diol (2-MPD) (10 equivalents; 3.395 mol; 306.00 g) is metered in within 30 minutes. The ethanol formed is distilled off. Once the metered addition is complete, the mixture is stirred for a further 4.5 hours. Once the product has cooled to room temperature, sodium ethoxide (w=21%; 0.012 equiv; 4.30 mmol; 1.45 g) is added to neutralize the sulfuric acid.

[0081] analysis: -GC: Free ethanol: 3.6% Ethanol after hydrolysis: 4.3% MPTES (1.1%), OCTEO (less than 0.1%), 2-methylpropane-1,3-diol (38%) 13 C NMR (100MHz): δ(ppm) 27.5(m,Si-(CH2)3-SH), 29.2(m,Si-(CH2)7-CH3), 64.0-65.8(m,-(O-CH2)2CH(CH3)), 70.1-70.8(m,-O-CH2-CH(CH3)-CH2-OH). Alkyl polyether group -O-(R 5 -O) m -R 6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=0.0:1 Molar ratio of structural unit C to silicon: [C] / [A+B]=1.75 Molar ratio of structural units A and B: [A] / [B]=0.4:1 29Si NMR: trialkoxysilane: 94 mol%; M structure: 6 mol% Four months later 29 Si NMR: trialkoxysilane: 88 mol%; M structure: 12 mol%

[0082] Comparative Example 2 Corresponding to Example 1 of European Patent No. 3094686 (MPTES:OCTEO:Marlosol=1:0.5:0.5) - 0.8 equivalents of HO 3-Mercaptopropyltriethoxysilane (1.00 equiv.; 1.75 mol; 417.00 g) is initially charged together with octyltriethoxysilane (0.50 equiv.; 0.880 mol; 242.00 g), which is heated to 85 °C. A mixture of HO (0.8 equiv.; 2.11 mol; 38.00 g) and concentrated hydrochloric acid (w = 37%; 0.005 equiv.; 8.00 mmol; 0.30 g) in ethanol (4.50 equiv.; 7.88 mol; 363.00 g) is slowly added dropwise, and the reaction mixture is stirred for a further 8.5 h. The solvent and hydrolyzed alcohol are removed under reduced pressure. To the oligomer thus obtained, Marlosol (0.50 equivalents; 0.880 mol; 368.00 g) and tetra-n-butyl titanate (0.0008 equivalents; 1.469 mmol; 0.50 g) are added. The mixture is heated to 140°C and the temperature is maintained for 1 hour. The ethanol formed is separated by distillation under reduced pressure.

[0083] analysis: -GC: Free ethanol: 0.7% Ethanol after hydrolysis: 3.7% MPTES (0.3%), OCTEO (0.1%) 13 C NMR (100MHz): δ(ppm)=27.5(m,Si-(CH2)3-SH), 29.2(m,Si-(CH2)7-CH3), 61.2(HO-(CH2-CH2-O)5-C 13 H 27 ), 61.5(Si-O-(CH2-CH2-O)5-C 13 H 27 ). Alkyl polyether group -O-(R 5 -O) m -R 6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=0.5:1 Molar ratio of structural units A and B: [A] / [B]=1.8:1 29 Si NMR: trialkoxysilane: 0 mol%; M structure: 48 mol%; D structure: 38 mol%; T structure: 14 mol% Four months later 29 Si NMR: trialkoxysilane: 0 mol%; M structure: 62 mol%; D structure: 35 mol%; T structure: 3 mol%

[0084] Example 1 (MPTES:OCTEO:2-MPD:Marlosol=1:2.33:10:1) 3-Mercaptopropyltriethoxysilane (1.00 equivalents; 0.344 mol; 81.00 g), octyltriethoxysilane (2.33 equivalents; 0.794 mol; 219.00 g), and Marlosol (1.00 equivalents; 1.132 mol; 476.12 g) are initially charged together with tetra-n-butyl titanate (0.0026 equivalents; 0.88 mmol; 0.30 g), which is heated to 130 °C. The ethanol formed is separated by distillation. As soon as the mixture reaches 130 °C, a vacuum of 200 mbar is applied and maintained for 30 minutes. The pressure is then reduced to 100 mbar for 30 minutes. The reaction mixture is cooled to room temperature, 2-methylpropane-1,3-diol (10.0 equivalents; 3.395 mol; 306.00 g) and tetra-n-butyl titanate (0.0026 equivalents; 0.88 mmol; 0.30 g) are added, and the mixture is again heated to 130°C. The ethanol formed is separated by distillation. As soon as the mixture reaches 130°C, a vacuum of 200 mbar is applied and maintained for 30 minutes, and then the pressure is reduced to 20 mbar within 30 minutes. The vacuum of 20 mbar is maintained for 1 hour, and the mixture is cooled back to room temperature.

[0085] analysis: -GC: Free ethanol: 0.1% Ethanol after hydrolysis: 0.2% MPTES (less than 0.1%), OCTEO (less than 0.1%), 2-methylpropane-1,3-diol (22%) 13 C NMR (100MHz): δ(ppm)=27.5(m,Si-(CH2)3-SH), 29.2(m,Si-(CH2)7-CH3), 61.2(HO-(CH2-CH2-O)5-C13H27), 61 .5(Si-O-(CH2-CH2-O)5-C13H27), 64.0-65.8(m,-(O-CH2)2CH(CH3)), 70.1-70.8(m,-O-CH2-CH(CH3)-CH2-OH). Molar ratio of structural unit C to silicon: [C] / [A+B]=1.16 Alkyl polyether group -O-(R 5 -O) m -R 6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=0.22:1 Molar ratio of structural units A and B: [A] / [B]=0.5:1 29 Si NMR: trialkoxysilane: 100 mol% Four months later 29 Si NMR: trialkoxysilane: 83 mol%; M structure: 17 mol%

[0086] Example 2 (MPTES:OCTEO:2-MPD:Marlosol=1:1:2.95:0.1) 3-Mercaptopropyltriethoxysilane (1.00 equiv.; 2.20 mol; 524.57 g), octyltriethoxysilane (1.00 equiv.; 2.20 mol; 602.20 g), 2-methylpropane-1,3-diol (2.95 equiv.; 6.425 mol; 579.00 g), Marlosol (0.10 equiv.; 0.216 mol; 90.69 g), and tetra-n-butyl titanate (0.00076 equiv.; 2.00 mmol; 0.57 g) are initially charged and heated to 130 °C. The temperature is maintained for 1.5 h. The formed ethanol is separated by distillation under reduced pressure (200-20 mbar), and the resulting product is then cooled to room temperature.

[0087] analysis: -GC: Free ethanol: 0.5% Ethanol after hydrolysis: 0.5% MPTES (less than 0.1%), OCTEO (1.1%), 2-methylpropane-1,3-diol (0.6%) 13 C NMR (100MHz): δ(ppm)=27.5(m,Si-(CH2)3-SH), 29.2(m,Si-(CH2)7-CH3), 61.2(HO-(CH2-CH2-O)5-C13H27), 61 .5(Si-O-(CH2-CH2-O)5-C13H27), 64.0-65.8(m,-(O-CH2)2CH(CH3)), 70.1-70.8(m,-O-CH2-CH(CH3)-CH2-OH). Molar ratio of structural unit C to silicon: [C] / [A+B]=1.40 Alkyl polyether group -O-(R 5 -O) m -R 6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=0.01:1 Molar ratio of structural units A and B: [A] / [B]=1:1 29Si NMR: trialkoxysilane: 100 mol% Four months later 29 Si NMR: trialkoxysilane: 95 mol%; M structure: 5 mol%

[0088] Example 3 (MPTES:OCTEO:2-MPD:Marlosol=1:0.5:2:0.5) 3-Mercaptopropyltriethoxysilane (1.00 equiv.; 1.75 mol; 417.00 g), octyltriethoxysilane (0.50 equiv.; 0.88 mol; 242.00 g), 2-methylpropane-1,3-diol (2.00 equiv.; 3.50 mol; 315.42 g), Marlosol (0.50 equiv.; 0.88 mol; 368.00 g), and tetra-n-butyl titanate (0.00038 equiv.; 1.67 mmol; 0.57 g) are initially charged and heated to 130 °C. The temperature is maintained for 1.5 h. The formed ethanol is separated by distillation under reduced pressure (200-20 mbar), and the resulting product is then cooled to room temperature.

[0089] analysis: GC: Free ethanol: 0.4% Ethanol after hydrolysis: 0.7% MPTES (0.1%), OCTEO (0.4%), 2-methylpropane-1,3-diol (1.1%) 13 C NMR (100MHz): δ(ppm)=27.5(m,Si-(CH2)3-SH), 29.2(m,Si-(CH2)7-CH3), 61.2(HO-(CH2-CH2-O)5-C13H27), 61 .5(Si-O-(CH2-CH2-O)5-C13H27), 64.0-65.8(m,-(O-CH2)2CH(CH3)), 70.1-70.8(m,-O-CH2-CH(CH3)-CH2-OH). Molar ratio of structural unit C to silicon: [C] / [A+B]=0.95 Alkyl polyether group -O-(R 5 -O) m -R6 Molar ratio of: [-O-(R 5 -O) m -R 6 ] / [A+B]=0.09:1 Molar ratio of structural units A and B: [A] / [B]=2:1 29 Si NMR: trialkoxysilane: 100 mol% Four months later 29 Si NMR: trialkoxysilane: 96 mol%; M structure: 4 mol%

[0090] Example 4 The formulation used for the rubber mixture is shown in Table 1 below, where the unit phr means parts by weight based on 100 parts of crude rubber used. Since the mercapto group is the only functional group bonded to the rubber, an oligomeric silane based on the reference silane according to Comparative Example 1 was used in an equimolar amount based on the mercapto group.

[0091] The molar mass of the mercapto-based oligomeric silane is calculated according to the following formula: 13 C and 29 It can be calculated from the integral of the Si NMR signal: M(g / mol) = [M(R 2 )×χ 13C (R 2 )+M(-(CH2) n -SH)×χ 13C (-(CH2) n -SH)+M(-O-(C(R 4 )2) n -)×χ 13C (-O-(C(R 4 )2) n -O))+M(-O-(R 5 -O) m -R 6 )×χ 13C (-O-(R 5 -O) m -R 6 )+ M(Si)×χ 29Si (trialkoxysilane) + (M(SiO 0.5)×χ 29Si (M structure)+(M(SiO))×χ 29Si (D structure)+(M(SiO 1.5 )×χ 29Si (T structure)] / χ 13C (-(CH2) n -SH) χ 13C (x)= 13 Molar ratio of component x based on the total amount of silane from the integration of the C NMR signal = Int(x) / (Int((-(CH2) n -SH)+Int(R 2 )) χ 29Si (x)= 29 Based on the total amount of silanes (trialkoxysilanes, M, D, and T structures) from the integration of Si NMR signals 29 Molar ratio from Si NMR = Int(x) / (Int(trialkoxysilane) + Int(M structure) + Int(D structure) + Int(T structure)) [Table 1]

[0092] [Table 2]

[0093] The polymer Buna® VSL 4526-2 is a solution-polymerized SBR copolymer manufactured by ARLANXEO Deutschland GmbH, with a styrene content of 26% by weight and a vinyl fraction of 45% by weight. The copolymer contains 37.5% TDAE oil and has a Mooney viscosity of 50 (ML 1+4 / 100°C).

[0094] The polymer Buna® CB 24 is a cis-1,4-polybutadiene (neodymium type) manufactured by ARLANXEO Deutschland GmbH, with a cis-1,4 content of at least 96% and a Mooney viscosity of 44.

[0095] ULTRASIL® 7000 GR is a readily dispersible silica manufactured by Evonik Industries AG and contains 160 ml 2 / g of CTAB surface area.

[0096] N330 is carbon black manufactured by Orion Engineered Carbons GmbH, the TDAE oil used is Vivatec 500 manufactured by Hansen & Rosenthal GmbH & Co. KG, Vulkanox® 4020 is 6PPD manufactured by LANXESS Distribution GmbH, Vulkanox® HS / LG is TMQ manufactured by Lanxess, Protektor™ G3108 is an anti-ozonant wax manufactured by Paramelt BV, Weisssiegel Spezial zinc oxide is ZnO manufactured by Grillo Zinkoxid GmbH, Palmera B1804 is palmitic / stearic acid manufactured by Caldic Deutschland GmbH & Co. KG, and Vulkacit® CZ is CBS manufactured by LANXESS Distribution GmbH. Uhoo TBzTD (Tetrabenzylthiuram disulfide) is a product manufactured by Hebi Uhoo Rubber Chemicals Co., Ltd. and is a ground sulfur product manufactured by Avokal GmbH.

[0097] The rubber mixture is prepared in three stages in an internal mixer according to Table 2.

[0098] [Table 3]

[0099] General methods for producing rubber mixtures and vulcanizates thereof are described in W. Hofmann, H. Gupta, "Handbuch der Kautschuktechnologie", Dr. Gupta Verlag, Ratingen 2001, chapter 10, pages 1-27 and 82-107.

[0100] Rubber testing is performed according to the test methods specified in Table 3.

[0101] [Table 4]

[0102] Vulcanization is carried out for 12 minutes at a temperature of 165° C. Table 4 reports the rubber data of the vulcanizates.

[0103] [Table 5]

[0104] The rubber mixtures containing the oligomeric silanes according to the invention show improved tear resistance compared to the reference mixtures.

Claims

1. containing at least structural units A, B and C in any linear, branched or cyclic arrangement, and an alkyl polyether group -O-(R ５ -O) ｍ -R ６ The oligomeric organosilane is characterized in that the molar ratio of 【Chemistry 1】 (In the formula, n=1 to 10, preferably 1 to 4, more preferably 3; R １ and R ３ are the same or different and independently represent —OH, (C1-C4)alkoxy, preferably ethoxy, OSiR ２ R ３ ２ , OSi((CH ２ ) ｎ SH)R ３ ２ and Structural unit C is bonded to the silicon atom of structural unit A or B via an oxygen atom to form an O—Si—O bond and terminates in an —OH group; or The same structural unit Si—O group or alkyl polyether group —O—(R ５ -O) ｍ -R ６ (In the formula, R ５ are the same or different and are branched or unbranched, saturated or unsaturated, aliphatic divalent C1 to C30 hydrocarbon groups, preferably CH ２ CH ２ where m has an average value of 1 to 30, preferably an average value of 5, and R ６ is an unsubstituted or substituted, branched or unbranched C1-C30 alkyl, preferably C13H17, C2-C30 alkenyl, C6-C14 aryl group, or C7-C40 aralkyl group), R ２ is a branched or unbranched, saturated or unsaturated aliphatic monovalent C1 to C30, preferably C1 to C8, more preferably C8 hydrocarbon group; R ４ are the same or different and are branched or unbranched, saturated or unsaturated C1-C10 alkyl, C1-C10 alkyl-OH, C1-C10 alkyl-NH ２ or H, and p=1 to 10.

2. The alkyl polyether group —O—(R ５ -O) ｍ -R ６ 2. The oligomeric organosilane of claim 1, wherein the molar ratio of is greater than 0 and less than 0.30, preferably greater than 0 and less than or equal to 0.10, more preferably in the range of 0.01 to 0.09, and most preferably in the range of 0.01 to 0.

08.

3. 2. The oligomeric organosilane of claim 1, wherein the molar ratio of structural units C to silicon is in the range of greater than 0 and less than 1.7, preferably in the range of 0.1 to 1.

5.

4. 2. The oligomeric organosilane of claim 1, wherein the molar ratio of structural units A to B is from 10:1 to 1:10, preferably from 3:1 to 1:3, more preferably from 2:1 to 1:

2.

5. The structural unit A is [—O—(EtO)Si(—(CH ２ )) ３ —SH)—], [—O—(MeO)Si(—(CH ２ )) ３ —SH)—], [—O—(EtO)Si(—(CH ２ )) ４ —SH)—], [—O—(EtO)Si(—(CH ２ )) ５ —SH)—], [—O—(EtO)Si(—(CH ２ )) ６ —SH)—], [—O—(C １３ H ２７ —(OCH ２ CH ２ )) ５ —O)Si(—(CH ２ )) ３ —SH)—], [—O—(HO—CH ２ —CH(CH ３ )—CH ２ —O)Si(—(CH ２ )) ３ —SH)—], 【Chemistry 2】 [-O-(HO-CH ２ -CH ２ -O)Si(-(EH ２ ) ３ -SH)-][-O-((EtO) ２ Si((CHH ２ ) ３ -SH)-O)Si(-(CH ２ ) ３ -SH)-][-O-((C １３ H ２７ -(OCH ２ HH ２ ) ５ -O)(E4O)Si(-(EH ２ ) ３ -SH)-O)Si((CH ２ ) ３ -SH)-][-O-(HO-CH ２ -EH(EH) ３ )-CH ２ -O)(E4O)Si(-(EH ２ ) ３ -SH)-O)Si((CH ２ ) ３ -SH)-][-O-((EtO) ２ Si((CHH ２ ) ７ -CH ３ )-O)Si(-(EH ２ ) ３ -SH)-][-O-((C １３ H ２７ -(OCH ２ HH ２ ) ５ -O)(E4O)Si(-(EH ２ ) ７ -CH ３ )-O)Si((EH ２ ) ３ -SH)-]or[-O-(HO-CH ２ -EH(EH) ３ )-CH ２ -O)(E4O)Si(-(EH ２ ) ７ -CH ３ )-O)Si((EH ２ ) ３ 2. The oligomeric organosilane of claim 1, wherein the organosilane is a hydroxyl group, ...

6. The structural unit B is [—O—(MeO)Si(—(CH ２ )) ７ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ２ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ３ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ４ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ５ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ６ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ７ —CH ３ ), [—O—(EtO)Si(—(CH ２ )) ２ —CH(CH ３ )) ２ ), [—O—(EtO)Si(—(CH ２ )) １５ —CH ３ ), [—O—(C １３ H ２７ —(OCH ２ CH ２ )) ５ —O)Si(—(CH ２ )) ２ —CH ３ ), [—O—(C １３ H ２７ —(OCH ２ CH ２ )) ５ —O)Si(—(CH ２ )) ３ —CH ３ ), [—O—(C １３ H ２７ —(OCH ２ CH ２ )) ５ —O)Si(—(CH ２ )) ４ —CH ３ )-]、[-O-(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ５ -CH ３ )-]、[-O-(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ６ -CH ３ )-]、[-O-(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ７ -CH ３ )-]、[-O-(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ２ -CH(CH ３ ) ２ )-]、[-O-(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) １５ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ２ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ３ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ４ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ５ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ６ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ７ -CH ３ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ２ -CH(CH ３ ) ２ )-]、[-O-(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) １５ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ２ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ３ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ４ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ５ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ６ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ７ -CH ３ )-]、[-O-(HO-CH ２ -CH ２ -O)Si(-(CH ２ ) ２ -CH(CH ３ ) ２ )-]、 【Transformation 3】 2. The oligomeric organosilane of claim 1, wherein

7. The structural unit C is [—O—CH ２ -CH(CH) ３ -CH ２ -] or [-O-CH ２ -CH ２ 2. The oligomeric organosilane of claim 1, wherein:

8. The structural unit A is [—O—(EtO)Si(—(CH ２ ) ３ —SH)—] or [—O—(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ３ —SH)—] or [—O—(HO-CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ３ -SH)-] or 【Chemistry 4】 and The structural unit B is [—O—(EtO)Si(—(CH ２ ) ７ -CH ３ )-] or [—O—(C １３ H ２７ -(OCH ２ CH ２ ) ５ -O)Si(-(CH ２ ) ７ -CH ３ )-] or [—O—(HO—CH ２ -CH(CH ３ )-CH ２ -O)Si(-(CH ２ ) ７ -CH ３ )-]or 【Transformation 5】 and The structural unit C is [—O—CH ２ -CH(CH) ３ -CH ２ 2. The oligomeric organosilane of claim 1, wherein:

9. Mercaptosilane D, alkylsilane E, polyol F, 【Transformation 6】 Formula HO-(R ５ -O) ｍ -R ６ 2. The method for preparing oligomeric organosilanes according to claim 1, characterized in that the alkyl polyether alcohol and the catalyst are mixed and reacted at a temperature of 20 to 180°C, preferably 90 to 150°C. (In the formula, R ２ , R ４ , R ５ , R ６ , n, m, p have the same definitions as above, R ７ are the same or different and are —OH, (C1-C4)alkoxy, preferably ethoxy, or an alkyl polyether group —O—(R ５ -O) ｍ -R ６ (In the formula, R ５ are the same or different and are branched or unbranched, saturated or unsaturated, aliphatic divalent C1 to C30 hydrocarbon groups, preferably CH ２ CH ２ m has an average value of 1 to 30, preferably an average value of 5; R ６ is unsubstituted or substituted branched or unbranched C1 to C30 alkyl, preferably C １３ H １７ , a C2 to C30 alkenyl, a C6 to C14 aryl group, or a C7 to C40 aralkyl group.

10. 10. The process for preparing oligomeric organosilanes according to claim 9, characterized in that components D and F are used in a molar ratio of 1:1 to 1:10, preferably 1:2 to 1:10, more preferably 1:2 to 1:4, and most preferably 1:2.1 to 1:

3.

11. 10. The method for preparing oligomeric organosilanes according to claim 9, wherein the catalyst is tetrabutyl orthotitanate.

12. 10. The method for preparing oligomeric organosilanes according to claim 9, wherein the catalyst is not deactivated after the reaction and remains in the product.

13. 10. Use of the oligomeric organosilane according to claim 1 in rubber mixtures.

14. 10. A rubber mixture containing the oligomeric organosilane of claim 1.

15. 15. Use of the rubber mixture according to claim 14 for the production of moldings, in particular pneumatic tires or tire treads.

Images