CA2406575A1 - Isobutylene-based elastomer blends - Google Patents
Isobutylene-based elastomer blends Download PDFInfo
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- CA2406575A1 CA2406575A1 CA002406575A CA2406575A CA2406575A1 CA 2406575 A1 CA2406575 A1 CA 2406575A1 CA 002406575 A CA002406575 A CA 002406575A CA 2406575 A CA2406575 A CA 2406575A CA 2406575 A1 CA2406575 A1 CA 2406575A1
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Abstract
The improved green strength, green elongation, and green relaxation properti es of isobutylene-based elastomers at elevated temperatures along with improved aging and barrier properties are achieved by blending semi-compatible, semi- crystalline copolymers with the isobutylene elastomers. The semi-crystalline copolymers are typically copolymers of ethylene and an alpha-olefin having from 4 to 16 carbon atoms. The improved properties are maintained in subsequent rubber compounds containing said blends and are particularly usef ul in tire and pharmaceutical container applications.
Description
TITLE: ISOBUTYLENE-BASED ELASTOMER BLENDS
FIELD OF INVENTION
This invention relates to isobutylene-based polymers, particularly halogenated isobutylene-based polymers, and more particularly to blends of semi-crystalline polymers with brominated butyl rubber having improved green (pre-cure) strength and improved impermeability, and methods for its preparation.
BACKGROUND OF THE INVENTION
to Isobutylene-based polymers have been blended with numerous compounds such as natural rubber in order to improve its various properties, such as elasticity, strength, air impermeability, etc. Natural rubber (NR) is known to crystallize upon extension and is known to have very high molecular weight fractions, both of which help improve its green properties. The terms "green properties" and "green strength"
are terms applied to denote the strength, cohesiveness and dimensional stability of rubber compounds before they are vulcanized or cured. Such properties axe important in fabricating rubber articles from green compounds, particularly composites such as tires, but also can be important in extruded items such as innertubes and molded articles such as pharmaceutical stoppers. Isobutylene-based polymers are therefore 2o blended with natural rubber when green properties need to be improved.
However, green strength properties of isobutylene-based polymers are often adverse to those of natural rubber, particularly at elevated temperatures of up to 40 to 70°C. Addition of natural rubber reduces the barrier properties of isobutylene-based polymer/natural rubber blends significantly, which is undesirable for applications requiring low permeability to gases, such as in tires and in bladder applications. Heat stability of cured compounds is also diminished in natural rubber blends.
Isobutylene-based polymers, particularly halogenated isobutylene-based polymers, and more particularly brominated butyl rubber are the primary blends of 3o most tire liners, heat resistant tubes, bladders and other commercially known products such as pharmaceutical ware. The term "butyl rubber" as employed herein is intended to refer to a vulcaxuzable rubbery copolymer containing, from 85 wt% to 99.5 wt%
FIELD OF INVENTION
This invention relates to isobutylene-based polymers, particularly halogenated isobutylene-based polymers, and more particularly to blends of semi-crystalline polymers with brominated butyl rubber having improved green (pre-cure) strength and improved impermeability, and methods for its preparation.
BACKGROUND OF THE INVENTION
to Isobutylene-based polymers have been blended with numerous compounds such as natural rubber in order to improve its various properties, such as elasticity, strength, air impermeability, etc. Natural rubber (NR) is known to crystallize upon extension and is known to have very high molecular weight fractions, both of which help improve its green properties. The terms "green properties" and "green strength"
are terms applied to denote the strength, cohesiveness and dimensional stability of rubber compounds before they are vulcanized or cured. Such properties axe important in fabricating rubber articles from green compounds, particularly composites such as tires, but also can be important in extruded items such as innertubes and molded articles such as pharmaceutical stoppers. Isobutylene-based polymers are therefore 2o blended with natural rubber when green properties need to be improved.
However, green strength properties of isobutylene-based polymers are often adverse to those of natural rubber, particularly at elevated temperatures of up to 40 to 70°C. Addition of natural rubber reduces the barrier properties of isobutylene-based polymer/natural rubber blends significantly, which is undesirable for applications requiring low permeability to gases, such as in tires and in bladder applications. Heat stability of cured compounds is also diminished in natural rubber blends.
Isobutylene-based polymers, particularly halogenated isobutylene-based polymers, and more particularly brominated butyl rubber are the primary blends of 3o most tire liners, heat resistant tubes, bladders and other commercially known products such as pharmaceutical ware. The term "butyl rubber" as employed herein is intended to refer to a vulcaxuzable rubbery copolymer containing, from 85 wt% to 99.5 wt%
combined isoolefin derived units having from 4 to 8 carbon atoms. Such copolymers and their preparation are well known. See, e.g., RUBBER TECHNOLOGY 284-321 (Chaprrian & Hall 1995). Halogenated butyl rubber, particularly brominated butyl rubber, is also well known. It may be prepared by treating a solution of butyl rubber, in an organic solvent, with bromine and recovering the brominated butyl rubber by contacting it with steam amd drying the resulting aqueous slurry.
Brominated butyl rubber typically contains less than one bromine atom per carbon-carbon double bond originally present in the polymer or from less than 3 wt%
l0 (weight percent) bromine. The Mooney viscosity of the halobutyl rubbers useful in the instant invention, measured at 125°C (ML 1+8), range from 20 to 80, more preferably from 25 to 55, and most preferably from 30 to 50. It is a relatively chemically resistant, rubbery polymer which can be compounded and cured to produce synthetic rubber with an outstanding air impermeability, useful in making tire innerliners and innertubes.
Brominated butyl rubber has a greater degree of reactivity than butyl rubber, so that it can be blended with other unsaturated polymers and co-vulcanized therewith, which the unreactivity of butyl precludes. Brominated butyl rubber vulcanizates, however, show good air impermeability, heat aging characteristics and general chemical resistance. It finds one of its principal uses in the tubeless tire innerliners. Such liners are in effect thin sheets of rubber, adhered to the tire carcass by co-vulcanization with the rubbers comprising the tire carcass. The heat aging characteristics air impermeability and co-vulcanizability of brominated butyl rubber render it suitable for use in such tire innerliners. Other known uses for halogenated butyl rubber include white sidewall compounds for tires, heat resistant tubes and bladders.
A deficiency of butyl and halobutyl rubber is its lack of green strength when 3o alone. In addition, the elongation characteristics of the uncured compounds can be used as a valuation of green strength. Lack of green strength renders difficult the processing and molding of rubber compounds based on butyl rubber. Green strength, viscosity and elastic memory are important properties influencing the processability of polymers and compounds in various end-use applications, e.g., tire fabrication. For example, in the manufacture of tire liners, very thin sheets of butyl rubber compound have to be prepared, applied to the green tire carcass and then cured. If the butyl or halobutyl rubber compound is deficient in green strength, there is risk of rupturing the thin sheets during processing unless very careful handling thereof is undertaken.
U.S. 4,256,857 discloses the improvement of green strength by treating the brominated butyl rubber with relatively small amounts of certain organic amine 1o compounds. Examples of suitable amine compounds include N,N-dimethyl hexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine and N,N-dimethylbenzylamine. These amine compounds have been found to provide green strength and allow the retention of good processing properties. While other amine compounds may be reacted with brominated butyl rubber to improve the strength of the rubber compound they generally also cause the rubber compound to be of inferior processing properties. In either case, heating and time requirements that are not efficient or practical for quick application for compounding in industrial applications.
2o U.S. 5,162,409 to Mo~ocskowski describes a rubber blend suitable for use in automobile tire treads wherein the blend comprises a halogenated isobutylene rubber which can be the sole rubber of the blend or one of a combination of rubbers.
A
preferred embodiment comprises a rubber component comprising 20 to 60 wt%
styrene/butadiene rubber, 20 to 60 wt% butadiene rubber, and 10 to 30 wt% of a halogenated rubber, a silica filler, and an organosilane cross-linking agent.
It is disclosed that in a preferred embodiment, the rubber blends comprise 10 to 30 parts per 100 parts rubber (phr) of untreated, precipitated silica employed with an effective amount of organosilane coupling agent, for example, 1 to 8 phr. However, the green strength properties of the isobutylene rubber or blends thereof are not significantly improved.
The prior art has not addressed the full complement of green strength properties. In particular, what is needed is a blend that has improved relaxation and other properties to allow the blend to be processed at elevated temperatures, for example, at around 50°C, or from about 40 to 70°C. The present invention provides for a novel blend which addresses the present need for improved green strength while maintaining adequate impermeability.
SUMMARY OF THE INVENTION
In accordance with the present invention, an embodiment is directed to a blend comprising an isobutylene-based polymer and a semi-crystalline copolymer (SCC) which improves green strength properties while maintaining the barrier and oxidative to heat aging properties. The SCCs are generally semi-compatible with isobutylene-based polymers and have crystalline melting points below the temperatures used in the mixing and shaping operations. An embodiment is a barrier membrane having an isobutylene-based polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer having a melting point of from 25°C to 105°C and a heat of fusion from 2 J/g to 120 J/g as determined by differential scanning calorimetry (DSC) in one embodiment, from 10 J/g to 90 J/g in another embodiment, and from 20 J/g to 80 J/g in yet another embodiment.
In accordance with another embodiment of the present invention, the blend is 2o an isobutylene-based polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer wherein the ethylene content is at least from 45 wt% by weight of the SCC. Generally, the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 16 carbon atoms in one embodiment.
The crystallinity arises from the ethylene derived units.
In accordance with a further embodiment, a tire innerliner or innertube is a brominated butyl rubber polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer blend wherein the semi-crystalline ethylene copolymer has a melting point by DSC of from 25°C to 105°C in one embodiment, from 25°C to 90°C
3o in another embodiment, and from 35°C to 80°C in yet another embodiment, and an average ethylene content of at least 45 wt% in one embodiment, and at least 60 wt%
in another embodiment, and at least 70 wt% in yet another embodiment, the wt%
relative to the total weight of the SCC.
DETAILED DESCRIPTION OF THE INVENTION
Brominated butyl rubber typically contains less than one bromine atom per carbon-carbon double bond originally present in the polymer or from less than 3 wt%
l0 (weight percent) bromine. The Mooney viscosity of the halobutyl rubbers useful in the instant invention, measured at 125°C (ML 1+8), range from 20 to 80, more preferably from 25 to 55, and most preferably from 30 to 50. It is a relatively chemically resistant, rubbery polymer which can be compounded and cured to produce synthetic rubber with an outstanding air impermeability, useful in making tire innerliners and innertubes.
Brominated butyl rubber has a greater degree of reactivity than butyl rubber, so that it can be blended with other unsaturated polymers and co-vulcanized therewith, which the unreactivity of butyl precludes. Brominated butyl rubber vulcanizates, however, show good air impermeability, heat aging characteristics and general chemical resistance. It finds one of its principal uses in the tubeless tire innerliners. Such liners are in effect thin sheets of rubber, adhered to the tire carcass by co-vulcanization with the rubbers comprising the tire carcass. The heat aging characteristics air impermeability and co-vulcanizability of brominated butyl rubber render it suitable for use in such tire innerliners. Other known uses for halogenated butyl rubber include white sidewall compounds for tires, heat resistant tubes and bladders.
A deficiency of butyl and halobutyl rubber is its lack of green strength when 3o alone. In addition, the elongation characteristics of the uncured compounds can be used as a valuation of green strength. Lack of green strength renders difficult the processing and molding of rubber compounds based on butyl rubber. Green strength, viscosity and elastic memory are important properties influencing the processability of polymers and compounds in various end-use applications, e.g., tire fabrication. For example, in the manufacture of tire liners, very thin sheets of butyl rubber compound have to be prepared, applied to the green tire carcass and then cured. If the butyl or halobutyl rubber compound is deficient in green strength, there is risk of rupturing the thin sheets during processing unless very careful handling thereof is undertaken.
U.S. 4,256,857 discloses the improvement of green strength by treating the brominated butyl rubber with relatively small amounts of certain organic amine 1o compounds. Examples of suitable amine compounds include N,N-dimethyl hexylamine, N,N-dimethyldodecylamine, N,N-dimethyloctadecylamine, N,N-diethyldecylamine and N,N-dimethylbenzylamine. These amine compounds have been found to provide green strength and allow the retention of good processing properties. While other amine compounds may be reacted with brominated butyl rubber to improve the strength of the rubber compound they generally also cause the rubber compound to be of inferior processing properties. In either case, heating and time requirements that are not efficient or practical for quick application for compounding in industrial applications.
2o U.S. 5,162,409 to Mo~ocskowski describes a rubber blend suitable for use in automobile tire treads wherein the blend comprises a halogenated isobutylene rubber which can be the sole rubber of the blend or one of a combination of rubbers.
A
preferred embodiment comprises a rubber component comprising 20 to 60 wt%
styrene/butadiene rubber, 20 to 60 wt% butadiene rubber, and 10 to 30 wt% of a halogenated rubber, a silica filler, and an organosilane cross-linking agent.
It is disclosed that in a preferred embodiment, the rubber blends comprise 10 to 30 parts per 100 parts rubber (phr) of untreated, precipitated silica employed with an effective amount of organosilane coupling agent, for example, 1 to 8 phr. However, the green strength properties of the isobutylene rubber or blends thereof are not significantly improved.
The prior art has not addressed the full complement of green strength properties. In particular, what is needed is a blend that has improved relaxation and other properties to allow the blend to be processed at elevated temperatures, for example, at around 50°C, or from about 40 to 70°C. The present invention provides for a novel blend which addresses the present need for improved green strength while maintaining adequate impermeability.
SUMMARY OF THE INVENTION
In accordance with the present invention, an embodiment is directed to a blend comprising an isobutylene-based polymer and a semi-crystalline copolymer (SCC) which improves green strength properties while maintaining the barrier and oxidative to heat aging properties. The SCCs are generally semi-compatible with isobutylene-based polymers and have crystalline melting points below the temperatures used in the mixing and shaping operations. An embodiment is a barrier membrane having an isobutylene-based polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer having a melting point of from 25°C to 105°C and a heat of fusion from 2 J/g to 120 J/g as determined by differential scanning calorimetry (DSC) in one embodiment, from 10 J/g to 90 J/g in another embodiment, and from 20 J/g to 80 J/g in yet another embodiment.
In accordance with another embodiment of the present invention, the blend is 2o an isobutylene-based polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer wherein the ethylene content is at least from 45 wt% by weight of the SCC. Generally, the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 16 carbon atoms in one embodiment.
The crystallinity arises from the ethylene derived units.
In accordance with a further embodiment, a tire innerliner or innertube is a brominated butyl rubber polymer and a SCC, the SCC being a semi-crystalline ethylene copolymer blend wherein the semi-crystalline ethylene copolymer has a melting point by DSC of from 25°C to 105°C in one embodiment, from 25°C to 90°C
3o in another embodiment, and from 35°C to 80°C in yet another embodiment, and an average ethylene content of at least 45 wt% in one embodiment, and at least 60 wt%
in another embodiment, and at least 70 wt% in yet another embodiment, the wt%
relative to the total weight of the SCC.
DETAILED DESCRIPTION OF THE INVENTION
5 The present invention is a blend of an isobutylene-based elastomer (such as,, for example, butyl rubber) and a semi-crystalline copolymer (SCC) that exhibits improved green strength, green elongation, and green relaxation properties. A
further embodiment of the present invention is a blend of any isobutylene-based elastomer and SCC which exhibits improved aging properties and improved barrier properties.
to The improvement in green strength according to the invention is achieved without substantial sacrifice of any of the other desirable properties or processability of isobutylene-based elastomers and does not interfere with the subsequent curing operations conventionally conducted with isobutylene-based elastomers or the usefulness of the vulcanizates so obtained.
The Semi-Crystalline Copolymer It was found that a class of preferably saturated (no backbone unsaturation), SCCs can be added to isobutylene-based polymers to improve green strength properties while maintaining the barrier and oxidative heat aging properties.
These 2o polymers are generally at least semi-compatible with isobutylene-based polymers and have crystalline melting points below the temperatures used in mixing and shaping operation. At handling and some further processing operations, such as tire building, done at temperatures below the crystalline melting point of the SCCs, the green properties are enhanced in blends of the present invention.
Generally, the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 16 carbon atoms in one embodiment, and in another embodiment the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 10 carbon atoms, wherein the SCC has some degree of crystallinity. In a further embodiment, the SCC is a copolymer of 1-butene derived units and another alpha-olefin derived unit, the other alpha-olefin having from 5 to 16 carbon atoms, wherein the SCC also has some degree of crystallinity. The SCC can also be a copolymer of ethylene and styrene.
More specifically, one embodiment of the SCC is, a thermoplastic copolymer, preferably random, of ethylene derived units an alpha-olefin derived units having from 4 to 16 carbon atoms, the SCC having a melting point by DSC analysis of from 25°C to 105°C in one embodiment, from 25°C to 90°C
in another embodiment, and from 35°C to 80°C in yet another embodiment, and an average ethylene content by weight of from at least 45% in one embodiment, and from at least 60% in another to embodiment, and from at least 70% in yet another embodiment, the wt%
relative to the total weight of the SCC. The SGG preferably has a heat of fusion from 2 J/g to 120 J/g as determined by DSC (differential scanning calorimetry) in one embodiment, from 10 J/g to 90 J/g as determined by DSC in another embodiment, and from 20 J/g to 80 J/g in yet another embodiment.
The SCC of the polymer blends of the present invention is a crystallizable copolymer of ethylene (or 1-butene) derived units, and another alpha-olefin derived unit having from 4 to 16 carbon atoms in one embodiment, and from 4 to 10 carbon atoms in another embodiment. In one embodiment when ethylene is one copolymer, the alpha-olefin unit is derived from 1-butene, and 1-octene in yet another embodiment. The crystallinity of the SCC axises from crystallizable ethylene sequences. Blends, and the process for producing blends wherein ethylene and C4 to C16 alpha-olefins are used are more fully described in U.S. 5,272,236, 5,665,800, 5,783,638, 5,191,052, 5,382,630, 5,382,631, and 5,084,534. In yet another embodiment, the SCC is copolymer of 1-butene derived units and a CS to Clo alpha olefin derived units, the crystallizable units being derived from the 1-butene.
The SCC of the present invention preferably includes a random crystallizable copolymer having a narrow compositional distribution. The SCC is statistically 3o random in the distribution of the ethylene and alpha-olefin comonomer sequences along the chain. There is substantially no statistically significant difference in the SCC, either among two polymer chains or along any one chain. Crystallization is measured by DSC, as described herein. In all SCC, the length and distribution of polyethylene sequences is consistent with the substantially random statistical crystallizable copolymerization.
The SCC desirably has a single broad melting transition as determined by DSC. Typically, a sample of the SCC will show secondary melting peaks adjacent to principal peak. These are considered together as single melting point and the highest of these peaks is considered the melting point. These SCC polymers have a melting point of less than 105°C in one embodiment, less than 100°C in another embodiment, to and between 25°C and 105°C in another embodiment, and between 25°C and 90°C in yet another embodiment, and between 35 °C and 80 °C in yet another embodiment, and a heat of fusion of less than 120 J/g in one embodiment, less than 90 J/g in another embodiment, and less than 80 J/g in yet another embodiment, as determined by DSC.
The weight average molecular weight of the SCC can be between 10,000 to 5,000,000 in one embodiment, and from 80,000 to 500,000 in another embodiment, with a polydispersity index (PDI) between 1.5 to 40.0 in one embodiment, between 1.8 to 5 in another embodiment, and between 1.8 to 3 in yet another embodiment. It 2o is desirable that the SCC have a Melt Index (MI) that is at a level of greater than l, so long as the crystallinity of the SCC is within the ranges stated above. The MI
can be between 0.1 and 5000 in one embodiment, greater than 35 in another embodiment, greater than 100 in yet another embodiment, between 0.1 and 1000 in yet another embodiment, and between 0.5 and 100 in yet another embodiment as measured by ASTM D1238.
The semi-crystalline nature, or diminished level of crystallinity, in the SCC
of the invention relative to a crystalline homopolymer of ethylene derived units, is obtained by incorporating from 5 to 55 wt% by weight alpha-olefin in one 3o embodiment, from 6 to 40 wt% by weight alpha-olefin in another embodiment, and from 8 to 30 wt% by weight alpha-olefin derived units in yet another embodiment into the copolymer, the wt% relative to the total weight of the SCC. The alpha-olefins comprise one or more members of the group C2, C4-C 16 alpha-olefins, and styrenes in one embodiment. As discussed above, one desirable alpha-olefin is a C4 (the EXACTTM 4033 plastomer, a C2, C4 copolymer, commercially available from ExxonMobil Chemical Company) and another is a Cg (the EXACTTM 8201 plastomer, a C2, Cg copolymer, commercially available from ExxonMobil Chemical Company).
More than one SCC as defined in the present application may be used as the SCC component of the invention. The different SCCs may differ in their crystalliiuty 1o so long as the crystallinity falls within the described ranges.
The semicrystalline polymer component may contain small quantities of at least one dime, desirably at least one of the dimes is a non-conjugated dime to aid in the vulcanization and other chemical modification when present. The amount of dime is limited to be no greater than 10 wt% and desirably no greater than 5 wt%.
The dime may be selected from the group consisting of those that are used for the vulcanization of ethylene propylene rubbers and desirably ethylidene norbornene, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene (available from DuPont Chemicals).
Rubber Component A second component of the blends of the invention is an isobutylene-based elastomeric copolymer or other rubber component. In one embodiment, isobutylene-based polymers are employed in the blend of the invention, while halogenated isobutylene-based polymers are employed in another embodiment of the blend, and brominated butyl rubber, including star branched butyl rubber, are employed in yet another embodiment of the blend of the invention. The aforementioned list of isobutylene-based polymers are available from ExxonMobil Chemical Co.
(Houston, TX) and described in LT.S. 2,631,984, 2,964,489, 3,099,644, and 5,021,509. The isobutylene-based polymer may be selected from the group consisting of butyl rubber, polyisobutylene, random copolymers of a C4 to C7 isomonoolefin and a para-alkylstyrene, such as EXXPROTM, available from ExxonMobil Chemical Co. and described in U.S. 5,162,445, 5,430,118, 5,426,167, 5,548,023, 5,548,029, and 5,654,379. However, the scope of the present invention is not limited to the aforementioned blends and may include any isobutylene-based elastomeric polymer.
Such other rubbers with which the brominated butyl of this invention may be blended include natural rubber, polyisobutylene rubber, ethylene co-polymers, such as ethylene cycloolefin and ethylene isobutylene copolymers, styrene-butadiene rubber, polybutadiene, polyisoprene and styrene-butadiene polymers and the lesser to unsaturated rubbers such as ethylene-propylene-dime polymers (EPDM). EPDM
is the ASTM designation for a terpolymer of ethylene, propylene and a non-conjugated diolefin. One embodiment of the EPDM terpolymer is VISTALON 2200TM grade, available from ExxonMobil Chemical Company. Additional acceptable polymers are described in U.S. 5,763,556 and 5,866,665.
An embodiment of the primary rubber component present is natural rubber.
Natural rubbers are described in detail by Subramaniam in RUBBER TECHNOLOGY
179-208 (Van Nostrand Reinhold Co. Inc., Maurice Morton, ed. 1987). Desirable embodiments of the natural rubbers of the present invention are selected from the 2o group consisting of Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20, and SMR 50 and mixtures thereof, wherein the natural rubbers have a Mooney viscosity at 100°C (ML 1+4) of from 30 to 120, more preferably from 40 to 65. The Mooney viscosity test referred to herein is in accordance with ASTM D-1646.
Fillers The blends of the present invention may have one or more filler components such as calcium carbonate, clay, silica, talc, titanium dioxide, and carbon black. In one embodiment, the filler is carbon black or modified carbon black. The filler is reinforcing grade carbon black present at a level of from 10 to 100 phr of the blend, 3o more preferably from 30 to 80 phr. Useful grades of carbon black as described in RUBBER TECHNOLOGY 59-85 (Van Nostrand Reinhold Co. Inc., Maurice Morton, ed.
1987) range from N110 to N990. More desirably, embodiments of the carbon black useful in, for example, tire treads are N229, N351, N339, N220, N234 and N110 provided in ASTM (D3037, D1510, and D3765). Embodiments of the carbon black useful in, for example, sidewalls in tires, are N330, N351, N550, N650, N660, and N762.
Preparation of the Blend The blends of the present invention typically have from 3 to 95 wt% of the SCC by weight of the blend in one embodiment, and from 5 to 30 wt% by weight of the blend in another embodiment. The components are blended by techniques known l0 to those skilled in the art, and is not limited therein by the method of blending or mixing.
The following data demonstrates improvements in green properties with little consequence to barrier or cured properties for the inventive blends. Moreover, the data suggest that blending of low molecular weight SCC with isobutylene-based polymers may enable reduction in plasticizer levels, such as oil and STRUKTOLTM
MS-40, (Struktol Chemicals, Akron, Ohio) to further reduce barrier disadvantages while maintaining good compound processability. Also, low molecular weight polyisobutylene polymer, i.e. polyisobutylene oil, can be used as a plasticizer in place of processing oils such as FLEXONTM 876 used in the present examples.
Plasticizers are added for obtaining acceptable processing characteristics such as mixing, milling, calendering, extrusion and molding. When low molecular weight SCC are added they can also act as plasticizers while the crystallinity of the SCC maintains improved green properties even at lower molecular weight.
Suitable barrier membranes, such as tire innerliner and innertube blends, may be prepared by using conventional mixing techniques including, e.g., kneading, roller milling, extruder mixing, internal mixing (such as with a BANBURYTM mixer), etc.
The sequence of mixing and temperatures employed are well known to the skilled rubber compounder, the objective being the dispersion of polymers, fillers, activators and curatives in the polymer matrix without excessive heat buildup. A useful mixing procedure utilizes a BANBURYTM mixer in which the polymeric components, fillers, and other resins, plasticizers, and oils are added and the blend mixed for the desired time to a particular temperature to achieve adequate dispersion of the ingredients.
Alternatively, the polymers and a portion of the fillers (e.g., one-third to two-thirds) are mixed for a short time (e.g., 1 to 3 minutes) followed by the remainder of the fillers and oil. Mixing is continued for 5 to 10 minutes at high rotor speed during which time the mixed components reach a temperature of 150°C. Following cooling, the components are mixed in a second step on a rubber mill or in a BANBURYTM
mixer during which the curing agent and optional accelerator are thoroughly and uniformly dispersed at a relatively low temperature, e.g., 80° to 105° C. Variations l0 in mixing will be readily apparent to those skilled in the art and the present invention is not limited to any specific mixing procedure. The mixing is performed to disperse all components of the blend thoroughly and uniformly.
The improved green strength blend of the present invention can be compounded alone or blended with other rubbers and processed with the same ingredients and the same procedures as used with conventional brominated butyl rubber, i.e. with fillers such as carbon black, silica or clay, with plasticizers, extender oils, such as isobutylene oil, low molecular weight polybutenes, and tackifiers and with vulcanizing agents such as zinc oxide and/or sulfur with or without additional 2o vulcanization accelerations. Such other rubbers with which the brominated butyl of this invention may be blended include natural rubber, polyisobutylene rubber, ethylene co-polymers, such as ethylene cycloolefin and ethylene isobutylene copolymers, styrene-butadiene rubber, polybutadiene, polyisoprene and styrene-butadiene polymers and the lesser unsaturated rubbers such as ethylene-propylene-diene polymers (EPDM). EPDM is the ASTM designation for a terpolymer of ethylene, propylene and a non-conjugated diolefin. An embodiment of an EPDM
terpolymer is VISTALON 2200TM grade, (ExxonMobil Chemical Company, Houston, TX). Additional acceptable polymers are described in U.S. 5,763,556 and 5,866,665.
3o The improved green strength blend of the present invention, alone or blended with other rubbers, may be cured by reaction with curatives well known in the art; the amounts of such curatives being those conventionally used. Generally, polymer blends, e.g., those used to produce tires, are often crosslinked. It is known that the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinlcs formed during the vulcanization reaction. (See, e.g., W.F. Helt, B.H. To & W.W
Paris, The Post Irulcahization Stabilization for NR, RUBBER WORLD 18-23 (1991)) Generally, polymer blends may be crosslinked by adding curative molecules, for example sulfur, zinc, metals, radical initiators, etc. followed by heating. This method may be accelerated and is often used for the vulcanization of elastomer blends. The mechanism for accelerated vulcanization of natural rubber involves complex interactions between the e o curative, accelerator, activators and polymers. Ideally, the entire available curative is consumed in the formation of effective crossliiiks that join together two polymer chains and enhance the overall strength of the polymer matrix. Numerous curatives are known in the art and include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2'-benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dehydrate (ERP 390), 2-(morpholinothio) benzothiazole (MBS or MOR), blends of 90% MOR and 10% MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEH); and MC sulfur. In addition, various vulcanization systems are known 2o in the art. (For example, see Formulation Design and Curing Characteristics of NBR
Mixes for Seals, RUBBER WORLD 25-30 (1993)). The amount of other compounding ingredients is within the ranges known in the axt.
The following examples include data that illustrates the improvements found to green elongation, green strength and relaxation integrity in barrier membranes and blends in general, such as tore innerliner model compounds. The barrier membranes and blends produced with the aforementioned blends may be used in the manufacture of articles, such as curable articles and/or vulcanizates, such tire innerliners, tire innertubes, pharmaceutical stoppers, roof sheeting, belts, tubes, hoses, and so on. The 3o barrier membrane may be used to prevent gas or fluid intrusion or leakage.
Test Methods I. Green strengthlstress relaxation The green strength tests follow the guidelines set by ASTM D4I2-87, and modified as described.
A. Sample preparation. Test pad samples are prepared from a 102 x 102 x 6.0 mm milled sample weighing approximately 85 + 5 grams. The uncured sample is placed between MYLARTM sheets in a room temperature mold, noting the direction of the mill grain. The mold is loaded in a curing press set at approximately 100°C and l0 pressed for a total of approximately five minutes; two minutes at low pressure (approximately 7800 lbs.) and three minutes at high pressure (30,000 lbs.).
The molded pad is then removed and allowed to sit at room temperature for at least approximately 24 hours before testing. The testing samples are cut in 12 mm wide x 75-mm long samples without removing the MYLARTM backing, with mill grain along the sample length.
B. Testihg. The standard test temperature is preferably 23 + 2°C (open laboratory atmosphere) or 50°C. Samples are tested using an Instron tester having the following settings:
2o Load Cell: 1000 Newtons Pneumatic jaws: set at 30-psi air pressure Crosshead speed: 127 mm/min Chart Speed: 50 mm/min Full Scale: 25 Newtons Jaw separation: 25 mm The MYLARTM backing is removed from each side of the sample, for example by using acetone. The sample thickness is measured and marked with a 25-mm benchmark. The ends of the sample are covered with MYLARTM on each side to prevent adhesion to the jaws. The sample is placed in the jaws of the tester, aligning the benchmark with the top and bottom edges of the jaws. The sample is stretched 100% (from 25 to 50 mm jaw separation). The tensile force is monitored after deformation is stopped until the tensile force exceeds the point at which the force decays by 75% (to 25% of the value after the crosshead is stopped).
C. Calculations. Using sample dimensions (width and thickness) and force data, the following can be calculated:
(i) Green strength: stress at 100% (at the point the crosshead stopped).
N/mm2 = Force (N)/(sample width (mm))(tluckness (mm)).
(ii) Relaxation Time (t75): from the recorder chart compute the time it took for the stress (force) to decay by 75% (from its value when relaxation started to the point l0 the stress decayed to 25% of this value). The time should be counted after the crosshead stopped (it should exclude the deformation time of 12 sec).
(iii) Test three (3) specimens for each compound. Report the median as green strength and time to 75% decay.
D. Normalization. Green strength and stress relaxation values obtained for various materials can be normalized against a given material. This is accomplished by dividing each resulting reference stress by the reference stress for the standard material. The normalization should be done for measurements using identical parameters. However, after normalization, materials measured with one or more 2o changes in the test parameters can still be compared if the standard material is the same material and was measured with both sets of parameters. For example, if the extent of decay is 75 % in one set of tests and 50 % in another set, both sets can be normalized against the same standard which is itself measured under both conditions.
Since decay follows an exponential form, a normalized relaxation time is not strongly dependent on the extent of decay.
Permeability was tested by the following method. Thin, vulcanized test specimens from the sample blends were mounted in diffusion cells and conditioned in an oil bath at 65°C. The time required for air to permeate through a given specimen is 3o recorded to determine its air permeability. Test specimens were circular plates with 12.7-cm diameter and 0.38-mm thickness.
The procedure used in the present application for Differential Scanning Calorimetry (DSC) is described as follows. Preferably, 6 mg to 10 mg of pellets is placed in a Differential Scanning Calorimeter and cooled to -50°C to -70°C. The sample is then heated at 20°C/min to attain a final temperature of 200°C to 220°C.
5 The thermal output is recorded as the area under the melting peak of the sample which IO
is typically at a maximum peak at 30°C to 175°C and occurs between the temperatures of 0°C and 200°C. The thermal output is measured in Joules as a measure of the heat of fusion. The melting point is recorded as the temperature of the greatest heat absorption within the range of melting temperature of the sample.
Further descriptions of the testing procedures are described in U.S.
5,071,913.
Green strength, viscosity and elastic memory are important properties affecting the processability of polymers and compounds in various end-use applications, e.g., tire fabrication. Tire innerliner compounds, for example, require low elastic memory. It 15 would be expected that this property would be enhanced by lower viscosity, but it must be balanced against the need to maintain acceptable green strength that directionally increases as viscosity increases. Lower viscosity polymers are also preferred for easier mixing and calendering.
Examples A series of compounds were mixed in an internal mixer using a model formulation. The compounds were based on one bromobutyl rubber (Sample 1), or blends of the bromobutyl rubber with the SCC according to the present invention (Samples 3-6), or with natural rubber (Sample 2). The SCC was introduced at levels of either 10 or 20 phr (parts per hundred rubber), the NR was introduced at 20 phr (Sample 2) as shown in the Table 1. Oil (STRUCTOLTM 40 MS) was introduced at 5 phr and carbon black was introduced at 60 phr in Samples 1-6.
The cure system shown in the Table 1 was incorporated on a mill. Table 2 3o describes two embodiments of the SCC used in the Sample blends 3-6.
Green properties of the compounds without the cure system components were measured at room temperature and at SO°C and shown in Table 3. It was found that for consistent results the samples for green properties testing had to be carefully calendered before molding. Samples were cut out of molded pads into strips of 2.S
inches (6.35 cm) long, O.S inch wide (1.27 cm) and 0.1 inch thick (0.254 cm), such that the length of the samples corresponded to the direction of the calendered sheet leaving the calender. In all tests the strips were clamped in a tensile tester such that the distance between the grips was 1 inch (2.54 cm). A green tensile test was also conducted at SO°C as shown in Table 3. For the tensile tests the same sample and test to configuration was used with the sample pulled to break at a rate of 10 inches per minute (25.4 cm/min). All tests were carried on in triplicates with the median value being the recorded one.
The results for room temperature green stress relaxation are expressed as the 1S green strength in Table 3. The green strength may be defined as being the stress at the end of extension (100% extension) after extension at S inch/min (12.7 cm/min), and the time to relax the stress by 7S% from the stress at the end of extension.
The time was measured from the instant the extension was stopped. The green strength test at SO°C uses similar parameters to the room temperature test. The parameters recorded 2o for the SO°C green tensile test were 100% modulus, and % elongation at break. The parameters were also reported as the median sample out of three runs. The results for green properties are given in Table 3 and for selected samples according to the present invention in the stress-time and stress-strain traces at SO°C in Table 3.
25 For room temperature green strength it can be seen that all samples with SCC
have higher green strength. Sample 1 representing the lowest commercially available molecular weight bromobutyl (commercially available as BR 2222, ExxonMobil Chemical Company, Houston TX) without a second polymer showed the fastest relaxation time. For the SO°C green strength, the relative ranking is similar; the 30 relaxation times are different between the Sample 1 and Samples 3-6 in that the values are less at SO°C than at room temperature. This is an advantageous property for high temperature processing of the uncured blends to form such articles as tires, where the uncured blend must be stretched and deformed into the desired shape, then maintain that shape after a desirably short period of time. An increase in elongation to break at 50°C is shown by all compounds containing 20 phr SCC. The higher elongation is important for maintaining material integrity when processing calendered sheets at higher temperature, such as between 40 and 70°C. The higher green strength also helps in handling by helping reducing deformation during processing.
Processability during mixing, milling and calendering (or other high temperature green compound shaping such as extrusion) was not adversely affected to by the addition of the SCC blends as experienced during sample preparation for this example. This behavior can be demonstrated in capillary flow as shown in the Table 4. Capillary extrusion was conducted in a Monsanto Processability Tester (MPT) instrument commercially available from Alpha Technologies of Akron, Ohio, at 100°C. The lower die swell at high shear rates of the SCC blends vs.
the 100%
bromobutyl formulation indicate reduced elasticity in processing which is helpful in shaping operations, even when high shear viscosities are similar. Viscosities may be further reduced if the molecular weight of the SCC is lowered, or the MI is increased.
Cured physical properties shown in the Tables 5 show that the modulus and 2o elongation at break are is not adversely affected upon addition of the SCC.
An important property for isobutylene-based polymers in gas containing applications is air impermeability. For example, barrier membranes, or innerliners in tires, and innertubes for tires and bicycles, must contain pressurized gas for extended periods of time, and thus must have a high degree of impermeability. The data in Table 5 establishes improved air° permeability at 65°C when blending isobutylene-based polymers with the SCC disclosed in this application as compared to natural rubber or amorphous polymers and blends thereof. Reducing oil levels can reduce permeability significantly, while an increase in carbon black level is only slightly advantageous. Since some low molecular weight (or high MI) semi crystalline polymers and copolymers can act as plasticizers, oil levels can be reduced to improve barrier properties without impacting processing operations. Thus, the blends of the present invention are useful for articles that require a. low gas permeability such as inner tubes and inner liners for automobile tires, truck tires, and tubes for bicycles, motorcycles, and other applications.
Although the invention has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and to scope of the present invention as defined by the appended claims.
All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted. Further, all documents cited herein, including testing procedures, are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted.
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further embodiment of the present invention is a blend of any isobutylene-based elastomer and SCC which exhibits improved aging properties and improved barrier properties.
to The improvement in green strength according to the invention is achieved without substantial sacrifice of any of the other desirable properties or processability of isobutylene-based elastomers and does not interfere with the subsequent curing operations conventionally conducted with isobutylene-based elastomers or the usefulness of the vulcanizates so obtained.
The Semi-Crystalline Copolymer It was found that a class of preferably saturated (no backbone unsaturation), SCCs can be added to isobutylene-based polymers to improve green strength properties while maintaining the barrier and oxidative heat aging properties.
These 2o polymers are generally at least semi-compatible with isobutylene-based polymers and have crystalline melting points below the temperatures used in mixing and shaping operation. At handling and some further processing operations, such as tire building, done at temperatures below the crystalline melting point of the SCCs, the green properties are enhanced in blends of the present invention.
Generally, the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 16 carbon atoms in one embodiment, and in another embodiment the SCC is a copolymer of ethylene derived units and alpha-olefin derived units, the alpha-olefin having from 4 to 10 carbon atoms, wherein the SCC has some degree of crystallinity. In a further embodiment, the SCC is a copolymer of 1-butene derived units and another alpha-olefin derived unit, the other alpha-olefin having from 5 to 16 carbon atoms, wherein the SCC also has some degree of crystallinity. The SCC can also be a copolymer of ethylene and styrene.
More specifically, one embodiment of the SCC is, a thermoplastic copolymer, preferably random, of ethylene derived units an alpha-olefin derived units having from 4 to 16 carbon atoms, the SCC having a melting point by DSC analysis of from 25°C to 105°C in one embodiment, from 25°C to 90°C
in another embodiment, and from 35°C to 80°C in yet another embodiment, and an average ethylene content by weight of from at least 45% in one embodiment, and from at least 60% in another to embodiment, and from at least 70% in yet another embodiment, the wt%
relative to the total weight of the SCC. The SGG preferably has a heat of fusion from 2 J/g to 120 J/g as determined by DSC (differential scanning calorimetry) in one embodiment, from 10 J/g to 90 J/g as determined by DSC in another embodiment, and from 20 J/g to 80 J/g in yet another embodiment.
The SCC of the polymer blends of the present invention is a crystallizable copolymer of ethylene (or 1-butene) derived units, and another alpha-olefin derived unit having from 4 to 16 carbon atoms in one embodiment, and from 4 to 10 carbon atoms in another embodiment. In one embodiment when ethylene is one copolymer, the alpha-olefin unit is derived from 1-butene, and 1-octene in yet another embodiment. The crystallinity of the SCC axises from crystallizable ethylene sequences. Blends, and the process for producing blends wherein ethylene and C4 to C16 alpha-olefins are used are more fully described in U.S. 5,272,236, 5,665,800, 5,783,638, 5,191,052, 5,382,630, 5,382,631, and 5,084,534. In yet another embodiment, the SCC is copolymer of 1-butene derived units and a CS to Clo alpha olefin derived units, the crystallizable units being derived from the 1-butene.
The SCC of the present invention preferably includes a random crystallizable copolymer having a narrow compositional distribution. The SCC is statistically 3o random in the distribution of the ethylene and alpha-olefin comonomer sequences along the chain. There is substantially no statistically significant difference in the SCC, either among two polymer chains or along any one chain. Crystallization is measured by DSC, as described herein. In all SCC, the length and distribution of polyethylene sequences is consistent with the substantially random statistical crystallizable copolymerization.
The SCC desirably has a single broad melting transition as determined by DSC. Typically, a sample of the SCC will show secondary melting peaks adjacent to principal peak. These are considered together as single melting point and the highest of these peaks is considered the melting point. These SCC polymers have a melting point of less than 105°C in one embodiment, less than 100°C in another embodiment, to and between 25°C and 105°C in another embodiment, and between 25°C and 90°C in yet another embodiment, and between 35 °C and 80 °C in yet another embodiment, and a heat of fusion of less than 120 J/g in one embodiment, less than 90 J/g in another embodiment, and less than 80 J/g in yet another embodiment, as determined by DSC.
The weight average molecular weight of the SCC can be between 10,000 to 5,000,000 in one embodiment, and from 80,000 to 500,000 in another embodiment, with a polydispersity index (PDI) between 1.5 to 40.0 in one embodiment, between 1.8 to 5 in another embodiment, and between 1.8 to 3 in yet another embodiment. It 2o is desirable that the SCC have a Melt Index (MI) that is at a level of greater than l, so long as the crystallinity of the SCC is within the ranges stated above. The MI
can be between 0.1 and 5000 in one embodiment, greater than 35 in another embodiment, greater than 100 in yet another embodiment, between 0.1 and 1000 in yet another embodiment, and between 0.5 and 100 in yet another embodiment as measured by ASTM D1238.
The semi-crystalline nature, or diminished level of crystallinity, in the SCC
of the invention relative to a crystalline homopolymer of ethylene derived units, is obtained by incorporating from 5 to 55 wt% by weight alpha-olefin in one 3o embodiment, from 6 to 40 wt% by weight alpha-olefin in another embodiment, and from 8 to 30 wt% by weight alpha-olefin derived units in yet another embodiment into the copolymer, the wt% relative to the total weight of the SCC. The alpha-olefins comprise one or more members of the group C2, C4-C 16 alpha-olefins, and styrenes in one embodiment. As discussed above, one desirable alpha-olefin is a C4 (the EXACTTM 4033 plastomer, a C2, C4 copolymer, commercially available from ExxonMobil Chemical Company) and another is a Cg (the EXACTTM 8201 plastomer, a C2, Cg copolymer, commercially available from ExxonMobil Chemical Company).
More than one SCC as defined in the present application may be used as the SCC component of the invention. The different SCCs may differ in their crystalliiuty 1o so long as the crystallinity falls within the described ranges.
The semicrystalline polymer component may contain small quantities of at least one dime, desirably at least one of the dimes is a non-conjugated dime to aid in the vulcanization and other chemical modification when present. The amount of dime is limited to be no greater than 10 wt% and desirably no greater than 5 wt%.
The dime may be selected from the group consisting of those that are used for the vulcanization of ethylene propylene rubbers and desirably ethylidene norbornene, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene (available from DuPont Chemicals).
Rubber Component A second component of the blends of the invention is an isobutylene-based elastomeric copolymer or other rubber component. In one embodiment, isobutylene-based polymers are employed in the blend of the invention, while halogenated isobutylene-based polymers are employed in another embodiment of the blend, and brominated butyl rubber, including star branched butyl rubber, are employed in yet another embodiment of the blend of the invention. The aforementioned list of isobutylene-based polymers are available from ExxonMobil Chemical Co.
(Houston, TX) and described in LT.S. 2,631,984, 2,964,489, 3,099,644, and 5,021,509. The isobutylene-based polymer may be selected from the group consisting of butyl rubber, polyisobutylene, random copolymers of a C4 to C7 isomonoolefin and a para-alkylstyrene, such as EXXPROTM, available from ExxonMobil Chemical Co. and described in U.S. 5,162,445, 5,430,118, 5,426,167, 5,548,023, 5,548,029, and 5,654,379. However, the scope of the present invention is not limited to the aforementioned blends and may include any isobutylene-based elastomeric polymer.
Such other rubbers with which the brominated butyl of this invention may be blended include natural rubber, polyisobutylene rubber, ethylene co-polymers, such as ethylene cycloolefin and ethylene isobutylene copolymers, styrene-butadiene rubber, polybutadiene, polyisoprene and styrene-butadiene polymers and the lesser to unsaturated rubbers such as ethylene-propylene-dime polymers (EPDM). EPDM
is the ASTM designation for a terpolymer of ethylene, propylene and a non-conjugated diolefin. One embodiment of the EPDM terpolymer is VISTALON 2200TM grade, available from ExxonMobil Chemical Company. Additional acceptable polymers are described in U.S. 5,763,556 and 5,866,665.
An embodiment of the primary rubber component present is natural rubber.
Natural rubbers are described in detail by Subramaniam in RUBBER TECHNOLOGY
179-208 (Van Nostrand Reinhold Co. Inc., Maurice Morton, ed. 1987). Desirable embodiments of the natural rubbers of the present invention are selected from the 2o group consisting of Malaysian rubber such as SMR CV, SMR 5, SMR 10, SMR 20, and SMR 50 and mixtures thereof, wherein the natural rubbers have a Mooney viscosity at 100°C (ML 1+4) of from 30 to 120, more preferably from 40 to 65. The Mooney viscosity test referred to herein is in accordance with ASTM D-1646.
Fillers The blends of the present invention may have one or more filler components such as calcium carbonate, clay, silica, talc, titanium dioxide, and carbon black. In one embodiment, the filler is carbon black or modified carbon black. The filler is reinforcing grade carbon black present at a level of from 10 to 100 phr of the blend, 3o more preferably from 30 to 80 phr. Useful grades of carbon black as described in RUBBER TECHNOLOGY 59-85 (Van Nostrand Reinhold Co. Inc., Maurice Morton, ed.
1987) range from N110 to N990. More desirably, embodiments of the carbon black useful in, for example, tire treads are N229, N351, N339, N220, N234 and N110 provided in ASTM (D3037, D1510, and D3765). Embodiments of the carbon black useful in, for example, sidewalls in tires, are N330, N351, N550, N650, N660, and N762.
Preparation of the Blend The blends of the present invention typically have from 3 to 95 wt% of the SCC by weight of the blend in one embodiment, and from 5 to 30 wt% by weight of the blend in another embodiment. The components are blended by techniques known l0 to those skilled in the art, and is not limited therein by the method of blending or mixing.
The following data demonstrates improvements in green properties with little consequence to barrier or cured properties for the inventive blends. Moreover, the data suggest that blending of low molecular weight SCC with isobutylene-based polymers may enable reduction in plasticizer levels, such as oil and STRUKTOLTM
MS-40, (Struktol Chemicals, Akron, Ohio) to further reduce barrier disadvantages while maintaining good compound processability. Also, low molecular weight polyisobutylene polymer, i.e. polyisobutylene oil, can be used as a plasticizer in place of processing oils such as FLEXONTM 876 used in the present examples.
Plasticizers are added for obtaining acceptable processing characteristics such as mixing, milling, calendering, extrusion and molding. When low molecular weight SCC are added they can also act as plasticizers while the crystallinity of the SCC maintains improved green properties even at lower molecular weight.
Suitable barrier membranes, such as tire innerliner and innertube blends, may be prepared by using conventional mixing techniques including, e.g., kneading, roller milling, extruder mixing, internal mixing (such as with a BANBURYTM mixer), etc.
The sequence of mixing and temperatures employed are well known to the skilled rubber compounder, the objective being the dispersion of polymers, fillers, activators and curatives in the polymer matrix without excessive heat buildup. A useful mixing procedure utilizes a BANBURYTM mixer in which the polymeric components, fillers, and other resins, plasticizers, and oils are added and the blend mixed for the desired time to a particular temperature to achieve adequate dispersion of the ingredients.
Alternatively, the polymers and a portion of the fillers (e.g., one-third to two-thirds) are mixed for a short time (e.g., 1 to 3 minutes) followed by the remainder of the fillers and oil. Mixing is continued for 5 to 10 minutes at high rotor speed during which time the mixed components reach a temperature of 150°C. Following cooling, the components are mixed in a second step on a rubber mill or in a BANBURYTM
mixer during which the curing agent and optional accelerator are thoroughly and uniformly dispersed at a relatively low temperature, e.g., 80° to 105° C. Variations l0 in mixing will be readily apparent to those skilled in the art and the present invention is not limited to any specific mixing procedure. The mixing is performed to disperse all components of the blend thoroughly and uniformly.
The improved green strength blend of the present invention can be compounded alone or blended with other rubbers and processed with the same ingredients and the same procedures as used with conventional brominated butyl rubber, i.e. with fillers such as carbon black, silica or clay, with plasticizers, extender oils, such as isobutylene oil, low molecular weight polybutenes, and tackifiers and with vulcanizing agents such as zinc oxide and/or sulfur with or without additional 2o vulcanization accelerations. Such other rubbers with which the brominated butyl of this invention may be blended include natural rubber, polyisobutylene rubber, ethylene co-polymers, such as ethylene cycloolefin and ethylene isobutylene copolymers, styrene-butadiene rubber, polybutadiene, polyisoprene and styrene-butadiene polymers and the lesser unsaturated rubbers such as ethylene-propylene-diene polymers (EPDM). EPDM is the ASTM designation for a terpolymer of ethylene, propylene and a non-conjugated diolefin. An embodiment of an EPDM
terpolymer is VISTALON 2200TM grade, (ExxonMobil Chemical Company, Houston, TX). Additional acceptable polymers are described in U.S. 5,763,556 and 5,866,665.
3o The improved green strength blend of the present invention, alone or blended with other rubbers, may be cured by reaction with curatives well known in the art; the amounts of such curatives being those conventionally used. Generally, polymer blends, e.g., those used to produce tires, are often crosslinked. It is known that the physical properties, performance characteristics, and durability of vulcanized rubber compounds are directly related to the number (crosslink density) and type of crosslinlcs formed during the vulcanization reaction. (See, e.g., W.F. Helt, B.H. To & W.W
Paris, The Post Irulcahization Stabilization for NR, RUBBER WORLD 18-23 (1991)) Generally, polymer blends may be crosslinked by adding curative molecules, for example sulfur, zinc, metals, radical initiators, etc. followed by heating. This method may be accelerated and is often used for the vulcanization of elastomer blends. The mechanism for accelerated vulcanization of natural rubber involves complex interactions between the e o curative, accelerator, activators and polymers. Ideally, the entire available curative is consumed in the formation of effective crossliiiks that join together two polymer chains and enhance the overall strength of the polymer matrix. Numerous curatives are known in the art and include, but are not limited to, the following: zinc oxide, stearic acid, tetramethylthiuram disulfide (TMTD), 4,4'-dithiodimorpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2,2'-benzothiazyl disulfide (MBTS), hexamethylene-1,6-bisthiosulfate disodium salt dehydrate (ERP 390), 2-(morpholinothio) benzothiazole (MBS or MOR), blends of 90% MOR and 10% MBTS (MOR 90), N-oxydiethylene thiocarbamyl-N-oxydiethylene sulfonamide (OTOS) zinc 2-ethyl hexanoate (ZEH); and MC sulfur. In addition, various vulcanization systems are known 2o in the art. (For example, see Formulation Design and Curing Characteristics of NBR
Mixes for Seals, RUBBER WORLD 25-30 (1993)). The amount of other compounding ingredients is within the ranges known in the axt.
The following examples include data that illustrates the improvements found to green elongation, green strength and relaxation integrity in barrier membranes and blends in general, such as tore innerliner model compounds. The barrier membranes and blends produced with the aforementioned blends may be used in the manufacture of articles, such as curable articles and/or vulcanizates, such tire innerliners, tire innertubes, pharmaceutical stoppers, roof sheeting, belts, tubes, hoses, and so on. The 3o barrier membrane may be used to prevent gas or fluid intrusion or leakage.
Test Methods I. Green strengthlstress relaxation The green strength tests follow the guidelines set by ASTM D4I2-87, and modified as described.
A. Sample preparation. Test pad samples are prepared from a 102 x 102 x 6.0 mm milled sample weighing approximately 85 + 5 grams. The uncured sample is placed between MYLARTM sheets in a room temperature mold, noting the direction of the mill grain. The mold is loaded in a curing press set at approximately 100°C and l0 pressed for a total of approximately five minutes; two minutes at low pressure (approximately 7800 lbs.) and three minutes at high pressure (30,000 lbs.).
The molded pad is then removed and allowed to sit at room temperature for at least approximately 24 hours before testing. The testing samples are cut in 12 mm wide x 75-mm long samples without removing the MYLARTM backing, with mill grain along the sample length.
B. Testihg. The standard test temperature is preferably 23 + 2°C (open laboratory atmosphere) or 50°C. Samples are tested using an Instron tester having the following settings:
2o Load Cell: 1000 Newtons Pneumatic jaws: set at 30-psi air pressure Crosshead speed: 127 mm/min Chart Speed: 50 mm/min Full Scale: 25 Newtons Jaw separation: 25 mm The MYLARTM backing is removed from each side of the sample, for example by using acetone. The sample thickness is measured and marked with a 25-mm benchmark. The ends of the sample are covered with MYLARTM on each side to prevent adhesion to the jaws. The sample is placed in the jaws of the tester, aligning the benchmark with the top and bottom edges of the jaws. The sample is stretched 100% (from 25 to 50 mm jaw separation). The tensile force is monitored after deformation is stopped until the tensile force exceeds the point at which the force decays by 75% (to 25% of the value after the crosshead is stopped).
C. Calculations. Using sample dimensions (width and thickness) and force data, the following can be calculated:
(i) Green strength: stress at 100% (at the point the crosshead stopped).
N/mm2 = Force (N)/(sample width (mm))(tluckness (mm)).
(ii) Relaxation Time (t75): from the recorder chart compute the time it took for the stress (force) to decay by 75% (from its value when relaxation started to the point l0 the stress decayed to 25% of this value). The time should be counted after the crosshead stopped (it should exclude the deformation time of 12 sec).
(iii) Test three (3) specimens for each compound. Report the median as green strength and time to 75% decay.
D. Normalization. Green strength and stress relaxation values obtained for various materials can be normalized against a given material. This is accomplished by dividing each resulting reference stress by the reference stress for the standard material. The normalization should be done for measurements using identical parameters. However, after normalization, materials measured with one or more 2o changes in the test parameters can still be compared if the standard material is the same material and was measured with both sets of parameters. For example, if the extent of decay is 75 % in one set of tests and 50 % in another set, both sets can be normalized against the same standard which is itself measured under both conditions.
Since decay follows an exponential form, a normalized relaxation time is not strongly dependent on the extent of decay.
Permeability was tested by the following method. Thin, vulcanized test specimens from the sample blends were mounted in diffusion cells and conditioned in an oil bath at 65°C. The time required for air to permeate through a given specimen is 3o recorded to determine its air permeability. Test specimens were circular plates with 12.7-cm diameter and 0.38-mm thickness.
The procedure used in the present application for Differential Scanning Calorimetry (DSC) is described as follows. Preferably, 6 mg to 10 mg of pellets is placed in a Differential Scanning Calorimeter and cooled to -50°C to -70°C. The sample is then heated at 20°C/min to attain a final temperature of 200°C to 220°C.
5 The thermal output is recorded as the area under the melting peak of the sample which IO
is typically at a maximum peak at 30°C to 175°C and occurs between the temperatures of 0°C and 200°C. The thermal output is measured in Joules as a measure of the heat of fusion. The melting point is recorded as the temperature of the greatest heat absorption within the range of melting temperature of the sample.
Further descriptions of the testing procedures are described in U.S.
5,071,913.
Green strength, viscosity and elastic memory are important properties affecting the processability of polymers and compounds in various end-use applications, e.g., tire fabrication. Tire innerliner compounds, for example, require low elastic memory. It 15 would be expected that this property would be enhanced by lower viscosity, but it must be balanced against the need to maintain acceptable green strength that directionally increases as viscosity increases. Lower viscosity polymers are also preferred for easier mixing and calendering.
Examples A series of compounds were mixed in an internal mixer using a model formulation. The compounds were based on one bromobutyl rubber (Sample 1), or blends of the bromobutyl rubber with the SCC according to the present invention (Samples 3-6), or with natural rubber (Sample 2). The SCC was introduced at levels of either 10 or 20 phr (parts per hundred rubber), the NR was introduced at 20 phr (Sample 2) as shown in the Table 1. Oil (STRUCTOLTM 40 MS) was introduced at 5 phr and carbon black was introduced at 60 phr in Samples 1-6.
The cure system shown in the Table 1 was incorporated on a mill. Table 2 3o describes two embodiments of the SCC used in the Sample blends 3-6.
Green properties of the compounds without the cure system components were measured at room temperature and at SO°C and shown in Table 3. It was found that for consistent results the samples for green properties testing had to be carefully calendered before molding. Samples were cut out of molded pads into strips of 2.S
inches (6.35 cm) long, O.S inch wide (1.27 cm) and 0.1 inch thick (0.254 cm), such that the length of the samples corresponded to the direction of the calendered sheet leaving the calender. In all tests the strips were clamped in a tensile tester such that the distance between the grips was 1 inch (2.54 cm). A green tensile test was also conducted at SO°C as shown in Table 3. For the tensile tests the same sample and test to configuration was used with the sample pulled to break at a rate of 10 inches per minute (25.4 cm/min). All tests were carried on in triplicates with the median value being the recorded one.
The results for room temperature green stress relaxation are expressed as the 1S green strength in Table 3. The green strength may be defined as being the stress at the end of extension (100% extension) after extension at S inch/min (12.7 cm/min), and the time to relax the stress by 7S% from the stress at the end of extension.
The time was measured from the instant the extension was stopped. The green strength test at SO°C uses similar parameters to the room temperature test. The parameters recorded 2o for the SO°C green tensile test were 100% modulus, and % elongation at break. The parameters were also reported as the median sample out of three runs. The results for green properties are given in Table 3 and for selected samples according to the present invention in the stress-time and stress-strain traces at SO°C in Table 3.
25 For room temperature green strength it can be seen that all samples with SCC
have higher green strength. Sample 1 representing the lowest commercially available molecular weight bromobutyl (commercially available as BR 2222, ExxonMobil Chemical Company, Houston TX) without a second polymer showed the fastest relaxation time. For the SO°C green strength, the relative ranking is similar; the 30 relaxation times are different between the Sample 1 and Samples 3-6 in that the values are less at SO°C than at room temperature. This is an advantageous property for high temperature processing of the uncured blends to form such articles as tires, where the uncured blend must be stretched and deformed into the desired shape, then maintain that shape after a desirably short period of time. An increase in elongation to break at 50°C is shown by all compounds containing 20 phr SCC. The higher elongation is important for maintaining material integrity when processing calendered sheets at higher temperature, such as between 40 and 70°C. The higher green strength also helps in handling by helping reducing deformation during processing.
Processability during mixing, milling and calendering (or other high temperature green compound shaping such as extrusion) was not adversely affected to by the addition of the SCC blends as experienced during sample preparation for this example. This behavior can be demonstrated in capillary flow as shown in the Table 4. Capillary extrusion was conducted in a Monsanto Processability Tester (MPT) instrument commercially available from Alpha Technologies of Akron, Ohio, at 100°C. The lower die swell at high shear rates of the SCC blends vs.
the 100%
bromobutyl formulation indicate reduced elasticity in processing which is helpful in shaping operations, even when high shear viscosities are similar. Viscosities may be further reduced if the molecular weight of the SCC is lowered, or the MI is increased.
Cured physical properties shown in the Tables 5 show that the modulus and 2o elongation at break are is not adversely affected upon addition of the SCC.
An important property for isobutylene-based polymers in gas containing applications is air impermeability. For example, barrier membranes, or innerliners in tires, and innertubes for tires and bicycles, must contain pressurized gas for extended periods of time, and thus must have a high degree of impermeability. The data in Table 5 establishes improved air° permeability at 65°C when blending isobutylene-based polymers with the SCC disclosed in this application as compared to natural rubber or amorphous polymers and blends thereof. Reducing oil levels can reduce permeability significantly, while an increase in carbon black level is only slightly advantageous. Since some low molecular weight (or high MI) semi crystalline polymers and copolymers can act as plasticizers, oil levels can be reduced to improve barrier properties without impacting processing operations. Thus, the blends of the present invention are useful for articles that require a. low gas permeability such as inner tubes and inner liners for automobile tires, truck tires, and tubes for bicycles, motorcycles, and other applications.
Although the invention has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and to scope of the present invention as defined by the appended claims.
All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted. Further, all documents cited herein, including testing procedures, are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted.
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Claims (23)
1. A blend comprising an isobutylene-based polymer and a semi-crystalline ethylene copolymer, the semi-crystalline ethylene copolymer having an ethylene derived content of at least 45 wt% based on the total weight of the semi-crystalline copolymer; wherein the cured blend possesses an air permeability from less than 8 x 10 -8 [cm3-cm/cm2-sec-atm] at 65°C.
2. The blend of Claim 1, wherein the semi-crystalline ethylene polymer has a melting point of from 25°C to 105°C and a heat of fusion from 2 J/g to 120 J/g as determined by DSC.
3. The blend of Claim 1, wherein the semi-crystalline ethylene copolymer has a heat of fusion from 10 J/g to 90 J/g as determined by DSC.
4. The blend of Claim 1, wherein the semi-crystalline ethylene copolymer has a heat of fusion from 20 J/g to 80 J/g as determined by DSC.
5. The blend of Claim 1, wherein the semi-crystalline copolymer further comprises one or more dienes.
6. The blend of Claim 5, wherein the diene is selected from the group comprising of ethylidene norbornene, vinyl norbornene, dicyclopentadiene and 1,4-hexadiene.
7. The blend of Claim 1, comprising from 3 to 95 wt% semi-crystalline copolymer by weight of the blend.
8. The blend of Claim 1, wherein the isobutylene-based polymer is selected from the group consisting of butyl rubber, polyisobutylene, random copolymers of a C4 to C7 isomonoolefin and a para-alkylstyrene and blends thereof.
9. The blend of Claim 1, wherein the isobutylene-based polymer is halogenated.
10. The blend or Claim 9, wherein the isobutylene-based polymer is brominated butyl rubber.
11. The blend of Claim 9, wherein the isobutylene-based polymer is a halogen-containing random copolymer of a C4 to C7 isomonoolefin and a para-alkylstyrene:.
12. The blend of Claim 1, wherein the semi crystalline copolymer comprises a random copolymer.
13. The blend of Claim 1, having an air permeability from less than 5 x 10 -8 [cm3-cm/cm2-sec-atm] at 65°C.
14. The blend of Claim 1, having a green strength from 0.1 MPa to 1 MPa at 100% modulus at 50°C.
15. The blend of Claim 1, further comprising one or more of the following compounds selected from the group consisting of amorphous polymer, oil, low molecular weight polybutenes, antioxidants, stabilizers, fillers, pigments, carbon black, and mixtures thereof.
16. The blend of Claim 1, wherein the blend is curable.
17. The blend of Claim 1, wherein the blend is a vulcanizate.
18. The blend of Claim 1, wherein the semi-crystalline copolymer is a random copolymer produced from:
a) ethylene monomers;
b) one or more other monomers selected from the group consisting of alpha-olefins having from 4 to 10 carbon atoms, styrenes; and c) optionally, one or more dienes.
a) ethylene monomers;
b) one or more other monomers selected from the group consisting of alpha-olefins having from 4 to 10 carbon atoms, styrenes; and c) optionally, one or more dienes.
19. An article of manufacture comprising the blend of Claim 1.
20. A method for producing a polymer blend comprising mixing an isobutylene-based polymer with a semi-crystalline copolymer, the semi-crystalline polymer having an ethylene content of at least 45 wt% by weight of the semi-crystalline copolymer; wherein the cured blend possesses an air permeability from less than 8 x 10 -8 [cm3-cm/cm2-sec-atm] at 65°C.
21. The method of Claim 20, further comprising adding one or more of the following compounds selected from the group consiting of amorphous polymers, oils, low molecular weight polybutenes, antioxidants, stabilizers, fillers, pigments, carbon black, and mixtures thereof.
22. The method of Claim 20, comprising from 3 to 95 wt% semi-crystalline copolymer by weight of the blend.
23. The method of Claim 20, comprising from 5 to 30 wt% semi-crystalline copolymer by weight of the blend.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20332900P | 2000-05-11 | 2000-05-11 | |
| US09/569,363 US6326433B1 (en) | 1999-05-19 | 2000-05-11 | Isobutylene based elastomer blends having improved strength elasticity, and reduced permeability |
| US60/203,329 | 2000-05-11 | ||
| US09/569,363 | 2000-05-11 | ||
| PCT/US2001/013588 WO2001085837A2 (en) | 2000-05-11 | 2001-04-26 | Isobutylene-based elastomer blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2406575A1 true CA2406575A1 (en) | 2001-11-15 |
Family
ID=26898525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002406575A Abandoned CA2406575A1 (en) | 2000-05-11 | 2001-04-26 | Isobutylene-based elastomer blends |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1360231A2 (en) |
| JP (1) | JP2004501231A (en) |
| CN (1) | CN1620477A (en) |
| AU (1) | AU2001257340A1 (en) |
| BR (1) | BR0110707A (en) |
| CA (1) | CA2406575A1 (en) |
| CZ (1) | CZ20023635A3 (en) |
| HU (1) | HUP0301774A3 (en) |
| MX (1) | MXPA02011070A (en) |
| PL (1) | PL365468A1 (en) |
| RU (1) | RU2266932C2 (en) |
| TW (1) | TW575623B (en) |
| WO (1) | WO2001085837A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050222335A1 (en) * | 2002-07-17 | 2005-10-06 | Exxonmobil Chemical Paens Inc. | Elastomeric blend for air barriers |
| US7906600B2 (en) * | 2004-12-29 | 2011-03-15 | Exxonmobil Chemical Patents Inc. | Processable filled, curable halogenated isoolefin elastomers |
| ATE553151T1 (en) * | 2007-06-06 | 2012-04-15 | Sumitomo Rubber Ind | RUBBER COMPOSITION FOR BEAD FILLERS AND TIRES THEREOF |
| JP4901591B2 (en) * | 2007-06-08 | 2012-03-21 | 住友ゴム工業株式会社 | Rubber composition for sidewall and pneumatic tire using the same |
| FR2938263B1 (en) * | 2008-07-24 | 2013-01-04 | Michelin Soc Tech | PROCESS FOR PRODUCING A SELF-SWITCHING COMPOSITION |
| FR2938264B1 (en) * | 2008-08-01 | 2013-08-16 | Michelin Soc Tech | PROCESS FOR PRODUCING A SELF-SWITCHING COMPOSITION |
| FR2955583B1 (en) | 2010-01-28 | 2012-01-27 | Michelin Soc Tech | PROCESS FOR PRODUCING A SELF-SWITCHING COMPOSITION |
| US8470922B2 (en) * | 2011-03-03 | 2013-06-25 | Exxonmobil Chemical Patents Inc. | Ethylene-vinyl alcohol based thermoplastic elastomers and vulcanizates |
| CN110240761B (en) * | 2018-03-08 | 2022-07-12 | 中国石油化工股份有限公司 | Rubber composition and application thereof, and vulcanized capsule and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1030699A (en) * | 1973-11-08 | 1978-05-02 | Polysar Limited | Halobutyl of improved green strength |
| US5157081A (en) * | 1989-05-26 | 1992-10-20 | Advanced Elastomer Systems, L.P. | Dynamically vulcanized alloys having two copolymers in the crosslinked phase and a crystalline matrix |
| CN1367801A (en) * | 1999-05-14 | 2002-09-04 | 杜邦唐弹性体公司 | High crystalline EAODM interpolymers |
| EP1181332B1 (en) * | 1999-05-19 | 2003-04-09 | ExxonMobil Chemical Patents Inc. | Isobutylene based elastomer blends having improved strength, elasticity, and reduced permeability |
| KR100743355B1 (en) * | 1999-09-03 | 2007-07-26 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Low Activation Temperature Adhesive Composition with High Peel Strength and Cohesive Failure |
-
2001
- 2001-04-26 MX MXPA02011070A patent/MXPA02011070A/en unknown
- 2001-04-26 CA CA002406575A patent/CA2406575A1/en not_active Abandoned
- 2001-04-26 HU HU0301774A patent/HUP0301774A3/en unknown
- 2001-04-26 CZ CZ20023635A patent/CZ20023635A3/en unknown
- 2001-04-26 EP EP01930842A patent/EP1360231A2/en not_active Withdrawn
- 2001-04-26 PL PL01365468A patent/PL365468A1/en not_active Application Discontinuation
- 2001-04-26 BR BR0110707-0A patent/BR0110707A/en not_active IP Right Cessation
- 2001-04-26 RU RU2002133091/04A patent/RU2266932C2/en not_active IP Right Cessation
- 2001-04-26 CN CN01809232.2A patent/CN1620477A/en active Pending
- 2001-04-26 WO PCT/US2001/013588 patent/WO2001085837A2/en not_active Application Discontinuation
- 2001-04-26 AU AU2001257340A patent/AU2001257340A1/en not_active Abandoned
- 2001-04-26 JP JP2001582432A patent/JP2004501231A/en not_active Withdrawn
- 2001-06-11 TW TW90111360A patent/TW575623B/en not_active IP Right Cessation
Also Published As
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|---|---|
| HUP0301774A3 (en) | 2006-11-28 |
| WO2001085837A2 (en) | 2001-11-15 |
| HUP0301774A2 (en) | 2003-08-28 |
| CZ20023635A3 (en) | 2003-10-15 |
| MXPA02011070A (en) | 2003-06-24 |
| TW575623B (en) | 2004-02-11 |
| BR0110707A (en) | 2003-01-28 |
| PL365468A1 (en) | 2005-01-10 |
| AU2001257340A1 (en) | 2001-11-20 |
| WO2001085837A3 (en) | 2003-09-04 |
| RU2266932C2 (en) | 2005-12-27 |
| CN1620477A (en) | 2005-05-25 |
| EP1360231A2 (en) | 2003-11-12 |
| JP2004501231A (en) | 2004-01-15 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |