CA2231302A1 - Rubber mixtures containing polysulphide polyether silanes - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The rubber mixtures according to the invention, containing at least one rubber, a filler, optionally additional rubber auxiliaries and at least one polysulphide polyether silane corresponding to the formula R1R2R3Si-X1-(-Sx- polyether-)m-(-Sx-X2-SiR1R2R3)n (I), are used for the preparation of rubber vulcanisates, from which in particular tyres having a low rolling resistance associated with a good wet skid resistance and ahigh abrasion resistance can be produced.
Description
Le A 32 283-Forei~n Countries / Bg/m/S-P
Rubber mixtures containin~ PolvsulPhide pol~ether silanes The present invention relates to novel rubber mixtures cont~ining polysulphide polyether silanes and to the use of these rubber mixtures for the preparation of5 rubber vulc~ni~ates. The rubber mixtures according to the invention are suitable for the production of mouldings, in particular for the production of tyres having a low rolling resistance associated with a good wet skid resistance, a high abrasion resistance as well as a high dynamic and thermal loading capacity.
10 A number of proposals have been formulated for solving the problem of producing tyres having a decreased rolling resistance. In the German Offenlegungsschrift documents 2 141 159, 2 141 160 and 2 255 577 and in US-PS 4,709,065, certain organosilanes are described as reinforcing additives, in particular for rubber vul-c~ni~tes containing silica. The use of such organosilanes for the production of silica-filled tyre treads is also described in EP 447 066. Through the combination of materials based on silica and of organosilanes, the rolling resistance of the tyres has been successfully decreased without, as is otherwise usual, impairing the abra-sion resistance and the wet skid resistance of the tyres. However, large quantities of a costly silane raw material which is expensive to prepare are required for the 20 preparation of the above-mentioned classes of compounds.
DE-A 44 06 947 and DE-A 19 54 9027 describe oligomeric reinforcing additives cont~ining sulphur and silicon which, with a lower content of costly silane raw material, produce results equally as good as those for previously described com-25 pounds having a higher silane content. A disadvantage, however, is that the solu-bility of compounds above a certain molecular weight decreases owing to the highpolysulphide content and the addition of other non-polar solvents is necessary in order to carry out the reaction. As a result of this at least part of the acquired ad-vantages of the raw materials is lost owing to the greater expenditure on proces-30 sing in the preparation.
It has now been found that certain polysulphide polyether silanes, despite the farhigher molecular weight, can be prepared in the same solvent as the low-molecular silanes. Furthermore the polysulphide polyether silanes according to the invention, 35 despite their far lower Si content, when used as reinforcing additives in silica-filled rubber vulcanisates are equally as effective as the low-molecular silanes and possess additional advantages owing to improved vulcanisation kinetics in the preparation of vulcanisates as well as advantages in the dynamic hysteresis of the vulcanisates.
The present invention therefore provides rubber mixtures containing at least one rubber, a filler, optionally additional rubber auxiliaries and at least one polysulphide polyether silane corresponding to the formula RlR R3Si-X -(-Sx-polyether-)m-(-Sx-X -SiR R R )n (I), wherein Rl, R and R3 are identical or different and denote 1 18 Y , Cl C18 alkoxy, C6-C12-phenyl or -phenoxy C -C
arylalkyl or alkylaryloxy, with the proviso that at least one of the groups Rl to R3 is an alkoxy, phenoxy or alkylaryloxy grOUp ~
xl and x2 are identical or different and represent divalent, linear or branched or cyclic, optionally unsaturated Cl-C12-alkyl groups, polyether represents a bi-, tri- or tetrafunctional polyethylene oxide polyether group, polypropylene oxide poly-ether group, polybutylene oxide polyether group, or a corresponding mixed polyether group having an average molecular weight of from 300 to 5,000, m represents an integer from 1 to 20, n represents a number from 1 to 4, and x denotes a number from 1 to 8, the polysulphide polyether silane being used in quantities of from 0.1 to 15 wt.~, based on the quantity of the rubber used in each case. Optionally unsaturated alkyl - 2a -is intended to include alkylene and alkyne.
The rubber mixtures according to the in~ention contain preferably from 0.1 to 10 wt.% of polysulphide polyether silane, particularly preferably 1 to 7.5 wt.%.
Le A 32 283-Forei~n Countries The rubber mixtures according to the invention contain preferably those poly-sulphide polyether silanes corresponding to the above formula, wherein Rl, R2 and R3 independently of one another denote methyl, ethyl, propyl or phenyl, with theproviso that at least one of the groups Rl to R3 represents a methoxy, ethoxy, S propoxy, butoxy or phenoxy group, and that Xl and x2 denote methylene, propylene, butylene, pentylene or hexylene groups and that Y represents a poly-ethylene oxide group, poly~ulopylene oxide group or a polyethylene oxide/poly-propylene oxide mixed polyether group having molecular weights of between 300 and lS00, which has been obtained by addition of at least 6 moles ethylene oxide10 and/or propylene oxide to an aliphatic or aromatic diol or amine and wherein n equals 1 and m denotes integers from 1 to 20.
Reinforcing additives corresponding to the formulae which follow below are particularly preferred:
(R-0)3 Si-CH2CH2CH2--S--~~sx CH2CH2CH2- Si (OR)3 (1) m wherein R = CH3, C2H5, x = 1 to 8, p = S to 30, m = 1 to 20, (R-0)3 Si -CH2CH2CH2 S--~O~SX--CH2CH2CH2- Si (OR)3 (2) _ p _ m wherein R= CH3, C2H5, x = 1 to 8, p = S to 30, m = 1 to 20, (R-0)3 Si -CH2CH2CH2 Sx~ \J~o~--~--Sx CH2CH2CH2- Si (OR)3 (3) -- --a-- b --c --m Le A 32 283-Forei~n Countries wherein R = CH3, C2H5, C3H7, x = 1 to 8, a= 3 to 20, b = 1 to 10, c = 3 to 20, m = 1 to 20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~/\~'\0~/ ~\Sx--CH2CH2CH2- Si (OR)3 --m (4) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 2 to 20, m= 1 to20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~/~/\o~ \sx--CH2CHZCH2- Si (OR)3 --m (S) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a= 3 to 20, b = 2 to 20, m = 1 to 20, (R-0)3 Si -CH2CH2CH2--S~ ~ (6) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a = 2 to 20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~\C411~ ~/--SX--CH2cH2cH2-si (OR)3 (7) wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 1 to 10, m = 1 to 20.
Le A 32 283-Foreign Countries Particularly preferred polysulphide polyether silanes are those corresponding to the following formula:
R1 \ R1 R2 /Si~CH--5~0/~m t ~3r R3 (8) wherein Rl, R2, R3 denote methyl, phenyl, methoxy, ethoxy, propoxy, butoxy, with the proviso that at least one of the groups is a methoxy, ethoxy, propoxy or butoxy group. q, r = 1 to 3, x = 1 to 8, p = 6 to 30, m = 1 to 20.
The polysulphide polyether silanes according to the invention may be used eitherindividually or mixed with one another. In this connection either the individualcompounds having a defined molecular weight may be used or mixtures of oligo-mers having a definite molecular weight distribution. For processing reasons, it is easier to prepare a mixture of oligomers of the above-mentioned polysulphide polyether silanes and to use them in this form. If the reinforcing additives are used in the form of a mixture of oligomers, the latter has an average molecular weight of about 800 to 10,000 as determined by gel permeation chromatography.
The novel polysulphide polyether silanes according to the invention may be prepared in various ways:-A) By the reaction of silanes cont~ining mercapto groups and dimercaptans and/or polymercaptans with sulphur dichloride or sulphur dichloride, with elimin~tion of HCl. The reaction may be carried out in a known per se manner at temperatures of from -30~C to +80~C, optionally in the presence of solvents, such as alcohols or aromatic hydrocarbons:
RlR2R3Si-X-SH+ HS-polyether-SH + SxCl2 ~
RIR2R3Si-Xx+2-(-polyether-Sx 2)m-X-SiRlR2R3 + HCl Le A 32 283-Foreign Countries For details regarding carrying out the reaction, reference may be made to Houben-Weyl, Methoden der organischen Chemie, Volume 9, pages 88 ff., (1955) and Volume E 11 (1985), Thieme Verlag, Stuttgart.
5 B) The polysulphide polyether silanes according to the invention may be prepared particularly advantageously by reacting haloalkyl silyl ethers and polyhalides with metal polysulphides in the presence of alcoholic solvents at temperatures of from approximately -20~C to +90~C:
RIR2R3Si-X-Hal + Hal-polyether-Hal + MeSx ~
RIR2R3Si-X,~-(-polyether-Sx)m-X-SiRlR2R3 + MeHal The metal polysulphides used are preferably those wherein Me represents lithium,sodium or potassium and x denotes a number from 2 to 8. The alcoholic solvents used are preferably methanol, ethanol, propanol, butanol, amyl alcohol, hexyl alco-hol, octanol, ethylene glycol and propylene glycol, butanediol and/or hexanediol as well as isomers thereof.
The polysulphide polyether silanes according to the invention may be added either in pure form to the rubber mixtures, or may be added thereto mounted on an inertorganic or inorganic support. Suitable support materials are in particular silicas, naturally occurring or synthetic silicates, aluminium oxide and carbon blacks.
Suitable fillers include both the fillers which are active for the rubber vulcanisates according to the invention and inactive fillers such as, for example:-- Highly disperse silicas, prepared, for example, by precipitation from solutions of silicates or by flame hydrolysis of silicon halides having specific surfaces of 5 to 1000 m2/g, preferably 20 to 400 m2/g (BET
surface area) and having primary particle sizes of 100 to 400 nm. The silicas may optionally also be present as mixed oxides with other metal oxides, such as the oxides of Al, Mg, Ca, Ba, Zn, Zr and Ti.
- Synthetic silicates, such as aluminium silicates or alkaline-earth metal sili-cates, such as magnesium silicate or calcium silicate, having BET surface areas of 20 to 400 m2/g and primary particle diameters of 10 to 400 nm Le A 32 283-Forei~n Countries - Naturally-occurring silicates, such as kaolin and other naturally-occurring silicas - Glass fibres and glass fibre products (mats, strands) or glass microbeads.
- Aluminium hydroxide or magnesium hydroxide - Carbon blacks. The carbon blacks to be used here are produced by the lampblack process, furnace process or gas black process and have BET
surface areas of 20 to 200 m2/g, for example, SAF, ISAF, HAF, FEF, or GPF carbon blacks.
Highly-disperse silicas having BET surface areas of 20 to 400 m2/g are preferably used.
The above-mentioned fillers are used in quantities of from 0 to 150 wt.%, preferably 10 to 100 wt.%, based on the quantity of the rubber used in each case.
The above-mentioned fillers may be used on their own or mixed with one another.
20 In one particular embodiment, the rubber mixtures contain as fillers a mixture of light-coloured fillers, such as highly-disperse silicas, and carbon blacks, the mixing ratio of light-coloured fillers to carbon blacks being 0.05 to 20, preferably 0.1 to 10. The polysulphide polyether silanes (I) may be used on their own as cross-linking agents. Other cross-linking agents which may be used for the rubber 25 mixtures according to the invention are, for example, sulphur and peroxides, to which may also be added the known vulcanisation accelerators, such as mercapto-benzothiazoles, mercaptosulphenamides, thiurams and thiocarbonates. Both the vulcanisation accelerators and the cross-linking agents may be used individually or mixed with one another. Sulphur is particularly preferred as a cross-linking agent.
30 The cross-linking agents and the vulcanisation accelerators are each used in quantities of from 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%, based on the rubberused in each case.
Other rubber auxiliaries may, of course, also be added to the rubber mixtures 35 according to the invention; examples of these additives are antioxidants, heat stabilisers, light stabilisers, antiozonants, processing agents, plasticisers, tackifiers, Le A 32 283-Forei~n Countries blowing agents, dyes, pigments, waxes, extenders, organic acids, reaction retarders, metal oxides, such as zinc oxide and magnesium oxide, as well as activators suchas triethanolamine, polyethylene glycol and hexanetriol, which are familiar to the rubber technologist.
The above-mentioned rubber auxiliaries are added in conventional quantities (0.1to 50 wt.%, based on the rubber used in each case). The most favourable quantityof auxiliary substance used can easily be determined by prelimin~ry tests and depends, incidentally, on the respective purpose of the rubber vulcanisates.
Besides natural rubber, synthetic rubbers are also suitable for the preparation of rubber mixtures according to the invention. Preferred synthetic rubbers are described, for example, in: W. Hofmann, Kautschl-kte~lnologie, Gentner Verlag, Stuttgart, 1980. They include polybutadiene, butadiene-acrylic acid-CI 4-alkyl ester copolymers, polychloroprene, polyisoprene, styrene-butadiene copolymers having styrene contents of 1 to 60 wt.%, preferably 20 to 50 wt.%, isobutylene-isoprenecopolymers, butadiene-acrylonitrile copolymers having acrylonitrile contents of 5 to 60 wt.%, preferably 10 to S0 wt.%, partly hydrogenated or completely hydrogenated butadiene-acrylonitrile copolymers and ethylene-propylene-diene copolymers. The rubbers may, of course, also be used mixed with one another.
Rubbers which are of interest for the production of automobile tyres are in particular anionically polymerised solution styrene-butadiene copolymers having a glass temperature of above -50~C, which optionally may be modified with silyl ethers or other functional groups, polybutadiene rubbers having a high 1,4-cis content (> 90%), which are prepared using catalysts based on Ni, Co, Ti or Nd, polybutadiene rubbers having a vinyl content of 0 to 75% and mixtures thereof (see, for example, EP-A 447 066).
The rubber mixtures are prepared in the conventional manner, in known mixing units, such as rolls, closed mixers and mixer-extruders, at composition tempera-tures of 100~C to 200~C and at shear rates of 1 to 1000 s~l.
The addition of the reinforcing additives according to the invention and the addition of the fillers is carried out preferably during the first part of the mixing process at composition temperatures of 100~C to 200~C and at the given shear Le A 32 283-Forei~n Countries g rates. The additions may however also take place later at lower temperatures of 40~C to 100~C, for example, together with sulphur and vulcanisation accelerators.
The rubber mixtures according to the invention may be vulcanised in the conven-5 tional manner (see, for example, G. Alliger, I.J. Sjothun, Vulc~ni7.~tion of Elasto-mers, Reinhold Publishing Corporation, New York, 1964). The vulcanisation is carried out at temperatures of from about 100~C to 200~C, preferably at 130~C to180~C, optionally at pressures of 10 to 200 bar.
10 The rubber vulc.~ni.c~tes according to the invention are particularly suitable for the production of moulded articles, for example, for the manufacture of cable sheaths, tubing, drive belts, conveyor belts, rollers, shoe soles, sealing rings and damping elements, but preferably for the production of tyres.
Le A 32 283-Forei~n Countries Examples Example 1 5 Cl-terminated bifunctional polvethvlene oxide Polvether havin~ a molecular wei~ht of aPprox. 400 238 g thionyl chloride was added over a period of two hours at a temperature of 50~C to 60~C to 400 g of a polyethylene glycol having an average molecular weight of 400 and 0.5 g pyridine. The mixture was then heated by passing nitrogen through it for 18 hours at 65~C to 70~C and degassed for a further 3 hours in a vacuum (20 mbar) at 70~C. 418 g of a colourless oil having a viscosity of 40 mPa.s was obtained.
15 Elemental analysis:
C H Cl calculated: 47.2 % 7.9 % 17.4 %
found: 47.2 % 7.8 % 15.5 %
Examnle 2 Cl-tern~in~ted bifunctional Polvethvlene oxide Polvether havin~ a molecular wei~ht of aPprox. 600 The procedure was as described in Example 1, with 600 g of a polyethylene oxide polyether having an average molecular weight of 600 being reacted with 238 g thionyl chloride in the presence of 0.5 g pyridine. 624 g of a brown oil having a viscosity of 90 mPa sec was obtained.
Le A 32 283-Foreign Countries Example 3 Cl-terminated bifunctional polyethvlene oxide polyether havin~ a molecular wei~ht of approx. 900 The procedure was as described in Example 1, with 450 g of a polyethylene oxide polyether having an average molecular weight of 900 being reacted with 119 g thionyl chloride in the presence of O.S g pyridine. 454 g of an almost colourless oil was obtained, which crystallised after a few days at room temperature. fp 35~C
10 to 40~C.
Elemental analysis:
C H Cl calculated: 51.1 % 8.5 % 70 %
found: 51.3 % 8.5 % 7.4 %
Example 4 Cl-terminated bifunctional polyethylene oxide Polvether havin~ a molecular wei~ht of approx. 1550 The procedure was as described in Example 1, with 750 g of a polyethylene oxide polyether having an average molecular weight of 1500 being reacted with 119 g thionyl chloride in the presence of 0.5 g pyridine. 755 g of an almost colourless oil was obtained, which crystallised on being cooled to room temperature.
Elemental analysis:
C H Cl calculated: 52.8 % 8.6 % 4.5 %
found: 52.8 % 8.6 % 4.4 %
Le A 32 283-Forei~n Countries Example 5 (C2HsO)3Si- C3H6 - S4 - polyether- S4 - C3H6 - Si(OC2Hs)3 containing a polyethylene oxide polyether having an average molecular weight of S approx. 600 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur were heated in 500 ml dry ethanol at 70~C for 30 minlltes. 240.8 g (1 mol) 3-chloropropyltrieth-oxysilane was then added dropwise thereto, followed by 318.5 g (0.5 mol) of a Cl-10 termin~ted polyethylene oxide polyether obtained as in Example 2 and the mixturewas stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 604 g of a brown oil having a viscosity of 230 mPa sec was obtained.
15 Elemental analysis:
C H S Si calculated: 42.6 % 7.6 % 20.2 % 4.4 %
found: 42.7 % 7.4 % 20.3 % 4.8 %
Example 6 (C2HsO)3Si- C3H6 - S4 - polyether - S4 - C3H6 - Si(OC2Hs)3 cont~inin~ a polyethylene oxide polyether having an average molecular weight of approx. 400 The procedure was as described in Example 5, with 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 240.8 g (1 mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 203.5 g (0.5 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 1 and the mixture was stirred for S hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 506 g of a brown oil having a viscosity of 120 mPa sec was obtained.
Le A 32 283-Forei~n Countries Elemental analysis:
C H S Si calculated: 40.7 % 7.4 % 25.6 % 5.6 %
found: 42.0 % 7.4 % 24.0 % 5.2 %
Example 7 (C2H5O)3si- C3H6- S4- polyether - S4- C3H6 - Si(O C2Hs)3 10 containing a polyethylene oxide polyether having an average molecular weight of approx. 900 The procedure was as described in Example 5, with 62.4 g (0.8 mol) anhydrous sodium sulphide and 76.8 g (2.4 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 192.4 g (0.8 mol) 3-chlolopr~yltriethoxysilane was then added dropwise thereto, followed by 381.2 g (0.4 mol) of a Cl-termin~ted polyethylene oxide polyether obtained as in Example 3 and the mixture was stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCl was filtered off. After evaporation, 644 g of a brown oil having a viscosity 20 of 820 mPa sec was obtained, which crystallised after prolonged standing at room temperature. fp 35~C.
Elemental analysis:
C H S Si calculated: 44.9 % 7.9 % 16.2 % 3.6 %
found: 44.9 % 7.9 % 15.9 % 3.3 %
Le A 32 283-Forei~n Countries Example 8 (C2HsO)3Si- C3H6 - S4 - polyether - S4 - C3H6 - Si(OC2Hs)3 cont~ining a polyethylene oxide polyether having an average molecular weight of S approx. 1500 The procedure was as described in Example S, with 39 g (O.S mol) anhydrous sodium sulphide and 48 g (l.S mol) sulphur being heated in S00 ml dry ethanol at70~C for 30 minutes. 120.4 g (O.S mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 375 g (0.25 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 4 and the mixture was stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 535 g of a brown oil was obtained, which crystallised rapidly at room temperature. fp 50~C to 55~C.
Elemental analysis:
C H S Si calculated: 47.7 % 8.2 % 11.8 % 2.6 %
found: 47.6 % 8.2 % 11.8 % 2.6 %
Example 9 (C2Hso)3si- C3H6 ~ (S4 - polyether)3 - S4- C3H6 - Si(O C2HS)3 containing a polyethylene oxide polyether having an average molecular weight of approx. 400 The procedure was as described in Example 5, with 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 120.4 g (O.S mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 305.3 g (0.75 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 1 and the mixture was stirred for S hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCl was filtered off. After evaporation, 496 g of a brown oil having a viscosity of 720 mPa sec was obtained.
Le A 32 283-Forei~n Countries Example 10: Solubility behaviour in ethanol in each case 30 parts by weight of a polysulphide silyl compound were heated in 70 parts by weight of ethanol for 5 minlltes at 70~C, during which the solubility in 5 the heated solvent was assessed:
Silyl compound Complete solubility Si content Examples according to the invention:
Compound from Example 5 yes 4.7 %
Compound from Example 6 yes 5.6 %
Compound from Example 7 yes 3.7 %
Compound from Example 8 yes 2.7 %
Compound from Example 9 yes 2.9 %
Comparison Examples:
Ex. 2 of DE-OS 2,141,160 yes 10.4 %
Ex. 1 of DE-A 195 49 027 no 5.8 %
Ex. 2 of DE-A 195 49 027 no 4.6 %
Ex. 3 of DE-A 195 49 027 no 3.8 %
Ex. 5 of DE-A 195 49 027 no 4.8 %
25 The results of the tests show that the polysulphide polyether silanes according to the invention, despite a lower content of costly silane raw material, exhibit a better solubility in the reaction medium (ethanol), so that it is possible to avoid the use of an expensive solvent mixture in the plepa~alion process.
Le A 32 283-Forei~n Countries Example 11: Comparison of vulcanisation kinetics The rubber mixtures below were prepared within 5 minutes at 140~C in a 1.5 1 kneader. Finally, sulphur and accelerator were added thereto on a roll at approx.
5 50~C. The vulcanisation kinetics were investigated at 160~C in the final mixtures by means of a Monsanto rheometer MDR 2000.
C 1, _ Examples Examples accordmg to the invention A B C D E F G
Solution SBR Buna VSL 4020-0 (Bayer) 75 75 75 75 75 75 75 BR Buna CB 11 (Bayer) 25 25 25 25 25 25 25 Silica Vulkasil S (Bayer) 80 80 80 80 80 i0 80 Carbon black Corax N 339 (Degussa) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Arom. oil Renopal 450 (Fuchs) 32.5 32.5 32.5 32.5 32.5 32.5 32.5 ZnO 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid ~ ~ Vulkanox 4020 (Bayer) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Wax Antilux 654 (Rhein Chemie) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Polysulph. silane as in Ex. I of DE 19 549 027 6.5 0 0 0 0 0 o Polysulph. silane as in Ex. 2 of DE 19 549 027 0 6.5 0 0 0 0 0 Polysulph. silane as m Ex. 3 of DE 19 549 027 0 0 6.5 0 0 0 0 Compound according to the invention Ex. 6 0 0 0 6.5 0 0 0 Compound according to the invention Ex. 5 0 0 0 0 6.5 0 0 Compound according to the invention Ex. 7 0 0 0 0 0 6.5 0 Compound accordingto the invention Ex. 9 0 0 0 0 0 0 6.5 CBS Vulkacit CZ (Bayer) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 DPG Vulkacit D (Bayer) 2 2 2 2 2 2 2 Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 r.~. time at 160~C
(TS 06) in minutes 2.4 2.2 2.1 2.8 3 3 2.6 Vl ' - time at 160~C
(t 90) in minutes 14.2 13.5 13.4 13.5 12.4 11.5 12 Le A 32 283-Forei~n Countries It is clear that the rubber mixtures cont~ining the compounds according to the invention exhibit a more favourable vulcanisation behaviour, that is, a longer period of workability and a shorter vulcanisation time.
5 Example 12 The rubber mixtures below were prepared within 5 minutes at 140~C in a 1.5 l kneader. Finally, sulphur and accelerator were added thereto on a roll at approx.
50~C.
Le A 32 283-Forei~n Countries Comparison Examples according Example to the invention A B C
Solution SBR Buna VSL 5025-1 (Bayer) 75 75 75 BR Buna CB 24 (Bayer) 25 25 25 Silica Vulkasil S (Bayer) 80 80 80 Carbon black Corax N339 (Degussa) 6.5 6.5 6.5 Aromatic oil Renopal 450 (Fuchs) 8 8 8 ZnO 2.5 2.5 2.5 Stearic acid Antiozonant Vulkanox 4020 (Bayer) 1.5 1.5 1.5 Wax Antilux 654 (Rhein Chemie) 1.5 1.5 1.5 Bis(triethoxysilylpropyl) tetrasulphide acc. to DE 2,255,577 6.5 0 0 Compound as in Example 6 0 6.5 0 Compound as in Example 7 0 0 6.5 CBS Vulkacit CZ (Bayer) 1.5 1.5 1.5 DPG Vulkacit D (Bayer) 2 2 2 Sulphur 1.5 1.5 1.5 The rubber mixtures were then vulcanised for 45 minutes at 160~C. The resulting vulcanisation properties were as follows:
Tensile stress at 100% elongation (MPa) 3.4 3.4 3.6 Tensile stress at 300% elongation (MPa) 13.7 14.5 13.2 Tensile strength (MPa) 19 18.2 17.9 Tear resistance (MPa) 35.1 43.1 40.2 Hardness (Shore A) at 23~C 73 73 74 Rebound elasticity at 23~C (%) 25 25 23 Rebound elasticity at 70~C (%) 46 48 46 From the vulcanisation properties it may be seen that the polysulphide polyether silanes according to the invention, despite a considerably decreased content of costly silane raw material as compared with prior art, lead to equal mechanical Le A 32 283-Forei~n Countries properties and moreover bring about advantages in the improved relationship of wet skid resistance to rolling resistance (greater difference between the rebound elasticities at 23~C and at 70~C).
Rubber mixtures containin~ PolvsulPhide pol~ether silanes The present invention relates to novel rubber mixtures cont~ining polysulphide polyether silanes and to the use of these rubber mixtures for the preparation of5 rubber vulc~ni~ates. The rubber mixtures according to the invention are suitable for the production of mouldings, in particular for the production of tyres having a low rolling resistance associated with a good wet skid resistance, a high abrasion resistance as well as a high dynamic and thermal loading capacity.
10 A number of proposals have been formulated for solving the problem of producing tyres having a decreased rolling resistance. In the German Offenlegungsschrift documents 2 141 159, 2 141 160 and 2 255 577 and in US-PS 4,709,065, certain organosilanes are described as reinforcing additives, in particular for rubber vul-c~ni~tes containing silica. The use of such organosilanes for the production of silica-filled tyre treads is also described in EP 447 066. Through the combination of materials based on silica and of organosilanes, the rolling resistance of the tyres has been successfully decreased without, as is otherwise usual, impairing the abra-sion resistance and the wet skid resistance of the tyres. However, large quantities of a costly silane raw material which is expensive to prepare are required for the 20 preparation of the above-mentioned classes of compounds.
DE-A 44 06 947 and DE-A 19 54 9027 describe oligomeric reinforcing additives cont~ining sulphur and silicon which, with a lower content of costly silane raw material, produce results equally as good as those for previously described com-25 pounds having a higher silane content. A disadvantage, however, is that the solu-bility of compounds above a certain molecular weight decreases owing to the highpolysulphide content and the addition of other non-polar solvents is necessary in order to carry out the reaction. As a result of this at least part of the acquired ad-vantages of the raw materials is lost owing to the greater expenditure on proces-30 sing in the preparation.
It has now been found that certain polysulphide polyether silanes, despite the farhigher molecular weight, can be prepared in the same solvent as the low-molecular silanes. Furthermore the polysulphide polyether silanes according to the invention, 35 despite their far lower Si content, when used as reinforcing additives in silica-filled rubber vulcanisates are equally as effective as the low-molecular silanes and possess additional advantages owing to improved vulcanisation kinetics in the preparation of vulcanisates as well as advantages in the dynamic hysteresis of the vulcanisates.
The present invention therefore provides rubber mixtures containing at least one rubber, a filler, optionally additional rubber auxiliaries and at least one polysulphide polyether silane corresponding to the formula RlR R3Si-X -(-Sx-polyether-)m-(-Sx-X -SiR R R )n (I), wherein Rl, R and R3 are identical or different and denote 1 18 Y , Cl C18 alkoxy, C6-C12-phenyl or -phenoxy C -C
arylalkyl or alkylaryloxy, with the proviso that at least one of the groups Rl to R3 is an alkoxy, phenoxy or alkylaryloxy grOUp ~
xl and x2 are identical or different and represent divalent, linear or branched or cyclic, optionally unsaturated Cl-C12-alkyl groups, polyether represents a bi-, tri- or tetrafunctional polyethylene oxide polyether group, polypropylene oxide poly-ether group, polybutylene oxide polyether group, or a corresponding mixed polyether group having an average molecular weight of from 300 to 5,000, m represents an integer from 1 to 20, n represents a number from 1 to 4, and x denotes a number from 1 to 8, the polysulphide polyether silane being used in quantities of from 0.1 to 15 wt.~, based on the quantity of the rubber used in each case. Optionally unsaturated alkyl - 2a -is intended to include alkylene and alkyne.
The rubber mixtures according to the in~ention contain preferably from 0.1 to 10 wt.% of polysulphide polyether silane, particularly preferably 1 to 7.5 wt.%.
Le A 32 283-Forei~n Countries The rubber mixtures according to the invention contain preferably those poly-sulphide polyether silanes corresponding to the above formula, wherein Rl, R2 and R3 independently of one another denote methyl, ethyl, propyl or phenyl, with theproviso that at least one of the groups Rl to R3 represents a methoxy, ethoxy, S propoxy, butoxy or phenoxy group, and that Xl and x2 denote methylene, propylene, butylene, pentylene or hexylene groups and that Y represents a poly-ethylene oxide group, poly~ulopylene oxide group or a polyethylene oxide/poly-propylene oxide mixed polyether group having molecular weights of between 300 and lS00, which has been obtained by addition of at least 6 moles ethylene oxide10 and/or propylene oxide to an aliphatic or aromatic diol or amine and wherein n equals 1 and m denotes integers from 1 to 20.
Reinforcing additives corresponding to the formulae which follow below are particularly preferred:
(R-0)3 Si-CH2CH2CH2--S--~~sx CH2CH2CH2- Si (OR)3 (1) m wherein R = CH3, C2H5, x = 1 to 8, p = S to 30, m = 1 to 20, (R-0)3 Si -CH2CH2CH2 S--~O~SX--CH2CH2CH2- Si (OR)3 (2) _ p _ m wherein R= CH3, C2H5, x = 1 to 8, p = S to 30, m = 1 to 20, (R-0)3 Si -CH2CH2CH2 Sx~ \J~o~--~--Sx CH2CH2CH2- Si (OR)3 (3) -- --a-- b --c --m Le A 32 283-Forei~n Countries wherein R = CH3, C2H5, C3H7, x = 1 to 8, a= 3 to 20, b = 1 to 10, c = 3 to 20, m = 1 to 20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~/\~'\0~/ ~\Sx--CH2CH2CH2- Si (OR)3 --m (4) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 2 to 20, m= 1 to20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~/~/\o~ \sx--CH2CHZCH2- Si (OR)3 --m (S) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a= 3 to 20, b = 2 to 20, m = 1 to 20, (R-0)3 Si -CH2CH2CH2--S~ ~ (6) wherein R= CH3, C2H5, C3H7, x = 1 to 8, a = 2 to 20, (R-0)3 Si -CH2CH2CH2--Sx~/ ~\C411~ ~/--SX--CH2cH2cH2-si (OR)3 (7) wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 1 to 10, m = 1 to 20.
Le A 32 283-Foreign Countries Particularly preferred polysulphide polyether silanes are those corresponding to the following formula:
R1 \ R1 R2 /Si~CH--5~0/~m t ~3r R3 (8) wherein Rl, R2, R3 denote methyl, phenyl, methoxy, ethoxy, propoxy, butoxy, with the proviso that at least one of the groups is a methoxy, ethoxy, propoxy or butoxy group. q, r = 1 to 3, x = 1 to 8, p = 6 to 30, m = 1 to 20.
The polysulphide polyether silanes according to the invention may be used eitherindividually or mixed with one another. In this connection either the individualcompounds having a defined molecular weight may be used or mixtures of oligo-mers having a definite molecular weight distribution. For processing reasons, it is easier to prepare a mixture of oligomers of the above-mentioned polysulphide polyether silanes and to use them in this form. If the reinforcing additives are used in the form of a mixture of oligomers, the latter has an average molecular weight of about 800 to 10,000 as determined by gel permeation chromatography.
The novel polysulphide polyether silanes according to the invention may be prepared in various ways:-A) By the reaction of silanes cont~ining mercapto groups and dimercaptans and/or polymercaptans with sulphur dichloride or sulphur dichloride, with elimin~tion of HCl. The reaction may be carried out in a known per se manner at temperatures of from -30~C to +80~C, optionally in the presence of solvents, such as alcohols or aromatic hydrocarbons:
RlR2R3Si-X-SH+ HS-polyether-SH + SxCl2 ~
RIR2R3Si-Xx+2-(-polyether-Sx 2)m-X-SiRlR2R3 + HCl Le A 32 283-Foreign Countries For details regarding carrying out the reaction, reference may be made to Houben-Weyl, Methoden der organischen Chemie, Volume 9, pages 88 ff., (1955) and Volume E 11 (1985), Thieme Verlag, Stuttgart.
5 B) The polysulphide polyether silanes according to the invention may be prepared particularly advantageously by reacting haloalkyl silyl ethers and polyhalides with metal polysulphides in the presence of alcoholic solvents at temperatures of from approximately -20~C to +90~C:
RIR2R3Si-X-Hal + Hal-polyether-Hal + MeSx ~
RIR2R3Si-X,~-(-polyether-Sx)m-X-SiRlR2R3 + MeHal The metal polysulphides used are preferably those wherein Me represents lithium,sodium or potassium and x denotes a number from 2 to 8. The alcoholic solvents used are preferably methanol, ethanol, propanol, butanol, amyl alcohol, hexyl alco-hol, octanol, ethylene glycol and propylene glycol, butanediol and/or hexanediol as well as isomers thereof.
The polysulphide polyether silanes according to the invention may be added either in pure form to the rubber mixtures, or may be added thereto mounted on an inertorganic or inorganic support. Suitable support materials are in particular silicas, naturally occurring or synthetic silicates, aluminium oxide and carbon blacks.
Suitable fillers include both the fillers which are active for the rubber vulcanisates according to the invention and inactive fillers such as, for example:-- Highly disperse silicas, prepared, for example, by precipitation from solutions of silicates or by flame hydrolysis of silicon halides having specific surfaces of 5 to 1000 m2/g, preferably 20 to 400 m2/g (BET
surface area) and having primary particle sizes of 100 to 400 nm. The silicas may optionally also be present as mixed oxides with other metal oxides, such as the oxides of Al, Mg, Ca, Ba, Zn, Zr and Ti.
- Synthetic silicates, such as aluminium silicates or alkaline-earth metal sili-cates, such as magnesium silicate or calcium silicate, having BET surface areas of 20 to 400 m2/g and primary particle diameters of 10 to 400 nm Le A 32 283-Forei~n Countries - Naturally-occurring silicates, such as kaolin and other naturally-occurring silicas - Glass fibres and glass fibre products (mats, strands) or glass microbeads.
- Aluminium hydroxide or magnesium hydroxide - Carbon blacks. The carbon blacks to be used here are produced by the lampblack process, furnace process or gas black process and have BET
surface areas of 20 to 200 m2/g, for example, SAF, ISAF, HAF, FEF, or GPF carbon blacks.
Highly-disperse silicas having BET surface areas of 20 to 400 m2/g are preferably used.
The above-mentioned fillers are used in quantities of from 0 to 150 wt.%, preferably 10 to 100 wt.%, based on the quantity of the rubber used in each case.
The above-mentioned fillers may be used on their own or mixed with one another.
20 In one particular embodiment, the rubber mixtures contain as fillers a mixture of light-coloured fillers, such as highly-disperse silicas, and carbon blacks, the mixing ratio of light-coloured fillers to carbon blacks being 0.05 to 20, preferably 0.1 to 10. The polysulphide polyether silanes (I) may be used on their own as cross-linking agents. Other cross-linking agents which may be used for the rubber 25 mixtures according to the invention are, for example, sulphur and peroxides, to which may also be added the known vulcanisation accelerators, such as mercapto-benzothiazoles, mercaptosulphenamides, thiurams and thiocarbonates. Both the vulcanisation accelerators and the cross-linking agents may be used individually or mixed with one another. Sulphur is particularly preferred as a cross-linking agent.
30 The cross-linking agents and the vulcanisation accelerators are each used in quantities of from 0.1 to 10 wt.%, preferably 0.1 to 5 wt.%, based on the rubberused in each case.
Other rubber auxiliaries may, of course, also be added to the rubber mixtures 35 according to the invention; examples of these additives are antioxidants, heat stabilisers, light stabilisers, antiozonants, processing agents, plasticisers, tackifiers, Le A 32 283-Forei~n Countries blowing agents, dyes, pigments, waxes, extenders, organic acids, reaction retarders, metal oxides, such as zinc oxide and magnesium oxide, as well as activators suchas triethanolamine, polyethylene glycol and hexanetriol, which are familiar to the rubber technologist.
The above-mentioned rubber auxiliaries are added in conventional quantities (0.1to 50 wt.%, based on the rubber used in each case). The most favourable quantityof auxiliary substance used can easily be determined by prelimin~ry tests and depends, incidentally, on the respective purpose of the rubber vulcanisates.
Besides natural rubber, synthetic rubbers are also suitable for the preparation of rubber mixtures according to the invention. Preferred synthetic rubbers are described, for example, in: W. Hofmann, Kautschl-kte~lnologie, Gentner Verlag, Stuttgart, 1980. They include polybutadiene, butadiene-acrylic acid-CI 4-alkyl ester copolymers, polychloroprene, polyisoprene, styrene-butadiene copolymers having styrene contents of 1 to 60 wt.%, preferably 20 to 50 wt.%, isobutylene-isoprenecopolymers, butadiene-acrylonitrile copolymers having acrylonitrile contents of 5 to 60 wt.%, preferably 10 to S0 wt.%, partly hydrogenated or completely hydrogenated butadiene-acrylonitrile copolymers and ethylene-propylene-diene copolymers. The rubbers may, of course, also be used mixed with one another.
Rubbers which are of interest for the production of automobile tyres are in particular anionically polymerised solution styrene-butadiene copolymers having a glass temperature of above -50~C, which optionally may be modified with silyl ethers or other functional groups, polybutadiene rubbers having a high 1,4-cis content (> 90%), which are prepared using catalysts based on Ni, Co, Ti or Nd, polybutadiene rubbers having a vinyl content of 0 to 75% and mixtures thereof (see, for example, EP-A 447 066).
The rubber mixtures are prepared in the conventional manner, in known mixing units, such as rolls, closed mixers and mixer-extruders, at composition tempera-tures of 100~C to 200~C and at shear rates of 1 to 1000 s~l.
The addition of the reinforcing additives according to the invention and the addition of the fillers is carried out preferably during the first part of the mixing process at composition temperatures of 100~C to 200~C and at the given shear Le A 32 283-Forei~n Countries g rates. The additions may however also take place later at lower temperatures of 40~C to 100~C, for example, together with sulphur and vulcanisation accelerators.
The rubber mixtures according to the invention may be vulcanised in the conven-5 tional manner (see, for example, G. Alliger, I.J. Sjothun, Vulc~ni7.~tion of Elasto-mers, Reinhold Publishing Corporation, New York, 1964). The vulcanisation is carried out at temperatures of from about 100~C to 200~C, preferably at 130~C to180~C, optionally at pressures of 10 to 200 bar.
10 The rubber vulc.~ni.c~tes according to the invention are particularly suitable for the production of moulded articles, for example, for the manufacture of cable sheaths, tubing, drive belts, conveyor belts, rollers, shoe soles, sealing rings and damping elements, but preferably for the production of tyres.
Le A 32 283-Forei~n Countries Examples Example 1 5 Cl-terminated bifunctional polvethvlene oxide Polvether havin~ a molecular wei~ht of aPprox. 400 238 g thionyl chloride was added over a period of two hours at a temperature of 50~C to 60~C to 400 g of a polyethylene glycol having an average molecular weight of 400 and 0.5 g pyridine. The mixture was then heated by passing nitrogen through it for 18 hours at 65~C to 70~C and degassed for a further 3 hours in a vacuum (20 mbar) at 70~C. 418 g of a colourless oil having a viscosity of 40 mPa.s was obtained.
15 Elemental analysis:
C H Cl calculated: 47.2 % 7.9 % 17.4 %
found: 47.2 % 7.8 % 15.5 %
Examnle 2 Cl-tern~in~ted bifunctional Polvethvlene oxide Polvether havin~ a molecular wei~ht of aPprox. 600 The procedure was as described in Example 1, with 600 g of a polyethylene oxide polyether having an average molecular weight of 600 being reacted with 238 g thionyl chloride in the presence of 0.5 g pyridine. 624 g of a brown oil having a viscosity of 90 mPa sec was obtained.
Le A 32 283-Foreign Countries Example 3 Cl-terminated bifunctional polyethvlene oxide polyether havin~ a molecular wei~ht of approx. 900 The procedure was as described in Example 1, with 450 g of a polyethylene oxide polyether having an average molecular weight of 900 being reacted with 119 g thionyl chloride in the presence of O.S g pyridine. 454 g of an almost colourless oil was obtained, which crystallised after a few days at room temperature. fp 35~C
10 to 40~C.
Elemental analysis:
C H Cl calculated: 51.1 % 8.5 % 70 %
found: 51.3 % 8.5 % 7.4 %
Example 4 Cl-terminated bifunctional polyethylene oxide Polvether havin~ a molecular wei~ht of approx. 1550 The procedure was as described in Example 1, with 750 g of a polyethylene oxide polyether having an average molecular weight of 1500 being reacted with 119 g thionyl chloride in the presence of 0.5 g pyridine. 755 g of an almost colourless oil was obtained, which crystallised on being cooled to room temperature.
Elemental analysis:
C H Cl calculated: 52.8 % 8.6 % 4.5 %
found: 52.8 % 8.6 % 4.4 %
Le A 32 283-Forei~n Countries Example 5 (C2HsO)3Si- C3H6 - S4 - polyether- S4 - C3H6 - Si(OC2Hs)3 containing a polyethylene oxide polyether having an average molecular weight of S approx. 600 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur were heated in 500 ml dry ethanol at 70~C for 30 minlltes. 240.8 g (1 mol) 3-chloropropyltrieth-oxysilane was then added dropwise thereto, followed by 318.5 g (0.5 mol) of a Cl-10 termin~ted polyethylene oxide polyether obtained as in Example 2 and the mixturewas stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 604 g of a brown oil having a viscosity of 230 mPa sec was obtained.
15 Elemental analysis:
C H S Si calculated: 42.6 % 7.6 % 20.2 % 4.4 %
found: 42.7 % 7.4 % 20.3 % 4.8 %
Example 6 (C2HsO)3Si- C3H6 - S4 - polyether - S4 - C3H6 - Si(OC2Hs)3 cont~inin~ a polyethylene oxide polyether having an average molecular weight of approx. 400 The procedure was as described in Example 5, with 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 240.8 g (1 mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 203.5 g (0.5 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 1 and the mixture was stirred for S hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 506 g of a brown oil having a viscosity of 120 mPa sec was obtained.
Le A 32 283-Forei~n Countries Elemental analysis:
C H S Si calculated: 40.7 % 7.4 % 25.6 % 5.6 %
found: 42.0 % 7.4 % 24.0 % 5.2 %
Example 7 (C2H5O)3si- C3H6- S4- polyether - S4- C3H6 - Si(O C2Hs)3 10 containing a polyethylene oxide polyether having an average molecular weight of approx. 900 The procedure was as described in Example 5, with 62.4 g (0.8 mol) anhydrous sodium sulphide and 76.8 g (2.4 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 192.4 g (0.8 mol) 3-chlolopr~yltriethoxysilane was then added dropwise thereto, followed by 381.2 g (0.4 mol) of a Cl-termin~ted polyethylene oxide polyether obtained as in Example 3 and the mixture was stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCl was filtered off. After evaporation, 644 g of a brown oil having a viscosity 20 of 820 mPa sec was obtained, which crystallised after prolonged standing at room temperature. fp 35~C.
Elemental analysis:
C H S Si calculated: 44.9 % 7.9 % 16.2 % 3.6 %
found: 44.9 % 7.9 % 15.9 % 3.3 %
Le A 32 283-Forei~n Countries Example 8 (C2HsO)3Si- C3H6 - S4 - polyether - S4 - C3H6 - Si(OC2Hs)3 cont~ining a polyethylene oxide polyether having an average molecular weight of S approx. 1500 The procedure was as described in Example S, with 39 g (O.S mol) anhydrous sodium sulphide and 48 g (l.S mol) sulphur being heated in S00 ml dry ethanol at70~C for 30 minutes. 120.4 g (O.S mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 375 g (0.25 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 4 and the mixture was stirred for 5 hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCI was filtered off. After evaporation, 535 g of a brown oil was obtained, which crystallised rapidly at room temperature. fp 50~C to 55~C.
Elemental analysis:
C H S Si calculated: 47.7 % 8.2 % 11.8 % 2.6 %
found: 47.6 % 8.2 % 11.8 % 2.6 %
Example 9 (C2Hso)3si- C3H6 ~ (S4 - polyether)3 - S4- C3H6 - Si(O C2HS)3 containing a polyethylene oxide polyether having an average molecular weight of approx. 400 The procedure was as described in Example 5, with 78 g (1 mol) anhydrous sodium sulphide and 96 g (3 mol) sulphur being heated in 500 ml dry ethanol at 70~C for 30 minutes. 120.4 g (O.S mol) 3-chloropropyltriethoxysilane was then added dropwise thereto, followed by 305.3 g (0.75 mol) of a Cl-terminated polyethylene oxide polyether obtained as in Example 1 and the mixture was stirred for S hours at 70~C. The mixture was cooled and then filtered and the precipitated NaCl was filtered off. After evaporation, 496 g of a brown oil having a viscosity of 720 mPa sec was obtained.
Le A 32 283-Forei~n Countries Example 10: Solubility behaviour in ethanol in each case 30 parts by weight of a polysulphide silyl compound were heated in 70 parts by weight of ethanol for 5 minlltes at 70~C, during which the solubility in 5 the heated solvent was assessed:
Silyl compound Complete solubility Si content Examples according to the invention:
Compound from Example 5 yes 4.7 %
Compound from Example 6 yes 5.6 %
Compound from Example 7 yes 3.7 %
Compound from Example 8 yes 2.7 %
Compound from Example 9 yes 2.9 %
Comparison Examples:
Ex. 2 of DE-OS 2,141,160 yes 10.4 %
Ex. 1 of DE-A 195 49 027 no 5.8 %
Ex. 2 of DE-A 195 49 027 no 4.6 %
Ex. 3 of DE-A 195 49 027 no 3.8 %
Ex. 5 of DE-A 195 49 027 no 4.8 %
25 The results of the tests show that the polysulphide polyether silanes according to the invention, despite a lower content of costly silane raw material, exhibit a better solubility in the reaction medium (ethanol), so that it is possible to avoid the use of an expensive solvent mixture in the plepa~alion process.
Le A 32 283-Forei~n Countries Example 11: Comparison of vulcanisation kinetics The rubber mixtures below were prepared within 5 minutes at 140~C in a 1.5 1 kneader. Finally, sulphur and accelerator were added thereto on a roll at approx.
5 50~C. The vulcanisation kinetics were investigated at 160~C in the final mixtures by means of a Monsanto rheometer MDR 2000.
C 1, _ Examples Examples accordmg to the invention A B C D E F G
Solution SBR Buna VSL 4020-0 (Bayer) 75 75 75 75 75 75 75 BR Buna CB 11 (Bayer) 25 25 25 25 25 25 25 Silica Vulkasil S (Bayer) 80 80 80 80 80 i0 80 Carbon black Corax N 339 (Degussa) 6.5 6.5 6.5 6.5 6.5 6.5 6.5 Arom. oil Renopal 450 (Fuchs) 32.5 32.5 32.5 32.5 32.5 32.5 32.5 ZnO 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Stearic acid ~ ~ Vulkanox 4020 (Bayer) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Wax Antilux 654 (Rhein Chemie) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Polysulph. silane as in Ex. I of DE 19 549 027 6.5 0 0 0 0 0 o Polysulph. silane as in Ex. 2 of DE 19 549 027 0 6.5 0 0 0 0 0 Polysulph. silane as m Ex. 3 of DE 19 549 027 0 0 6.5 0 0 0 0 Compound according to the invention Ex. 6 0 0 0 6.5 0 0 0 Compound according to the invention Ex. 5 0 0 0 0 6.5 0 0 Compound according to the invention Ex. 7 0 0 0 0 0 6.5 0 Compound accordingto the invention Ex. 9 0 0 0 0 0 0 6.5 CBS Vulkacit CZ (Bayer) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 DPG Vulkacit D (Bayer) 2 2 2 2 2 2 2 Sulphur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 r.~. time at 160~C
(TS 06) in minutes 2.4 2.2 2.1 2.8 3 3 2.6 Vl ' - time at 160~C
(t 90) in minutes 14.2 13.5 13.4 13.5 12.4 11.5 12 Le A 32 283-Forei~n Countries It is clear that the rubber mixtures cont~ining the compounds according to the invention exhibit a more favourable vulcanisation behaviour, that is, a longer period of workability and a shorter vulcanisation time.
5 Example 12 The rubber mixtures below were prepared within 5 minutes at 140~C in a 1.5 l kneader. Finally, sulphur and accelerator were added thereto on a roll at approx.
50~C.
Le A 32 283-Forei~n Countries Comparison Examples according Example to the invention A B C
Solution SBR Buna VSL 5025-1 (Bayer) 75 75 75 BR Buna CB 24 (Bayer) 25 25 25 Silica Vulkasil S (Bayer) 80 80 80 Carbon black Corax N339 (Degussa) 6.5 6.5 6.5 Aromatic oil Renopal 450 (Fuchs) 8 8 8 ZnO 2.5 2.5 2.5 Stearic acid Antiozonant Vulkanox 4020 (Bayer) 1.5 1.5 1.5 Wax Antilux 654 (Rhein Chemie) 1.5 1.5 1.5 Bis(triethoxysilylpropyl) tetrasulphide acc. to DE 2,255,577 6.5 0 0 Compound as in Example 6 0 6.5 0 Compound as in Example 7 0 0 6.5 CBS Vulkacit CZ (Bayer) 1.5 1.5 1.5 DPG Vulkacit D (Bayer) 2 2 2 Sulphur 1.5 1.5 1.5 The rubber mixtures were then vulcanised for 45 minutes at 160~C. The resulting vulcanisation properties were as follows:
Tensile stress at 100% elongation (MPa) 3.4 3.4 3.6 Tensile stress at 300% elongation (MPa) 13.7 14.5 13.2 Tensile strength (MPa) 19 18.2 17.9 Tear resistance (MPa) 35.1 43.1 40.2 Hardness (Shore A) at 23~C 73 73 74 Rebound elasticity at 23~C (%) 25 25 23 Rebound elasticity at 70~C (%) 46 48 46 From the vulcanisation properties it may be seen that the polysulphide polyether silanes according to the invention, despite a considerably decreased content of costly silane raw material as compared with prior art, lead to equal mechanical Le A 32 283-Forei~n Countries properties and moreover bring about advantages in the improved relationship of wet skid resistance to rolling resistance (greater difference between the rebound elasticities at 23~C and at 70~C).
Claims (9)
1. A rubber composition comprising at least one rubber, a filler, and at least one polysulphide polyether silane corresponding to the formula R1R2R3Si-X1-(-Sx-polyether-)m-(-Sx-X2-SiR1R2R3)n (I), wherein R1, R2 and R3 are identical or different and denote C1-C18-alkyl, C1-C18 alkoxy, C6-C12-phenyl or -phenoxy, C7-C18- arylalkyl or alkylaryloxy, with the proviso that at least one of the groups R1 to R3 is an alkoxy, phenoxy or alkylaryloxy group, x1 and x2 are identical or different and represent divalent, linear or branched or cyclic, optionally unsaturated C1-C12-alkyl groups, polyether represents a bi-, tri- or tetrafunctional polyethylene oxide polyether group, polypropylene oxide polyether group, polybutylene oxide polyether group, or a corresponding mixed polyether group having an average molecular weight of from 300 to 5,000, m represents an integer from 1 to 20, n represents a number from 1 to 4, and x denotes a number from 1 to 8, the polysulphide polyether silane (I) being used in quantities of from 0.1 to 15 wt.%, based on the quantity of the rubber used in each case.
2. A composition according to claim 1, comprising from 1 to 7.5 wt.% of the silane of formula (I).
3. A composition according to claim 1 or 2, further comprising a cross-linking agent.
4. A composition according to claim 1, 2 or 3, further comprising an additive selected from antioxidants, heat stabilisers, light stabilisers, antiozonants, processing agents, plasticisers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, reaction retarders, metal oxides, and activators.
5. A composition according to any one of claims 1 to 4, wherein R1, R2 and R3 independently of one another denote methyl, ethyl, propyl or phenyl, with the proviso that at least one of the groups R1 to R3 represents a methoxy, ethoxy, propoxy, butoxy or phenoxy group, and that X1 and x2 denote methylene, propylene, butylene, pentylene or hexylene groups and that Y represents a polyethylene oxide group, polypropylene oxide group or a polyethylene oxide/polypropylene oxide mixed polyether group having molecular weights of between 300 and 1,500, which has been obtained by addition of at least 6 moles ethylene oxide and/or propylene oxide to an aliphatic or aromatic diol or amine and wherein n equals l and m denotes integers from 1 to 20.
6. A composition according to any one of claims 1 to 4, wherein the compound of formula (I) is represented by one of the following formulae (1) to (7) wherein R = CH3, C2H5, x = 1 to 8, p = 5 to 30, m = 1 to 20, wherein R = CH3, C2H5, x = 1 to 8, p = 5 to 30, m = 1 to 20, wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 1 to 10, c = 3 to 20, m = 1 to 20, wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20 b = 2 t 20, m = 1 to 20, wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 2 to 20, m = 1 to 20, wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 2 to 20, wherein R = CH3, C2H5, C3H7, x = 1 to 8, a = 3 to 20, b = 1 to 10, m = 1 to 20.
7. A composition according to any one of claims 1 to 4, wherein the compound of formula (I) is represented by the following formula (8) wherein R1, R2, R3 denote methyl, phenyl, methoxy, ethoxy, propoxy, butoxy, with the proviso that at least one of the groups is a methoxy, ethoxy, propoxy or butoxy group and q, r = 1 to 3, x = 1 to 8, p = 6 to 30, m = 1 to 20.
8. A process for preparing a vulcanisate which comprises vulcanising a composition according to any one of claims 1 to 7.
9. A use of a rubber composition according to any one of claims 1 to 7 for the preparation of a rubber vulcanisate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19709873.8 | 1997-03-11 | ||
DE19709873A DE19709873A1 (en) | 1997-03-11 | 1997-03-11 | Rubber mixtures containing polysulfidic polyether silanes |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2231302A1 true CA2231302A1 (en) | 1998-09-11 |
Family
ID=7822896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002231302A Abandoned CA2231302A1 (en) | 1997-03-11 | 1998-03-06 | Rubber mixtures containing polysulphide polyether silanes |
Country Status (5)
Country | Link |
---|---|
US (1) | US5977225A (en) |
EP (1) | EP0864608B1 (en) |
JP (1) | JPH10251456A (en) |
CA (1) | CA2231302A1 (en) |
DE (2) | DE19709873A1 (en) |
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WO2002020534A1 (en) * | 2000-09-08 | 2002-03-14 | Crompton Corporation | Hydrocarbon core polysulfide silane coupling agents for filled elastomer compositions |
US6635700B2 (en) | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
US7687558B2 (en) | 2006-12-28 | 2010-03-30 | Momentive Performance Materials Inc. | Silated cyclic core polysulfides, their preparation and use in filled elastomer compositions |
US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
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US7781606B2 (en) | 2006-12-28 | 2010-08-24 | Momentive Performance Materials Inc. | Blocked mercaptosilane coupling agents, process for making and uses in rubber |
US7960460B2 (en) | 2006-12-28 | 2011-06-14 | Momentive Performance Materials, Inc. | Free-flowing filler composition and rubber composition containing same |
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US7968635B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US7968636B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing silated cyclic core polysulfides |
US7968633B2 (en) | 2006-12-28 | 2011-06-28 | Continental Ag | Tire compositions and components containing free-flowing filler compositions |
US8592506B2 (en) | 2006-12-28 | 2013-11-26 | Continental Ag | Tire compositions and components containing blocked mercaptosilane coupling agent |
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DE19829390A1 (en) * | 1998-07-01 | 2000-01-05 | Degussa | New oligomeric organosilicon compounds, their use in rubber mixtures and for the production of moldings |
US6130306A (en) * | 1999-03-11 | 2000-10-10 | Dow Corning S. A. | Moisture curable oxyalkylene polymer containing composition |
JP2001261891A (en) * | 1999-05-17 | 2001-09-26 | Yokohama Rubber Co Ltd:The | Rubber composition |
US6469089B2 (en) * | 1999-10-08 | 2002-10-22 | Cabot Corporation | Elastomeric compounds with improved wet skid resistance and methods to improve wet skid resistance |
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JP4405897B2 (en) * | 2004-10-27 | 2010-01-27 | 住友ゴム工業株式会社 | Run-flat tire rubber composition and run-flat tire comprising the same |
US20060173118A1 (en) * | 2005-01-28 | 2006-08-03 | Sumitomo Rubber Industries, Ltd. | Rubber composition and tire having tread comprising thereof |
JP4566888B2 (en) * | 2005-01-28 | 2010-10-20 | 住友ゴム工業株式会社 | Rubber composition and tire having tread using the same |
JP4421547B2 (en) * | 2005-02-10 | 2010-02-24 | 住友ゴム工業株式会社 | Rubber composition and tire having tread using the same |
JP4405932B2 (en) | 2005-02-23 | 2010-01-27 | 住友ゴム工業株式会社 | Rubber composition and racing tire having a tread comprising the same |
DE102005020535B3 (en) | 2005-05-03 | 2006-06-08 | Degussa Ag | Preparation of mercapto organyl(alkoxysilane) comprises reaction of bis(alkoxysilylorganyl)polysulfide with hydrogen in the presence of an alcohol and a doped metal catalyst (containing e.g. (iron) compound and a doping component) |
DE102005038791A1 (en) | 2005-08-17 | 2007-02-22 | Degussa Ag | New organosilicon compounds based on triethanolamine, useful as components of rubber mixtures for making e.g. tires, tubes and cable coatings |
DE102005060122A1 (en) | 2005-12-16 | 2007-06-21 | Degussa Gmbh | Process for the preparation of (mercaptoorganyl) alkyl polyether silanes |
DE102006008670A1 (en) * | 2006-02-24 | 2007-08-30 | Degussa Gmbh | Filled styrene-butadiene mix for molding, tire, tire tread, cable or roller covering, hose, drive or conveyor belt, tire, shoe sole, sealing ring or damping element contains organo-silane polysulfide with long-chain alkyl-polyether groups |
DE102006027235A1 (en) * | 2006-06-09 | 2008-01-17 | Evonik Degussa Gmbh | rubber compounds |
US9447262B2 (en) | 2011-03-02 | 2016-09-20 | Momentive Performance Materials Inc. | Rubber composition containing blocked mercaptosilanes and articles made therefrom |
EP2557083A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Networked organosilicon polysulphides |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE2141160C3 (en) * | 1971-08-17 | 1982-01-21 | Degussa Ag, 6000 Frankfurt | Organosilicon compounds containing sulfur |
DE2141159C3 (en) * | 1971-08-17 | 1983-11-24 | Degussa Ag, 6000 Frankfurt | Organosilicon compounds containing sulfur |
JPS6267092A (en) * | 1985-09-20 | 1987-03-26 | Shin Etsu Chem Co Ltd | Organosilicone compound containing polysulfide group and rubber composition containing same |
DE69119125T3 (en) * | 1990-03-02 | 2001-01-11 | Bridgestone Corp | tire |
DE4406947A1 (en) * | 1994-03-03 | 1995-09-07 | Bayer Ag | Rubber mixtures containing reinforcement additives containing sulfur / silicon |
DE19549027A1 (en) * | 1995-06-16 | 1996-12-19 | Bayer Ag | Rubber mixtures containing oligomeric silanes |
US5827912A (en) * | 1995-06-16 | 1998-10-27 | Bayer Ag | Rubber compounds containing oligomeric silanes |
-
1997
- 1997-03-11 DE DE19709873A patent/DE19709873A1/en not_active Withdrawn
-
1998
- 1998-02-26 DE DE59806840T patent/DE59806840D1/en not_active Expired - Fee Related
- 1998-02-26 EP EP98103321A patent/EP0864608B1/en not_active Expired - Lifetime
- 1998-03-04 US US09/034,618 patent/US5977225A/en not_active Expired - Fee Related
- 1998-03-05 JP JP10069225A patent/JPH10251456A/en active Pending
- 1998-03-06 CA CA002231302A patent/CA2231302A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
EP0864608B1 (en) | 2003-01-08 |
EP0864608A1 (en) | 1998-09-16 |
DE19709873A1 (en) | 1998-09-17 |
DE59806840D1 (en) | 2003-02-13 |
JPH10251456A (en) | 1998-09-22 |
US5977225A (en) | 1999-11-02 |
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