EP0713509A1 - Compatibilization of polar and nonpolar elastomer blends using functionalized ethylene/propylene copolymers or ethylene/propylene/diene terpolymers - Google Patents
Compatibilization of polar and nonpolar elastomer blends using functionalized ethylene/propylene copolymers or ethylene/propylene/diene terpolymersInfo
- Publication number
- EP0713509A1 EP0713509A1 EP93917018A EP93917018A EP0713509A1 EP 0713509 A1 EP0713509 A1 EP 0713509A1 EP 93917018 A EP93917018 A EP 93917018A EP 93917018 A EP93917018 A EP 93917018A EP 0713509 A1 EP0713509 A1 EP 0713509A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- epdm
- composition
- rubber
- functionalized
- phr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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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
Definitions
- This invention is related to co-pending application U.S. Serial No. 827,772, filed January 29, 1992.
- This invention relates to the field of compatibilization technology.
- this invention relates to the use of functionalized EP or EPDM rubbers such as carboxylated ethylene/propylene/copolymers, sulfonated or epoxidized ethylene propylene/diene terpolymers as compatibilizers for polar/nonpolar elastomer blends.
- the single phase blend is miscible.
- miscibility does not imply ideal molecular mixing but suggests that the level of molecular mixing is adequate to yield macroscopic properties expected of a single-phase material.
- the formation of two-phase elastomer blend is not necessarily an unfavorable event since many useful properties, characteristic of a single phase, may be preserved in the blend composition while other properties may be averaged according to the blend composition.
- Proper control of overall elastomer blend morphology and good adhesion between the phases are in any case required in order to achieve good mechanical properties.
- Compatibility means the absence of separation or stratification of the components of the polymeric alloy during the expected useful lifetime of the product (Gaylord, N.G., in “Copoly ers, Polyblends and Composites", Advances in Chemistry Series 142, American Chemical Society: Washington, D.C., 1975, p. 76). "Technological compatibilization”, according to Coran and co- workers [Rubber Chem. Technol.
- Block Copolymers Ed by S.L. Agarwal, Plenum, New York, 1970, p. 79.
- Two elastomers form a compatible mixture when they have at least one of the following characteristics: o Segmental structural identity.
- a graft or block copolymer of butadiene and styrene is compatible with either polybutadiene or polystyrene, o Miscibility or partial miscibility with each other.
- poly (vinyl chloride) , PVC, poly (ethylacrylate) , PEA, poly (methylacrylate) , PMMA have solubility parameters in the 9.4-9.5 range and form compatible mixtures.
- NBR nitrile rubber
- Neoprene or polychloroprene rubber has been the material of choice in most power transmission belts, due to its unique combination of properties: oil resistance, toughness, dynamic flex life, good adhesion to other materials and heat resistance up to 100°C.
- CR belts have kept pace with the needs of the automotive industry, but recently there is a need for new materials for more demanding applications.
- CR belts are encountering greater heat duress in service due to increasing underhood temperatures (up to 150°C) .
- the CR belts must have a lower failure rate with high mean life, even when high temperatures are not encountered.
- neoprene belts are desirable.
- the above requirement for neoprene belts could be satisfied by blending with polyolefin elastomers such as ethylene/propylene rubber (EP) or ethylene/propylene/diene terpolymer (EPDM) which have better heat/ozone and cut growth resistance.
- EP ethylene/propylene rubber
- EPDM ethylene/propylene/diene terpolymer
- elastomers such as polybutadiene or polyisoprene may be, in some cases reasonably compatible with olefin/diene elastomers and may be readily co-vulcanized because of the high availability of sites of ethylenic unsaturation
- other elastomers such as polychloroprene, and like materials containing polar groups along the chain and/or a relatively low degree of ethylenic unsaturation are not so readily co-vulcanized.
- a compatibilizer for polar/nonpolar rubber blends such as CR/EPDM, CR/EP could be found.
- functionalized EP or EPDM such as sulfonated EPDM, epoxidized EPDM and carboxylated EP as a compatibilizer for polar/nonpolar rubber blends is not known.
- a modifier is not necessarily a compatibilizer
- the use as a modifier means that the blend produced is binary rather than the preferred ternary blend produced by compatibilization.
- Modifiers can improve tack and typically improve dynamic properties at room temperature. Indeed, modifiers tend to behave much like plasticizers or lubricants.
- Compatibilizers on the other hand, have the ability to alter the interfacial situation of an incompatible blend which results in synergistic improvement of blend properties at both room temperatures and at high end use temperatures.
- the eff ⁇ - t of compatibilizers is similar to that of surfactants having the ability to mix oil and water which is often referred to as "emulsification effect" in the field of colloids.
- the role of the compatibilizer in an elastomer blend is manifold: (1) reduce the interfacial energy between the phases, (2) permit a finer dispersion during mixing, (3) provide a measure of stability against gross phase segregation, and (4) result in improved interfacial adhesion.
- U.S. Patent No. 4,397,987 to Cornell discloses Maleated EPDM as a modifier for nitrile rubber.
- U.S. Patent 4,307,204 to DuPont discloses an expandable, curable elastomeric sponge composition based on ethylene/propylene/diene terpolymer (EPDM) elastomer or polychloroprene elastomer, which composition further contains a minor amount of an ionomer resin which is an ethylene polymer or copoly er containing at least about 50 mole percent acid functional groups, which groups are at least 50% neutralized by metal ions.
- EPDM ethylene/propylene/diene terpolymer
- ionomer resin which is an ethylene polymer or copoly er containing at least about 50 mole percent acid functional groups, which groups are at least 50% neutralized by metal ions.
- acid-modified ethylene polymers which may also include acid-modified EPDM terpolymers, are disclosed to improve the balance of curing and expanding properties of the polymer composition when used to prepare cured expanded materials.
- None of the aforementioned disclosures addresses the development of compatibilized polychloroprene/EPDM or EP which not only exhibit improved resistance to ozone or oxygen attack and improved heat stability, but also exhibit a retention and in some cases improvement of important physical properties such as tensile strength, elongation, modulus and resistance to abrasion at room and end use temperatures.
- compatibilizers for polar/nonpolar elastomer blends is disclosed herein.
- EPDM or EP modified with different functional groups particularly carboxylated or sulfonated or epoxidized EPDM or EP have been found to compatibilize polar/nonpolar elastomer blends, including, but not limited to, neoprene/EPDM or EP by improving the overall properties of the said blends.
- the present invention provides for neoprene/EPDM or EP blend compositions and vulcanizates thereof having improved heat, ozone and cut growth resistance comprising: a compatibilized blend of neoprene/EPDM (or EP) , and 1 to about 15 phr of a functionalized EPDM or EP particularly maleated or sulfonated or epoxidized ethylene/propylene/diene terpolymers or ethylene/propylene copolymers.
- blends of this invention may be readily co-vulcanized and formed into shaped, heat, ozone, cut growth and oil resistant articles such as automotive drive belts and automotive hoses which not only exhibit improved heat, ozone and cut growth resistance but also have retained or enhanced physical properties such as abrasion resistance, modulus, elongation and tensile strength.
- the functionalized EPDM or EP are excellent compatibilizers for neoprene rubber and ethylene/propylene rubber (CR/EP) blends, and neoprene rubber and ethylene/propylene/diene (CR/EPDM) blends.
- the compatibilizers of this invention comprise EPDM or EP rubbers modified with functional groups selected from the group consisting of ⁇ , ⁇ - unsaturated carboxylic acids and anhydrides thereof, epoxy or sulfonic acid and derivatives thereof.
- "MA" is herein defined to include maleic acid and maleic anhydride.
- the EPDM is a random copolymer of ethylene/propylene/and a diene, where the ethylene is present at 35-80 wt. %, and the diene is present at 0 to 15 wt.%, based upon the weight of the copolymer.
- the EPDM polymer can be produced by the well known Zeigler-Natta polymerization method.
- the dienes useful in producing EPDM copolymers are typically 1,4-hexadiene, cycloalkylidene norbornenes, etc.
- the EP or EPDM is then typically grafted by any process known in the art with maleic acid, maleic anhydride, or other , ⁇ -unsaturated mono- or dicarboxylic acids or anhydrides thereof, or epoxidized or sulfonated following known literature procedures.
- the rubbers and the compatibilizer may be blended, formed, or otherwise mixed by any one of a number of suitable methods.
- the rubbers useful in this invention include: ethylene/propylene rubber, (EP) , ethylene/propylene/diene terpolymer, (EPDM) , polychloroprene, (neoprene or CR rubber) , butadiene rubber (BR) , styrene/butadiene rubber (SBR) , natural rubber (NR) , and polyisoprene rubber (IR) , butyl, halobutyl, poly(isobutylene-co-4-methyl styrene), and brominated poly(isobutylene-co-4-methyl styrene) rubber.
- the EP rubbers useful in this invention are random copolymers of ethylene and propylene where the copolymer has an ethylene content of 30 to 85 wt.%, based upon the weight of the copolymer.
- the EP copolymer can be produced by the well known Zeigler-Natta polymerization method.
- the EPDM Rubbers to be compatibilized in this invention are random copolymers of ethylene/propylene/ and a diene, where the ethylene is present at 35-80 wt.%, and the diene is present at 0 to 15 wt.%, based upon the weight of the copolymer.
- the EPDM polymer can be produced by the well known Zeigler-Natta polymerization method.
- the dienes useful in producing EPDM copolymers are typically 1,4-hexadiene, alkylidene norbornenes, etc.
- neoprene rubbers useful in this invention are polymers of chloroprene. These can be produced by the well known free radical polymerization method.
- the functionalized EPDM or EP rubbers of this invention are useful for compatibilizing Neoprene/EP and neoprene/EPDM blends.
- This invention provides a process for compatibilizing rubber blends comprising blending a functionalized EP or EPDM with two or more different rubbers.
- this invention relates to a process for compatibilizing polar/nonpolar rubber blends comprising:
- This invention further relates to compatibilized compositions of polar and nonpolar rubbers, and a functionalized EPDM or EP.
- this invention relates to compatibilized rubber blends comprising a functionalized EPDM or EP wherein the functional groups, preferably are MA, sulfonic acid or epoxy group; at least one polar rubber and at least one nonpolar rubber.
- this invention provides a new approach for compounding rubber blends using functionalized, particularly maleated, EP copolymer or EPDM terpolymer as the compatibilizer.
- EP copolymer or EPDM terpolymers are excellent agents for compatibilizing neoprene/ethylene-propylene rubber and neoprene/ethylene-propylene-diene blends
- the particular maleated EP or EPDM rubbers useful as compatibilizers in the present invention include those manufactured and sold by EXXON CHEMICAL CO. under the name trade name Exxelor VA 1801 and Exxelor VA 1803.
- the compatibilizers of this invention comprise functionalized EP or EPDM.
- EPDM or EP as used herein, unless otherwise indicated, includes terpolymers, tetrapolymers, etc., preferably of ethylene, and a C 3 -C 28 alpha-olefin, typically propylene, and/or a non-conjugated diolefin or mixtures of such diolefins which may also be used.
- the amount of the non-conjugated diolefin will generally range from about 0.5 to 20 wt. percent, preferably about 1 to about 7 wt. percent, based on the total amount of ethylene and alpha-olefin present.
- non-conjugated dienes that may be used as the third monomer in the terpolymer include: a. Straight chain acyclic dienes such as: 1,4- hexadiene; 1,5-heptadiene; 1,6-octadiene. b. Branched chain acyclic dienes such as: 5- methyl-1,4-hexadiene; 3,7-dimethyl 1,6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene. c.
- Single ring alicyclic dienes such as: 1,4- cyclo-hexadiene; 1, 5-cyclooctadiene; 1,5-cyclo- dodecadiene; 4-vinylcyclohexene; 1-allyl, 4- isopropylidene cyclo-hexane; 3-allyl-cyclopentene; 4-allyl cyclohexene and l-isopropenyl-4-(4-butenyl) cyclohexane.
- Multi-single ring alicyclic dienes such as: 4,4 ⁇ -dicyclo-pentenyl and 4, 4 '-dicyclohexenyl.
- Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene; bicyclo (2.2.1) hepta 2,5-diene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as: ethylidene norbornene; 5-methylene-6- methyl-2- norbornene; 5-methylene-6, 6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclo-pentylidene)-2- norbornene and 5-cyclohexylidene-2-norbornene; etc.
- EPDM elastomer contains from about 60 to about 80% by weight ethylene, from about 15 to about 35% by weight propylene and from about 3 to about 7% by weight of non-conjugated diene. Synthesis of EPDM is well known in the art. G. ver Strate, Encyclopedia of Polymer Science and
- the EP or EPDM is grafted with a functional group, typically an acid group, wherein t-tiB functional group may be selected from carboxylic acids (such as maleic acid, fumaric acid, citraconic acid, itaconic acid, acrylic acid, methacrylic acid, himic acid, etc. ... and anhydrides thereof, preferably maleic acid or maleic anhydride) , sulfonic acids and epoxy groups.
- carboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid, acrylic acid, methacrylic acid, himic acid, etc. ... and anhydrides thereof, preferably maleic acid or maleic anhydride
- carboxylated refers to EP or EPDM polymers as described above which have been modified by inclusion into the polymer chain of from about 0.05 to about 10% by weight of an unsaturated polycarboxylic acid or lower alkyl esters or anhydrides thereof.
- the reaction of the EP or EPDM with an unsaturated mono or dicarboxylic acids and derivatives thereof, can be carried out in the presence of a free radical source.
- the EP or EPDM may be reacted with unsaturated mono or polycarboxylic acids, and derivatives thereof, at temperatures generally less than 300°C, preferably from about 150°-250°C, in the presence of free radical sources.
- Suitable free radical sources are, for example peroxides such as ditertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, p-menthane peroxide, p-menthane hydroperoxide compounds or azo compounds, such as azobis (isobutyronitrile) , or irradiation sources.
- Suitable irradiation sources include, for example, those from cobalt, uranium, thorium, and the like and ultraviolet light.
- Preferably, from about 0.05 to about 10 percent organic unsaturated polycarboxylic acid, anhydride or esters thereof, based on the weight of the EP or EPDM, can be used.
- Suitable unsaturated mono or polycarboxylic acids and derivatives thereof include maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, aconitic anhydride, itaconic anhydride, the half or full esters derived therefrom, such as methyl, ethyl, dimethyl maleate, dimethyl fumaratte, methyl ethyl maleate, dibutyl maleate, dipropyl maleate, and the like, or those compounds which form these compounds at elevated reaction temperatures such as citric acid, for example.
- the reaction may be carried out either in a batchwise or in a continuous manner with contact times on the order of about 1 minute to about 2 hours.
- the reaction of the EP or EPDM can be carried out in an extruder or a Banbury mixer. This process can be used for EP or EPDM having a melt viscosity greater than 5,000 cp. at 190°C, up to a viscosity of 500,000 cp. at 190°C.
- the acid functionality may also be incorporated in the EP or EPDM polymer chain by copolymerizing the unsaturated polycarboxylic acid or derivative thereof with the olefin or the olefin and diene monomers during the formation of the EP or EPDM.
- Polymers prepared by copolymerization of ethylene and such acid monomers are disclosed in US Patent 3264272.
- the preferred method for preparing the carboxylated EP or EPDM for the purposes of this invention is to graft the unsaturated acid monomer onto the polymer backbone, preferably in the presence of a free radical generator such as an organic peroxide.
- a free radical generator such as an organic peroxide.
- the amount of unsaturated polycarboxylic acid monomer or derivative thereof incorporated into the EP or EPDM polymer according to this invention may generally range from about 0.05 to 10.0 percent by weight, more preferably from about 0.1 to about 5 percent by weight, and most preferably from about 0.15 to about 1.0 percent by weight, based on the weight of EP or EPDM polymer.
- the carboxylated EP or EPDM polymers used in this invention are solid materials having a number average molecular weight (Mn) in the range of from about 15,000 up to about 150,000, more preferably from about 25,000 up to about 90,000, as measured by Gel Permeation Chromatography (GPC) .
- Mn number average molecular weight
- the EPDM-Epoxy, one of the compatibilizers of this invention can be obtained either by direct epoxidation of the unsaturation sites of the EPDM or by grafting a monomer containing an epoxy groups on to EPDM.
- the use of the term epoxy group hereinafter includes epoxies obtained by either method. Details of these synthetic techniques to prepare EPDM-Epoxy are well known in the art, as disclosed in U.S.
- the EPDM terpolymer (Vistalon 7000) was reacted with meta- chloroperoxybenzoic acid in toluene solution for six hours and the reaction product was isolated by diluting the reaction mixture with isopropyl alcohol, collecting the precipitated polymer and then drying in a vacuum oven. The presence of epoxy group in the reaction product was confirmed by analyzing the FTIR spectrum for the absorption band at 857 cm -1 which was characteristic of an epoxy group.
- the sulfonated elastomeric polymers which are preferred for the purpose of this invention are water insoluble and include sulfonated terpolymers of ethylene, propylene and a diene, preferably non- conjugated diene (EPDM) .
- the water insoluble sulfonated polymers of the instant invention will comprise from about 4 to about 200 milli equivalents of pendant sulfonate groups per 100 grams of polymer, more preferably from 10 to 100 meq. pendant sulfonate groups.
- the sulfonated elastomers utilized in the instant invention are neutralized with elements from Groups I?, and IIA and with transition elements selected from Groups IVB, VB,
- Zinc and sodium neutralizing ions are preferred.
- Neutralization of the cited polymers with appropriate metal hydroxides, metal acetates, metal oxides or ammonium hydroxide, etc. can be conducted by means well known in the art.
- the sulfonated elastomers of the instant invention may vary in number average molecular weight from 1,000 to 10,000,000 preferably 5,000 to 1,000,0000 most preferably from 10,000 to 600,000. These polymers may be prepared by methods known in the art, for example, see U.S. Patent No. 3,642,728, incorporated herein by reference.
- sulfonated polymers for use in the instant invention are sulfonated ethylene/propylene terpolymers which may be prepared by the procedures described in U.S. Patent Nos. 3,870,841 and 4,119,616 incorporated herein by reference.
- the rubbers which can be compatibilized using these terpolymers include, but are not limited to ethylene/propylene rubber, neoprene, nitrile rubber, ethylene/proprylene/diene terpolymers, SBR, Butyl, halobutyl, poly (isobutylene-co-4-methylstyrene) , brominated poly (isobutylene-co-4-methyl styrene) , natural rubber and the like.
- EPDM or EP as used herein includes terpolymers, tetrapolymers, etc. , preferably of ethylene, and a c 3 ⁇ c 28 alpha-olefin, preferably propylene and/or a non-conjugated diolefin or mixtures of such diolefins which may also be used.
- the amount of the non-conjugated diolefin will generally range from about 0.5 to 20 wt. percent, preferably about 1 to 7 wt. percent, based on the total amount of ethylene and alpha-olefin present.
- non-conjugated dienes that may be used as the third monomer in the terpolymer include: a. Straight chain acyclic dienes such as : 1,4- hexadiene; 1,5-heptadiene; 1, 6-octadiene. b. Branched chain acyclic dienes such as: 5- methyl-1, 4-hexadiene; 3,7-dimethyl 1, 6-octadiene; 3,7-dimethyl 1,7-octadiene; and the mixed isomers of dihydro-myrcene and dihydro-cymene. c.
- Single ring alicyclic dienes such as : 1,4- cycl-hexadiene; 1,5 cyclooctadiene; 1,5-cyclo- dodecadiene; 4-vinylcyclohexene; 1-allyl, 4- isopropylidene cyclo-hexane; 3-allyl-cyclopentene; 4-ally cyclohexene and l-isopropenyl-4-(4-butenyl) cyclohexane.
- Multi-single ring alicyclic dienes such as: 4,4"-dicyclo- pentenyl and 4,4" -dicyclohexenyl.
- Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydroindene; methyl tetrahydroindene; dicyclopentadiene; bicyclo (2.2.1) hepta 2,5-diene; alkyl, alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as: ethylidene norbornene; 5-methylene-6- methyl-2- norbornene; 5-methylene-6, 6-dimethyl-2-norbornene; 5-propenyl-2-norbornene; 5-(3-cyclo-pentylidene)-2- norbornene and 5-cyclohexylidene-2-norbornene; etc.
- the most preferred EPDM elastomer contains from about 60 to about 80% by weight ethylene, from about 15 to about 35% by weight propylene and from about 3 to about 7% by weight of non-conjugated diene. Synthesis of EPDM is well known in the art. G. ver Strate, Encyclopedia of Polymer Science and Engineering, vol. 6, 2nd Ed., 1986, p. 522-564.
- the polychloroprene elastomer used as the major component in the elastomer blend in one embodiment of the present invention is a commercially available material, commonly referred to as CR or neoprene rubber. It is available in a number of grades and molecular weights, all of which elastomeric grades are suitable for use in the compositions of this invention.
- the preferred grade is Neoprene GRT which is more resistant to crystallization and is based on a copolymer of chloroprene and 2,3- dichloro-1, 3-butadiene. Neoprene synthesis is also well known in the art.
- C. A. Hargraves et al. Encyclopedia of Polymer Science and Technology, vol. 3, p. 705-730.
- the polychloroprene preferably constitutes the major component of the mixture of elastomers of the present invention, but may be generally present in a range of from about 30 to 90% by weight based on total elastomer content. It is also within the scope of the present invention to provide elastomer compositions based on blends of the polychloroprene and other polar rubbers.
- the vulcanizable composition of the present invention also includes a conventional mixed vulcanizing system for EP or EPDM and polychloroprene.
- vulcanizing systems include a metal oxide such as zinc oxide, magnesium oxide and mixtures thereof, used either alone or mixed with one or more organic accelerators or supplemental curing agents such as an amine, a phenolic compound, a sulfonamide, thiazole, a thiuram compound, thiourea or sulfur.
- organic accelerators or supplemental curing agents such as an amine, a phenolic compound, a sulfonamide, thiazole, a thiuram compound, thiourea or sulfur.
- Organic peroxides may also be used as curing agents.
- the zinc or magnesium oxide is normally present at a level of from about 1 to about 10 parts by weight per 100 parts by weight of elastomer blend, and the sulfur and supplemental curing agents or curing accelerators, where used, may be present at a level of from about 0.1 to about 5 parts by weight per 100 parts by weight of elastomer blend.
- the elastomers blend composition of this invention may also contain other additives such as lubricants, fillers, plasticizers, tackifiers, coloring agents, blowing agents, and antioxidants.
- fillers examples include inorganic fillers such as carbon black, silica, calcium carbonate, talc and clay, and organic fillers such as high- ⁇ tyrene resin, coumarone-indene resin, phenolic resins, lignin, modified elamine resins and petroleum resins.
- lubricants include petroleum-type lubricants such as oils, paraffins, and liquid paraffins, coal tar-type lubricants such as coal tar and coal tar pitch; fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as Ticinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; and synthetic polymeric substances such as petroleum resins.
- petroleum-type lubricants such as oils, paraffins, and liquid paraffins
- coal tar-type lubricants such as coal tar and coal tar pitch
- fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil
- tall oil waxes such as beeswax, carnauba wax and lanolin
- plasticizers include hydrocarbon oils, e.g. paraffin, aromatic and naphthenic oils, phthalic acid esters, adipic acid esters, sebacic acid esters and phosphoric acid-type plasticizers.
- plasticizers include hydrocarbon oils, e.g. paraffin, aromatic and naphthenic oils, phthalic acid esters, adipic acid esters, sebacic acid esters and phosphoric acid-type plasticizers.
- tackif.. ars are petroleum resins, coumarone-indene resins, terpene-phenol resins, and xylene/formaldehyde resins.
- coloring agents are inorganic and organic pigments.
- blowing agents are sodium bicarbonate, ammonium carbonate, N,N'- dinitrosopenta- methylenetetramine, azocarbonamide, azobis-isobutyronitrile, benzene ⁇ ulfonyl hydrazide, toluenesulfonyl hydrazide, calcium amide, p-toluenesulfonyl azide, salicyclic acid, phthalic acid and urea.
- the compatibilized elastomers blend composition of this invention may be prepared and blended on any suitable mixing device such as an internal mixer (Brabender Plasticorder) , a Banbury Mixer, an extruder, a kneader or a similar mixing device.
- the EP or EPDM rubber to be compatibilized is typically present at about 1JD to 9_0 phr, more preferably 1 . 5 to 5 . 0 phr, most preferably 2_0 to _____0_ phr.
- the modified EPDM or EP is typically present at .1 to 60 phr, more preferably 5 to 30 phr, most preferably 5 to 20 phr.
- the CR is typically present at 10 to £0 phr, preferably 30 to 80 phr, more preferably 4_0 to 7_0 phr (phr meaning parts per hundred rubber) .
- Blending temperatures and times may range from about 45 to 180°C and from about 1 to 10 minutes respectively.
- the mixture is then vulcanized by the further mixing-in of crosslinking agents and accelerators followed by heating the resulting blend to a temperature of from about 100° to 250°C, more preferably from about 125 to 200"C for a period of time ranging from about 1 to 60 minutes.
- Molded articles including but not limited to belts, hoses, air springs & power transmission belts are prepared by shaping the prevulcanized formulation using an extruder or a mold, and subjecting the composition to temperatures and curing times as set forth above.
- Neoprene (CR) GRT is a polychloroprene made by DuPont.
- Vistalon 7000 (abbr. V 7000) is a fast curing, high diene ethylene-propylene terpolymer (EPDM) , available from EXXON CHEMICAL COMPANY, with a Mooney viscosity ML(1+4) @ 125°C of 60 and an ethylene content of 70 wt. %.
- EXXELOR VA 1801 is maleated EP rubber with ethylene content of 77 wt.%, melt flow rate: 9 g/10 minutes (10 Kg load at 230°C) and maleic anhydride content of 1 0.7 wt.%.
- N650 and N762 are two well known, general purpose, moderately reinforcing carbon blacks. They are standard as defined by ASTM D 1765-89 and are manufactured by a number of different companies including: Continental Carbon, J. M. Huber,
- Sundex 790 is a standard aromatic processing aid (oil) used for compounding of a variety of rubbers: NR, SBR, CR, IIR, BR, EP, EPDM. Similar to the carbon blacks, it is manufactured by a number of companies: Harwick, Matrochem, R. E. Carroll.
- (F) Octa ine is an antioxidant used primarily with CR, NR, and SBR. It gives excellent protection against heat, oxygen, and flexing. Chemically, it is a reaction product of diphenyl-amine and diisobutylene. It is manufactured by Uniroyal Chemical.
- AgeRite HP-S is an antioxidant used in rubber compounding (similarly to Octamine) . It is a blend of dioctylated diphenylamines and diphenyl-p- phenylene-diamine and is manufactured by R. T. Vanderbilt.
- (H) Maglite D is a magnesium oxide, which is used as a curing agent in our compound. It is manufactured by CP. Hall and Merck Chemical.
- the milled elastomer composition was then sheeted off the mill at a thickness of about 0.1 inch, placed in a 6 inch by 6 inch by 0.075 inch mold and cured at a temperature of about 160°C for a period of 20 minutes.
- the property evaluation of the molded samples were done using standard test procedures shown in Table 1.
- Example 1 The process of Example 1 was repeated except that the elastomer composition consisted of a mixture of 70 parts polychloroprene and 30 parts EPDM (V7000) . All other ingredients are as set forth in Table 2, Ex. 2.
- Example 3 The process of Example 1 was repeated except that the elastomer composition consisted of a mixture of 70 parts polychloroprene, 30 parts EPDM and 10 parts EP-MA (EXXELOR VA 1801) the compatibilizer of this invention. Other ingredients are set forth in Table 2, Ex. 3.
- Neoprene in Neoprene/EPDM blends A small amount (10 wt.%) of the V 7000 Epoxy was sufficient to bring out the synergistic effect in the properties of the above blends. It was even better in the case of sulfonated EPDM, - as shown in Table 3, example 5, 5 wt.% of sulfonated EPDM was all that was needed to improve the properties of Neoprene/EPDM blends.
- Neoprene/EPDM/EP-MA blends were in agreement with our previous findings, - improved compatibility of Neoprene/EPDM/EP-MA blends. It is reasonable to extrapolate these results to other, similar functionalized EPDM which, in theory, could act as compatibilizers for Neoprene/EPDM blends.
- Such functionalized EPDM can be: EPDM-Amine, EPDM- Hydroxy, EPDM-SH, EPDM-C0 2 H.
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1993/006411 WO1995002011A1 (en) | 1993-07-07 | 1993-07-07 | Compatibilization of polar and nonpolar elastomer blends using functionalized ethylene/propylene copolymers or ethylene/propylene/diene terpolymers |
Publications (1)
Publication Number | Publication Date |
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EP0713509A1 true EP0713509A1 (en) | 1996-05-29 |
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ID=22236750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93917018A Withdrawn EP0713509A1 (en) | 1993-07-07 | 1993-07-07 | Compatibilization of polar and nonpolar elastomer blends using functionalized ethylene/propylene copolymers or ethylene/propylene/diene terpolymers |
Country Status (4)
Country | Link |
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EP (1) | EP0713509A1 (en) |
JP (1) | JPH08511810A (en) |
CA (1) | CA2166681A1 (en) |
WO (1) | WO1995002011A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HUP9904581A3 (en) * | 1996-12-18 | 2001-01-29 | Exxon Chemical Patents Inc Bay | Compatibilized polymer blends formed using a multifunctional agent |
AU757562B2 (en) | 1997-12-31 | 2003-02-27 | Bridgestone Corporation | Tire components containing functionalized polyolefins |
DE69823676T2 (en) * | 1998-12-11 | 2005-04-28 | Bridgestone Corp. | Tire components containing functionalized polyolefins |
JP5898978B2 (en) * | 2012-01-30 | 2016-04-06 | 株式会社ブリヂストン | Rubber composition for air spring and air spring using the same |
CA2882515C (en) | 2012-08-31 | 2016-10-18 | Soucy Techno Inc. | Rubber compositions reinforced with fibers and nanometric filamentary structures, and uses thereof |
CA2925928C (en) | 2013-10-18 | 2018-06-19 | Soucy Techno Inc. | Rubber compositions and uses thereof |
WO2015089647A1 (en) | 2013-12-19 | 2015-06-25 | Soucy Techno Inc. | Rubber compositions and uses thereof |
WO2016130881A1 (en) * | 2015-02-12 | 2016-08-18 | Eastman Chemical Company | Elastomeric compositions comprising ionomers |
US20160237258A1 (en) * | 2015-02-12 | 2016-08-18 | Eastman Chemical Company | Process for making elastomeric compositions comprising ionomers |
CN105400088B (en) * | 2015-12-11 | 2017-12-01 | 中北大学 | A kind of ethylene propylene diene rubber and neoprene co-vulcanization material and preparation method thereof |
EP4003689A1 (en) * | 2019-07-31 | 2022-06-01 | Danfoss Power Solutions II Technology A/S | Low permeation type c air conditioning hose |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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ZA814605B (en) * | 1980-07-14 | 1982-07-28 | Uniroyal Inc | Nitrile rubber/epdm graft blends |
JPS6250352A (en) * | 1985-08-29 | 1987-03-05 | Tonen Sekiyukagaku Kk | Non-rigid olefin resin composition |
CA2051411A1 (en) * | 1989-04-28 | 1990-10-29 | Robert C. Keller | Compatible blends of ethylene-propylene rubber and polychloroprene or nitrile rubbers |
-
1993
- 1993-07-07 WO PCT/US1993/006411 patent/WO1995002011A1/en not_active Application Discontinuation
- 1993-07-07 CA CA002166681A patent/CA2166681A1/en not_active Abandoned
- 1993-07-07 JP JP5505603A patent/JPH08511810A/en active Pending
- 1993-07-07 EP EP93917018A patent/EP0713509A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO9502011A1 * |
Also Published As
Publication number | Publication date |
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CA2166681A1 (en) | 1995-01-19 |
WO1995002011A1 (en) | 1995-01-19 |
JPH08511810A (en) | 1996-12-10 |
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