Elastomer compositions for use in a hydrocarbon resistant hose
A heat tolerant, pressure resistant elastomeric composition comprising a blend of a first ethylene-vinyl ester copolymer and a second copolymer selected from the group consisting of chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE), polychloroprene (CR), ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), polyvinyl acetate (PVA), nitrile-butadiene rubber (NBR), hydrogenated nitrile-butadiene rubber (HNBR), and mixtures thereof; a hose manufactured therefrom; and a method for preparing the hose are described.
1 . A vulcanized, heat tolerant, pressure and hydrocarbon resistant elastomeric automotive component exhibiting improved hydrocarbon fluid impermeability, wherein said automotive component comprises:
about 10 to 50% by weight of a blend comprising a first ethylene-vinyl ester copolymer and a second polymeric member selected from the group consisting of an ethylene-acrylic elastomer, an alkyl acrylate copolymer, and mixtures thereof; and
about 25 to 75% by weight of a plurality of additives selected from the group consisting of process aids, fillers, plasticizers, metal oxides, metal hydroxides, peroxides, coagents, antioxidants and combinations thereof.
2 . The automotive component of claim 1 , wherein said first ethylene-vinyl ester copolymer is an ethylene-vinyl acetate copolymer and said second polymeric member is an ethylene-acrylic elastomer.
3 . The automotive component of claim 2 , wherein said ethylene-vinyl acetate copolymer contains about 40 to 90% vinyl acetate.
4 . The automotive component of claim 2 , wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate.
5 . The automotive component of claim 2 , wherein said blend contains about 10 to 90 weight percent ethylene-vinyl acetate copolymer and about 90 to 10 weight percent ethylene-acrylic elastomer.
6 . The automotive component of claim 1 further comprising 0 to about 75% by weight of an elastomeric polymer selected from the group consisting of chlorinated polyolefin, chlorosulfonated polyolefin, polychloroprene, ethylene-acrylic rubber, alkyl acrylate copolymer, polyvinyl acetate, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, ethylene-propylene diene terpolymer, styrene-butadiene rubber, ethylene-propylene rubber, butyl rubber, cis-polybutadiene, cis-polyisoprene, polyurethane, polyamide and combinations thereof.
7 . The automotive component of claim 1 , wherein said one or more additives comprises:
about 0.1 to 8% by weight one or more processing aids selected from the group consisting of stearic acid, stearates, 1-octanedecanamine, polyethylene, amines, oils, organic esters, organic phosphate esters and combinations thereof;
about 20 to 60% by weight one or more fillers selected from the group consisting of carbon black, graphite, silicone dioxide, fumed silica, precipitated silica, diatomaceous earth, magnesium carbonate, calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, mica, aluminum sulfate, calcium sulfate, wollastonite, molybdenum disulfide, clay, calcium carbonate and combinations thereof;
about 3 to 15% by weight one or more plasticizers selected from the group consisting of hydrocarbons, glycols, aldehydes, ethers, esters, ether-ester, trioctyl trimellitate and combinations thereof;
about 0.1 to 10% by weight one or more metal oxides and/or hydroxides selected from the group consisting of zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide and combinations thereof;
about 0.5 to 4% by weight one or more peroxides selected from the group consisting of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; a,a′-bis-(t-butylperoxy)-p-diisopropylbenzene; dicumyl peroxide; di-t-butyl peroxide; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; 2,4-dichlorobenzoyl peroxide; benzoyl peroxide; p-chlorobenzoyl peroxide; 4,4-bis(t-butylperoxy) valerate; t-butylcumyl peroxide; di-t-amyl peroxide; t-butyl hydroperoxide and combinations thereof;
about 0.1 to 5% by weight one or more coagents selected from the group consisting of maleimides, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, 1,2-vinyl polybutadiene, di- and tri-functional methacrylates, diacrylates, metal ion versions thereof and combinations thereof; and
about 0.1 to 3% by weight one or more antioxidants selected from the group consisting of phenols, hydrocinnamates, hydroquinones, hydroquinolines, diphenylamines, mercaptobenzimidazoles and combinations thereof.
8 . The automotive component of claim 7 , wherein said composition comprises:
about 10 to 90% by weight of an ethylene-vinyl acetate copolymer, wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate;
about 90 to 10% by weight of an ethylene-acrylic elastomer;
about 0.2 to 0.7% by weight stearic acid;
about 23 to 38% by weight carbon black;
about 2 to 5% by weight silicon dioxide;
about 3 to 7% by weight trioctyl trimellitates;
about 0.1 to 7% by weight adipate type plasticizer;
about 0.1 to 8% by weight magnesium oxide;
about 0.1 to 0.75% by weight 1-octanedecanamine;
about 0.1 to 0.75% by weight organic phosphate ester;
about 0.5 to 4% by weight organic peroxide;
about 0.25 to 1% by weight triallyl cyanurate;
about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;
about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinones, hydroquinolines and mixtures thereof.
9 . The automotive component of claim 1 , wherein said automotive component is selected from the group consisting of automotive hoses, transmission belts, seals, dampers, engine mounts, air duct housing, gaskets and CV joint boots.
10 . The automotive component of claim 9 , wherein said automotive component is a hose.
11 . A method for preparing a vulcanized, heat tolerant, pressure and hydrocarbon resistant automotive component having improved hydrocarbon fluid impermeability, said method comprising:
providing a first ethylene- vinyl ester copolymer; wherein said vinyl ester is a vinyl ester of a C 2 to C 6 lower carboxylic acid;
providing a second polymeric material comprising a polymeric material selected from the group consisting of ethylene-acrylic elastomer (AEM), alkyl-acrylate copolymer (ACM), ), and mixtures thereof;
providing one or more additives selected from the group consisting of process aids, fillers, plasticizers, metal oxides, metal hydroxide, peroxides, coagents, antioxidants and combinations thereof;
blending said first ethylene-vinyl ester copolymer, said second polymeric material, and said one or more additives to form an elastomeric composition comprising said first ethylene-vinyl ester copolymer, said second polymeric material, and said; one or more additives;
forming said automotive component from said elastomeric composition; and
vulcanizing said automotive component.
12 . The method of claim 11 , wherein said ethylene-vinyl ester is ethylene-vinyl acetate and said second polymeric material is an ethylene-acrylic elastomer.
13 . The method of claim 12 , wherein said ethylene-vinyl acetate contains about 40 to 80% vinyl acetate.
14 . The method of claim 12 , wherein said ethylene-vinyl acetate copolymer contains about 50 to 80% vinyl acetate.
15 . The method of claim 12 , wherein said elastomeric composition comprises about 10 to 90% by weight said first ethylene-vinyl ester copolymer; about 90 to 10% second polymeric material, and about 25 to 75% by weight of one or more additives.
16 . The method of claim 11 , further comprising about 0 to about 75% by weight of an elastomeric polymer selected from the group consisting of chlorinated polyolefin, chlorosulfonated polyolefin, polychloroprene, polyvinyl acetate, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber and combinations thereof.
17 . The method of claim 11 wherein one or more of said additives comprises:
about 0 to 8% by weight one or more processing aids selected from the group consisting of stearic acid, stearates, 1-octanedecanamine, polyethylene, amines, oils, organic esters, organic phosphate esters and combinations thereof;
about 20 to 60% by weight one or more fillers selected from the group consisting of carbon black, graphite, silicone dioxide, fumed silica, precipitated silica, diatomaceous earth, magnesium carbonate, calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, mica, aluminum sulfate, calcium sulfate, wollastonite, molybdenum disulfide, clay, calcium carbonate and combinations thereof;
about 3 to 15% by weight one or more plasticizers selected from the group consisting of hydrocarbons, glycols, aldehydes, ethers, esters, ether-ester, trioctyl trimellitate and combinations thereof;
about 0 to 10% by weight one or more metal oxides and/or hydroxides selected from the group consisting of zinc oxide, zinc hydroxide, magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, aluminum hydroxide and combinations thereof;
about 0.5 to 4% by weight one or more peroxides selected from the group consisting of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; a,a′-bis-(t-butylperoxy)-p-diisopropylbenzene; dicumyl peroxide; di-t-butyl peroxide; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane; 2,4-dichlorobenzoyl peroxide; benzoyl peroxide; p-chlorobenzoyl peroxide; 4,4-bis(t-butylperoxy) valerate; t-butylcumyl peroxide; di-t-amyl peroxide; t-butyl hydroperoxide and combinations thereof;
about 0 to 5% by weight one or more coagents selected from the group consisting of maleimides, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate, 1,2-vinyl polybutadiene, di- and tri-functional methacrylates, diacrylates, metal ion versions thereof and combinations thereof; and
about 0 to 3% by weight one or more antioxidants selected from the group consisting of phenols, hydrocinnamates, hydroquinones, hydroquinolines, diphenylamines, mercaptobenzimidazoles and combinations thereof.
18 . The method of claim 17 , wherein said composition comprises:
about 10 to 90% by weight of an ethylene-vinyl acetate copolymer containing about 50 to 80% vinyl acetate;
about 90 to 10% by weight of an ethylene-acrylic elastomer;
about 0.2 to 0.7% by weight stearic acid;
about 23 to 38% by weight carbon black;
about 2 to 5% by weight silicon dioxide;
about 3 to 7% by weight trioctyl trimellitate;
about 1 to 7% by weight adipate type plasticizer;
about 1 to 8% by weight magnesium oxide;
about 0.1 to 0.75% 1-octanedecanamine;
about 0.1 to 0.75% organic phosphate ester;
about 0.5 to 4% by weight organic peroxide;
about 0.25 to 1% by weight triallyl cyanurate;
about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;
about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinolines and mixtures thereof.
19 . The method of claim 11 , wherein said automotive component is selected from the group consisting of hoses, belts, seals, dampers, engine mounts, and CV joint boots.
20 . The method of claim 19 , wherein said automotive component is hoses, said method further comprising applying a reinforcing layer comprising natural or synthetic fibers selected from the group consisting of cotton, polyester, nylon, rayon, and aramid; or metal wire, said method further comprising applying a cover layer on an outer surface of said reinforcing layer, said cover layer comprising a synthetic elastomer selected from the group consisting of styrene-butadiene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide copolymer, polyvinyl chloride, and blends thereof.
21 . In a vulcanized hose for conveying fluids in an automotive engine cooler, transmission oil cooler, power transmission cooler, radiator or heater, the improvement which comprises employing as an inner tubular structure of the hose, a heat tolerant, pressure and hydrocarbon resistant composition exhibiting improved hydrocarbon fluid impermeability compared to conventional hose-forming compositions, wherein said composition comprises:
about 10 to 90% by weight of a n ethylene-vinyl acetate copolymer containing about 50 to 80% vinyl acetate;
about 90 to 10% by weight of an ethylene-acrylic elastomer;
about 0.2 to 0.7% by weight stearic acid;
about 23 to 38% by weight carbon black;
about 2 to 5% by weight silicon dioxide;
about 3 to 7% by weight trioctyl trimellitate;
about 1 to 7% by weight adipate type plasticizer;
about 1 to 8% by weight magnesium oxide;
about 0.1 to 0.75% by weight 1-octanedecanamine;
about 0.1 to 0.75% by weight organic phosphate ester;
about 0.5 to 4% by weight organic peroxide;
about 0.25 to 1% by weight triallyl cyanurate;
about 0.25 to 1% by weight N,N′, n-phenylenedimaleimide;
about 0.25 to 2% by weight antioxidant selected from the group consisting of phenols, hydrocinnamates, diphenylamines, hydroquinones, hydroquinolines and mixtures thereof. said hose further including a reinforcing layer over said tubular structure, said reinforcing layer comprising natural or synthetic fibers selected from the group consisting of cotton, polyester, nylon, rayon and aramid; or metal wire, and a cover layer over said reinforcing layer, said cover layer comprising a synthetic elastomeric selected from the group consisting of styrene-butadiene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide copolymer, polyvinyl chloride, and blends thereof.