CA2339080C - Filled elastomeric butyl compounds - Google Patents
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- CA2339080C CA2339080C CA002339080A CA2339080A CA2339080C CA 2339080 C CA2339080 C CA 2339080C CA 002339080 A CA002339080 A CA 002339080A CA 2339080 A CA2339080 A CA 2339080A CA 2339080 C CA2339080 C CA 2339080C
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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Abstract
The invention provides a process for preparing a filled halobutyl elastomer, which comprises mixing a halobutyl elastomer, particles of filler and an additive containing both amino and alcohol functional groups, and curing the filled elastomer wi th sulfur or other curative systems. This invention has the advantages of (a) not evolvin g alcohol either during the manufacture or subsequent use of the article manufactured from the compound, and (b) significantly reducing the cost of the compound.
Description
MAR 02 '01 16:25 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.04i24 FILLED ELASTOMERIC BUTYL COMPOUNDS
Field of the Invention:
The present invention relates to haiogenated butyl elastomers, in particular bromobutyl elastomers.
Background of the invention:
z o It is known that reinforcing fillers such as carbon black and silica greatly improve the strength and fatigue properties of elastomeric compounds. It is also known that chemical interaction occurs between the elastomer and the filler. For example, good interaction between carbon black and highly unsaturated elastomers such as polybutadiene (BR) and styrene butadiene copolymers (SBR) occurs because of the is large number of carbon-carbon double bonds present in these copolymers.
Butyl eiastomers may have only one tenth, or fewer, of the carbon-carbon double bonds found in BR or SBR, and compounds made from butyl elastomers are known to interact poorly with carbon black. For example, a compound prepared by mixing carbon black with a combination of BR and butyl elastomers results in domains of BR, which contain 20 most of the carbon black, and butyl domains which contain very little carbon black. It is also known that butyl compounds have poor abrasion resiss,tance.
Canadian Patent Application 2,293,149 shows that it is possible to produce filled butyl elastomer compositions with much improved properties by combining halobutyl 25 elastomers with silica and specific silanes. These silanes act as dispersing and bonding agents between the halogenated butyl elastomer and the filler. However, one disadvantage of the use of silanes is the evolution of af'cohol during the process of manufacture and potentially during the use of the manufacitured article produced by this process. Additionally, silanes significantly increase the cost of the resulting 30 manufactured article_ Summarv of the tnvention:
The present invention provides a process for preparing compositions containing 35 halobutyl elastomers in which there is enhanced interactioni between the elastomer and . _.._.. . . ...__ ' _._ _ .__...__.. III
MAR 02 '01 16:25 FR BAYER LAW & PATENT5.0416 240 5426 ,F0 918199539538 P.05/24 a filler, especially a mineral filler. The invention also provides filled halobutyl elastomer compositions which have improved properties when compared to known carbon black-filled hafobutyl elastomeric compositions. In particular it provides a means to produce such filled compositions without the evolution of alcohol, and at significantly reduced cost, compared to processes known in the art.
Surprisingly, it has been discovered that certain organic compounds containing at feast one basic nitrogen-containing group and at least one hydroxyl group enhance the interaction of halobutyl elastomers with mineral fillers, resulting in improved compound io properties such as tensile strength and abrasion (Ql1N). Of particular interest are compounds containing primary amine and hydroxyl groups such as ethanolamine.
These organic compounds are believed to disperse and bond the silica to the halogenated elastomers.
t5 Accordingly, in one aspect the present invention provides a process which comprises mixing a halobutyl elastomer with a filler, especiaEly a mineral filler, in the presence of an additive which is an organic compound which has at least one hydroxyl group and at least one basic nitrogen-containing group, and curing the resulting filled halobutyl efastomer. The resulting composition, having improved properties, forms another 2o aspect of the invention.
The halobutyl elastomer that is admixed with the filler and the silane may be a mixture with another elastomer or elastomeric compound. The halobutyl elastomer should constitute more than 5% of any such mixture. Preferably the halobutyl elastomer should 25 constitute at least 10% of any such mixture. In some cases it is preferred not to use mixtures but to use the halobutyl elastomer as the sole elastomer. If mixtures are to be used, however, then the other elastomer may be, for example, natural rubber, polybutadiene, styrerte-butadiene or poly-chloroprene or an elastomer compound containing one or more of these elastomers.
The filled halobutyl elastomer can be cured to obtain a product which has improved properties, for instance in abrasion resistance, rolling resistance and traction. Curing can be effected with sulfur. The preferred amount of suilfur is form about 0.3 to about
Field of the Invention:
The present invention relates to haiogenated butyl elastomers, in particular bromobutyl elastomers.
Background of the invention:
z o It is known that reinforcing fillers such as carbon black and silica greatly improve the strength and fatigue properties of elastomeric compounds. It is also known that chemical interaction occurs between the elastomer and the filler. For example, good interaction between carbon black and highly unsaturated elastomers such as polybutadiene (BR) and styrene butadiene copolymers (SBR) occurs because of the is large number of carbon-carbon double bonds present in these copolymers.
Butyl eiastomers may have only one tenth, or fewer, of the carbon-carbon double bonds found in BR or SBR, and compounds made from butyl elastomers are known to interact poorly with carbon black. For example, a compound prepared by mixing carbon black with a combination of BR and butyl elastomers results in domains of BR, which contain 20 most of the carbon black, and butyl domains which contain very little carbon black. It is also known that butyl compounds have poor abrasion resiss,tance.
Canadian Patent Application 2,293,149 shows that it is possible to produce filled butyl elastomer compositions with much improved properties by combining halobutyl 25 elastomers with silica and specific silanes. These silanes act as dispersing and bonding agents between the halogenated butyl elastomer and the filler. However, one disadvantage of the use of silanes is the evolution of af'cohol during the process of manufacture and potentially during the use of the manufacitured article produced by this process. Additionally, silanes significantly increase the cost of the resulting 30 manufactured article_ Summarv of the tnvention:
The present invention provides a process for preparing compositions containing 35 halobutyl elastomers in which there is enhanced interactioni between the elastomer and . _.._.. . . ...__ ' _._ _ .__...__.. III
MAR 02 '01 16:25 FR BAYER LAW & PATENT5.0416 240 5426 ,F0 918199539538 P.05/24 a filler, especially a mineral filler. The invention also provides filled halobutyl elastomer compositions which have improved properties when compared to known carbon black-filled hafobutyl elastomeric compositions. In particular it provides a means to produce such filled compositions without the evolution of alcohol, and at significantly reduced cost, compared to processes known in the art.
Surprisingly, it has been discovered that certain organic compounds containing at feast one basic nitrogen-containing group and at least one hydroxyl group enhance the interaction of halobutyl elastomers with mineral fillers, resulting in improved compound io properties such as tensile strength and abrasion (Ql1N). Of particular interest are compounds containing primary amine and hydroxyl groups such as ethanolamine.
These organic compounds are believed to disperse and bond the silica to the halogenated elastomers.
t5 Accordingly, in one aspect the present invention provides a process which comprises mixing a halobutyl elastomer with a filler, especiaEly a mineral filler, in the presence of an additive which is an organic compound which has at least one hydroxyl group and at least one basic nitrogen-containing group, and curing the resulting filled halobutyl efastomer. The resulting composition, having improved properties, forms another 2o aspect of the invention.
The halobutyl elastomer that is admixed with the filler and the silane may be a mixture with another elastomer or elastomeric compound. The halobutyl elastomer should constitute more than 5% of any such mixture. Preferably the halobutyl elastomer should 25 constitute at least 10% of any such mixture. In some cases it is preferred not to use mixtures but to use the halobutyl elastomer as the sole elastomer. If mixtures are to be used, however, then the other elastomer may be, for example, natural rubber, polybutadiene, styrerte-butadiene or poly-chloroprene or an elastomer compound containing one or more of these elastomers.
The filled halobutyl elastomer can be cured to obtain a product which has improved properties, for instance in abrasion resistance, rolling resistance and traction. Curing can be effected with sulfur. The preferred amount of suilfur is form about 0.3 to about
2.0 parts by weight per hundred parts of rubber. An acl:ivator, for example zinc oxide, may also be used, in an amount of from about 5 parts to about 2 parts by weight. Other ingredients, for instance stearic acid, antioxidants, or accelerators may also be added to the elastomer prior to curing. Sulphur curing is then effected in known manner. See, for instance, chapter 2, "The Compounding and Vulcanization of Rubber", of "Rubber Technology", 3'd edition, published by Chapman & Hall, 1995.
Other curatives known to cure halobutyl elastomers may also be used. A number of compounds are known to cure BIIR, for example, such as bis dienophiles (for example HVA2) phenolic resins, amines, amino-acids, peroxides, zinc oxide and the like.
Combinations of the aforementioned curatives may also be used.
The mineral-filled halobutyl elastomer of the invention can be admixed with other elastomers or elastomeric compounds before it is subjected to the curing with sulphur.
This is discussed further below.
Detailed Description of the Invention The phrase "halobutyl efastomer(s)" as used herein refers to a chlorinated or brominated butyl elastomer. Brominated butyl elastomers are preferred and the invention is illustrated, by way of example, with reference to such bromobutyl elastomers. It should be understood, however, that the invention extends to the use of chlorinated butyl elastomers.
Thus, halobutyl elastomers suitable for use in the practice of this invention include, but are not limited to, brominated butyl elastomers. Such elastomers may be obtained by bromination of butyl rubber (which is a copolymer of isobutylene and a co-monomer that is usually a C4 to C6 conjugated diolefin, preferably isoprene). Co-monomers other than conjugated diolefins can be used, however, and mention is made of alkyl-substituted vinyl aromatic co-monomers such as C1-C4-alkyl substituted styrene. An example of such an 3o elastomer which is commercially available is brominated isobutylene methylstyrene copolymer (BIMS) in which the co-monomer is p-methylstyrene.
Brominated butyl elastomer typically contains from about 1 to about 3 weight percent of isoprene and from about 97 to about 99 weight percent of isobutylene (based upon the
Other curatives known to cure halobutyl elastomers may also be used. A number of compounds are known to cure BIIR, for example, such as bis dienophiles (for example HVA2) phenolic resins, amines, amino-acids, peroxides, zinc oxide and the like.
Combinations of the aforementioned curatives may also be used.
The mineral-filled halobutyl elastomer of the invention can be admixed with other elastomers or elastomeric compounds before it is subjected to the curing with sulphur.
This is discussed further below.
Detailed Description of the Invention The phrase "halobutyl efastomer(s)" as used herein refers to a chlorinated or brominated butyl elastomer. Brominated butyl elastomers are preferred and the invention is illustrated, by way of example, with reference to such bromobutyl elastomers. It should be understood, however, that the invention extends to the use of chlorinated butyl elastomers.
Thus, halobutyl elastomers suitable for use in the practice of this invention include, but are not limited to, brominated butyl elastomers. Such elastomers may be obtained by bromination of butyl rubber (which is a copolymer of isobutylene and a co-monomer that is usually a C4 to C6 conjugated diolefin, preferably isoprene). Co-monomers other than conjugated diolefins can be used, however, and mention is made of alkyl-substituted vinyl aromatic co-monomers such as C1-C4-alkyl substituted styrene. An example of such an 3o elastomer which is commercially available is brominated isobutylene methylstyrene copolymer (BIMS) in which the co-monomer is p-methylstyrene.
Brominated butyl elastomer typically contains from about 1 to about 3 weight percent of isoprene and from about 97 to about 99 weight percent of isobutylene (based upon the
3 hydrocarbon content of the polymer) and from about 1 to about 4 weight percent bromine (based upon the bromobutyl polymer). A typical bromobutyl polymer has a molecular weight, expressed as the Mooney viscosity (ML 1+ 8 at 125 C), of from about 28 to about 55.
For use in the present invention the brominated butyl elastomer preferably contains from about 1 to about 2 weight percent of isoprene and from about 98 to about 99 weight percent of isobutylene (based upon the hydrocarbon content of the polymer) and from about 0.5 to about 2.5 weight percent, preferably from about 0.75 to about 2.3 weight io percent, of bromine (based upon the brominated butyl polymer).
A stabilizer may be added to the brominated butyl elastomer. Suitable stabilizers include calcium stearate and epoxidized soybean oil, preferably used in an amount of from about 0.5 to about 5 parts by weight per 100 parts by weight of the brominated butyl rubber.
Examples of suitable brominated butyl elastomers include Bayer Bromobutyl 2030, Bayer Bromobutyl 2040 (BB2040), and Bayer Bromobutyl X2 commercially available from Bayer. Bayer BB2040 has a Mooney viscosity (RPML 1+8 @ 125 C) of 39 4, a bromine content of 2.0 0.3 wt% and an approximate molecular weight of 500,000 grams per mole.
The brominated butyl elastomer used in the process of this invention may also be a graft copolymer of a brominated butyl rubber and a polymer based upon a conjugated diolefin monomer. Our co-pending Canadian Patent Application 2,279,085 is directed towards a process for preparing such graft copolymers by mixing solid brominated butyl rubber with a solid polymer based on a conjugated diolefin monomer which also includes some C-S-(S)n-C bonds, where n is an integer from 1 to 7, the mixing being carried out at a temperature greater than about 50 C and for a time sufficient to cause grafting. The 3o bromobutyl elastomer of the graft copolymer can be any of those described above. The conjugated diolefins that can be incorporated in the graft copolymer generally have the structural formula :
RI Ri I
R - CH=C - C=CHZ
For use in the present invention the brominated butyl elastomer preferably contains from about 1 to about 2 weight percent of isoprene and from about 98 to about 99 weight percent of isobutylene (based upon the hydrocarbon content of the polymer) and from about 0.5 to about 2.5 weight percent, preferably from about 0.75 to about 2.3 weight io percent, of bromine (based upon the brominated butyl polymer).
A stabilizer may be added to the brominated butyl elastomer. Suitable stabilizers include calcium stearate and epoxidized soybean oil, preferably used in an amount of from about 0.5 to about 5 parts by weight per 100 parts by weight of the brominated butyl rubber.
Examples of suitable brominated butyl elastomers include Bayer Bromobutyl 2030, Bayer Bromobutyl 2040 (BB2040), and Bayer Bromobutyl X2 commercially available from Bayer. Bayer BB2040 has a Mooney viscosity (RPML 1+8 @ 125 C) of 39 4, a bromine content of 2.0 0.3 wt% and an approximate molecular weight of 500,000 grams per mole.
The brominated butyl elastomer used in the process of this invention may also be a graft copolymer of a brominated butyl rubber and a polymer based upon a conjugated diolefin monomer. Our co-pending Canadian Patent Application 2,279,085 is directed towards a process for preparing such graft copolymers by mixing solid brominated butyl rubber with a solid polymer based on a conjugated diolefin monomer which also includes some C-S-(S)n-C bonds, where n is an integer from 1 to 7, the mixing being carried out at a temperature greater than about 50 C and for a time sufficient to cause grafting. The 3o bromobutyl elastomer of the graft copolymer can be any of those described above. The conjugated diolefins that can be incorporated in the graft copolymer generally have the structural formula :
RI Ri I
R - CH=C - C=CHZ
4 MAR 02 '01 16:26 FR BAYER LAW & PATENTS 0416 240 5426 T'0 918199539538 P.08/24 wherein R is a hydrogen atom or an alkyl group containing from 'f to 8 carbon atoms and wherein R1 and Ri 1 can be the same or different and are selected from the group consisting of hydrogen atoms and alkyl groups containing from I to 4 carbon atoms.
Some representative non-limiting examples of suitable conjugated diolefins include 1,3-butadiene, isoprene, 2-methyl-1,3-pentadiene, 4-butyl-1 õ3-pentadiene, 2,3-dimethyl-1,3-pentadiene 1,3-hexadiene, 1,3-octadiene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene and the like. Conjugated diolefin monomers containing from 4 to 8 carbon atoms are preferred, 1,3-butadiene and isoprene being jo especially preferred.
The polymer based on a conjugated diene monomer can be a homopolymer, or a copolymer of two or more conjugated diene monomers, or a copolymer with a vinyl aromatic monomer.
is The vinyl aromatic monomers which can optionally be used are selected so as to be copolymerizable with the conjugated diolefin monomers being employed.
Generally, any vinyl aromatic monomer which is known to polymerize with organo-alkali metal initiators can be used_ Such vinyi aromatic monomers usually contain from 8 to zo carbon atoms, preferably from 8 to 14 carbon atoms. Soime examples of vinyl aromatic monomers which can be so co-polymerized include styrene, alpha-methyl styrene, various alkyl styrenes including p-methylstyrene, p-methoxy styrene, 1-vinyinaphthalene, 2-vinyl naphthalene, 4-vinyl toluene ancl the like. Styrene is preferred for copolymerization with 1,3-butadiene alone or for terpolymerization with both 1,3-25 butadiene and isoprene.
The filler is composed of particles of a mineral, and exaimples include silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and the like, as well as mixtures thereof. These mineral particles have hydroxyl groups on their surface, 3o rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the butyl eiastomer_ For many purposes, the preferred mineral is silica, especially silica prepared by the carbon dioxide precipitation of sodium silicate.
Some representative non-limiting examples of suitable conjugated diolefins include 1,3-butadiene, isoprene, 2-methyl-1,3-pentadiene, 4-butyl-1 õ3-pentadiene, 2,3-dimethyl-1,3-pentadiene 1,3-hexadiene, 1,3-octadiene, 2,3-dibutyl-1,3-pentadiene, 2-ethyl-1,3-pentadiene, 2-ethyl-1,3-butadiene and the like. Conjugated diolefin monomers containing from 4 to 8 carbon atoms are preferred, 1,3-butadiene and isoprene being jo especially preferred.
The polymer based on a conjugated diene monomer can be a homopolymer, or a copolymer of two or more conjugated diene monomers, or a copolymer with a vinyl aromatic monomer.
is The vinyl aromatic monomers which can optionally be used are selected so as to be copolymerizable with the conjugated diolefin monomers being employed.
Generally, any vinyl aromatic monomer which is known to polymerize with organo-alkali metal initiators can be used_ Such vinyi aromatic monomers usually contain from 8 to zo carbon atoms, preferably from 8 to 14 carbon atoms. Soime examples of vinyl aromatic monomers which can be so co-polymerized include styrene, alpha-methyl styrene, various alkyl styrenes including p-methylstyrene, p-methoxy styrene, 1-vinyinaphthalene, 2-vinyl naphthalene, 4-vinyl toluene ancl the like. Styrene is preferred for copolymerization with 1,3-butadiene alone or for terpolymerization with both 1,3-25 butadiene and isoprene.
The filler is composed of particles of a mineral, and exaimples include silica, silicates, clay (such as bentonite), gypsum, alumina, titanium dioxide, talc and the like, as well as mixtures thereof. These mineral particles have hydroxyl groups on their surface, 3o rendering them hydrophilic and oleophobic. This exacerbates the difficulty of achieving good interaction between the filler particles and the butyl eiastomer_ For many purposes, the preferred mineral is silica, especially silica prepared by the carbon dioxide precipitation of sodium silicate.
5 Dried amorphous silica particles suitable for use in accordance with the invention have a mean agglomerate particle size between 1 and 100 microns, preferably between 10 and 50 microns and most preferably between 10 and 25 microns. It is preferred that less than percent by volume of the agglomerate particles are below 5 microns or over 50 microns 5 in size. A suitable amorphous dried silica moreover has a BET surface area, measured in accordance with DIN (Deutsche Industrie Norm) 66131, of between 50 and 450 square meters per gram and a DBP absorption, as measured in accordance with DIN
53601, of between 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight. Suitable silica fillers are to available under the trademarks HiSiITM 210, HiSiIT"' 233 and HiSiITM 243 from PPG
Industries Inc. Also suitable are VulkasilTM S and VulkasilT"' N, from Bayer AG.
The additive contains at least one hydroxyl group, which (without being bound to any particular theory) may react with the mineral filler, and at least one group containing a basic nitrogen atom, which (without being similarly bound) may react with the active halogen in a halogenated butyl elastomer (for example with the active bromine atom in a brominated butyl elastomer). Functional groups containing -OH may be, for example, alcohols or carboxylic acids. Functional groups containing a basic nitrogen atom include, but are not limited to, amines (which can be primary, secondary or tertiary) and amides. Preferred are primary alkyl amine groups such as aminoethyl, aminopropyl and the like.
Examples of additives which give enhanced physical properties to mixtures of halobutyl elastomers and silica include proteins, aspartic acid, 6-aminocaproic acid, diethanolamine and triethanolamine. Preferably, the additive should contain a primary alcohol group and a primary amino group separated by methylene bridges, which may be branched.
Such compounds have the general formula HO-A-NH2; wherein A represents a Cl to C20 alkylene group, which may be linear or branched.
More preferably, the number of methylene groups between the two functional groups should be between 1 and 4. Examples of preferred additives include monoethanolamine and 3-amino-1-propanol.
53601, of between 150 and 400 grams per 100 grams of silica, and a drying loss, as measured according to DIN ISO 787/11, of from 0 to 10 percent by weight. Suitable silica fillers are to available under the trademarks HiSiITM 210, HiSiIT"' 233 and HiSiITM 243 from PPG
Industries Inc. Also suitable are VulkasilTM S and VulkasilT"' N, from Bayer AG.
The additive contains at least one hydroxyl group, which (without being bound to any particular theory) may react with the mineral filler, and at least one group containing a basic nitrogen atom, which (without being similarly bound) may react with the active halogen in a halogenated butyl elastomer (for example with the active bromine atom in a brominated butyl elastomer). Functional groups containing -OH may be, for example, alcohols or carboxylic acids. Functional groups containing a basic nitrogen atom include, but are not limited to, amines (which can be primary, secondary or tertiary) and amides. Preferred are primary alkyl amine groups such as aminoethyl, aminopropyl and the like.
Examples of additives which give enhanced physical properties to mixtures of halobutyl elastomers and silica include proteins, aspartic acid, 6-aminocaproic acid, diethanolamine and triethanolamine. Preferably, the additive should contain a primary alcohol group and a primary amino group separated by methylene bridges, which may be branched.
Such compounds have the general formula HO-A-NH2; wherein A represents a Cl to C20 alkylene group, which may be linear or branched.
More preferably, the number of methylene groups between the two functional groups should be between 1 and 4. Examples of preferred additives include monoethanolamine and 3-amino-1-propanol.
6 The amount of filler to be incorporated into the halobutyl elastomer can vary between wide limits. Typical amounts of filler range from about 20 parts to about 120 parts by weight, preferably from about 30 parts to about 100 parts, more preferably from about 40 to about 80 parts per hundred parts of elastomer. The amount of the additive used is dependent upon the molecular/equivalent weight of each specific compound. One important factor is the number/weight of nitrogen per unit weight of the compound. The level of nitrogen may range from about 0.1 to about 5 parts per hundred (phr) of halobutyl rubber, preferably from about 0.125 to about 1 phr and, more preferably, from about 0.3 to about 0.7 phr. Up to about 40 parts of processing oil, preferably from about io 5 to about 20 parts, per hundred parts of elastomer, may be present.
Further, a lubricant, for example a fatty acid such as stearic acid, may be present in an amount up to about 3 parts by weight, more preferably in an amount up to 2 parts by weight.
Carbon black is not normally used as a filler in the halobutyl elastomer compositions of the invention, but in some embodiments it may be present in an amount up to about 40 phr. If the mineral filler is silica and it is used with carbon black, the silica should constitute at least 55% by weight of the total of silica and carbon black. If the halobutyl elastomer composition of the invention is blended with another elastomeric composition, that other composition may contain carbon black as a filler.
The halobutyl elastomer, filler and additive are mixed together, suitably at a temperature in the range of from about 25 to about 200 C. It is preferred that the temperature in one of the mixing stages be greater than about 60 C, and a temperature in the range of from about 90 to about 150 C is particularly preferred. Normally the mixing time does not exceed about one hour; a time in the range from about 2 to 30 minutes is usually adequate. The mixing is suitably carried out on a two-roll mill mixer, which provides good dispersion of the filler within the elastomer. Mixing may also be carried out in a BanburyTM mixer, or in a HaakeTM or BrabenderTM miniature internal mixer. An extruder also provides good mixing, and has the further advantage that it permits shorter mixing times. It is also possible to carry out the mixing in two or more stages.
Further, the mixing can be carried out in different apparatuses, for example one stage may be carried out in an internal mixer and another in an extruder.
The enhanced interaction between the filler and the halobutyl elastomer results in improved properties for the filled elastomer. These improved properties include higher
Further, a lubricant, for example a fatty acid such as stearic acid, may be present in an amount up to about 3 parts by weight, more preferably in an amount up to 2 parts by weight.
Carbon black is not normally used as a filler in the halobutyl elastomer compositions of the invention, but in some embodiments it may be present in an amount up to about 40 phr. If the mineral filler is silica and it is used with carbon black, the silica should constitute at least 55% by weight of the total of silica and carbon black. If the halobutyl elastomer composition of the invention is blended with another elastomeric composition, that other composition may contain carbon black as a filler.
The halobutyl elastomer, filler and additive are mixed together, suitably at a temperature in the range of from about 25 to about 200 C. It is preferred that the temperature in one of the mixing stages be greater than about 60 C, and a temperature in the range of from about 90 to about 150 C is particularly preferred. Normally the mixing time does not exceed about one hour; a time in the range from about 2 to 30 minutes is usually adequate. The mixing is suitably carried out on a two-roll mill mixer, which provides good dispersion of the filler within the elastomer. Mixing may also be carried out in a BanburyTM mixer, or in a HaakeTM or BrabenderTM miniature internal mixer. An extruder also provides good mixing, and has the further advantage that it permits shorter mixing times. It is also possible to carry out the mixing in two or more stages.
Further, the mixing can be carried out in different apparatuses, for example one stage may be carried out in an internal mixer and another in an extruder.
The enhanced interaction between the filler and the halobutyl elastomer results in improved properties for the filled elastomer. These improved properties include higher
7 MAR 02 '01 16:27 FR BAYER LAW & PATENTS 0416 240 5426 1-0 918199539538 P.11124 tensile strength, higher abrasion resistance, lower permeability and better dynamic properties. These render the filled elastomers particularly suitable for a number of applications, including, but not limited to, use in tire treads and tire sidewalls, tire innerliners, tank linings, hoses, rollers, conveyor belts, curing bladders, gas masks, pharmaceutical enclosures and gaskets.
In a preferred embodiment of the invention, bromobiutyl elastomer, silica particles, additive and, optionally, processing oil extender are mixed on a two-roll mill at a nominal mill temperature of 25 C. The mixed compound is then placed on a two-roll mill and io mixed at a temperature above 60 C. It is preferred that the temperature of the mixing is not too high, and more preferably does not exceed about 150 C, since higher temperatures may cause curing to proceed undesirably far and thus impede subsequent processing. The product of mixing these four ingredients at a temperature not exceeding about 150 C is a compound which has good stress/strain properties and is which can be readily processed further on a warm mill with the addition of curatives.
The filled halobutyl rubber compositions of the inverition, and in particular filled bromobutyl rubber compositions, find many uses, but mention is made particularly of use in tire tread compositions. Important features of a tire tread composition are that it 20 shall have low rolling resistance, good traction, particularly in the wet, and good abrasion resistance so that it is resistant to wear. Compositions of the invention display these desirable properties. Thus, an indicator of traction is tan 8 at 0 C, with a high tan S at 0 C correlating with good traction. An indicator of rolfing resistance is tan 5 at 60 C, with a low tan S at 60 C correlating with low roiling resistance. Rolling resistance is a 25 measure of the resistance to forward movement of the tire, and low rolling resistance is desired to reduce fuel consumption. Low values of loss modulus at 60 C are also indicators of low rolling resistance. As is demonstrated in the examples below, compositions of the invention display high tan 3 at 0 C, low tan S at 60 C and low loss modulus at 60 C.
The filled halobutyl elastomers of this invention can be further mixed with other rubbers, for example natural rubber, butadiene rubber, styrene-butadiene rubber and isoprene rubbers, and compounds contain these elastomers.
In a preferred embodiment of the invention, bromobiutyl elastomer, silica particles, additive and, optionally, processing oil extender are mixed on a two-roll mill at a nominal mill temperature of 25 C. The mixed compound is then placed on a two-roll mill and io mixed at a temperature above 60 C. It is preferred that the temperature of the mixing is not too high, and more preferably does not exceed about 150 C, since higher temperatures may cause curing to proceed undesirably far and thus impede subsequent processing. The product of mixing these four ingredients at a temperature not exceeding about 150 C is a compound which has good stress/strain properties and is which can be readily processed further on a warm mill with the addition of curatives.
The filled halobutyl rubber compositions of the inverition, and in particular filled bromobutyl rubber compositions, find many uses, but mention is made particularly of use in tire tread compositions. Important features of a tire tread composition are that it 20 shall have low rolling resistance, good traction, particularly in the wet, and good abrasion resistance so that it is resistant to wear. Compositions of the invention display these desirable properties. Thus, an indicator of traction is tan 8 at 0 C, with a high tan S at 0 C correlating with good traction. An indicator of rolfing resistance is tan 5 at 60 C, with a low tan S at 60 C correlating with low roiling resistance. Rolling resistance is a 25 measure of the resistance to forward movement of the tire, and low rolling resistance is desired to reduce fuel consumption. Low values of loss modulus at 60 C are also indicators of low rolling resistance. As is demonstrated in the examples below, compositions of the invention display high tan 3 at 0 C, low tan S at 60 C and low loss modulus at 60 C.
The filled halobutyl elastomers of this invention can be further mixed with other rubbers, for example natural rubber, butadiene rubber, styrene-butadiene rubber and isoprene rubbers, and compounds contain these elastomers.
8 The invention is further illustrated in the following examples and the accompanying Figure 1.
Description of tests:
Abrasion resistance: DIN 53-516 (60 grit Emery paper) Dynamic Property Testing Dynamic testing (Tan 8 at 0 C and 60 C, Loss modulus at 60 C) were carried out using the Rheometrics RSA II. The RSA II is a dynamic mechanical analyzer for io characterizing the properties of vulcanized elastomeric materials.
The dynamic mechanical properties give a measure of traction with the best traction usually obtained with high values of Tan 8 at 0 C. Low values of Tan 8 at 60 C., and in particular, low loss modulus at 60 C. are indicators of low rolling resistance.
Cure geometry: ASTM D 52-89 MDR2000E Rheometer at 3 arc and 1.7 Hz Permeability. ASTM D 14-34 The invention is further illustrated in the following examples.
Description of Ingredients and General Mixing Procedure:
Hi-SiIT"" 233 - silica - a product of PPG
SunparTM 2280 - paraffinic oil produced by Sun Oil.
Pro-Cote 5000 is a low molecular weight, chemically modified soy polymer designed as a multi-functional coating additive and binder. It is produced by Protein Technologies International, located in St Louis, MO, USA.
The brominated butyl elastomer, silica, oil and a bonding compound were mixed on a 6"
X 12" two-roll mill with the rolls running at 24 and 32 rpm. The mill roll was set at 25 C, with a total incorporation time of 10 minutes. The mixed compounds were then "heat treated" for a further 10 minutes with the roll temperature at 110 C. The final rubber temperature was125 C. Curatives were then added to the cooled sample with the mill at 25 C.
Description of tests:
Abrasion resistance: DIN 53-516 (60 grit Emery paper) Dynamic Property Testing Dynamic testing (Tan 8 at 0 C and 60 C, Loss modulus at 60 C) were carried out using the Rheometrics RSA II. The RSA II is a dynamic mechanical analyzer for io characterizing the properties of vulcanized elastomeric materials.
The dynamic mechanical properties give a measure of traction with the best traction usually obtained with high values of Tan 8 at 0 C. Low values of Tan 8 at 60 C., and in particular, low loss modulus at 60 C. are indicators of low rolling resistance.
Cure geometry: ASTM D 52-89 MDR2000E Rheometer at 3 arc and 1.7 Hz Permeability. ASTM D 14-34 The invention is further illustrated in the following examples.
Description of Ingredients and General Mixing Procedure:
Hi-SiIT"" 233 - silica - a product of PPG
SunparTM 2280 - paraffinic oil produced by Sun Oil.
Pro-Cote 5000 is a low molecular weight, chemically modified soy polymer designed as a multi-functional coating additive and binder. It is produced by Protein Technologies International, located in St Louis, MO, USA.
The brominated butyl elastomer, silica, oil and a bonding compound were mixed on a 6"
X 12" two-roll mill with the rolls running at 24 and 32 rpm. The mill roll was set at 25 C, with a total incorporation time of 10 minutes. The mixed compounds were then "heat treated" for a further 10 minutes with the roll temperature at 110 C. The final rubber temperature was125 C. Curatives were then added to the cooled sample with the mill at 25 C.
9 MAR 02 '01 16:28 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.13/24 Example I
A number of different additives containing hydroxyl and nitrogen atoms were compared with 3 different silane additives commonly used in elastomer. silica compounds. A
compound containing no bonding agent was also prepared, as a control sample_ The bonding agents used were :
(i) 6-Amino caproic acid ;
(ii) Aspartic acid ;
io (iii) Pro-Cote 5000 (soy protein) ;
(iv) Triethanolamine ;
(v) 2-Amino-2-methyl-1 -propanol ;
(vi) 3-Amino-l-propanol ; and (vii) Monoethanolamine.
The three.commonly used silanes used for comparison purposes were :
(a) Amino propyl triethoxy siiane ;
(b) Si69, bis[3-(triethoxysilyE)propy!]- tetrasulfane [(C2Hr5O)3Si-(CH2)3-Sa--(CH2)3-Si(OC2H5)3] ; and (c) Silquest 1589, bis[3-(triethoxysilyl)propyl]- disuifane (G2H50) 3SI-((:H2)3-Sa-(C H2)3-SI(OC2H5)3]=
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additive, 60 parts per hundred rubber (phr) of silica filler (Hisil 233) and 10plhr of oil extender (Sunpar 2280) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid and sulfur, and 1.5phir. of ZnO) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(gp) +
A number of different additives containing hydroxyl and nitrogen atoms were compared with 3 different silane additives commonly used in elastomer. silica compounds. A
compound containing no bonding agent was also prepared, as a control sample_ The bonding agents used were :
(i) 6-Amino caproic acid ;
(ii) Aspartic acid ;
io (iii) Pro-Cote 5000 (soy protein) ;
(iv) Triethanolamine ;
(v) 2-Amino-2-methyl-1 -propanol ;
(vi) 3-Amino-l-propanol ; and (vii) Monoethanolamine.
The three.commonly used silanes used for comparison purposes were :
(a) Amino propyl triethoxy siiane ;
(b) Si69, bis[3-(triethoxysilyE)propy!]- tetrasulfane [(C2Hr5O)3Si-(CH2)3-Sa--(CH2)3-Si(OC2H5)3] ; and (c) Silquest 1589, bis[3-(triethoxysilyl)propyl]- disuifane (G2H50) 3SI-((:H2)3-Sa-(C H2)3-SI(OC2H5)3]=
Brominated isoprene isobutylene rubber (BIIR) was mixed with the additive, 60 parts per hundred rubber (phr) of silica filler (Hisil 233) and 10plhr of oil extender (Sunpar 2280) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients (1 phr of stearic acid and sulfur, and 1.5phir. of ZnO) were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(gp) +
10 minutes at 170 C (for DIN Abrasion testing) or tc,(gQ) + 5 minutes at 170 C
and 3o tested. Table 1 gives the product compositions, and physical property data for three commonly used silanes and for a compound containing no filler bonding agent.
The data in Table 1 clearly shows the effect of adding silanes to assist in the dispersion and bonding of the filler in the brominated butyl elastomer. The ratio M300JM100 is commonly used as a relative measure of the degree of filler reinforcement in an t0 MAR 02 '01 16:28 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.14/24 elastomer compound (the higher the ratio the higher the reinforcement). M300 /
M'I00 for the control (no silane) is 1.6 and for silanes ranges from 5.4 to 7.3.
Table 2 gives the product compositions and physical property data for representative s additives used in the practice of this invention.
The data in Table 2 show that the products of this inverition have M300 / M100 values of between 2.4 and 7Ø In comparison with the data in Table 1, this shows that all the additives in Table 2 provide some degree of reinforcement. Figure 1, a plot of the stress strain data, also shows this reinforcement.
Examination of the DIN Abrasion test data show that: the additives improve wear, although the sample containing no bonding agent wws too soft too test. It is also noteworthy that preferred additives, exemplified by 3-amino-l-propanol and mono-ethanolamine, show much higher values for Tan S at 60 C and much lower values for the loss modulus at 60 C than the other additives.
Examale 2 Comparisons were made for mono-, di-, and tri- ethanolaniine in a compound containing BIIR + Hi-Sil 233.
6rominated isoprene isobutylene rubber (BIIR) was mixed with the various additives and 60phr of silica filler (Hisil 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients, 1 phr o1F stearic acid and sulfur, and 1.5phr. of Zna, were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(90) + 10 minutes at 170 C (for DIN
Abrasion testing) or tc(go) + 5 minutes at 170 C and tested. Table 3 gives the product compositions, and physical property data in comparison with amino-propyl triethoxy silane.
The M300 ! M'100 data in Table 3 show that the primary is better than the secondary which is better than the tertiary amine in dispersing and bonding the filler to the BIlR_ The rnono-ethanolamine also has the highest Tan b at 60 C. and the lowest values for the loss modulus at 60 C.
MAR 02 '01 16:28 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.15/24 Example 3:
To investigate the effect of the concentration of the dispersing and bonding agent, the concentration of 3-amino-1-propanol was varied from 1.41, to 2.8 to 5.4phr.
Brominated isoprene isobutylene rubber (BfiR) was mixed with 3-amino-l-propanol and 60phr of silica filler (Hisil 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients, I phr, of stearic acid and sulfur, and 1.6phr, of ZnO, were then added on a cool mill to each of the compounds. The compounds were io then cured for either tc(go) + 10 minutes at 170 C (for DIN Abrasion testing) or tc(go) +
5 minutes at 170 C and tested. Table 4 gives the prodiuct compositions, and physical property data in comparison with amino-propyl triethoxy silane.
The data in Table 4 show that a level of 2.8phr. is superior to that of either 1.4 or 5.4 phr. of 3-amino-l-propanol.
Example 4.
To investigate the effect of the number of methylene (-Cl-12-) groups between the amine and the alcohol functional groups, monoethanolamine, 3-amino-1--propanol, and amino-l-pentanol were compared with the same equivaf'ent number of amino groups.
The data is shown in Table 5.
The data in Table 5 shows poorer properties for 5- arnino-l-pentanol compared to monoethanolamine and 3-amino-1-propanol.
T
MAR 02 '01 16-29 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.16/24 CQDE: OOCW 96 106 105 93 Additive (control) (c) (b) (a) Additive amount (phr,). 0 8.6 9.8 8 STRESS STRAIN (Die C DUMSELLS, cure tc9O+5 @ 170 C., tested cQ 23 C) Hard. Shore A2 Inst. (pts.) 61 62 59 51 Ultimate Tensile (MPa) 6.6 16.2 16.9 15.2 Ultimate Elongation (%) 890 431 494 309 Stress @ 50 (MPa) 0.89 1.13 1.03 0.95 Stress Q 100 (MPa) 0.87 1.83 1.59 2 Stress tt~ 200 (MPa) 1.01 4.8 4.23 6.89 Stress Q 300 (MPa) 1.39 9.94 8.88 14.5 M300/M100 1.6 5.43 5.58 7.3 DIE C TEAR (cured tc90+5 Q 170 C., tested Q R.T.) Tear Strength (kN/m) 18.7 25.8 30.3 18.8 DIN ABRASION (cure tc9O+5 @ 170 C.,) Abrasion Volume Loss (mms) NR 235 198 230 sample defomied RSA 8, TEMPERATURE SWEEP (2 C/min, 60sec soak. 70radls, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.32 0.65 0.66 0.77 Tan deftaQ +60 C. 0.10 0.16 0.16 0.11 Loss modulus@ +60 C. 1.90 0.79 0.63 0.45 MDR CURE CHARACTERISTICS (1.7Hz, 170deg.C., 3 arc, 60 mins.) MH (dN.m) 22.8 34.5 32.8 38.4 ML (dN.m) 14.7 6.7 7.3 11.8 ts 1(min) 1.02 0.72 0.54 0.66 ts 2(min) 1.98 0.9 0.66 0.84 t' 10 (min) 0.86 1.11 0.74 0.94 t' 50 (min) 5.61 5.84 2.34 3.36 t 90 (min) 23.9 22.3 10.8 9.1 t 95 (min) 28.6 26.2 13.1 11.0 ._ _ .... .. _........ ........ ... . .. ._ i~.
MAR 02 '01 16:29 FR BAYER LAW 8. PATENTS 0416 240 5426 1'0 918199539538 P.17/24 CODE:OOCVIt 100 107 95 108 98 99 1101 Additive (i) (ii) (iii) (iv) (v) (vi) (vii) Additive amount (phr.). 4.8 4.8 8 5.4 3.25 23 2.2 STRESS STRAIN (Die C DUM8ELLS, cure tc9O+5 @ 170 C., tested @ 23 C.,) Hard. Shore A2 Inst. 61 60 58 62 64 54 50 (pts.) Ultimate Tensile (MPa) 13.1 12.9 9.5 16.3 15.8 19.0 17.8 Ultimate Elongation (%) 853 856 702 768 807 453 395 Stress @ 50 (MPa) 0.82 0.82 0.88 0.8E; 1-02 1.03 0.91 Stress @ 100 (MPa) 0.94 0.94 1.04 1.09 1.27 1.9 1.76 Stress @ 200 (MPa) 1.4 1.39 1.75 1.95 2.23 5.74 5.77 Stress @ 300 (MPa) 2.28 2.32 2.99 3.27 3.96 11.48 12.27 M300/M100 2.4 2.47 2.9 3.00 3.1 6.0 6.97 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kNlm) 48.3 56.0 27.0 51.9 55.7 29.5 25.0 DIN ABRASION (cure tc9O+5 @ 170 C.,) Abrasion Volume Loss 615 210 651 543 422 262 423 (mrns) RSA II, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc9O+5 170 C) Tan delta@ 0 C. 0.33 0.31 0.45 0.36 0.33 0.55 0.59 Tan delta@ +60 C. 0,13 0.13 0.14 0.11 0.11 0.10 0.11 Loss modulus@ +60 C. 2.23 2.36 1.42 2.27 1.60 0.86 0.77 MDR CURE CHARACTERISTICS (1.7Hz, 170deg.C, 3 arc, 60 mins.) MH (dN.m) 29.6 30.3 25.2 38.5 34.9 42.6 37.2 ML (dN.m) 12.1 11.8 12.4 9.3 9.0 10.4 9.0 ts 1(min) 0.72 0.66 0.96 0.6 0.9 0.48 0.66 ts 2(min) 0.96 0.9 1.38 0.72 1.2 0.6 0.84 t' 10 (min) 0.85 0,84 1.05 0.82 1.37 0.71 0.95, t' 50 (min) 3.08 3.13 5.47 2.55 5.38 3.08 4.26 t' 90 (min) 9.6 9.6 26.4 8.5 14.6 9.5 12.3 t' 95 (min) 12.0 12.3 32.8 11.3 17.5 12.0 14.9 MAR 02 '01 16:29 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.18/24 TABLE 3.
CODE OOCW... 217 218 219 220 Additive (a) (vii) diethanotamine (iv) Additive amount (phr.) 8 2.2 3.9 5.4 STRESS STRAIN (Die C DUMBELLS, t90+5 Qa 170 C., tested @ 23 C.) Hard. Shore A2 Inst. (pts.) 57 58 67 70 Ultimate Tensile (MPa) 16.5 18.5 20.1 17.6 tlftimate Elongation (%) 278 329 545 658 Stress @ 50 (MPa) 1.17 1_3 1.37 1.17 Stress @ 100 (MPa) 2.43 2.69 2.08 1.46 Stress @ 200 (MPa) 8.75 8.5 5.21 2.94 Stress @ 300 (MPa) 17.92 16.81 10.1 6 300M / 100M 7.4 6.2 4.9 4.1 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 19.0 27.8 42.1 47.3 DIN ABRASION (cure tc90+10 @ 170 C.,) Abrasion Volume Loss (mm') 113 90 138 145 RSA !I, TEMPERATURE SWEEP (2 Clmin, 60sec soak, 70radJs, cured tc90+5 @ 170 C) Tan defta@ 0 C. 0.806 0.639 0.436 0.374 Tan deita@ +60 C. 0.109 0.105 0.096 0.085 Lvss modulus@ +60 C, 0.397 1.040 1.928 2.309 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 17C- C.).
MH (dN.m) 46.9 45.3 46.6 48.0 ML (dN.m) 16.3 12.3 10.8 12.8 ts 1(min) 0.6 0.48 0.66 0.96 ts 2(min) 0.78 0.54 0.9 1.26 t' 10 (min) 0.88 0.65 1_16 1.64 t' 50 (min) 2_81 2_59 4.8 5.44 t 90 (min) 7.5 7.63 13.09 12.63 t' 95 (min) 9.16 9.48 15.94 14.9 ii MAR 02 '01 16:29 FR BAYER LAIJ & PATENTS 0416 240 5426 TO 918199539538 P.19/24 TABLE 4.
CODE OOCW... 221 2;22 223 3-amino-l-propanol (phr.). 1.4 2,8 5.4 STRESS STRAIN (Die C DUMSELLS. t90+5 @ 170 C_, tested @ 23 C.) Hard. Shore A2 lnst. (pts.) 60 58 79 Ultimate Tensile (MPa) 18.1 18.0 10.0 Ultimate Etongation (%) 402 319 202 Stress @ 50 (MPa) 1.37 1.24 2.42 Stress @ 100 (MPa) 2.3 , 2.49 4.31 Stress @ 200 (MPa) 6.2 8.14 9.83 Stress @ 300 (MPa) 12.61 16.5 300M /100M 5.5 6.6 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 32.6 25.6 30.2 200M 150M 4.5 6.6 4.1 DIN ABRASION (cure tc90+10 0 170 C.,) Abrasion Volume Loss (mm$) 135 109 298 RSA !f, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.591 0.644 0.407 Tan delta@ +60 C. 0.106 0.108 0.080 Loss modulus@ +60 C. 1.176 0.888 1.303 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 170 C.).
MH (dN.m) 41.0 45.6 61.5 ML (dN.m) 10_1 1:3.3 26.2 ts 1(min) 0.72 0.48 0.42 ts 2(min) 0.84 0.6 0.48 t' 10 (min) 1.01 0,69 0.58 t' 50 (min) 4.12 2.4 1.8 t 90 (min) 11.4 6.66 5.44 t' 95 (min) 13.91 8.28 6.7 MAR 02 '01 16:29 FR BAYER LAW & PATENTS 0416 240 5426 1'0 918199539538 P.20/24 TABLE S.
CODE OOCW... 218 4:22 224 Additive (vii) I,vi) 5-amino-1-pentanol Additive amount (phr.). 2.2 2.8 3.8 STRESS STRAIN (Die C DUMBELLS, t90+5 a~ 170 C., testeci @ 23 C.) Hard. Shore A2 tnst. (pts.) 58 .58 75 Ultimate Tensile (MPa) 18.5 18.0 14.6 Ultimate Elongation {%) 329 319 227 StrEss @ 50 (MPa) 1.3 1.24 2.03 Stress @ 100 (Mpa) 2.69 2.49 4.16 Stress @ 200 (MPa) 8.5 $.14 12.05 Stress Q 300 (MPa) 16.81 16,5 300M / 100M 6.2 6.6 200M / 50M 6.5 6.6 5.9 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 27.8 25.6 24.9 DIN ABRASION (cure tc90+10 @ 170 C.,) Abrasion Volume Loss (mm$) 90 109 173 RSA II, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.64 0.64 0.49 Tan deita@ +60 C. 0.10 0.11 0.09 Loss modulus@ +60 G. 1.04 0.89. 0.99 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 170 C.).
MH (dN.m) 45.3 45.6 56.7 ML (dN.m) 12.3 13.3 21 _4 ts 1(min) 0.48 0.48 0.42 ts 2(min) 0.54 0.6 0.54 t 10 (min) 0.65 0,69 0.59 t' 50 (min) 2.59 2.4 1.78 Y 90 (min) 7.63 6.66 5.72 t' 95 (min) 9.48 828 7.42
and 3o tested. Table 1 gives the product compositions, and physical property data for three commonly used silanes and for a compound containing no filler bonding agent.
The data in Table 1 clearly shows the effect of adding silanes to assist in the dispersion and bonding of the filler in the brominated butyl elastomer. The ratio M300JM100 is commonly used as a relative measure of the degree of filler reinforcement in an t0 MAR 02 '01 16:28 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.14/24 elastomer compound (the higher the ratio the higher the reinforcement). M300 /
M'I00 for the control (no silane) is 1.6 and for silanes ranges from 5.4 to 7.3.
Table 2 gives the product compositions and physical property data for representative s additives used in the practice of this invention.
The data in Table 2 show that the products of this inverition have M300 / M100 values of between 2.4 and 7Ø In comparison with the data in Table 1, this shows that all the additives in Table 2 provide some degree of reinforcement. Figure 1, a plot of the stress strain data, also shows this reinforcement.
Examination of the DIN Abrasion test data show that: the additives improve wear, although the sample containing no bonding agent wws too soft too test. It is also noteworthy that preferred additives, exemplified by 3-amino-l-propanol and mono-ethanolamine, show much higher values for Tan S at 60 C and much lower values for the loss modulus at 60 C than the other additives.
Examale 2 Comparisons were made for mono-, di-, and tri- ethanolaniine in a compound containing BIIR + Hi-Sil 233.
6rominated isoprene isobutylene rubber (BIIR) was mixed with the various additives and 60phr of silica filler (Hisil 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients, 1 phr o1F stearic acid and sulfur, and 1.5phr. of Zna, were then added on a cool mill to each of the compounds. The compounds were then cured for either tc(90) + 10 minutes at 170 C (for DIN
Abrasion testing) or tc(go) + 5 minutes at 170 C and tested. Table 3 gives the product compositions, and physical property data in comparison with amino-propyl triethoxy silane.
The M300 ! M'100 data in Table 3 show that the primary is better than the secondary which is better than the tertiary amine in dispersing and bonding the filler to the BIlR_ The rnono-ethanolamine also has the highest Tan b at 60 C. and the lowest values for the loss modulus at 60 C.
MAR 02 '01 16:28 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.15/24 Example 3:
To investigate the effect of the concentration of the dispersing and bonding agent, the concentration of 3-amino-1-propanol was varied from 1.41, to 2.8 to 5.4phr.
Brominated isoprene isobutylene rubber (BfiR) was mixed with 3-amino-l-propanol and 60phr of silica filler (Hisil 233) on a 6" x 12" mill under the mixing conditions described above. Identical curative ingredients, I phr, of stearic acid and sulfur, and 1.6phr, of ZnO, were then added on a cool mill to each of the compounds. The compounds were io then cured for either tc(go) + 10 minutes at 170 C (for DIN Abrasion testing) or tc(go) +
5 minutes at 170 C and tested. Table 4 gives the prodiuct compositions, and physical property data in comparison with amino-propyl triethoxy silane.
The data in Table 4 show that a level of 2.8phr. is superior to that of either 1.4 or 5.4 phr. of 3-amino-l-propanol.
Example 4.
To investigate the effect of the number of methylene (-Cl-12-) groups between the amine and the alcohol functional groups, monoethanolamine, 3-amino-1--propanol, and amino-l-pentanol were compared with the same equivaf'ent number of amino groups.
The data is shown in Table 5.
The data in Table 5 shows poorer properties for 5- arnino-l-pentanol compared to monoethanolamine and 3-amino-1-propanol.
T
MAR 02 '01 16-29 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.16/24 CQDE: OOCW 96 106 105 93 Additive (control) (c) (b) (a) Additive amount (phr,). 0 8.6 9.8 8 STRESS STRAIN (Die C DUMSELLS, cure tc9O+5 @ 170 C., tested cQ 23 C) Hard. Shore A2 Inst. (pts.) 61 62 59 51 Ultimate Tensile (MPa) 6.6 16.2 16.9 15.2 Ultimate Elongation (%) 890 431 494 309 Stress @ 50 (MPa) 0.89 1.13 1.03 0.95 Stress Q 100 (MPa) 0.87 1.83 1.59 2 Stress tt~ 200 (MPa) 1.01 4.8 4.23 6.89 Stress Q 300 (MPa) 1.39 9.94 8.88 14.5 M300/M100 1.6 5.43 5.58 7.3 DIE C TEAR (cured tc90+5 Q 170 C., tested Q R.T.) Tear Strength (kN/m) 18.7 25.8 30.3 18.8 DIN ABRASION (cure tc9O+5 @ 170 C.,) Abrasion Volume Loss (mms) NR 235 198 230 sample defomied RSA 8, TEMPERATURE SWEEP (2 C/min, 60sec soak. 70radls, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.32 0.65 0.66 0.77 Tan deftaQ +60 C. 0.10 0.16 0.16 0.11 Loss modulus@ +60 C. 1.90 0.79 0.63 0.45 MDR CURE CHARACTERISTICS (1.7Hz, 170deg.C., 3 arc, 60 mins.) MH (dN.m) 22.8 34.5 32.8 38.4 ML (dN.m) 14.7 6.7 7.3 11.8 ts 1(min) 1.02 0.72 0.54 0.66 ts 2(min) 1.98 0.9 0.66 0.84 t' 10 (min) 0.86 1.11 0.74 0.94 t' 50 (min) 5.61 5.84 2.34 3.36 t 90 (min) 23.9 22.3 10.8 9.1 t 95 (min) 28.6 26.2 13.1 11.0 ._ _ .... .. _........ ........ ... . .. ._ i~.
MAR 02 '01 16:29 FR BAYER LAW 8. PATENTS 0416 240 5426 1'0 918199539538 P.17/24 CODE:OOCVIt 100 107 95 108 98 99 1101 Additive (i) (ii) (iii) (iv) (v) (vi) (vii) Additive amount (phr.). 4.8 4.8 8 5.4 3.25 23 2.2 STRESS STRAIN (Die C DUM8ELLS, cure tc9O+5 @ 170 C., tested @ 23 C.,) Hard. Shore A2 Inst. 61 60 58 62 64 54 50 (pts.) Ultimate Tensile (MPa) 13.1 12.9 9.5 16.3 15.8 19.0 17.8 Ultimate Elongation (%) 853 856 702 768 807 453 395 Stress @ 50 (MPa) 0.82 0.82 0.88 0.8E; 1-02 1.03 0.91 Stress @ 100 (MPa) 0.94 0.94 1.04 1.09 1.27 1.9 1.76 Stress @ 200 (MPa) 1.4 1.39 1.75 1.95 2.23 5.74 5.77 Stress @ 300 (MPa) 2.28 2.32 2.99 3.27 3.96 11.48 12.27 M300/M100 2.4 2.47 2.9 3.00 3.1 6.0 6.97 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kNlm) 48.3 56.0 27.0 51.9 55.7 29.5 25.0 DIN ABRASION (cure tc9O+5 @ 170 C.,) Abrasion Volume Loss 615 210 651 543 422 262 423 (mrns) RSA II, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc9O+5 170 C) Tan delta@ 0 C. 0.33 0.31 0.45 0.36 0.33 0.55 0.59 Tan delta@ +60 C. 0,13 0.13 0.14 0.11 0.11 0.10 0.11 Loss modulus@ +60 C. 2.23 2.36 1.42 2.27 1.60 0.86 0.77 MDR CURE CHARACTERISTICS (1.7Hz, 170deg.C, 3 arc, 60 mins.) MH (dN.m) 29.6 30.3 25.2 38.5 34.9 42.6 37.2 ML (dN.m) 12.1 11.8 12.4 9.3 9.0 10.4 9.0 ts 1(min) 0.72 0.66 0.96 0.6 0.9 0.48 0.66 ts 2(min) 0.96 0.9 1.38 0.72 1.2 0.6 0.84 t' 10 (min) 0.85 0,84 1.05 0.82 1.37 0.71 0.95, t' 50 (min) 3.08 3.13 5.47 2.55 5.38 3.08 4.26 t' 90 (min) 9.6 9.6 26.4 8.5 14.6 9.5 12.3 t' 95 (min) 12.0 12.3 32.8 11.3 17.5 12.0 14.9 MAR 02 '01 16:29 FR BAYER LAW & PATENTS 0416 240 5426 TO 918199539538 P.18/24 TABLE 3.
CODE OOCW... 217 218 219 220 Additive (a) (vii) diethanotamine (iv) Additive amount (phr.) 8 2.2 3.9 5.4 STRESS STRAIN (Die C DUMBELLS, t90+5 Qa 170 C., tested @ 23 C.) Hard. Shore A2 Inst. (pts.) 57 58 67 70 Ultimate Tensile (MPa) 16.5 18.5 20.1 17.6 tlftimate Elongation (%) 278 329 545 658 Stress @ 50 (MPa) 1.17 1_3 1.37 1.17 Stress @ 100 (MPa) 2.43 2.69 2.08 1.46 Stress @ 200 (MPa) 8.75 8.5 5.21 2.94 Stress @ 300 (MPa) 17.92 16.81 10.1 6 300M / 100M 7.4 6.2 4.9 4.1 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 19.0 27.8 42.1 47.3 DIN ABRASION (cure tc90+10 @ 170 C.,) Abrasion Volume Loss (mm') 113 90 138 145 RSA !I, TEMPERATURE SWEEP (2 Clmin, 60sec soak, 70radJs, cured tc90+5 @ 170 C) Tan defta@ 0 C. 0.806 0.639 0.436 0.374 Tan deita@ +60 C. 0.109 0.105 0.096 0.085 Lvss modulus@ +60 C, 0.397 1.040 1.928 2.309 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 17C- C.).
MH (dN.m) 46.9 45.3 46.6 48.0 ML (dN.m) 16.3 12.3 10.8 12.8 ts 1(min) 0.6 0.48 0.66 0.96 ts 2(min) 0.78 0.54 0.9 1.26 t' 10 (min) 0.88 0.65 1_16 1.64 t' 50 (min) 2_81 2_59 4.8 5.44 t 90 (min) 7.5 7.63 13.09 12.63 t' 95 (min) 9.16 9.48 15.94 14.9 ii MAR 02 '01 16:29 FR BAYER LAIJ & PATENTS 0416 240 5426 TO 918199539538 P.19/24 TABLE 4.
CODE OOCW... 221 2;22 223 3-amino-l-propanol (phr.). 1.4 2,8 5.4 STRESS STRAIN (Die C DUMSELLS. t90+5 @ 170 C_, tested @ 23 C.) Hard. Shore A2 lnst. (pts.) 60 58 79 Ultimate Tensile (MPa) 18.1 18.0 10.0 Ultimate Etongation (%) 402 319 202 Stress @ 50 (MPa) 1.37 1.24 2.42 Stress @ 100 (MPa) 2.3 , 2.49 4.31 Stress @ 200 (MPa) 6.2 8.14 9.83 Stress @ 300 (MPa) 12.61 16.5 300M /100M 5.5 6.6 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 32.6 25.6 30.2 200M 150M 4.5 6.6 4.1 DIN ABRASION (cure tc90+10 0 170 C.,) Abrasion Volume Loss (mm$) 135 109 298 RSA !f, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.591 0.644 0.407 Tan delta@ +60 C. 0.106 0.108 0.080 Loss modulus@ +60 C. 1.176 0.888 1.303 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 170 C.).
MH (dN.m) 41.0 45.6 61.5 ML (dN.m) 10_1 1:3.3 26.2 ts 1(min) 0.72 0.48 0.42 ts 2(min) 0.84 0.6 0.48 t' 10 (min) 1.01 0,69 0.58 t' 50 (min) 4.12 2.4 1.8 t 90 (min) 11.4 6.66 5.44 t' 95 (min) 13.91 8.28 6.7 MAR 02 '01 16:29 FR BAYER LAW & PATENTS 0416 240 5426 1'0 918199539538 P.20/24 TABLE S.
CODE OOCW... 218 4:22 224 Additive (vii) I,vi) 5-amino-1-pentanol Additive amount (phr.). 2.2 2.8 3.8 STRESS STRAIN (Die C DUMBELLS, t90+5 a~ 170 C., testeci @ 23 C.) Hard. Shore A2 tnst. (pts.) 58 .58 75 Ultimate Tensile (MPa) 18.5 18.0 14.6 Ultimate Elongation {%) 329 319 227 StrEss @ 50 (MPa) 1.3 1.24 2.03 Stress @ 100 (Mpa) 2.69 2.49 4.16 Stress @ 200 (MPa) 8.5 $.14 12.05 Stress Q 300 (MPa) 16.81 16,5 300M / 100M 6.2 6.6 200M / 50M 6.5 6.6 5.9 DIE C TEAR (cured tc90+5 @ 170 C., tested @ R.T.) Tear Strength (kN/m) 27.8 25.6 24.9 DIN ABRASION (cure tc90+10 @ 170 C.,) Abrasion Volume Loss (mm$) 90 109 173 RSA II, TEMPERATURE SWEEP (2 C/min, 60sec soak, 70rad/s, cured tc90+5 @ 170 C) Tan delta@ 0 C. 0.64 0.64 0.49 Tan deita@ +60 C. 0.10 0.11 0.09 Loss modulus@ +60 G. 1.04 0.89. 0.99 MDR CURE CHARACTERISTICS (1.7 Hz., 3 arc, 60' @ 170 C.).
MH (dN.m) 45.3 45.6 56.7 ML (dN.m) 12.3 13.3 21 _4 ts 1(min) 0.48 0.48 0.42 ts 2(min) 0.54 0.6 0.54 t 10 (min) 0.65 0,69 0.59 t' 50 (min) 2.59 2.4 1.78 Y 90 (min) 7.63 6.66 5.72 t' 95 (min) 9.48 828 7.42
Claims (47)
1. A process for preparing a filled cured halobutyl elastomer composition which comprises: admixing a halobutyl elastomer, particles of a mineral filler and an additive comprising an aminoalcohol to form a mixture; and, curing the mixture to form a cured composition suitable for further use.
2. The process according to claim 1, wherein the aminoalcohol is a compound of formula HO-A-NH2; wherein A is a linear or branched C1 to C20 alkylene group.
3. The process according to claim 2, wherein A is a C1 to C4 alkylene group.
4. The process according to claim 1, wherein the additive is selected from the group consisting of ethanolamine and 3-amino-1-propanol.
5. The process according to any one of claims 1 to 4, wherein the amount of additive used results in a nitrogen level in the elastomer of from about 0.1 to about 5 parts per hundred parts of elastomer.
6. The process according to claim 5, wherein the amount of additive used results in a nitrogen level in the elastomer of from about 0.125 to about 1 parts per hundred parts of elastomer.
7. The process according to claim 6, wherein the amount of additive used results in a nitrogen level in the elastomer of from about 0.3 to about 0.7 parts per hundred parts of elastomer.
8. The process according to any one of claims 1 to 7, wherein the filler comprises silica.
9. The process according to claim 8, wherein the filler consists essentially of silica.
10. The process according to claim 8, wherein the silica is prepared by carbon dioxide precipitation of sodium silicate.
11. The process according to claim 8, wherein the silica is selected from the group consisting of HiSil .TM. 210, HiSil .TM. 233, HiSil .TM. 243, Vulkasil .TM. S
and Vulkasil .TM. N.
and Vulkasil .TM. N.
12. The process according to claims 8, 10 or 11, wherein the filler additionally comprises carbon black.
13. The process according to any one of claims 8 to 12, wherein the filler has a particle size of from 1 to 100 microns.
14. The process according to any one of claims 1 to 13, wherein the filled halobutyl elastomer is admixed with another elastomer or elastomeric compound before it is subjected to curing.
15. The process according to any one of claims 1 to 14, wherein the filled halobutyl elastomer is cured with 0.3 to 2.0 parts by weight of sulfur.
16. The process according to any one of claims 1 to 15, wherein the halobutyl elastomer is a brominated butyl elastomer.
17. The process according to any one of claims 1 to 16, wherein the halobutyl elastomer comprises isobutylene and isoprene.
18. The process according to any one of claims 1 to 17, wherein the halobutyl elastomer comprises a vinyl aromatic monomer.
19. The process according to claim 18, wherein the vinyl aromatic monomer is a styrene monomer.
20. The process according to claim 19, wherein the styrene monomer is para-methylstyrene.
21. The process according to any one of claims 1 to 20, wherein the composition is suitable for use in tire treads and tire sidewalls, tire innerliners, tank linings, hoses, rollers, conveyor belts, curing bladders, gas masks, pharmaceutical enclosures and gaskets.
22. The process according to claim 21, wherein the composition is suitable for use as a tread for a vehicle tire.
23. The process according to claim 21, wherein the composition is suitable for use as an inner liner for a vehicle tire.
24. A cured composition comprising a halobutyl elastomer, particles of a mineral filler and an additive comprising an aminoalcohol, wherein the cured composition is suitable for further use.
25. The cured composition according to claim 24, wherein the aminoalcohol is a compound of formula HO-A-NH2; wherein A is a linear or branched C1 to C20 alkylene group.
26. The composition according to claim 25, wherein A is a C1 to C4 alkylene group.
27. The cured composition according to claim 24, wherein the additive is selected from the group consisting of ethanolamine and 3-amino-1-propanol.
28. The cured composition according to any one of claims 24 to 27, wherein the amount of additive used results in a nitrogen level in the elastomer of from about 0.1 to about 5 parts per hundred parts of elastomer
29. The cured composition according to any one of claims 24 to 28, wherein the filler comprises silica.
30. The cured composition according to claim 29, wherein the filler consists essentially of silica.
31. The cured composition according to claim 29, wherein the silica is prepared by carbon dioxide precipitation of sodium silicate.
32. The cured composition according to claim 29, wherein the silica is selected from the group consisting of HiSil .TM. 210, HiSil .TM. 233, HiSil .TM. 243, Vulkasil .TM. S and Vulkasil .TM. N.
33. The cured composition according to any one of claims 29, 31 or 32, wherein the filler additionally comprises carbon black.
34. The cured composition according to any one of claims 29 to 33, wherein the filler has a particle size of from 1 to 100 microns.
35. The cured composition according to any one of claims 24 to 34, wherein the composition exhibits increased abrasion resistance as compared with compositions not containing the additive that are otherwise identical.
36. The cured composition according to any one of claims 24 to 35, wherein the composition is suitable for use in tire treads, tire sidewalls, tire innerliners, tank linings, hoses, rollers, conveyor belts, curing bladders, gas masks, pharmaceutical enclosures and gaskets.
37. The cured composition according to claim 36, wherein the composition is suitable for use as a tread for a vehicle tire.
38. The cured composition according to claim 36, wherein the composition is suitable for use as an inner liner for a vehicle tire.
39. The cured composition according to any one of claims 24 to 38, wherein the halobutyl elastomer is a brominated butyl elastomer.
40. The cured composition according to any one of claims 24 to 39, wherein the halobutyl elastomer comprises isobutylene and isoprene.
41. The cured composition according to any one of claims 24 to 40, wherein the halobutyl elastomer comprises a vinyl aromatic monomer.
42. The cured composition according to claim 41, wherein the vinyl aromatic monomer is a styrene monomer.
43. The cured composition according to claim 42, wherein the styrene monomer is para-methylstyrene.
44. A filled, cured halobutyl elastomer composition prepared by a process according to any one of claims 1 to 23.
45. The filled, cured elastomer composition according to claim 44 in the form of a tread for a vehicle tire.
46. The filled, cured elastomer composition according to claim 44 in the form of an innerliner for a vehicle tire.
47. The filled, cured elastomer composition according to any one of claims 44 to 46, wherein the composition exhibits increased abrasion resistance as compared with compositions not containing the additive that are otherwise identical.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002339080A CA2339080C (en) | 2001-03-02 | 2001-03-02 | Filled elastomeric butyl compounds |
| DE60211403T DE60211403T2 (en) | 2001-03-02 | 2002-02-18 | Filler-containing elastomeric butyl compounds |
| EP02003181A EP1236766B1 (en) | 2001-03-02 | 2002-02-18 | Filled elastomeric butyl compounds |
| JP2002053962A JP4280804B2 (en) | 2001-03-02 | 2002-02-28 | Filled halobutyl elastomer composition |
| US10/085,874 US7279518B2 (en) | 2001-03-02 | 2002-02-28 | Filled elastomeric butyl compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002339080A CA2339080C (en) | 2001-03-02 | 2001-03-02 | Filled elastomeric butyl compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2339080A1 CA2339080A1 (en) | 2002-09-02 |
| CA2339080C true CA2339080C (en) | 2009-11-17 |
Family
ID=4168475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002339080A Expired - Fee Related CA2339080C (en) | 2001-03-02 | 2001-03-02 | Filled elastomeric butyl compounds |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7279518B2 (en) |
| EP (1) | EP1236766B1 (en) |
| JP (1) | JP4280804B2 (en) |
| CA (1) | CA2339080C (en) |
| DE (1) | DE60211403T2 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2364174A1 (en) | 2001-11-27 | 2003-05-27 | Bayer Inc. | Filled elastomeric butyl compounds with improved scorch safety |
| CA2368363A1 (en) | 2002-01-17 | 2003-07-17 | Rui Resendes | Silica-filled elastomeric compounds |
| CA2386098C (en) * | 2002-05-13 | 2010-07-06 | Bayer Inc. | Silica-filled elastomeric compounds |
| CA2418822C (en) * | 2003-02-13 | 2010-11-30 | Bayer Inc. | Method to produce silica reinforced elastomer compounds |
| CA2452910A1 (en) * | 2003-12-12 | 2005-06-12 | Bayer Inc. | Butyl rubber composition for tire treads |
| US20050137314A1 (en) * | 2003-12-17 | 2005-06-23 | Spadone Leighton R. | Tire with innerliner for prevention of vapor permeation |
| CA2465301C (en) * | 2004-04-28 | 2012-02-07 | John Scott Parent | Process to produce silica-filled elastomeric compounds |
| CA2471006A1 (en) * | 2004-06-23 | 2005-12-23 | Bayer Inc. | Silica reinforced elastomer compounds prepared with dry liquid modifiers |
| CN101080452B (en) * | 2004-12-16 | 2012-08-01 | 兰科瑟斯有限公司 | Silica-filled elastomeric compounds |
| US20070100041A1 (en) * | 2005-11-03 | 2007-05-03 | Rui Resendes | Filled elastomeric compounds |
| CA2564446A1 (en) * | 2005-11-04 | 2007-05-04 | Lanxess Inc. | Method to produce reinforced halobutyl elastomer compounds |
| JP4823882B2 (en) * | 2005-12-19 | 2011-11-24 | 住友ゴム工業株式会社 | Rubber composition for inner liner and tire having inner liner using the same |
| US7714051B2 (en) | 2006-08-07 | 2010-05-11 | The Goodyear Tire & Rubber Company | Rubber compounds containing polyoxyalkylene amines |
| CA2604409C (en) | 2006-12-22 | 2015-04-07 | Lanxess Inc. | Butyl rubber ionomer nanocomposites |
| JP5574562B2 (en) * | 2007-07-11 | 2014-08-20 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire using the same |
| ES2396507T3 (en) * | 2007-10-19 | 2013-02-22 | LANXESS International S.A. | Butyl rubber compounds comprising a three component mixed modifier system |
| KR101319591B1 (en) | 2011-08-29 | 2013-10-16 | 동아타이어공업주식회사 | Anti-vibration rubber composition for vehicle mount |
| JP5921605B2 (en) * | 2014-06-03 | 2016-05-24 | 住友ゴム工業株式会社 | Rubber composition for tire and pneumatic tire using the same |
| WO2016055953A1 (en) * | 2014-10-07 | 2016-04-14 | Bridgestone Corporation | Rubber compound for tyre portions |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1482839A (en) * | 1974-10-29 | 1977-08-17 | Sanyo Trading Co | Vulcanisable rubber compositions and vulcanised rubber prepared therefrom |
| US4286079A (en) * | 1978-07-10 | 1981-08-25 | Sanyo Trading Co., Inc. | Curable composition |
| EP0546516B1 (en) * | 1991-12-10 | 1996-09-25 | Bridgestone Corporation | Rubber composition for cleaning metal mold and method for cleaning |
| US5428099A (en) * | 1993-05-19 | 1995-06-27 | Exxon Chemical Patents Inc. | Method to control carbon black distribution in elastomer blends |
| CA2279085C (en) | 1999-07-29 | 2008-10-07 | Bayer Inc. | Rubber composition |
| DE60008328T2 (en) * | 1999-08-27 | 2004-12-09 | Bridgestone Corp. | Rubber composition containing silicon dioxide or silicate and an amine salt |
| CA2293149A1 (en) | 1999-12-24 | 2001-06-24 | Bayer Inc. | Elastomeric butyl compounds with improved chemical bonding between the butyl elastomer and the filler |
| WO2001062846A1 (en) * | 2000-02-28 | 2001-08-30 | Bridgestone Corporation | Rubber composition for inner liner |
| DE60108520T2 (en) * | 2000-12-06 | 2006-01-12 | Pirelli Pneumatici Società per Azioni | PROCESS FOR PRODUCTION; FORMING AND VULCANIZING TIRES FOR VEHICLE WHEELS |
-
2001
- 2001-03-02 CA CA002339080A patent/CA2339080C/en not_active Expired - Fee Related
-
2002
- 2002-02-18 EP EP02003181A patent/EP1236766B1/en not_active Expired - Lifetime
- 2002-02-18 DE DE60211403T patent/DE60211403T2/en not_active Expired - Lifetime
- 2002-02-28 US US10/085,874 patent/US7279518B2/en not_active Expired - Fee Related
- 2002-02-28 JP JP2002053962A patent/JP4280804B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP1236766B1 (en) | 2006-05-17 |
| EP1236766A2 (en) | 2002-09-04 |
| JP2002309002A (en) | 2002-10-23 |
| DE60211403T2 (en) | 2006-09-21 |
| JP4280804B2 (en) | 2009-06-17 |
| EP1236766A3 (en) | 2003-07-09 |
| CA2339080A1 (en) | 2002-09-02 |
| DE60211403D1 (en) | 2006-06-22 |
| US20020156173A1 (en) | 2002-10-24 |
| US7279518B2 (en) | 2007-10-09 |
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