CA2316002A1 - Functionalized low double bond rubbers - Google Patents
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- CA2316002A1 CA2316002A1 CA002316002A CA2316002A CA2316002A1 CA 2316002 A1 CA2316002 A1 CA 2316002A1 CA 002316002 A CA002316002 A CA 002316002A CA 2316002 A CA2316002 A CA 2316002A CA 2316002 A1 CA2316002 A1 CA 2316002A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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Abstract
The present invention concerns functionalized low double bond iso-olefin- and EPDM-rubbers with a double bond content of 0.001 to 10 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S n-R.
The functionalized low double bond iso-olefin- and EPDM rubbers according to the present invention may be readily manufactured by reaction of corresponding low double bond rubbers with sulfenyl chlorides and are particularly suitable for the manufacture of adhesives, sealants, paints, vulcanizates and as rubber components in rubber/polymer blends.
The functionalized low double bond iso-olefin- and EPDM rubbers according to the present invention may be readily manufactured by reaction of corresponding low double bond rubbers with sulfenyl chlorides and are particularly suitable for the manufacture of adhesives, sealants, paints, vulcanizates and as rubber components in rubber/polymer blends.
Description
Le A 33 924-Foreign Countries Bg/ngb/NT
FUNCTIONALIZED LOW DOUBLE BOND RUBBERS
FIELD OF THE INVENTION
S
The present invention concerns functionalized iso-olefin- and EPDM-rubbers with low double bond content, in which the functional group is specially bonded to the rubber by means of sulfur bridges, a process for the production of the rubbers, and use of the rubbers in the manufacture of rubber moldings, adhesives, sealants, paints and rubber/polymer blends.
BACKGROUND OF THE INVENTION
The polarity of functionalized rubbers is different from that of the starting polymers and for such reason, they offer advantages for the manufacturing of rubber mixtures and rubber vulcanizates. For example, such advantages are due to improved adhesion to fillers and reinforcing materials, for the manufacture of paints and sealants, and as compatibility agents and rubber components in elastomer-modified plastics and as compatibility agents in polymer blends.
As a consequence of the lower number of reactive positions, the secondary functionalization of rubbers with a low double bond content is significantly more difficult than that of rubbers with a high double bond content, and as a rule, it requires several complex reaction stages and/or extreme reaction conditions, which can lead to changes in the microstructure and uneven distribution of the functional groups in the rubber.
Hence, according to US 5,162,445, the uniform functionalization of iso-olefin copolymers requires the copolymerization of iso-olefins with p-methyl styrene, followed by radical bromination of the aromatic methyl group and subsequent nucleophilic substitution reaction of the bromine in the benzyl group. In addition to the complex, mufti-stage manufacturing method, the benzyl groups in the end product are also sensitive to high temperatures.
The addition of N-chiorothiosulfonamides to EPDM rubbers, as described in EP
508 169 and 733 651, produces side groups sensitive to hydrolysis because of the -S-N-SOz bond.
The radical addition of mercapto compounds, as described in DE 2 653 144 for special polybutadiene rubbers, is unsuccessful in the case of rubbers with a low double bond content, such as butyl rubber and ethylene/propylene/diene rubber (EPDM). An adduct of a hydrogenated nitrile rubber and a sulfenyl chloride is further known. The adduct may be vulcanized and used to prepare seals, gaskets or mechanical goods. The adduct is characterized by having a surprisingly low level of gel.
SUMMARY OF THE INVENTION
The object of the present invention was to provide functionalized rubbers whose functional groups are bonded to the rubber by hvdrolytically stable means and which can be manufactured more easily and economically in comparison with the known methods.
DETAILED DESCRIPTION OF THE INVENTION
Therefore, the present invention provides functionalized low double bond iso-olefin and EPDNI-rubbers having a double bond content of 0.001 to 10 wt.°,'°, preferably 0.01 to ~ wt.°i°, more preferably 0.0~ to 3 wt.%, and a content of hvdrolyticallv stable functional groups not bonded by means of benzyl groups of 0.01 to ?~
wt.°6, preferably 0.01 to 1 ~ wt.°, o, and more preferably 0.1 to 10 wt.°,'°, whereby the functional groups have the structure Le A 33 924-Foreign Countries -Sn-R
wherein R stands for a linear or branched C~-C36 alkyl radical, preferably a C, to C,g alkyl radical or a CS-C36, preferably a CS to Coo cycloalkyl radical, whereby the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally, may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C~-C~H, preferably C~-C~z carboxylic acid ester radicals, amino, C1-C~Z monoalkyl and dialkyl amino radicals and ammonium salts thereof, C,-C,Z trialkyl ammonium salts and by nitro groups or by halogen atoms; and further for a C6-C~2 aryl radical, C7-C36, preferably C~-C,g aralkyl radical, or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, whereby the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, carboxylic acid halide groups, C~-C~8 carboxylic acid ester groups, amino, C,-C,z monoalkyl and dialkylamino radicals and ammonium salts thereof, C~-C,Z trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from l, 2 or 3.
Preferred radicals for use as the radical R are those listed below by formulae:
S S
i~
N N ~ N
Le A 33 924-Foreign Countries CI
CI
CI
CIOC~ HOOCH HZSC~ZOOC~
H5C200C~ H»C800C~ HsCsOOC
CIOC~ HOOCH HSCZOOC~
HO~ HO
CI-The C=C double bond content of the rubber refers to the number of C=C groups as a percentage by weight relative to rubber.
The invention also provides a process for the manufacture of the functionalized iso-S olefin- and EPDM-rubbers with low double bond content, characterized in that a low double bond rubber with a double bond content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.05 to 3 wt.%, is reacted with 0.01 to 25 parts by weight, preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of rubber, of a sulfenyl chloride with the following general formula X-S"-R
wherei n X stands for a halogen atom, preferably chlorine or bromine, and R and n have the meaning given for the functional groups listed above, at temperatures in the range from -120°C to +200°C.
The sulfenyl halides represented below by formulae are preferably used in the process according to the present invention:
S
/~--S-Hal ~ />-S-Hai I ~>-S-Hal N ~ N
~S~HaI ~SiHal /~SWHaI ~g~Hal S/Hal SiHal S ~H al S ~'H a( S-Hal \ , S-Hal CI3C~S~HaI
CIOC~S~HaI HOOC~S~Hai HZSC~ZOOC~S~HaI
Sw S
HSCZOOC~S~HaI HnCe00C~ Hal HSCsOOC~ ~Hal CIOC~S~HaI HO~~S~HaI HSCZOOC~S'-Hai HO~S~HaI /N~S,HaI
HO~S~HaI
Hal~
In the above formulae, the halogen (Hal) preferably denotes chlorine.
Le A 33 924-Foreign Countries The sulfenyl halides are manufactured by means of methods known per se, thus, for example, by reaction of disulfides with halogens, as described in US
2,257,974, or from mercaptans and halogens, see Liebigs Ann. Chem. 391, 57 (1912) in this respect, or from mercaptans and sulfur dichloride or disulfur dichloride, or by reaction of sulfenic acids, sulfenic acid esters or sulfenic acid amides with halogen halides, as described in Chem. Ber. 57, 755 (1924). The sulfenyl halides may also be manufactured in the presence of low double bond rubbers without isolating the sulfenyl halide, whereby optionally, the rubber is additionally halogenated with excess halogen.
The sulfenyl halides are reacted with the rubbers, in solid or dissolved state, at temperatures of preferably -30 to 150°C; the reaction is preferably performed in a solvent. Examples of suitable solvents include aliphatic or cycloaliphatic hydro-1 S carbons, such as butane, isobutane, pentane, hexane, cyclohexane, octane, isooctane, halogenated hydrocarbons, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chloro-propane, chlorobutane, or chlorinated aromatic hydrocarbons, such as chlorobenzene.
The content of dissolved rubber lies in the range from 0.1 to approx. 40 wt.%, preferably 10 - 25 wt.%, and as a rule, the highest possible content is chosen for economic reasons.
The reaction of the low double bond rubbers with the sulfenyl halides is performed as an addition of a halogen atom and hydrolytically stable addition of the corresponding radicals to the double bonds. Depending on the type of rubber and the nature of the double bond, hydrogen halide may also be released during the course of the addition, such that double bonds re-form. The release of hydrogen halide may optionally, be promoted by the addition of acid scavengers and bases.
Preferred low double bond iso-olefin- and EPDM-rubbers that are reacted with the sulfenyl halides are:
-(A) Iso-olefin terpolymers consisting of iso-olefins having 4 to 16 carbon atoms, conjugated diolefins having 4 to 6 carbon atoms and optionally also mono- or polyunsaturated compounds having 2 to 20 carbon atoms, with a molecular weight of 10,000 to 3,000,000 g/mol, preferably 50,000 to 2,000,000 g/mol, and more preferably 100,000 to 1,000,000 g/mol, whereby the molar ratio of iso-olefins to diolefins to unsaturated organic compounds, made up to 100, is 50 to 99.5 : 0.5 to 20 : 0 to 30, preferably 80 to 99.5 : 0.5 to 10 : 0 to 20, and more preferably 90 to 99.5 : 0.~ to 10 : 0 to 10.
Preferred iso-olefins are isobutene, 2-methyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene and (3-pinene, particularly isobutene and 2-methyl-1-butene.
Preferred conjugated diolefins are isoprene, butadiene, 2,3-dimethyl butadiene, cyclopentadiene, methylcyclopentadiene, 1,3-cyclohexadiene, and more preferably isoprene.
Examples of mono- or polyunsaturated compounds include olefins and vinyl aromatics, preferably 1-olefins having 2 to 20 carbon atoms, such as ethene, propene, 1-butene, I-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 5-vinyl-2-norbornene, preferably ethene and propene, and vinyl aromatics, particularly styrene, p-methyl styrene, alpha-methyl styrene and vinyl naphthalene with styrene and p-methyl styrene being most preferred.
?~
Corresponding chlorinated and brominated rubbers with chlorine or bromine contents of 0.01 to ~ wt.%, preferably 0.1 to 3 wt.%, are also suitable.
Suitable terpolymers have a Mooney viscosity ML l+8 (125°C) of ~
to 200, 3u preferably ?0 to 100. See I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989, pages 168 to 180 in this respect. Most Le A 33 924-Foreign Countries _g_ preferred products of this nature are commercially available as butyl rubber, bromobutyl and chlorobutyl rubber (e.g. Polysar Butyl~ from Bayer AG).
(B) Ethylene/propylene/diene terpolymers (EPDM): these comprise rubbers in which the ratio by weight of ethylene to propylene monomer lies in the range 30:70 to 70:30 and which may display 1 to 20 C=C double bonds per 1000 carbon atoms. Examples of suitable dime monomers in EPDM include:
conjugated dimes, e.g. isoprene and butadiene-1,3, and non-conjugated dimes having 5 to 25 C atoms, e.g. 1,4-pentadiene, 1,4-hexadiene, 1,5-hexa-dime, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene; cyclic dimes, e.g.
cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene;
alkylidene and alkenyl norbornenes, e.g. 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-S-nor-bornene and tricyclodiene. The non-conjugated dimes hexadiene-1,5, ethylidene norbornene and dicyclopentadiene are preferred. The dime content in EPDM is preferably 0.5 to 10 wt.% relative to EPDM. Preferred products display Mooney viscosities ML 1+4 (125°C) of 10 to 200, preferably 15 to 100. See I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989, pages 131 to 143 in this respect. Such EPDM rubbers are commercially available (e.g. Buna EP from Bayer AG).
The polarity of the low double bond functionalized iso-olefin- and EPDM-rubbers according to the present invention is different from that of the starting polymers, and for such reason, they offer advantages in the manufacture of rubber mixtures with improved filler/rubber interaction, improved adhesion to reinforcing materials and improved compatibility with other polar rubbers, for example.
Suitable fillers for the rubber mixtures include all known fillers used in the rubber industry, including both active and inactive fillers.
The following are worthy of mention:
highly dispersed silicic acids, manufactured, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific S surface areas of S to 1000, preferably 20 to 400 m2/g (BET surface area) and with primary particle sizes of 10 to 400 nm. The silicic acids may optionally also take the form of mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides;
- synthetic silicates, such as ammonium silicate, alkaline-earth silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20 to 400 m''/g and primary particle diameters of 10 to 400 nm;
- natural silicates such as kaolin and other naturally occurring silicic acid;
- glass fibers and Mass fiber products (mats, strands) or glass microbeads;
- metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide;
- metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate;
- metal hydroxides, such as aluminum hydroxide, magnesium hydroxide;
- carbon blacks. The carbon blacks for use in this context are produced using the lampblack, furnace black or channel black process and have BET surface areas of 20 to 200 my%g, e.g. SAf, ISAF, HAF, FEF or GPF carbon blacks;
;0 - rubber gels, particularly those based on polybutadiene, butadiene;styrene copolymers, butadiene/acrylonitrile copolymers and polychloroprene.
Highly dispersed silicic acids and/or carbon blacks are preferably used as fillers.
The rubber mixtures may contain, in addition to the low double bond functionalized iso-olefin- and EPDM-rubbers according to the present invention, other known rubbers. In addition to natural rubber, these are particularly synthetic rubbers.
Preferred synthetic rubbers are described by way of example in W. Hofinann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980, and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They include, inter alia ABR - butadiene/acrylic acid-C,-C4-alkylester copolymers ACM - polyacrylate rubber BR - polybutadiene CR - polychloroprene CM - chlorinated polyethylene CSM - chlorosulfonated polyethylene ECO - epichlorohydrin rubber EPDM - ethylene/propylene/diene terpolymer FKM - fluororubber IR - polyisoprene IIR - isobutylene/isoprene copolymers NBR - butadiene/acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-40 wt.%
HNBR - partially hydrogenated or fully hydrogenated NBR
rubber Q - silicone rubber SBR - styrene,~utadiene copolymers with styrene contents of 1-60, preferably ?0-~0 wt.,' together with mixtures of these rubbers.
Naturally, the rubber mixtures according to the present invention may also contain other rubber auxiliary substances, which promote the crosslinking of the vulcanizates produced from the rubber mixtures, for example, or which improve the physical Le A 33 924-Foreign Countries properties of the vulcanizates produced from the rubber mixtures according to the present invention for their particular intended application.
Sulfur or sulfur-yielding compounds can be used as crosslinking agents, for example, as can radical-yielding crosslinking agents such as organic peroxides.
Moreover, as S mentioned, the rubber mixtures according to the present invention may also contain further auxiliary substances, such as the known reaction accelerators, antioxidants, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators.
The rubber auxiliary substances according to the present invention are used in the conventional, known quantities, whereby the quantity used is governed by the subsequent intended application of the rubber mixtures. Quantities of rubber auxiliary substances in the range from 2 to 70 parts by weight, relative to 100 parts 1 S by weight of rubber, are customary, for example.
The rubber mixtures may be produced, for example, by mixing the low double bond functionalized rubbers according to the invention with the appropriate fillers, optionally further rubbers and rubber auxiliary substances in suitable mixing devices, such as compounders, rolls or extruders.
The present invention also provides the use of the rubbers according to the present invention in the manufacture of vulcanizates, which, in turn, are used for the manufacture of rubber moldings, particularly for the manufacture of tires, e.g. tire inner tubes, tire treads, sidewalk and inner liners, as well as engineering rubber goods, e.g. bladders, hoses and rubberized fabric.
The functiona(ized low double bond iso-olefin- and EPDM-rubbers according to the present invention may, moreover, also be used in the manufacture of adhesives, sealants, paints and as rubber components in rubber/polymer blends.
Le A 33 924-Foreign Countries ~~rnr~rnT ~~
Example 1 Butyl rubber modified with 3.3 wt.% thiobenzothiazole groups 1.42 g chlorine was introduced into a suspension of 6.64 g dithiodibenzothiazole (Vulkacit DM, Bayer AG) in 80 ml dry chlorobenzene at 0°C, such that a clear orange-colored solution of mercaptobenzothiazole sulfene chloride was formed.
This solution was added at room temperature with agitation to a solution of 200 g butyl rubber Polysar Butyl 402 (isobutylene/isoprene terpolymer from Bayer AG
with 2.2 mol% isoprene incorporated by polymerization, corresponding to 0.9 wt.%
C=C double bond content) in 2 1 cyclohexane. After 4 hours of stirring at 80°C, the mercaptobenzothiazole sulfene chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 1 g Vulkanox BKF
(phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo at 70°C, 206 g of a light colored polymer with viscosity ML 1+4 (100°C) 50 was obtained.
In addition to the aliphatic protons in the butyl rubber, the 'H-NMR also displays signals for the aromatic protons in the mercaptobenzothiazole at 7.3 - 8 ppm and signals for olefinic protons at 5 - 5.2 ppm. Average molecular weight (M~,, determined by GPC): 382,000.
Elementary analysis: sulfur: 1.2 wt.%
nitrogen: 0.3 wt.%
chlorine: 0.22 Le A 33 924-Foreign Countries Example 2 EPDM rubber modified with 3.3 wt.% thiobenzothiazole groups 3.6 g chlorine was introduced into a suspension of 16.6 g dithiodibenzothiazole (Vulkacit DM, Bayer AG) in 100 ml dry chlorobenzene at 0°C, such that a clear orange-colored solution of mercaptobenzothiazole sulfene chloride was formed.
This solution was added at room temperature with agitation to a solution of 500 g Buna EP T 3950 (EPDM rubber from Bayer AG, with 56 wt.% ethylene content and 11 wt.% ENB content, corresponding to 2.2 wt.% C=C double bond content) in 4 1 cyclohexane. After 4 hours of stirnng at room temperature, the mercapto-benzothiazole sulfene chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 1 g Vulkanox BKF (phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo at 70°C, 516 g of a light colored polymer was obtained. ML 1+4 (100°C) 72.
Example 3 Butyl rubber modified with 2.4 wt.% 3-thiopropionic acid groups A solution of 16 g 3-chlorothiopropionic acid chloride (CAS-RN 14274-19-2) in 100 ml chlorobenzene was added at room temperature with agitation to a solution of 500 g butyl rubber Polysar Butyl 402 (isobutylene/isoprene terpolymer from Bayer AG with 2.2 mol% isoprene incorporated by polymerization, corresponding to 0.9 wt.% C=C double bond content) in 4 1 cyclohexane. After 4 hours of stirring, the 3-chlorothiopropionic acid chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 100 g water and 1 g Vulkanox BKF (phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo ax 70°C, S 16 g of a light colored polymer with viscosity ML 1+4 (100°C) 50 was obtained.
Example 4 Butyl rubber modified with 1 wt.% 3-thiopropionic acid groups.
According to the procedure of example 3 7.95 g (0.05 mol) 3-chloropropionic acid chloride was reacted with X00 g butyl nzbber Polysar Butyl 402. X06 g light coloured butyl rubber were obtained with viscosity ML 1+4 (100°C) 79 and sulfur content 0.35 wt.%.
Example ~
The following substances were mixed in a 1.~ liter kneader (speed of rotation 70 rpm;
filling ratio 65%, initial temperature 50°C, duration 5 minutes). The mixture was subsequently removed and sulfur and accelerator were admixed on a roller at a roller temperature of 40°C:
Mixture of Constituents Comparison Example 4.A
the following were mixed in the 1.~ 1 kneader:
butyl rubber Polysar Butyl 402 (Bayer) 30 0 functionalized butylrubber according to example 4 0 30 natural rubber TSR ~ 70 70 carbon black Corax N 339 (Degussa) ~0 ~0 stearic acid 2 zinc oxide RS (Bayer AG) > >
anti ageing agent Vulkanox -X020 ( Bayer) l.p 1.~
anti a~ein~ went Vulkanox HS (Bayer ) 1 1 the following were admixed on a roller.
sulfenamide accelerator Vuikacit CZ (Bayer) 1.4 i.4 sulfur 1.2 1.2 mixture viscosity ML 1+4 (100°C) 83 91 The mixture were subsequently vulcanised at 160°C . Vulcanisation time 10 minutes.
Properties of the vulcanites: Comparison Example 4.A
stress at 300% elongation (MPa) 14.2 14.8 tensile strength (MPa) 18 22.1 elongation at break (%) 380 440 hardness at 23C (Shore A) 69 68 rebound resilience at 23C (%) 28 28 tear resistance DIN 5351 (N/mm) 15.3 5~
abrasion (DIN ~3 516) 141 126 The test results verified the enhanced level of the mechanic properties of the rubber vulcanisates according to the invention containing functionalized butyl rubber, especially the higher tensile strength and higher tear resistance and improved abrasion resistance.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
CLAIMS:
I. Functionalized low double bond iso-olefin- and BPDM-rubbers with a double bond content of 0.001 to 10 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl soups of 0.01 to 25 wt_%, wherein the functional groups have the structure -S~-R
wherein R stands for a linear or branched C,-C;6 alkyl radical or a C_-C;6 cycloalkyi radical. wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl. carboxylate ~rouos. by lj carboxylic acid halide radicals, by C,-C,s carboxylic acid ester radicals. amino. C;-Ci2 monoalkyl and dialkyl amino radicals and ammonium salts thereof. C~-C,Z triallcyl ammonium salts and by vitro groups or by halogen atoms, and further for a C5-C ~ Z aryl radical, C~-C;6 aralkyl radical or a mono-, di- or tticyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may Likewise be substituted by hydroxyl groups, carboxyl soups, carboxylate groups, C_-C=6 carboxylic acid halide groups, Ci-C18 carboxylic acid ester groups, amino, C1-C1~ monoalkyl and dialkylamino radicals and ammonium salts thereof, C:-C12 trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, ? or 3.
;0 ?. Process for the manutacture of functionaiized low double bond iso-oletin-and EPDM-rubbers according to claim 1, according to which rubber with a double _ 17-bond content of 0.001 to 10' wt.% is reacted with 0.01 to 25 parts by weight, relative to 100 parts by weight of rubber, of sulfenyl chloride with the following general formula X-Sn-R
j where X stands for a halogen atom and R stands for a linear or branched Cl-C36 alkyl radical or a C;-C36 i0 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl. carboxytate groups. by carboxylic acid halide radicals. by Cv-C,s carboxylic acid ester radicals. amino, C,-C,~ monoalkyi and dialkyl amino radicals and 15 ammonium salts thereof, C~-C,: trialkyl ammonium salts and by vitro soups or by halogen atoms, and further for a Co-Cn aryl radical, C~-C;6 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups. carboxyl soups. carboxyiate groups, C-,-Cla carboxylic acid halide groups, C=-C16 carboxylic acid ester groups, amino, C.:-C1~ monoalkyl and dialkvlamino radicals and ammonium salts thereof, C=-C<< trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from I. ? or ~.
at temperatures in the range from -l?0°c to - 200°C.
3. Rubber vulcanizates comprising functionalized low double bond iso-olefin-or EPD~f-rubbers with a double bor:d content of 0.001 to 10 wt.°. o and a content -LS-of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S~-R
where R stands for a linear or branched C,-C36 alkyl radical or a C;-C36 cycloallcyl radical, wherein the hydrocarbon chains may be intemtpted by one or more oxygen. sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate soups, by carboxylic acid halide radicals. by C,-C,g carboxylic acid ester radicals, amino, C,-C,~ monoalkyi and dialkyl amino radicals and ammonium salts thereof, C.-C,, trialkyl ammonium salts and by nitro groups or by halogen atoms. and further for a Cti-C i ~ aryl : a.dical, C~-C;6 aralkyl radical or a mono-. di- or tricyciic heterocyclic radical with 1~ nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hvdroxv_ 1 groups. carboxyl groups, carboxylate soups, C1-C16 carboxylic acid halide groups, C1-C1~ carboxylic acid ester groups, amino, C-_-C-;~ monoalkyl and dialkylamino radicals and ammonium salts thereof, '0 C,-C1~ trialkyl ammonium salts, vitro groups and by halogen. atoms, and ' n stands for a whole number selected from 1, ? or ~.
?5 4. Rubber molding comprising functionalized low double bond iso-olefin- or EPDM-rubbers with a double bond content of 0.001 to 10 wt.°,% and a content of hydrolyticallv stable functional groups not bonded by means of benzyi soups of 0.01 to -~ wt.°%, wherein the functional groups have the structure -Sn-R
where R. stands for a linear or branched C~-C36 alkyl radical or a CS-C3s cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C i-C ~ $ carboxylic acid ester radicals, amino, C 1-C 12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C,-C,z trialkyl ammonium salts and by vitro groups or by halogen atoms, and further for a C6-C 1 z aryl radical, CrC;6 aralkyl radical or a mono-, di- or tricyciic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, ara.llcyl radicals and the heterocyciic radicals may likewise be substituted by hydroxyl soups, carboxyl soups, carboxylate groups, C, -C1a carboxylic acid halide groups , C1-C18 carboxyl is acid ester groups, amino, C:-ClZ monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C1z trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
Fetherstonhaugh & Co.
Ottawa, Canada Patent Agents
FUNCTIONALIZED LOW DOUBLE BOND RUBBERS
FIELD OF THE INVENTION
S
The present invention concerns functionalized iso-olefin- and EPDM-rubbers with low double bond content, in which the functional group is specially bonded to the rubber by means of sulfur bridges, a process for the production of the rubbers, and use of the rubbers in the manufacture of rubber moldings, adhesives, sealants, paints and rubber/polymer blends.
BACKGROUND OF THE INVENTION
The polarity of functionalized rubbers is different from that of the starting polymers and for such reason, they offer advantages for the manufacturing of rubber mixtures and rubber vulcanizates. For example, such advantages are due to improved adhesion to fillers and reinforcing materials, for the manufacture of paints and sealants, and as compatibility agents and rubber components in elastomer-modified plastics and as compatibility agents in polymer blends.
As a consequence of the lower number of reactive positions, the secondary functionalization of rubbers with a low double bond content is significantly more difficult than that of rubbers with a high double bond content, and as a rule, it requires several complex reaction stages and/or extreme reaction conditions, which can lead to changes in the microstructure and uneven distribution of the functional groups in the rubber.
Hence, according to US 5,162,445, the uniform functionalization of iso-olefin copolymers requires the copolymerization of iso-olefins with p-methyl styrene, followed by radical bromination of the aromatic methyl group and subsequent nucleophilic substitution reaction of the bromine in the benzyl group. In addition to the complex, mufti-stage manufacturing method, the benzyl groups in the end product are also sensitive to high temperatures.
The addition of N-chiorothiosulfonamides to EPDM rubbers, as described in EP
508 169 and 733 651, produces side groups sensitive to hydrolysis because of the -S-N-SOz bond.
The radical addition of mercapto compounds, as described in DE 2 653 144 for special polybutadiene rubbers, is unsuccessful in the case of rubbers with a low double bond content, such as butyl rubber and ethylene/propylene/diene rubber (EPDM). An adduct of a hydrogenated nitrile rubber and a sulfenyl chloride is further known. The adduct may be vulcanized and used to prepare seals, gaskets or mechanical goods. The adduct is characterized by having a surprisingly low level of gel.
SUMMARY OF THE INVENTION
The object of the present invention was to provide functionalized rubbers whose functional groups are bonded to the rubber by hvdrolytically stable means and which can be manufactured more easily and economically in comparison with the known methods.
DETAILED DESCRIPTION OF THE INVENTION
Therefore, the present invention provides functionalized low double bond iso-olefin and EPDNI-rubbers having a double bond content of 0.001 to 10 wt.°,'°, preferably 0.01 to ~ wt.°i°, more preferably 0.0~ to 3 wt.%, and a content of hvdrolyticallv stable functional groups not bonded by means of benzyl groups of 0.01 to ?~
wt.°6, preferably 0.01 to 1 ~ wt.°, o, and more preferably 0.1 to 10 wt.°,'°, whereby the functional groups have the structure Le A 33 924-Foreign Countries -Sn-R
wherein R stands for a linear or branched C~-C36 alkyl radical, preferably a C, to C,g alkyl radical or a CS-C36, preferably a CS to Coo cycloalkyl radical, whereby the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally, may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C~-C~H, preferably C~-C~z carboxylic acid ester radicals, amino, C1-C~Z monoalkyl and dialkyl amino radicals and ammonium salts thereof, C,-C,Z trialkyl ammonium salts and by nitro groups or by halogen atoms; and further for a C6-C~2 aryl radical, C7-C36, preferably C~-C,g aralkyl radical, or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, whereby the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, carboxylic acid halide groups, C~-C~8 carboxylic acid ester groups, amino, C,-C,z monoalkyl and dialkylamino radicals and ammonium salts thereof, C~-C,Z trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from l, 2 or 3.
Preferred radicals for use as the radical R are those listed below by formulae:
S S
i~
N N ~ N
Le A 33 924-Foreign Countries CI
CI
CI
CIOC~ HOOCH HZSC~ZOOC~
H5C200C~ H»C800C~ HsCsOOC
CIOC~ HOOCH HSCZOOC~
HO~ HO
CI-The C=C double bond content of the rubber refers to the number of C=C groups as a percentage by weight relative to rubber.
The invention also provides a process for the manufacture of the functionalized iso-S olefin- and EPDM-rubbers with low double bond content, characterized in that a low double bond rubber with a double bond content of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, more preferably 0.05 to 3 wt.%, is reacted with 0.01 to 25 parts by weight, preferably 0.01 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of rubber, of a sulfenyl chloride with the following general formula X-S"-R
wherei n X stands for a halogen atom, preferably chlorine or bromine, and R and n have the meaning given for the functional groups listed above, at temperatures in the range from -120°C to +200°C.
The sulfenyl halides represented below by formulae are preferably used in the process according to the present invention:
S
/~--S-Hal ~ />-S-Hai I ~>-S-Hal N ~ N
~S~HaI ~SiHal /~SWHaI ~g~Hal S/Hal SiHal S ~H al S ~'H a( S-Hal \ , S-Hal CI3C~S~HaI
CIOC~S~HaI HOOC~S~Hai HZSC~ZOOC~S~HaI
Sw S
HSCZOOC~S~HaI HnCe00C~ Hal HSCsOOC~ ~Hal CIOC~S~HaI HO~~S~HaI HSCZOOC~S'-Hai HO~S~HaI /N~S,HaI
HO~S~HaI
Hal~
In the above formulae, the halogen (Hal) preferably denotes chlorine.
Le A 33 924-Foreign Countries The sulfenyl halides are manufactured by means of methods known per se, thus, for example, by reaction of disulfides with halogens, as described in US
2,257,974, or from mercaptans and halogens, see Liebigs Ann. Chem. 391, 57 (1912) in this respect, or from mercaptans and sulfur dichloride or disulfur dichloride, or by reaction of sulfenic acids, sulfenic acid esters or sulfenic acid amides with halogen halides, as described in Chem. Ber. 57, 755 (1924). The sulfenyl halides may also be manufactured in the presence of low double bond rubbers without isolating the sulfenyl halide, whereby optionally, the rubber is additionally halogenated with excess halogen.
The sulfenyl halides are reacted with the rubbers, in solid or dissolved state, at temperatures of preferably -30 to 150°C; the reaction is preferably performed in a solvent. Examples of suitable solvents include aliphatic or cycloaliphatic hydro-1 S carbons, such as butane, isobutane, pentane, hexane, cyclohexane, octane, isooctane, halogenated hydrocarbons, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, chloro-propane, chlorobutane, or chlorinated aromatic hydrocarbons, such as chlorobenzene.
The content of dissolved rubber lies in the range from 0.1 to approx. 40 wt.%, preferably 10 - 25 wt.%, and as a rule, the highest possible content is chosen for economic reasons.
The reaction of the low double bond rubbers with the sulfenyl halides is performed as an addition of a halogen atom and hydrolytically stable addition of the corresponding radicals to the double bonds. Depending on the type of rubber and the nature of the double bond, hydrogen halide may also be released during the course of the addition, such that double bonds re-form. The release of hydrogen halide may optionally, be promoted by the addition of acid scavengers and bases.
Preferred low double bond iso-olefin- and EPDM-rubbers that are reacted with the sulfenyl halides are:
-(A) Iso-olefin terpolymers consisting of iso-olefins having 4 to 16 carbon atoms, conjugated diolefins having 4 to 6 carbon atoms and optionally also mono- or polyunsaturated compounds having 2 to 20 carbon atoms, with a molecular weight of 10,000 to 3,000,000 g/mol, preferably 50,000 to 2,000,000 g/mol, and more preferably 100,000 to 1,000,000 g/mol, whereby the molar ratio of iso-olefins to diolefins to unsaturated organic compounds, made up to 100, is 50 to 99.5 : 0.5 to 20 : 0 to 30, preferably 80 to 99.5 : 0.5 to 10 : 0 to 20, and more preferably 90 to 99.5 : 0.~ to 10 : 0 to 10.
Preferred iso-olefins are isobutene, 2-methyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene and (3-pinene, particularly isobutene and 2-methyl-1-butene.
Preferred conjugated diolefins are isoprene, butadiene, 2,3-dimethyl butadiene, cyclopentadiene, methylcyclopentadiene, 1,3-cyclohexadiene, and more preferably isoprene.
Examples of mono- or polyunsaturated compounds include olefins and vinyl aromatics, preferably 1-olefins having 2 to 20 carbon atoms, such as ethene, propene, 1-butene, I-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 5-vinyl-2-norbornene, preferably ethene and propene, and vinyl aromatics, particularly styrene, p-methyl styrene, alpha-methyl styrene and vinyl naphthalene with styrene and p-methyl styrene being most preferred.
?~
Corresponding chlorinated and brominated rubbers with chlorine or bromine contents of 0.01 to ~ wt.%, preferably 0.1 to 3 wt.%, are also suitable.
Suitable terpolymers have a Mooney viscosity ML l+8 (125°C) of ~
to 200, 3u preferably ?0 to 100. See I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989, pages 168 to 180 in this respect. Most Le A 33 924-Foreign Countries _g_ preferred products of this nature are commercially available as butyl rubber, bromobutyl and chlorobutyl rubber (e.g. Polysar Butyl~ from Bayer AG).
(B) Ethylene/propylene/diene terpolymers (EPDM): these comprise rubbers in which the ratio by weight of ethylene to propylene monomer lies in the range 30:70 to 70:30 and which may display 1 to 20 C=C double bonds per 1000 carbon atoms. Examples of suitable dime monomers in EPDM include:
conjugated dimes, e.g. isoprene and butadiene-1,3, and non-conjugated dimes having 5 to 25 C atoms, e.g. 1,4-pentadiene, 1,4-hexadiene, 1,5-hexa-dime, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene; cyclic dimes, e.g.
cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene;
alkylidene and alkenyl norbornenes, e.g. 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-S-nor-bornene and tricyclodiene. The non-conjugated dimes hexadiene-1,5, ethylidene norbornene and dicyclopentadiene are preferred. The dime content in EPDM is preferably 0.5 to 10 wt.% relative to EPDM. Preferred products display Mooney viscosities ML 1+4 (125°C) of 10 to 200, preferably 15 to 100. See I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989, pages 131 to 143 in this respect. Such EPDM rubbers are commercially available (e.g. Buna EP from Bayer AG).
The polarity of the low double bond functionalized iso-olefin- and EPDM-rubbers according to the present invention is different from that of the starting polymers, and for such reason, they offer advantages in the manufacture of rubber mixtures with improved filler/rubber interaction, improved adhesion to reinforcing materials and improved compatibility with other polar rubbers, for example.
Suitable fillers for the rubber mixtures include all known fillers used in the rubber industry, including both active and inactive fillers.
The following are worthy of mention:
highly dispersed silicic acids, manufactured, for example, by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific S surface areas of S to 1000, preferably 20 to 400 m2/g (BET surface area) and with primary particle sizes of 10 to 400 nm. The silicic acids may optionally also take the form of mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides;
- synthetic silicates, such as ammonium silicate, alkaline-earth silicate such as magnesium silicate or calcium silicate, with BET surface areas of 20 to 400 m''/g and primary particle diameters of 10 to 400 nm;
- natural silicates such as kaolin and other naturally occurring silicic acid;
- glass fibers and Mass fiber products (mats, strands) or glass microbeads;
- metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide;
- metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate;
- metal hydroxides, such as aluminum hydroxide, magnesium hydroxide;
- carbon blacks. The carbon blacks for use in this context are produced using the lampblack, furnace black or channel black process and have BET surface areas of 20 to 200 my%g, e.g. SAf, ISAF, HAF, FEF or GPF carbon blacks;
;0 - rubber gels, particularly those based on polybutadiene, butadiene;styrene copolymers, butadiene/acrylonitrile copolymers and polychloroprene.
Highly dispersed silicic acids and/or carbon blacks are preferably used as fillers.
The rubber mixtures may contain, in addition to the low double bond functionalized iso-olefin- and EPDM-rubbers according to the present invention, other known rubbers. In addition to natural rubber, these are particularly synthetic rubbers.
Preferred synthetic rubbers are described by way of example in W. Hofinann, Kautschuktechnologie, Gentner Verlag, Stuttgart 1980, and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier, Amsterdam 1989. They include, inter alia ABR - butadiene/acrylic acid-C,-C4-alkylester copolymers ACM - polyacrylate rubber BR - polybutadiene CR - polychloroprene CM - chlorinated polyethylene CSM - chlorosulfonated polyethylene ECO - epichlorohydrin rubber EPDM - ethylene/propylene/diene terpolymer FKM - fluororubber IR - polyisoprene IIR - isobutylene/isoprene copolymers NBR - butadiene/acrylonitrile copolymers with acrylonitrile contents of 5-60, preferably 10-40 wt.%
HNBR - partially hydrogenated or fully hydrogenated NBR
rubber Q - silicone rubber SBR - styrene,~utadiene copolymers with styrene contents of 1-60, preferably ?0-~0 wt.,' together with mixtures of these rubbers.
Naturally, the rubber mixtures according to the present invention may also contain other rubber auxiliary substances, which promote the crosslinking of the vulcanizates produced from the rubber mixtures, for example, or which improve the physical Le A 33 924-Foreign Countries properties of the vulcanizates produced from the rubber mixtures according to the present invention for their particular intended application.
Sulfur or sulfur-yielding compounds can be used as crosslinking agents, for example, as can radical-yielding crosslinking agents such as organic peroxides.
Moreover, as S mentioned, the rubber mixtures according to the present invention may also contain further auxiliary substances, such as the known reaction accelerators, antioxidants, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides and activators.
The rubber auxiliary substances according to the present invention are used in the conventional, known quantities, whereby the quantity used is governed by the subsequent intended application of the rubber mixtures. Quantities of rubber auxiliary substances in the range from 2 to 70 parts by weight, relative to 100 parts 1 S by weight of rubber, are customary, for example.
The rubber mixtures may be produced, for example, by mixing the low double bond functionalized rubbers according to the invention with the appropriate fillers, optionally further rubbers and rubber auxiliary substances in suitable mixing devices, such as compounders, rolls or extruders.
The present invention also provides the use of the rubbers according to the present invention in the manufacture of vulcanizates, which, in turn, are used for the manufacture of rubber moldings, particularly for the manufacture of tires, e.g. tire inner tubes, tire treads, sidewalk and inner liners, as well as engineering rubber goods, e.g. bladders, hoses and rubberized fabric.
The functiona(ized low double bond iso-olefin- and EPDM-rubbers according to the present invention may, moreover, also be used in the manufacture of adhesives, sealants, paints and as rubber components in rubber/polymer blends.
Le A 33 924-Foreign Countries ~~rnr~rnT ~~
Example 1 Butyl rubber modified with 3.3 wt.% thiobenzothiazole groups 1.42 g chlorine was introduced into a suspension of 6.64 g dithiodibenzothiazole (Vulkacit DM, Bayer AG) in 80 ml dry chlorobenzene at 0°C, such that a clear orange-colored solution of mercaptobenzothiazole sulfene chloride was formed.
This solution was added at room temperature with agitation to a solution of 200 g butyl rubber Polysar Butyl 402 (isobutylene/isoprene terpolymer from Bayer AG
with 2.2 mol% isoprene incorporated by polymerization, corresponding to 0.9 wt.%
C=C double bond content) in 2 1 cyclohexane. After 4 hours of stirring at 80°C, the mercaptobenzothiazole sulfene chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 1 g Vulkanox BKF
(phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo at 70°C, 206 g of a light colored polymer with viscosity ML 1+4 (100°C) 50 was obtained.
In addition to the aliphatic protons in the butyl rubber, the 'H-NMR also displays signals for the aromatic protons in the mercaptobenzothiazole at 7.3 - 8 ppm and signals for olefinic protons at 5 - 5.2 ppm. Average molecular weight (M~,, determined by GPC): 382,000.
Elementary analysis: sulfur: 1.2 wt.%
nitrogen: 0.3 wt.%
chlorine: 0.22 Le A 33 924-Foreign Countries Example 2 EPDM rubber modified with 3.3 wt.% thiobenzothiazole groups 3.6 g chlorine was introduced into a suspension of 16.6 g dithiodibenzothiazole (Vulkacit DM, Bayer AG) in 100 ml dry chlorobenzene at 0°C, such that a clear orange-colored solution of mercaptobenzothiazole sulfene chloride was formed.
This solution was added at room temperature with agitation to a solution of 500 g Buna EP T 3950 (EPDM rubber from Bayer AG, with 56 wt.% ethylene content and 11 wt.% ENB content, corresponding to 2.2 wt.% C=C double bond content) in 4 1 cyclohexane. After 4 hours of stirnng at room temperature, the mercapto-benzothiazole sulfene chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 1 g Vulkanox BKF (phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo at 70°C, 516 g of a light colored polymer was obtained. ML 1+4 (100°C) 72.
Example 3 Butyl rubber modified with 2.4 wt.% 3-thiopropionic acid groups A solution of 16 g 3-chlorothiopropionic acid chloride (CAS-RN 14274-19-2) in 100 ml chlorobenzene was added at room temperature with agitation to a solution of 500 g butyl rubber Polysar Butyl 402 (isobutylene/isoprene terpolymer from Bayer AG with 2.2 mol% isoprene incorporated by polymerization, corresponding to 0.9 wt.% C=C double bond content) in 4 1 cyclohexane. After 4 hours of stirring, the 3-chlorothiopropionic acid chloride had been completely reacted and the pale yellow color of the solution was discolored. After addition of 100 g water and 1 g Vulkanox BKF (phenolic antioxidant from Bayer AG), the rubber was recovered by means of steam distillation. After drying in vacuo ax 70°C, S 16 g of a light colored polymer with viscosity ML 1+4 (100°C) 50 was obtained.
Example 4 Butyl rubber modified with 1 wt.% 3-thiopropionic acid groups.
According to the procedure of example 3 7.95 g (0.05 mol) 3-chloropropionic acid chloride was reacted with X00 g butyl nzbber Polysar Butyl 402. X06 g light coloured butyl rubber were obtained with viscosity ML 1+4 (100°C) 79 and sulfur content 0.35 wt.%.
Example ~
The following substances were mixed in a 1.~ liter kneader (speed of rotation 70 rpm;
filling ratio 65%, initial temperature 50°C, duration 5 minutes). The mixture was subsequently removed and sulfur and accelerator were admixed on a roller at a roller temperature of 40°C:
Mixture of Constituents Comparison Example 4.A
the following were mixed in the 1.~ 1 kneader:
butyl rubber Polysar Butyl 402 (Bayer) 30 0 functionalized butylrubber according to example 4 0 30 natural rubber TSR ~ 70 70 carbon black Corax N 339 (Degussa) ~0 ~0 stearic acid 2 zinc oxide RS (Bayer AG) > >
anti ageing agent Vulkanox -X020 ( Bayer) l.p 1.~
anti a~ein~ went Vulkanox HS (Bayer ) 1 1 the following were admixed on a roller.
sulfenamide accelerator Vuikacit CZ (Bayer) 1.4 i.4 sulfur 1.2 1.2 mixture viscosity ML 1+4 (100°C) 83 91 The mixture were subsequently vulcanised at 160°C . Vulcanisation time 10 minutes.
Properties of the vulcanites: Comparison Example 4.A
stress at 300% elongation (MPa) 14.2 14.8 tensile strength (MPa) 18 22.1 elongation at break (%) 380 440 hardness at 23C (Shore A) 69 68 rebound resilience at 23C (%) 28 28 tear resistance DIN 5351 (N/mm) 15.3 5~
abrasion (DIN ~3 516) 141 126 The test results verified the enhanced level of the mechanic properties of the rubber vulcanisates according to the invention containing functionalized butyl rubber, especially the higher tensile strength and higher tear resistance and improved abrasion resistance.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
CLAIMS:
I. Functionalized low double bond iso-olefin- and BPDM-rubbers with a double bond content of 0.001 to 10 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl soups of 0.01 to 25 wt_%, wherein the functional groups have the structure -S~-R
wherein R stands for a linear or branched C,-C;6 alkyl radical or a C_-C;6 cycloalkyi radical. wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl. carboxylate ~rouos. by lj carboxylic acid halide radicals, by C,-C,s carboxylic acid ester radicals. amino. C;-Ci2 monoalkyl and dialkyl amino radicals and ammonium salts thereof. C~-C,Z triallcyl ammonium salts and by vitro groups or by halogen atoms, and further for a C5-C ~ Z aryl radical, C~-C;6 aralkyl radical or a mono-, di- or tticyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may Likewise be substituted by hydroxyl groups, carboxyl soups, carboxylate groups, C_-C=6 carboxylic acid halide groups, Ci-C18 carboxylic acid ester groups, amino, C1-C1~ monoalkyl and dialkylamino radicals and ammonium salts thereof, C:-C12 trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, ? or 3.
;0 ?. Process for the manutacture of functionaiized low double bond iso-oletin-and EPDM-rubbers according to claim 1, according to which rubber with a double _ 17-bond content of 0.001 to 10' wt.% is reacted with 0.01 to 25 parts by weight, relative to 100 parts by weight of rubber, of sulfenyl chloride with the following general formula X-Sn-R
j where X stands for a halogen atom and R stands for a linear or branched Cl-C36 alkyl radical or a C;-C36 i0 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl. carboxytate groups. by carboxylic acid halide radicals. by Cv-C,s carboxylic acid ester radicals. amino, C,-C,~ monoalkyi and dialkyl amino radicals and 15 ammonium salts thereof, C~-C,: trialkyl ammonium salts and by vitro soups or by halogen atoms, and further for a Co-Cn aryl radical, C~-C;6 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups. carboxyl soups. carboxyiate groups, C-,-Cla carboxylic acid halide groups, C=-C16 carboxylic acid ester groups, amino, C.:-C1~ monoalkyl and dialkvlamino radicals and ammonium salts thereof, C=-C<< trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from I. ? or ~.
at temperatures in the range from -l?0°c to - 200°C.
3. Rubber vulcanizates comprising functionalized low double bond iso-olefin-or EPD~f-rubbers with a double bor:d content of 0.001 to 10 wt.°. o and a content -LS-of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S~-R
where R stands for a linear or branched C,-C36 alkyl radical or a C;-C36 cycloallcyl radical, wherein the hydrocarbon chains may be intemtpted by one or more oxygen. sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate soups, by carboxylic acid halide radicals. by C,-C,g carboxylic acid ester radicals, amino, C,-C,~ monoalkyi and dialkyl amino radicals and ammonium salts thereof, C.-C,, trialkyl ammonium salts and by nitro groups or by halogen atoms. and further for a Cti-C i ~ aryl : a.dical, C~-C;6 aralkyl radical or a mono-. di- or tricyciic heterocyclic radical with 1~ nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hvdroxv_ 1 groups. carboxyl groups, carboxylate soups, C1-C16 carboxylic acid halide groups, C1-C1~ carboxylic acid ester groups, amino, C-_-C-;~ monoalkyl and dialkylamino radicals and ammonium salts thereof, '0 C,-C1~ trialkyl ammonium salts, vitro groups and by halogen. atoms, and ' n stands for a whole number selected from 1, ? or ~.
?5 4. Rubber molding comprising functionalized low double bond iso-olefin- or EPDM-rubbers with a double bond content of 0.001 to 10 wt.°,% and a content of hydrolyticallv stable functional groups not bonded by means of benzyi soups of 0.01 to -~ wt.°%, wherein the functional groups have the structure -Sn-R
where R. stands for a linear or branched C~-C36 alkyl radical or a CS-C3s cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C i-C ~ $ carboxylic acid ester radicals, amino, C 1-C 12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C,-C,z trialkyl ammonium salts and by vitro groups or by halogen atoms, and further for a C6-C 1 z aryl radical, CrC;6 aralkyl radical or a mono-, di- or tricyciic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, ara.llcyl radicals and the heterocyciic radicals may likewise be substituted by hydroxyl soups, carboxyl soups, carboxylate groups, C, -C1a carboxylic acid halide groups , C1-C18 carboxyl is acid ester groups, amino, C:-ClZ monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C1z trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
Fetherstonhaugh & Co.
Ottawa, Canada Patent Agents
Claims (4)
1. Functionalized low double bond iso-olefin- and EPDM-rubbers with a double bond content of 0.001 to 10 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S n - R
wherein R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals amino C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
wherein R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals amino C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
2. Process for the manufacture of functionalized low double bond iso-olefin- and EPDM-rubbers according to claim 1, according to which rubber with a double bond content of 0.001 to 10 wt.% is reacted with 0.01 to 25 parts by weight, relative to 100 parts by weight of rubber, of sulfenyl chloride with the following general formula X - S n - R
where x stands for a halogen atom and R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3, at temperatures in the range from -120°C to +200°C.
where x stands for a halogen atom and R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3, at temperatures in the range from -120°C to +200°C.
3. Rubber vulcanizates comprising functionalized low double bond iso-olefin- or EPDM-rubbers with a double bond content of 0.001 to l0 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S n - R
where R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C1-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from, 1, 2 or 3.
where R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by nitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C1-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, nitro groups and by halogen atoms, and n stands for a whole number selected from, 1, 2 or 3.
4. Rubber molding comprising functionalized low double bond iso-olefin- or EPDM-rubbers with a double bond content of 0.001 to 10 wt.% and a content of hydrolytically stable functional groups not bonded by means of benzyl groups of 0.01 to 25 wt.%, wherein the functional groups have the structure -S n - R
where R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by vitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
where R stands for a linear or branched C1-C36 alkyl radical or a C5-C36 cycloalkyl radical, wherein the hydrocarbon chains may be interrupted by one or more oxygen, sulfur or nitrogen atoms and additionally may be substituted by hydroxyl, carboxyl, carboxylate groups, by carboxylic acid halide radicals, by C1-C18 carboxylic acid ester radicals, amino, C1-C12 monoalkyl and dialkyl amino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts and by vitro groups or by halogen atoms, and further for a C6-C12 aryl radical, C7-C36 aralkyl radical or a mono-, di- or tricyclic heterocyclic radical with nitrogen, oxygen and sulfur as heteroatoms, wherein the aryl radicals, aralkyl radicals and the heterocyclic radicals may likewise be substituted by hydroxyl groups, carboxyl groups, carboxylate groups, C1-C18 carboxylic acid halide groups, C1-C18 carboxylic acid ester groups, amino, C1-C12 monoalkyl and dialkylamino radicals and ammonium salts thereof, C1-C12 trialkyl ammonium salts, vitro groups and by halogen atoms, and n stands for a whole number selected from 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19938859A DE19938859A1 (en) | 1999-08-17 | 1999-08-17 | Functionalized double-bond rubbers |
| DE19938859.8 | 1999-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2316002A1 true CA2316002A1 (en) | 2001-02-17 |
Family
ID=7918592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002316002A Abandoned CA2316002A1 (en) | 1999-08-17 | 2000-08-14 | Functionalized low double bond rubbers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1077222A1 (en) |
| JP (1) | JP2001072712A (en) |
| CA (1) | CA2316002A1 (en) |
| DE (1) | DE19938859A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE50007804D1 (en) * | 2000-12-11 | 2004-10-21 | Roth Werke Gmbh | Compatible plastic mixture and manufacturing process |
| WO2004020475A1 (en) * | 2002-08-30 | 2004-03-11 | Bridgestone Corporation | Functionalized polymers and improved vulcanizates therefrom |
| JP2007039500A (en) * | 2005-08-01 | 2007-02-15 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire using the rubber composition for air permeation-preventing layer |
| JP5574644B2 (en) * | 2009-09-04 | 2014-08-20 | 三井化学株式会社 | Release agent, resin composition, and resin molded body |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2257974A (en) * | 1939-06-22 | 1941-10-07 | Us Rubber Co | Thiazyl sulphur halide |
| US2417093A (en) * | 1941-09-06 | 1947-03-11 | Jasco Inc | Sulfurized, milled, and cured polymer |
| GB842557A (en) * | 1956-07-16 | 1960-07-27 | Exxon Research Engineering Co | Chemical modification of isoolefin-multiolefin copolymers |
| NL239215A (en) * | 1958-05-19 | |||
| GB1420297A (en) * | 1974-03-08 | 1976-01-07 | Du Pont | Copolymers |
| US4340694A (en) * | 1978-02-02 | 1982-07-20 | Exxon Research & Engineering Co. | Crosslinking and chemical modification agents for olefin containing polymers |
| CH652729A5 (en) * | 1982-04-28 | 1985-11-29 | Ciba Geigy Ag | LIGHT CROSSLINKABLE POLYMERS WITH SIDE-SIDED THIOAETHERIMIDYL GROUPS. |
| FR2647796B1 (en) * | 1989-05-31 | 1991-09-13 | Bp Chem Int Ltd | PROCESS FOR THE MANUFACTURE OF NEW POLYMERS COMPRISING CHAINS DERIVED FROM A POLYBUTENE |
-
1999
- 1999-08-17 DE DE19938859A patent/DE19938859A1/en not_active Ceased
-
2000
- 2000-08-04 EP EP00116218A patent/EP1077222A1/en not_active Withdrawn
- 2000-08-14 CA CA002316002A patent/CA2316002A1/en not_active Abandoned
- 2000-08-17 JP JP2000247506A patent/JP2001072712A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1077222A1 (en) | 2001-02-21 |
| DE19938859A1 (en) | 2001-02-22 |
| JP2001072712A (en) | 2001-03-21 |
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