WO2011025593A1 - Elastomeric compositions and their use in articles - Google Patents
Elastomeric compositions and their use in articles Download PDFInfo
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- WO2011025593A1 WO2011025593A1 PCT/US2010/041689 US2010041689W WO2011025593A1 WO 2011025593 A1 WO2011025593 A1 WO 2011025593A1 US 2010041689 W US2010041689 W US 2010041689W WO 2011025593 A1 WO2011025593 A1 WO 2011025593A1
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- alloy
- succinic anhydride
- anhydride
- elastomer
- isobutylene
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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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- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- 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
-
- 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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to thermoplastic elastomeric compositions. More particularly, the present invention is directed to a thermoplastic elastomeric composition comprising compounds that act as both an extender and reactive plasticizer for the thermoplastic in the composition.
- the present invention is related to thermoplastic elastomeric compositions particularly useful for tire and other industrial rubber applications, reinforced or otherwise, that require impermeability characteristics.
- EP 0 722 850 Bl discloses a low-permeability thermoplastic elastomeric composition that is excellent as an innerliner in pneumatic tires.
- This composition comprises a low permeability thermoplastic in which is dispersed a low permeability rubber.
- EP 0 969 039 Al discloses a similar composition and teaches that the small particle size rubber dispersed in the thermoplastic was important to achieve acceptable durability of the resulting composition.
- thermoplastic elastomer composed of a rubber and a thermoplastic for use as an innerliner in a tire.
- a flexible material of the type disclosed therein has low heat resistance.
- the thermoplastic material in the composition has a melting point less than the tire vulcanization temperature, when the tire curing bladder is released at the end of the curing cycle, the inside surface of the tire may have defects due to the thermoplastic material of the composition sticking to rubber of the curing bladder.
- the present invention is directed to a thermoplastic elastomeric composition having improved characteristics over previously known similar compositions.
- the present invention is directed to a dynamically vulcanized alloy containing at least one isobutylene-containing elastomer and at least one thermoplastic resin, wherein the elastomer is present as a dispersed phase of small vulcanized or partially vulcanized particles in a continuous phase of the thermoplastic resin.
- the dynamically vulcanized alloy also contains therein an anhydride functionalized oligomer.
- the oligomer of the anhydride functionalized oligomer, prior to functionalization has a molecular weight in the range of
- the oligomer has a molecular weight in the range of 750 to 2500.
- the oligomer is an alkyl, an aryl, or an alkenyl oligomer and the anhydride is either a maleic or a succinic anhydride.
- the succinic anhydride functionalized polymer is a poly-n-alkyl succinic anhydride or a poly-iso-alkyl succcinic anhydride.
- the functionalized oligomer is selected from the group consisting of poly-isobutylene succinic anhydride, polyisobutene succinic anhydride, polybutene succinic anhydride, polyisopentene succinic anhydride, polypentene succinic anhydride, polyoctenyl succinic anhydride, polyisooctenyl succinic anhydride, poly-hexenyl succinic anhydride, poly-dodecenyl succinic anhydride.
- the alloy contains 2 to 35 phr of the succinic anhydride functionalized polymer, based on the amount of the isobutylene-containing elastomer in the alloy.
- the alloy further includes a plasticizer.
- the plasticizer may be a polyamide, tertiary amine, secondary diamine, ester, or sulfonamide.
- the ratio of succinic anhydride functionalized polymer to plasticizer is in the range of 0.15 to 3.0.
- the alloy is substantially free of any acrylates and preferably, the alloy is devoid of any acrylates.
- the isobutylene containing elastomer is a halogenated butyl rubber.
- the isobutylene containing elastomer is a random copolymer of isobutylene and an alkylstyrene.
- the alkylstyrene is paramethylstyrene.
- the elastomer may be halogenated with bromine or chlorine.
- the isobutylene containing elastomer is present in the alloy in an amount in the range of 2 to 90 weight percent.
- the thermoplastic resin is selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins, polyphenyleneoxide, polyphenylene sulfide, polystyrene, styrene-acrylonitrile resins, styrene maleic anhydride resins, aromatic polyketones, ethylene vinyl acetate, ethylene vinyl alcohol, and mixtures thereof.
- the alloy has a Shore A hardness of at least 70.
- Polymer may be used to refer to homopolymers, copolymers, interpolymers, terpolymers, etc.
- a copolymer may refer to a polymer comprising at least two monomers, optionally with other monomers.
- the monomer is present in the polymer in the polymerized form of the monomer or in the polymerized form of a derivative from the monomer (i.e., a monomeric unit).
- the phrase comprising the (respective) monomer or the like is used as shorthand.
- Rubber refers to any polymer or composition of polymers consistent with the ASTM D 1566 definition: "a material that is capable of recovering from large deformations, and can be, or already is, modified to a state in which it is essentially insoluble, if vulcanized, (but can swell) in a solvent." Rubbers are often also referred to as elastomers; the term elastomer may be used herein interchangeably with the term rubber.
- phr is parts per hundred rubber or "parts”, and is a measure common in the art wherein components of a composition are measured relative to a total of all of the elastomer components.
- the total phr or parts for all rubber components, whether one, two, three, or more different rubber components is present in a given recipe is normally defined as 100 phr. All other non-rubber components are ratioed against the 100 parts of rubber and are expressed in phr. This way one can easily compare, for example, the levels of curatives or filler loadings, etc., between different compositions based on the same relative proportion of rubber without the need to recalculate percentages for every component after adjusting levels of only one, or more, component(s).
- Isoolefin refers to any olefin monomer having at least one carbon having two substitutions on that carbon.
- Multiolefin refers to any monomer having two or more double bonds.
- the multiolefin is any monomer comprising two conjugated double bonds such as a conjugated diene like isoprene.
- Useful elastomeric compositions for this invention comprise a mixture of monomers, the mixture having at least (1) a C 4 to C 7 isoolefin monomer component with (2) a multiolefin, monomer component.
- the isoolefin is present in a range from 70 to 99.5 wt% by weight of the total monomers in one embodiment, and 85 to 99.5 wt% in another embodiment.
- the multiolefin component is present in amounts in the range of from 30 to about 0.5 wt% in one embodiment, and from 15 to 0.5 wt% in another embodiment. In yet another embodiment, from 8 to 0.5 wt% of the monomer mixture is multiolefin.
- the isoolefin is a C 4 to C7 compound, non-limiting examples of which are compounds such as isobutylene, isobutene, 2-methyl-l-butene, 3 -methyl- 1-butene, 2-methyl- 2-butene, 1-butene, 2-butene, methyl vinyl ether, indene, vinyltrimethylsilane, hexene, and 4- methyl-1-pentene.
- the multiolefin is a C 4 to Ci 4 multiolefin such as isoprene, butadiene, 2,3- dimethyl-l,3-butadiene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, and piperylene.
- Other polymerizable monomers such as styrene and dichlorostyrene are also suitable for homopolymerization or copolymerization in butyl rubbers.
- Preferred elastomers useful in the practice of this invention include isobutylene- based copolymers.
- an isobutylene based elastomer or a polymer refers to an elastomer or a polymer comprising at least 70 mol% repeat units from isobutylene and at least one other polymerizable unit.
- the isobutylene-based copolymer may or may not be halogenated.
- the elastomer is a butyl-type rubber or branched butyl-type rubber, especially halogenated versions of these elastomers.
- Useful elastomers are unsaturated butyl rubbers such copolymers of olefins or isoolefins and multiolefins.
- Non-limiting examples of unsaturated elastomers useful in the method and composition of the present invention are poly(isobutylene-co-isoprene), polyisoprene, polybutadiene, polyisobutylene, poly(styrene-co-butadiene), natural rubber, star-branched butyl rubber, and mixtures thereof.
- Useful elastomers in the present invention can be made by any suitable means known in the art, and the invention is not herein limited by the method of producing the elastomer.
- One embodiment of the butyl rubber polymer of the invention is obtained by reacting 95 to 99.5 wt% of isobutylene with 0.5 to 8 wt% isoprene, or from 0.5 wt% to 5.0 wt% isoprene in yet another embodiment.
- Elastomeric compositions of the present invention may also comprise at least one random copolymer comprising a C 4 to C7 isomonoolefins, such as isobutylene, and an alkylstyrene comonomer, such as para-methylstyrene, containing at least 80%, more alternatively at least 90% by weight of the para-isomer and optionally include functionalized interpolymers wherein at least one or more of the alkyl substituents groups present in the styrene monomer units contain benzylic halogen or some other functional group.
- a random copolymer comprising a C 4 to C7 isomonolefins, such as isobutylene, and an alkylstyrene comonomer, such as para-methylstyrene, containing at least 80%, more alternatively at least 90% by weight of the para-isomer and optionally include functionalized interpolymers wherein at least one or more of the alky
- the functional group X may be halogen or some other functional group which may be incorporated by nucleophilic substitution of benzylic halogen with other groups such as carboxylic acids; carboxy salts; carboxy esters, amides and imides; hydroxy; alkoxide; phenoxide; thiolate; thioether; xanthate; cyanide; cyanate; amino and mixtures thereof.
- These functionalized isomonoolefin copolymers, their method of preparation, methods of functionalization, and cure are more particularly disclosed in U.S. Patent No. 5,162,445.
- the elastomer comprises random polymers of isobutylene and 0.5 to 20 mol% para-methylstyrene wherein up to 60 mol% of the methyl substituent groups present on the benzyl ring is functionalized with a halogen such a bromine or chlorine (para- (bromomethylstyrene)), an acid, or an ester.
- the functionality is selected such that it can react or form polar bonds with functional groups present in the matrix polymer, for example, acid, amino or hydroxyl functional groups, when the polymer components are mixed at high temperatures.
- exemplary copolymers contain from 0.2 to 10 wt% of bromine, based on the weight of the polymer, from 0.4 to 6 wt% bromine in another embodiment, and from 0.6 to 5.6 wt% in another embodiment, are substantially free of ring halogen or halogen in the polymer backbone chain.
- the random polymer is a copolymer of C 4 to C 7 isoolefin derived units (or isomonoolefin), para-methylstyrene derived units and para-(halomethylstyrene) derived units, wherein the para-(halomethylstyrene) units are present in the polymer from 0.4 to 3.0 mol% based on the total number of para-methylstyrene, and wherein the para-methylstyrene derived units are present from 3 to 15 wt% based on the total weight of the polymer in one embodiment, and from 4 to 10 wt% in another embodiment.
- the para-(halomethylstyrene) is para-(bromomethylstyrene).
- thermoplastic resins may be used singly or in combination and generally contain nitrogen, oxygen, halogen, sulfur or other groups capable of interacting with an aromatic functional groups such as halogen or acidic groups.
- Suitable thermoplastic resins include resins selected from the group consisting or polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins (ABS), polyphenyleneoxide (PPO), polyphenylene sulfide (PPS), polystyrene, styrene- acrylonitrile resins (SAN), styrene maleic anhydride resins (SMA), aromatic polyketones (PEEK, PED, and PEKK), ethylene copolymer resins (EVA or EVOH) and mixtures thereof.
- Suitable polyamides comprise crystalline or resinous, high molecular weight solid polymers including copolymers and terpolymers having recurring amide units within the polymer chain.
- Polyamides may be prepared by polymerization of one or more epsilon lactams such as caprolactam, pyrrolidine, lauryllactam and aminoundecanoic lactam, or amino acid, or by condensation of dibasic acids and diamines. Both fiber-forming and molding grade nylons are suitable.
- polyamides examples include polycaprolactam (nylon-6), polylauryllactam (nylon- 12), polyhexamethyleneadipamide (nylon-6,6) polyhexamethyleneazelamide (nylon-6,9), polyhexamethylenesebacamide (nylon-6,10), polyhexamethyleneisophthalamide (nylon-6, IP) and the condensation product of 11-amino- undecanoic acid (nylon- 11).
- Commercially available polyamides may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160 and 260 0 C being preferred.
- Preferred polyesters are derived from aromatic dicarboxylic acids such as naphthalenic or phthalic acids and C 2 to C 4 diols, such as polyethylene terephthalate and polybutylene terephthalate. Preferred polyesters will have a melting point in the range of 160 0 C to 260 0 C.
- Poly(phenylene ether) (PPE) resins which may be used in accordance with this invention are well known, commercially available materials produced by the oxidative coupling polymerization of alkyl substituted phenols. They are generally linear, amorphous polymers having a glass transition temperature in the range of 190 0 C to 235°C.
- Ethylene copolymer resins useful in the invention include copolymers of ethylene with unsaturated esters of lower carboxylic acids as well as the carboxylic acids per se.
- copolymers of ethylene with vinylacetate or alkyl acrylates for example methyl acrylate and ethyl acrylate can be employed.
- These ethylene copolymers typically comprise about 60 to about 99 wt% ethylene, preferably about 70 to 95 wt% ethylene, more preferably about 75 to about 90 wt% ethylene.
- ethylene copolymer resin means, generally, copolymers of ethylene with unsaturated esters of lower (Ci - C 4 ) monocarboxylic acids and the acids themselves; e.g. acrylic acid, vinyl esters or alkyl acrylates. It is also meant to include both “EVA” and “EVOH”, which refer to ethylene- vinylacetate copolymers, and their hydrolyzed counterpart ethylene-vinyl alcohols.
- Dynamic vulcanization is used herein to connote a vulcanization process in which the vulcanizable elastomer is vulcanized in the presence of a thermoplastic under conditions of high shear and elevated temperature.
- the vulcanizable elastomer is simultaneously crosslinked and preferably becomes dispersed as fine sub micron size particles of a "micro gel” within the thermoplastic.
- the resulting material is often referred to as a dynamically vulcanized alloy ("DVA").
- Scrap or flashing can also be salvaged and reprocessed; those skilled in the art will appreciate that conventional elastomeric thermoset scrap, comprising only elastomer polymers, cannot readily be reprocessed due to the cross-linking characteristics of the vulcanized polymer.
- thermoplastic may be present in an amount ranging from about 10 to 98 wt%, preferably from about 20 to 95 wt%
- the elastomer may be present in an amount ranging from about 2 to 90 wt%, preferably from about 5 to 80 wt%, based on the polymer blend.
- Suitable curing components include sulfur, metal oxides, organometallic compounds, radical initiators.
- Common curatives include ZnO, CaO, MgO, A12O3, CrO3, FeO, Fe2O3, and NiO. These metal oxides can be used in conjunction with metal stearate complexes (e.g., the stearate salts of Zn, Ca, Mg, and Al), or with stearic acid or other organic acids and either a sulfur compound or an alkyl or aryl peroxide compound or diazo free radical initiators. If peroxides are used, peroxide co-agent commonly used in the art may be employed. The use of peroxide curative may be avoided if the thermoplastic resin is one such that the presence of peroxide would cause the thermoplastic resin to cross-link.
- accelerants also known as accerlerators
- Suitable curative accelerators include amines, guanidines, thioureas, thiazoles, thiurams, sulfenamides, sulfenimides, thiocarbamates, xanthates, and the like.
- the curatives may be added just before the elastomer and thermoplastic resin are combined or even after the thermoplastic has melted and been mixed with the rubber.
- discrete rubber particle morphology in a continuous thermoplastic matrix is the preferred morphology, the invention is not limited to only this morphology and may also include morphologies where both the elastomer and the thermoplastic are continuous. Sub-inclusions of the thermoplastic inside the rubber particles may also be present.
- Compatibilizers may be employed due to the difference in solubility of the thermoplastic resins and elastomers in the DVA. Such compatilizers are thought to function by modifying, and in particular reducing, the surface tension between the rubber and thermoplastic components of the composition.
- Suitable compatibilizers include ethylenically unsaturated nitrile-conjugated diene-based high saturation copolymer rubbers (HNBR), epoxylated natural rubbers (ENR), acrylate rubber, and mixtures thereof, as well as copolymers having the same structure of the thermoplastic resin or the elastomeric polymer, or a structure of a copolymer having an epoxy group, carbonyl group, halogen group, amine group, maleated group, oxazoline group, or hydroxyl group capable of reacting with the thermoplastic resin or the elastomer.
- HNBR ethylenically unsaturated nitrile-conjugated diene-based high saturation copolymer rubbers
- EMR epoxylated natural rubbers
- acrylate rubber and mixtures thereof, as well as copolymers having the same structure of the thermoplastic resin or the elastomeric polymer, or a structure of a copolymer having an epoxy group, carbony
- the amount of compatibilizer is typically about 0.5 to about 10 parts by weight; preferably about 3 to about 8 parts by weight, based upon 100 parts by weight of the total of the elastomer.
- Components previously used to compatibilize the viscosity between the elastomer and thermoplastic components include low molecular weight polyamides, maleic anhydride grafted polymers having a molecular weight on the order of 10,000 or greater, methacrylate copolymers, tertiary amines and secondary diamines.
- Examples include maleic anhydride- grafted ethylene-ethyl acrylate copolymers (a solid rubbery material available from Mitsui- DuPont as AR-201 having a melt flow rate of 7 g/10 min measured per JIS K6710) and butylbenzylsulfonamide (BBSA).
- the anhydride functionalized oligomer is fixed within the DVA, and does not volatize out like conventional plasticizers/compatibilizers during post DVA processing operations such as film blowing or tire curing.
- the resulting DVA has a low volatile organic compound emissions. This is believed to be most applicable when using polar thermoplastics.
- the melting point of a polyamide thermoplastic phase is invariant when the anhydrides are used, contrary to traditional plasticizers for polyamide thermoplastics such as n-butyl benzene sulfonamides that negatively depress the melting point of the thermoplastic.
- Both maleic and succinic anhydrides are useful in the present invention.
- Preferred anhydrides are substituted succinic anhydrides, wherein the substitution can be an alkyl, aryl, or alkenyl.
- the substituted succinic anhydride may be prepared by thermal or chloro methods known in the art of reacting an alkyl, aryl, or olefin with maleic anhydride.
- the oligomer, including copolymers of lower olefins, being reacted with the maleic or succininc anhydride has a molecular weight in the range of about 500 to 5000, alternatively 750 to 2500, or alternatively 500 to 1500.
- the oligomer may also have a molecular weight in the ranges of 1000 to 5000, 800 to 2500, or 750 to 1250.
- substituted succinic anhydrides include poly-isobutylene succinic anhydride, n- octenyl succinic anhydride, n-hexenyl succinic anhydride, and dodocenyl succinic anhydride.
- the succinic anhydride may also replace the plasticizer or a portion of the plasticizers, such as butyl benzene sulfonamide or other sulfonamides, which are commonly used in a polyamide-based DVA compound.
- the succinic anhydride replaces a portion of the plasticizer, the total amount of replacement is not more than the original amount of plasticizer needed to formulate the DVA.
- the total amount of succinic anhydride and plasticizer is also within the above stated ranges of a minimum amount of about 2 phr, 5 phr, or 10 phr to a maximum amount of amount 15 phr, 20 phr, 25 phr, 30 phr, or 35 phr.
- the alloy of any preceding embodiment A to G, wherein the alloy further comprises a plasticizer, the plasticizer being selected from the group consisting of polyamides, tiertiary amines, secondary diamines, esters, and sulfonamides.
- a plasticizer being selected from the group consisting of polyamides, tiertiary amines, secondary diamines, esters, and sulfonamides.
- thermoplastic resin is selected from the group consisting of polyamides, polyimides, polycarbonates, polyesters, polysulfones, polylactones, polyacetals, acrylonitrile-butadiene-styrene resins, polyphenyleneoxide, polyphenylene sulfide, polystyrene, styrene-acrylonitrile resins, styrene maleic anhydride resins, aromatic polyketones, ethylene vinyl acetates, ethylene vinyl alcohols, and mixtures thereof.
- Samples were prepared of both comparative DVAs, A and B of Table 3, and exemplary DVAs made in accordance with the present invention.
- the components used in the samples are identified in Table 2 below.
- the PIBSA form for the practice of this invention is not restricted to the examples used and other commercial offerings which are diluted in oil may also be employed, especially if the molecular weight of the starting PIBSA renders it too viscous.
- the PIBSAs may also be heated so they can be easily dispensed in mixing equipment and also to facilitate their incorporation and mixing.
- the solid state strength properties are maintained while improved is the desired fluidity of the DVA as measured by the various reductions in LCR viscosity. Also desired is a Shore A hardness of at least 70, and most preferably at least 75.
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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JP2012526758A JP6100527B2 (en) | 2009-08-27 | 2010-07-12 | Elastomer compositions and their use in products |
RU2012107224/04A RU2556992C2 (en) | 2009-08-27 | 2010-07-12 | Elastomeric compositions and use thereof in articles |
CN201080037872.5A CN102482463B (en) | 2009-08-27 | 2010-07-12 | Elastomeric compositions and their use in articles |
CA2771419A CA2771419C (en) | 2009-08-27 | 2010-07-12 | Elastomeric compositions and their use in articles |
IN946DEN2012 IN2012DN00946A (en) | 2009-08-27 | 2010-07-12 | |
EP10734614.0A EP2470601B1 (en) | 2009-08-27 | 2010-07-12 | Elastomeric compositions and their use in articles |
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US12/548,797 | 2009-08-27 | ||
US12/548,797 US8809455B2 (en) | 2009-08-27 | 2009-08-27 | Elastomeric compositions and their use in articles |
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US (1) | US8809455B2 (en) |
EP (1) | EP2470601B1 (en) |
JP (1) | JP6100527B2 (en) |
CN (1) | CN102482463B (en) |
CA (1) | CA2771419C (en) |
IN (1) | IN2012DN00946A (en) |
RU (1) | RU2556992C2 (en) |
WO (1) | WO2011025593A1 (en) |
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Also Published As
Publication number | Publication date |
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IN2012DN00946A (en) | 2015-04-10 |
JP2013502506A (en) | 2013-01-24 |
CA2771419A1 (en) | 2011-03-03 |
CN102482463B (en) | 2014-08-13 |
CN102482463A (en) | 2012-05-30 |
JP6100527B2 (en) | 2017-03-22 |
US20110054093A1 (en) | 2011-03-03 |
EP2470601A1 (en) | 2012-07-04 |
RU2556992C2 (en) | 2015-07-20 |
US8809455B2 (en) | 2014-08-19 |
EP2470601B1 (en) | 2016-02-17 |
RU2012107224A (en) | 2013-09-10 |
CA2771419C (en) | 2015-05-12 |
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