CN101081915A - Fluid-resistant heat-proof chlorinated polyethylene - Google Patents
Fluid-resistant heat-proof chlorinated polyethylene Download PDFInfo
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- CN101081915A CN101081915A CN 200610106030 CN200610106030A CN101081915A CN 101081915 A CN101081915 A CN 101081915A CN 200610106030 CN200610106030 CN 200610106030 CN 200610106030 A CN200610106030 A CN 200610106030A CN 101081915 A CN101081915 A CN 101081915A
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- 239000012530 fluid Substances 0.000 title claims abstract description 29
- 239000004709 Chlorinated polyethylene Substances 0.000 title claims description 45
- 229920001971 elastomer Polymers 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000005060 rubber Substances 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 229920002681 hypalon Polymers 0.000 claims abstract description 20
- 230000005540 biological transmission Effects 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 10
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims abstract description 9
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 27
- 229920002125 Sokalan® Polymers 0.000 claims description 22
- 239000004584 polyacrylic acid Substances 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 12
- 239000004902 Softening Agent Substances 0.000 claims description 11
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000005987 sulfurization reaction Methods 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims 2
- 241000872198 Serjania polyphylla Species 0.000 claims 1
- -1 polypropylene Polymers 0.000 abstract description 17
- 239000000654 additive Substances 0.000 abstract description 11
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 abstract 2
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 abstract 2
- 229920001155 polypropylene Polymers 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 239000000126 substance Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002516 radical scavenger Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- 230000032683 aging Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
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- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 5
- 241001441571 Hiodontidae Species 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
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- 235000012424 soybean oil Nutrition 0.000 description 3
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- 239000012745 toughening agent Substances 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
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- 125000005591 trimellitate group Chemical group 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical class CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical class CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
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- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 description 1
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- GCAWOEQIXXCPJH-UHFFFAOYSA-N C=C.C=C.[S] Chemical group C=C.C=C.[S] GCAWOEQIXXCPJH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001279 adipic acids Chemical class 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The chlorinated rubber composition tolerant to various kinds of fluid, such as transmission fluid, is mixture of chlorinated polyethylene elastomer, vinyl acrylate elastomer and/or polypropylene rubber, as well as optional chlorosulfonated polyethylene. The chlorinated rubber composition may be applied in making different products, such as pipe, and may be added with different kinds of additives, such as stuffing, plasticizer, vulcanizing agent, etc. The heat resistant rubber composition is mixture of chlorinated polyethylene elastomer, vinyl acrylate elastomer and/or polypropylene rubber, ethylene-octylene copolymer and ternary ethylene-propylene-diene copolymer. The heat resistant rubber composition may be applied in making coating or sheath for the chlorinated rubber pipe.
Description
Technical field
The present invention relates to a kind of chlorinated polyethylene rubber composition, it has good fluid-resistant, for example automatic transmission fluid or has good high heat resistance.
Background technology
Up to now, most rubber compounding things are used as sheet material, tubing, liner etc.Do not have good anti-transmission fluid but do not exist always, the chlorinated polyethylene rubber composition of especially up-to-date " E-fluid ".
Similarly, when polytype high heat resistance rubber is utilized, do not know to have under about 150 ℃ the mixture of good heat resistance, this mixture is polyethylene elastomer body, ethylene-octene copolymer and ethylene-acrylic acid and/or polyacrylic acid elastomerics always.
Summary of the invention
Fluid-resistant rubber comprises the polyacrylic acid elastomerics that the chlorinatedpolyethylene of 70 weight parts and about 5～about 49 weight parts have the ethylene-acrylic acid elastomerics of about 10～about 25 mooney viscosities (ML 1+4/100 ℃) and/or have about 10～about 70 mooney viscosities usually.
Rubber combination with high heat resistance comprises the chlorinated polyethylene rubber of the chloride about 25 weight % of 70 weight parts～about 45 weight % usually, about 5～about 49 weight part octene content are about the ethylene-octene copolymer of 25 weight %～about 55 weight %, about 5～about 49 weight part mooney viscosities are that about 10～about 25 ethylene-acrylic acid elastomerics and/or mooney viscosity are the EPDM rubber that about polyacrylic acid rubber of 10～about 70 and optional about 10～about 50 weight parts contain about 30～about 70 weight % ethylene repeating units and about 0.1 weight %～about 8 weight % diene repeat units.
Description of drawings
Fig. 1 is the synoptic diagram of the anti-knot of test
Embodiment
The fluid-resistant rubber combination
It is elastomeric that the various components of chlorinated rubber composition all are based at least a chlorinatedpolyethylene of 70 weight parts.The normally about 25 weight % of cl content in the chlorination elastomer～about 50 weight % are about 30 weight %～about 45 weight % ideally, are preferably about 36 weight %～about 42 weight %.The elastomeric example of chlorinatedpolyethylene that is fit to is a document and well known in the prior art, the specific commercial examples of this compounds comprises: contain about 36 weight % chlorine, mooney viscosity (ML 1+4/100 ℃) is about 100 Tyrin CM0836, contain about 36 weight % chlorine, mooney viscosity is about 80 Tyrin CM0136 and contains about 42 weight % chlorine, and mooney viscosity is about 80 Tyrin CM 4211P.These all Tyrin chlorinatedpolyethylene elastomericss all can obtain from DuPont Dow.
The mooney viscosity of mentioning among the present invention all is meant (ML 1+4/100 ℃) mooney viscosity.
The elastomeric importance of chlorinatedpolyethylene of the present invention is that they can both be vulcanized ideally by those superoxide of hereinafter mentioning, and by various thio-compoundss, for example thiadiazoles derivative sulfuration also can be vulcanized by radiation simultaneously.If two or more chlorinatedpolyethylene elastomerics combinations are used, normally about 1～about 99 weight % of the amount of any one elastomerics in all chlorinatedpolyethylene elastomericss so, be about 25 weight %～about 75 weight % ideally, it is in the elastomeric gross weight of chlorinatedpolyethylene.
Another important component of chlorinated rubber composition is at least a ethylene-acrylic acid elastomerics, and wherein vinylformic acid can be the alkyl acrylate that moieties has about 1～about 8 carbon atoms of ideal, preferably methyl acrylate.The ethylene-acrylic acid elastomerics has about mooney viscosity of 10～about 25 usually, is about 13～about 19 ideally.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 5～about 49 weight parts of the elastomeric total amount of one or more ethylene-acrylic acids are about 5～about 40 weight parts ideally, preferably about 25～about 35 weight parts.The elastomeric example of suitable ethylene-acrylic acid comprises the various Vamac elastomericss that can obtain from the DuPont industrial copolymer, Vamac D for example, Vamac DLS, Vamac G, Vamac GLS and Vamac HG and highly preferred Vamac DP.
Substitute as ethylene-acrylic acid is elastomeric, or conduct any part therewith, known one or more polyacrylic acid elastomericss of those this areas and document can be used.Generally speaking, these polyacrylic acid elastomericss contain the alkyl acrylate repeating unit that moieties has about 1～about 8 carbon atoms of ideal, preferably methyl acrylate or ethyl propenoate.Usually, partly the have an appointment vinylformic acid alcoxyl base ester of 1～about 5 carbon atoms of a spot of alkoxyl group also can use, preferably methoxy or ethoxy.The mooney viscosity of one or more acrylic elastomer normally about 10～about 70, preferably about 25～about 40 or 55.With respect to the described chlorinatedpolyethylene elastomerics of 70 weight parts, normally about 5～about 49 weight parts of the elastomeric amount of polyacrylic acid are about 5～about 40 weight parts ideally, preferably about 25～about 35 weight parts.The polyacrylic acid elastomerics can be used as the elastomeric alternative use of one or more ethylene-acrylic acids, also can partly substitute use.That is to say, described chlorinatedpolyethylene elastomerics with respect to 70 weight parts, the elastomeric arbitrary combination of ethylene-acrylic acid elastomerics or polyacrylic acid can be used with the total amount of about 5～about 49 weight parts, it is desirable to about 5～about 40 weight parts, preferably about 25～about 35 weight parts.Owing to the present invention relates to peroxide cure, so use those can be by the polyacrylic ester of peroxide cure.Because polyacrylic ester has saturated skeleton, so by introducing copolyreaction sulfuration point, for example crosslinked by using suitable peroxide reactions compound such as carboxylic acid to wait to realize.Suitable polyacrylic acid elastomerics is the HyTemp PV-04 that Zeon Chemicals makes.
A component of choosing wantonly but wishing of chlorinated rubber composition is a chlorosulfonated polyethylene, and the chlorine that it contains the 25 weight %～about 45 weight % that have an appointment usually it is desirable to about 30 weight %～about 40 weight %, preferably about 33 weight %～about 38 weight %.The content of sulphur is normally low-down, and its gross weight based on chlorosulfonated polyethylene is about 0.25 weight %～about 2 weight %, it is desirable to about 0.5 weight %～about 1.5 weight %, preferably about 0.75 weight %～about 1.25 weight %.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, when using, normally about 5～about 49 weight parts of the consumption of one or more chlorosulfonated polyethylenes it is desirable to about 10～about 40 weight parts, preferably about 25～about 35 weight parts.The example of suitable compound comprises the various Hypalon compounds that DuPont Dow produces, Hypalon20 for example, Hypalon 30 and preferably contain the Hypalon 40 of about 35 weight % chlorine and about 1 weight % sulphur.
Chlorinated rubber composition of the present invention usually and those this areas and the compound use of the known conventional additive of document, for example activator and/or acid scavenger, processing aid, also can be used as the various fillers, softening agent of toughener, for example be the coagent, lubricant, stablizer etc. of vulcanizing agent, for example vulcanization leveller of various superoxide.
Activator and/or acid scavenger comprise various metal hydroxidess and/or carbonate, aluminum magnesium hydrocarbonate for example, metal oxide, for example magnesium dioxide, plumbous oxide, organic bases lead (organic lead bases) etc.Preferred activator/acid scavenger is Maglite D or the DE that C.P.Hall company produces.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, the such activator and/or the total amount of acid scavenger are normally low-down, such as about 3～20 weight parts, it is desirable to about 5～about 15 weight parts.
Processing aid comprises multiple wax, for example low molecular weight polyethylene wax, polystyrene wax, paraffin, lipid acid etc., and polyethylene wax is preferred.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 0.1～about 10 weight parts of processing aid appropriate vol it is desirable to about 1～about 5 weight parts.
Appropriate filler comprises kaolin, mica, calcium, carbonate etc.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 5～about 80 weight parts of the amount of described filler.Preferably have high surface area and about iodine number of 25～about 32 such as the such reinforcing filler of carbon black.Special example comprises N762, N774, N550 and the N990 that Cancarb produces.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 50～about 300 weight parts of the amount of toughener it is desirable to about 100～about 250 weight parts, preferably about 125～about 200 weight parts.
Various types of softening agent, one or more epoxy soybean oils for example, various biphthalates, for example Phthalic acid, diallyl ester, two (2-ethylhexyl) phthalic ester, di-isopropyl phthalic ester, linear C
8～C
10Phthalic ester and linear C
7～C
11Phthalic ester, various trimellitates, for example three (2-ethylhexyl) trimellitate, partially benzene three different monooctyl esters and benzene three ester in the different ninth of the ten Heavenly Stems partially, various adipic acid esters, for example di-isooctyladinpate, two (2-ethylhexyl) adipic acid ester, diisononyl adipate and diisodecyl adipate, various azelates, two (2-ethylhexyl) azelate for example, various glutarates, diisodecyl glutarate for example, various sebates, for example two (2-ethylhexyl) sebate can be used for giving thermally-stabilised and light stability.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 1～about 60 weight parts of the total amount of the softening agent that one or more are dissimilar it is desirable to about 7～about 50 weight parts.
The sulfuration compound it is desirable to superoxide, and all kinds are known in this area and document.The example of suitable superoxide comprises 4,4-bis(t-butylperoxy) butyl valerate, TBPB tertiary butyl perbenzoate, 2,5-dimethyl-2,5-two (t-butylperoxy)-3-hexin, normal-butyl-4,4-bis(t-butylperoxy) valerate, 1,1-bis(t-butylperoxy) 3,3,5-trimethyl-cyclohexane, two (2-t-butyl peroxy sec.-propyl) benzene, dibenzoyl peroxide, 2,5-2, dicumyl peroxide and their combination.Preferred superoxide comprise can from HarwickStandard obtain respectively with Vulcup 40KE and Trigonox 20-40B-PD represent 2,2 '-two (t-butyl peroxy isopropyl benzenes) and 1,1-bis(t-butylperoxy) 3,3,5-trimethyl-cyclohexane.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 0.1～about 10 weight parts of total amount of one or more sulfuration compounds it is desirable to about 3～about 6 weight parts.
Coagent generally includes two types: the type i and the common Type II that only influences sulfided state that are used for improving sulfided state and speed of reaction.The example of suitable type i coagent comprises the methacrylic ester product, trimethylolpropane trimethacrylate (TMPTMA) for example, with various bismaleimidess, N for example, N '-m-phenylene dimaleimide (HVA-2), with various acrylate, Viscoat 295 (TMPTA) for example.The Type II coagent that is fit to comprises triallylcyanurate (TAC), cyanacrylate (TAIC), diallyl terephthalate and 1,2-vinyl polybutadiene (Ricons) etc.Also have various other coagents, they are the same also to be that this area and document are known.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 0.1～about 15 weight parts of the total amount of one or more coagents it is desirable to about 3～about 12 weight parts.
Above all cpds and component are cooperated, form needed final use shape subsequently, for example pipe.More specifically, the ideal engagement process is included in the continuous high-shear mixer and mixes all unvulcanised compounds (except vulcanizing agent and coagent) and last one or more polymkeric substance that add with random order.Like this, in any order, with one or more promoting agents and/or sour remover, one or more processing aids, one or more for example filler and one or more softening agent of reinforcing filler add separately with random order, mix all joining in the high-shear mixer mixed simultaneously continuously up to them.General any high-shear mixer all is suitable, has used Thyssen KruppGK 250 E in the following embodiments.So various additives be added into and mix after, polymkeric substance, just one or more chlorinatedpolyethylene elastomericss, one or more optional chlorosulfonated polyethylenes and one or more ethylene-acrylic acid elastomericss generally add with random order, mix usually till obtaining the homogeneous mixture.Compounding rubber can cool off in any way then, is piled into tabular, and ideal has a kind of anti-fissuring agent in its surface.When needed, compounding chlorinated rubber composition of the present invention can join one with the same or different high shear device of the employed mixing tank of compounding rubber forming process in and mix at low temperatures with one or more vulcanizing agents and one or more coagents, composition can not vulcanize like this.The compounding rubber of Containing Sulfur additive can be extruded into the shape of any needs, for example pipe with forcing machine.Chlorinated rubber composition of the present invention has a better preserve time limit usually, approximately is 35～45 days, so they can transfer to terminal source mill, vulcanizes under suitable temperature then.
Suitable final form comprises sheet material, sebific duct, flexible pipe and sealing member.Because compounding rubber has good anti-transmission fluidity, a desirable end-use of chlorinated rubber composition of the present invention is as transmitting system of vehicle transmission the liquid particularly sebific duct or the flexible pipe of E-type transmission fluid.The specification sheets of E type automatic transmission fluid is the WSA-M96D26-A of Ford Motor Company.Such specification sheets is as described below substantially:
Sebific duct, Reinforced Rubber, anti-automatic WSA-M96D26-A transmission fluid
1. field
This specification sheets has defined a kind of with one deck cloth enhanced synthetic rubber tube straight or moulding, and it has good anti-transmission fluidity.
2. use
This specification sheets is issued for an automatic transmission oil cooling sebific duct at first.This sebific duct can long-term exposure at automatic transmission fluid with in up to 125 ℃ air up to 150 ℃.About the application in temperature more than 125 ℃, please consider WSA-M96D13-A.
3. requirement
3.1 quality system requirement
Material supplier and part manufacturers must abide by quality system and require QS-9000.It is the initial conditions of raw material that raw material specification requires.Need one to be used for uninterrupted control plan of producing checking.Before manufactured parts was submitted to, this plan must be checked and checks and approves through relevant Ford raw material operation (activity) and/or Ford supplier technological aid (STA).The consistence that suitable statistical tool can be used to analyze processing/production data and guarantees raw material processing.
The raw material that the part manufacturers of these raw materials of use must use Ford to check and approve in its product must be abideed by the control plan that processing is checked and approved by STA and related raw material operation.
3.2 ir spectrophotometry is measured and/or thermal analysis
Ford Motor Company can arbitrarily carry out infrared and/or thermal analysis to the raw material/part that offers this specification sheets.To constitute reference standard for checking and approving infrared spectra and the thermogram set up at first, and will continue to file in the specified feedstock laboratory.All samples will produce corresponding infrared spectra of reference standard and the thermogram of testing down with similarity condition.
3.3 adjust and test condition
Here all test values of Xian Shiing all are based on preceding placement of test and are no less than 24 hours except as otherwise noted under the condition of 23+/-2 ℃ temperature of controlling and 50+/-5% relative humidity, and the sample of under similarity condition, testing.
3.4 sebific duct structure
Sebific duct is made up of level and smooth boring (bore) synthetic rubber hose and high temperature resistant, oil resistant synthetic rubber tectum (with reference to 5.2 sections).Be coated with a suitable braiding reinforced fabric individual layer on the flexible pipe.Sebific duct can connect mutually with a curling metal end accessory.
3.5 raw material test
Below test will carry out at complete sebific duct or from the test specimen of their that cutting-outs.These test specimens scale off from the complete part upper punch, can wear into or be torn into the thickness that needs in case of necessity.When infeasible, can use from what make with same raw material, have the sample that downcuts on the mold pressing test panel of identical sulfided state.Test panel has following size: 150 * 150mm, min * 2.0+/-0.2mm.
3.6 original performance
| Flexible pipe | Tectum | ||
| 3.6.1 | Hardness, international (ISO 1183, A/ASTMD 1415 methods) | 65-80 | 65-80 |
| 3.6.2 | Hardness, durometer A (ISO 868/ASTM D 2240, instant, gummed examination group) | 65-80 | 65-80 |
| 3.6.3 | Tensile strength, MPa, min (ISO 37/ASTM D4123, mould C) | 9 | 9 |
| 3.6.4 | Elongation, %, min (ASTMD 412, mould C) | 110 | 200 |
| 3.6.5 | Ozone resistance, grade, maximum (FLTM BP 101-01m program A or B) | 0 | 0 |
| 3.6.6 | Compression set, %, maximum (ISO 815/ASTM D 395, method B, 125+/-2 ℃ following 70 hours) | 60 | 65 |
3.7 aged properties
| 3.7.1 | Thermal ageing has only tectum (ISO 188/ASTM D 573,150+/-2 ℃ following 168 hours) | |
| Changes in hardness | 0 arrives+10IRHD | |
| Tensile strength changes, maximum | -10％ | |
| Elongation at break changes, maximum | -40％ | |
| Visual assessment | ||
| There is not bonding or crack, surface during doubling |
| 3.7.2 | Thermal ageing has only tectum (ISO 188/ASTM D 573,120+/-2 ℃ following 1000 hours) | |
| Changes in hardness | 0 to 25IRHD | |
| Tensile strength changes, maximum | -20％ | |
| Elongation at break changes, maximum | -65％ | |
| Visual assessment | ||
| There is not bonding or crack, surface during doubling |
| 3.7.3 | Be immersed in the current automatic transmission fluid of producing, has only flexible pipe (ISO 1817/ASTMD 471,150+/-2 ℃ following 168 hours are referring to 5.1 sections) | |
| Changes in hardness | 15IRHD | |
| Tensile strength changes, maximum | -50％ | |
| Elongation at break changes, maximum | -65％ | |
| Volume change | 0 to+35% | |
| Visual assessment | ||
| There is not bonding or crack, surface during doubling |
| 3.7.4 | Be immersed in the current automatic transmission fluid of producing, has only flexible pipe (ISO 1817/ASTM D 471,135+/-2 ℃ following 1000 hours are referring to 5.1 sections) | |
| Changes in hardness | 15IRHD | |
| Tensile strength changes, maximum | -60％ | |
| Elongation at break changes, maximum | -85％ | |
| Volume change | 0 to 35% | |
| Visual assessment | ||
| There is not bonding or crack, surface during doubling |
| 3.7.5 | Be immersed among the oily IRM 903 (ISO 1817/ASTM D 471,150+/-2 ℃ following 168 hours) | |
| Changes in hardness | -25IRHD | |
| Tensile strength changes, maximum | -40％ | |
| Elongation at break changes, maximum | -55％ | |
| Volume change, maximum | 0 to+65% | |
| Visual assessment | ||
| There is not bonding or crack, surface during doubling |
3.8 complete part
| 3.8.1 | Burst pressure, minimum (ASTMD 380) | 6.9MPa |
| 3.8.2 | Bounding force, minimum (ASTM D 413, cloth method, type A) | 1.4N/mm |
| 3.8.3 | Tensile strength (ASTM D 380,25mm/ branch) |
Only when connecting joint and the supporting use of sebific duct, just use this requirement.This making-up unit must be stood the pulling force of minimum 1.1kN and not cause leakage that sebific duct separates, is of coupled connections with connecting joint or the breaking of sebific duct.
| 3.8.4 | Low temperature flexibility oil degradation/cold soaking bubble | There are not fragmentation or crack |
Testing method: be full of in the sebific duct assembly current produce check and approve automatic transmission fluid (referring to 5.1 sections), the sealing all of the port, ℃ following thermal ageing is 24 hours in 150+/-2.Assembly after aging ℃ is adjusted 24 hours down in-40+/-1 after being cooled to 23+/-2 ℃.Adjust the back and in a cold casket sebific duct assembly is adjusted the core bending around a temperature, the radius of this core equals the minimum bending radius of 10 times of internal diameters.Bending will be finished in 4 seconds.
| 3.8.5 | The acceleration shock test |
Testing method: sebific duct assembly and/or knocked-down sebific duct, be full of in advance when appropriate current produce check and approve automatic transmission fluid (referring to 5.1 sections), all of the port sealing, before Impact Test in 150+/-2 ℃ following thermal ageing 70 hours.For initial requirement, the assembly after aging must stand 250,000 impact cycle and not break or show any failure sign under maximum working pressure (MWP) 1.1MPa.The sebific duct assembly of removing from testing table and the burst pressure of test on average are no more than 20% of 3.8.1 section firstling mean value.Thereafter the assembly after cycle proof test will require to wear out can stand 100,000 impact cycle and not lose efficacy under maximum working pressure (MWP) 1.1MPa, the temperature that keeps transmission fluid simultaneously is 150 ℃, and ambient room temperature is 125 ℃.The spalling intensity level of sebific duct assembly is lower than firstling (3.8.1 and 3.8.3 section) mean value and on average is no more than 15% after 100,000 impact cycle.
| The Impact Test condition: | |
| The oil temperature | 150+/-3℃ |
| Ambient stable | 125+/-5℃ |
| Cycle rate | The 30-40 branch |
| Loop-around data: | |
| The pressure rise time | 0.20+/-0.02 second |
| The high pressure hold-time | 0.65+/-0.02 second |
| Pressure descends | 0.20+/-0.10 second |
| Pressure change | 0-1.10MPa |
| Accommodating pressure-transmitting liquid | The current automatic transmission fluid of producing (referring to 5.1 sections) |
| 3.8.5.1 | Oil resistant and thermotolerance |
After completing successfully 100,000 impact cycle according to the 3.8.5 section, the standardized A STM test specimen that takes off from sebific duct will can not surpass following numerical value:
| Flexible pipe | Tectum | |
| Hardness changes maximum | -15 | +15 |
| Tensile strength changes, %, maximum | -50 | +35 |
| Elongation at break changes, %, maximum | -60 | -65 |
| 3.8.6 | Anti-knot |
Testing method: insert the sebific duct that needs length on test fixture, every end is all fixed with metal holder.When sebific duct is installed, be in 5 seconds in the plane the same and direction with its free state curvature with its bending.Anchor clamps are placed in the baking box of 120+/-2 ℃ 1 hour.Anchor clamps are shifted out from baking box, in 5 minutes, one had the sebific duct of specific direct steel ball on being installed in anchor clamps and pass through.Ball must freely pass through.
| Internal diameter general range mm | The specimen length minimum+/-3.0mm mm | Spherical diameter mm |
| 7.1-8.7 | 300 | 3.20+/-0.05 |
| 8.8-10.1 | 350 | 3.95+/-0.05 |
| 12.1-13.3 | 450 | 5.5+/-0.05 |
With reference to figure 1:
Sample is selected: the product sebific duct of selecting to carry out the knot test will have thin as far as possible wall thickness.Record comprise wall thickness, ovality and size " A " (seeing accompanying drawing) as a result the time, this size is that sample is measured on test fixture the time.
Can better understand the present invention by the following examples, these embodiment only are used for illustrating the present invention, do not play the qualification effect.
Table 1
| Component | Chemical name | Component function | Embodiment A |
| Tyrin CM 0836 | Chlorinated polyethylene alkene polymer-36% chlorine, Mooney 100 | Polymkeric substance | 70 |
| Vamac DP | High-level methacrylic ester is arranged, the composition attribute in ethylene/acrylic acid elastomerics-polymkeric substance | Polymkeric substance | 30 |
| Maglite DE | Magnesium dioxide | Promoting agent/acid scavenger | 3.5 |
| DHT-4A-2 | Aluminum magnesium hydrocarbonate | Promoting agent/acid scavenger | 7.5 |
| AC Poly617A | Polyethylene wax | Processing aid | 2 |
| N990 | Carbon black | Filler | 135 |
| Hubercarb Q325 | Lime carbonate | Filler | 10 |
| Paraplex G62 | Epoxy soybean oil | Softening agent | 15 |
| Plasthall P-670 | The polyester adipic acid ester | Softening agent | 27 |
| Vulcup 40KE | 2,2 '-two (t-butylperoxies two | Vulcanizing agent | 5 |
| Isopropyl benzene) | |||
| Trigonox 29-40B- PD | 1-1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane | Vulcanizing agent | 0.15 |
| TACDLC-A | Triallyl cyanurate | Coagent | 7.5 |
| Vanax MBM | N, N '-m-phenyl dimaleimide | Coagent | 0.5 |
| Add up to | 313.15 |
Embodiment
The various components of table 1 are carried out compounding with method above-mentioned.Just for example mix all unvulcanised components one by one in those continuous high-shear mixers of making by Farrel or Krupp, mix with last one or more polymkeric substance that add then at one.Total mixing time is about 3～about 10 minutes, is preferably about 4 minutes, and the mixing temperature of mixing tank is about 250 ～about 320 , is preferably about 300 .After cooling, form tabular, then with chlorinated polyethylene composition and shown in vulcanizing agent under about 200 ～250 low temperature, mix, be extruded into the flexible pipe shape then.Next flexible pipe was vulcanized about 13 minutes under about 345 , test then.Embodiment 1,3 and 4 is rubber combinations of testing after various products generate, and embodiment 2 makes with the sebific duct form, and the rubber combination that therefrom shifts out and test.Obtain following performance:
Table 2
| Embodiment 1 (product) | The sebific duct (off hose) that embodiment 2 cuts off | Embodiment 3 (product) | Embodiment 4 (product) | |
| WSA-M96D26-A | ||||
| Tensile strength, pound (1305 minutes) | 1470 | - | 1680 | 1620 |
| Elongation, % (110% minute) | 212 | 175 | 190 | 193 |
| Durometer, (65-80) | 73 | 65 | 73 | 73 |
| 50% modulus | - | - | 420 | 404 |
| Compression set stacks | - | - | - | - |
| 125 ℃ following 70 hours, 60% maximum | 61 | 54.1 | 60.7 | 61.6 |
| ATF-D, 150 ℃ following 168 hours | ||||
| Tensile strength changes, % (50 % maximum) | -3 | 3 | 0 | 5 |
| Elongation change, % (65% maximum) | -37 | -23 | -22 | -25 |
| Changes in hardness, (15pts. maximum) | -2 | -11 | -1 | -1 |
| Volume % changes, 0/+35% | 8.3 | 7 | 9.4 | 8.2 |
| ATF-E, 150 ℃ following 168 hours | 8 | 14 | 5 | 32 |
| Tensile strength changes, % (50 % maximum) | -60 | -62 | -51 | -52 |
| Elongation change, % (65% maximum) | 9 | -2 | 9 | 12 |
| Changes in hardness, (1pts. maximum) | 9.9 | 6.1 | 10.7 | 9.2 |
| Volume % changes, 0/+35% | - | - | 1082 | 1218 |
| 50% modulus | 8 | 14 | 5 | 32 |
| IRM903 oil, 150 ℃ following 168 hours |
| Tensile strength changes, % (40 % maximum) | 8 | 14 | 5 | 32 |
| Elongation change, % (55% maximum) | -60 | -62 | -51 | -52 |
| Changes in hardness, (25pts. maximum) | 9 | -2 | 9 | 12 |
| Volume % changes, 0/+65% | 9.9 | 6.1 | 10.7 | 9.2 |
Embodiment 1 to 4 has provided about in every performance, such as the low superior results that changes on tensile strength, elongation, hardness and the high temperature lower volume transformation efficiency.And this tubing has passed through the test of " E " type transmission fluid.
High heat-resistant rubber comosition
The prescription of high heat-resistant rubber comosition is based on one or more chlorinatedpolyethylene elastomericss of 70 weight parts.The normally about 25 weight % of the amount of chlorine～about 45 weight % in the elastomerics are preferably about 25 weight %～about 30 weight %.If two or more chlorinatedpolyethylene elastomerics combinations are used, the normally about 1 weight % of the amount of any one elastomerics in all chlorinatedpolyethylene elastomericss～about 99 weight % are about 25 weight %～about 75 weight % ideally so.Such elastomerics is that this area and document are known.The elastomeric example of this suitable chlorinatedpolyethylene comprises: contain about 30 weight % chlorine, mooney viscosity (ML1+4/100 ℃) is about 65 Tyrin CM0730, contain about 36 weight % chlorine, mooney viscosity is about 100 Tyrin CM 0836 and contains about 36 weight % chlorine, and mooney viscosity is about 80 Tyrin CM0136.These Tyrin chlorinatedpolyethylene elastomericss all DuPont Dow are produced.
An importance of the present invention has been to use ethylene-octene copolymer, its elastomeric consumption of one or more chlorinatedpolyethylenees with respect to 70 weight parts is about 5～about 49 weight parts, it is desirable to about 12～about 30 weight parts, preferably about 10～about 20 weight parts.Such multipolymer contains the 25～about 55 weight % that have an appointment usually, it is desirable to the octene unit of about 35 weight %～about 45 weight %.Ideal, this multipolymer also have the melting index of about low-gravity of 08.5～about 08.7 and about 0.25～about 5.0dg/min.Such multipolymer can be the Engaged polymkeric substance that DuPont Dow produces, for example Engaged CL 8001, Engaged CL 8002, Engaged EG 8200 and preferred Engaged EG8150.
An important component that is used for forming high heat-resistant rubber comosition comprises one or more ethylene-acrylic acid elastomericss usually, wherein acrylate moiety can be an alkyl acrylate, wherein alkyl has about 1～about 8 carbon atoms, preferably methyl acrylates ideally.This ethylene-acrylic acid elastomerics has about mooney viscosity of 10～about 25 usually, and preferably about 13～about 19.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 5～about 49 weight parts of the elastomeric total amount of one or more ethylene-acrylic acids, ideal is about 5 to about 35, preferably about 10～about 30 weight parts.Suitable elastomerics example comprises VamacD, Vamac DLS, Vamac G, Vamac GLS and Vamac HG, and highly preferred VamacDP.
Substitute as ethylene-acrylic acid is elastomeric, or conduct any part therewith, known one or more polyacrylate elastomer of those this areas and document can be used.Generally speaking, these polyacrylate elastomer contain the alkyl acrylate repeating unit that moieties has about 1～about 8 carbon atoms of ideal, preferably methyl acrylate or ethyl propenoate.Usually, also can use a spot of alkoxyl group partly have an appointment the vinylformic acid alcoxyl base ester of 1～about 5 carbon atoms, preferably methoxy or ethoxy.The mooney viscosity of one or more acrylate elastomers normally about 10～about 70, preferably about 25～about 40 or 55.With respect to the described chlorinatedpolyethylene elastomerics of 70 weight parts, normally about 5～about 49 weight parts of the elastomeric amount of polyacrylic are about 5～about 35 weight parts ideally, preferably about 10～about 30 weight parts.The polyacrylic acid based elastomers can be used as the elastomeric alternative use of one or more ethylene-acrylic acids, also can partly substitute use.That is to say, described chlorinatedpolyethylene elastomerics with respect to 70 weight parts, the elastomeric arbitrary combination of ethylene-acrylic acid elastomerics or polyacrylic acid can be used with the total amount of about 5～about 49 weight parts, it is desirable to about 5～about 35 weight parts, preferably about 10～about 30 weight parts.Owing to the present invention relates to peroxide cure, so use those can be by the polyacrylic ester of peroxide cure.Because polyacrylic ester has saturated skeleton, so by introducing copolyreaction sulfuration point, for example crosslinked by using suitable peroxide reactions compound such as carboxylic acid to wait to realize.Suitable polyacrylic acid elastomerics is the HyTemp PV-04 that ZeonChemicals makes.
An optional components of high heat-resistant rubber comosition is various EPDM polymkeric substance, wherein based on the gross weight of multipolymer, the normally about 30 weight % of the amount of ethylene repeating unit～about 70 weight %, preferably about 35 weight %～about 60 weight %, the normally about 0.1 weight % of the amount of diene～about 8 weight % it is desirable to about 0.2 weight %～about 2 weight %.With respect to one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 10～about 50 weight parts of the amount of EPDM rubber it is desirable to about 12～about 35 weight parts, preferably about 15～about 25 weight parts.A preferred commercially available example like this is the Nordel IP NDR-125 that R.T.Vanderbilt produces.
An optional components of chlorinated rubber composition is a chlorosulfonated polyethylene, and the chlorine that it contains the 25 weight %～about 45 weight % that have an appointment usually it is desirable to about 30 weight %～about 40 weight %, preferably about 33 weight %～about 38 weight %.The content of sulphur is normally low-down, and its gross weight based on chlorosulfonated polyethylene is about 0.25 weight %～about 2 weight %, it is desirable to about 0.5 weight %～about 1.5 weight %, preferably about 0.75 weight %～about 1.25 weight %.With respect to described one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 5～about 49 weight parts of the consumption of one or more chlorosulfonated polyethylenes it is desirable to about 10～about 40 weight parts, preferably about 25～about 35 weight parts.The example of suitable compound comprises the various Hypalon compounds that DuPont Dow produces, and for example Hypalon 20, Hypalon 30 and preferably contain the Hypalon 40 of about 35 weight % chlorine and about 1 weight % sulphur.
Use one or more antioxidants to help to improve the high heat resistance of composition.Have various antioxidants, they are the same also to be that this area and document are known.The particular preferred example of compound comprises and tetramethylolmethane three esters and 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid blended four [methylene radical (3,5-di-t-butyl-4-hydroxyl phenylpropionic acid)] methane like this; The sulphur di ethylene bis (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate and similar substance.With respect to one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 0.1～about 4 weight parts of the total amount of one or more such compounds it is desirable to about 0.5～about 2 weight parts.The commercial example of this antioxidant comprises Irganox1010 and the Irganox 1035 that Ciba Speciality Chemicals produces.
High heat resistant rubber combination can contain the known conventional additive of those this areas and document usually.Such additive with above-mentioned can be the same, just various promoting agents and/or acid scavenger, processing aid, also can be used as the coagent, lubricant, stablizer etc. of various fillers, softening agent, vulcanizing agent, for example promoting agent of toughener.Since the relevant additive of chlorinated rubber composition this and fluid-resistant is described in the existing institute of preamble, they this by whole introducings to do reference.Generally speaking, can use the additive of same-type, and the amount of various additives also is the same.But for carbon black, the general amount of using still less, it is about 10～about 200 weight parts with respect to the elastomeric consumption of one or more chlorinatedpolyethylenees of 70 weight parts, it is desirable to about 70～about 150 weight parts.In addition, with respect to one or more chlorinatedpolyethylene elastomericss of 70 weight parts, normally about 5～about 50 weight parts of the amount of pearl filler it is desirable to about 10～about 40 weight parts.
Various vulcanizing agents and coagent (promotor) also can use.There are various such compounds, and are that this area and document are known.As for special chemical example and special commercial example, the same compound relevant that can use preamble to mention usually with chlorinated rubber composition, and also the consumption of vulcanizing agent and vulcanization active additive is also identical usually.Therefore, they are all introduced to do reference at this.
Of the present invention one preferred final use be form with flexible pipe with high heat-resistant rubber comosition around fluid-resistant vinyl chloride rubber composition co-extrusion, form lamination flexible pipe, sebific duct and analogue.In order to improve the intensity of sebific duct, can use the fortifying fibre of non-braiding or preferred braiding.
Preferred final an application is and automobile automatic drive liquid the sebific duct structure that E type fluid for example above-mentioned uses.
Can better understand the present invention by the following examples, these embodiment only are used for illustrating the present invention, do not play the qualification effect.
In the prescription of the high heat-resistant rubber comosition of table 3, various additives add in the high-shear mixer with random order one by one, add various polymkeric substance then, for example each adding is a kind of, mixes the blend that obtains a kind of high heat-resistant rubber comosition then under suitable temperature and time.In fact the compounding process is the same with above-mentioned fluid-resistant chlorinated rubber composition.Therefore, the high-shear mixer of use also is the same.Normally about 250 of the mixing temperature of the high-shear mixer relevant with high heat-resistant rubber comosition～about 320 are preferably about 300 .Mixing time can be about 3～about 10 minutes, is preferably about 4 minutes.As previously mentioned, in case composition is mixed, it can cool off and store.Sometimes, next add one or more vulcanizing agents and vulcanization aid, and under the low temperature of for example about 200 ～about 250 , mix, so just do not make the vulcanization of rubber.
In case need to form the finished product, the high heat-resistant rubber comosition of Containing Sulfur compound can mix under higher temperature, forms or be configured as suitable the finished product, sulfuration is about 10～about 18 minutes under about 330 ～about 360 .Suitable the finished product comprise sheet material, the sheath on tubing or sebific duct, sealing agent and analogue.
Table 3
| Component | Chemical name | Component function | Embodiment A |
| Tyrin CM0730 | Chlorinated polyethylene alkene polymer-30% chlorine, Mooney 65 | Polymkeric substance | 70 |
| Engage 8150 | Ethylene-octene polymkeric substance-39% comonomer, 868sp. proportion, melting index 0.5dg/min | Polymkeric substance | 15 |
| Vamac DP | Horizontal methacrylic ester is arranged, the composition attribute in ethylene/acrylic acid binary polymer-polymkeric substance | Polymkeric substance | 15 |
| Maglite DE | Magnesium dioxide | Promoting agent/acid scavenger | 3.5 |
| AC Poly617A | Polyethylene wax | Processing aid | 2 |
| Irganox 1010 | With tetramethylolmethane three esters and 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid blended four [methylene radical (3,5-di-t-butyl-4-hydroxyl phenylpropionic acid)] methane | Antioxidant | 1 |
| DHT-4A-2 | Aluminum magnesium hydrocarbonate | Promoting agent/acid scavenger | 7.5 |
| N990 | Carbon black | Filler | 90 |
| Hubercarb Q325 | Lime carbonate | Filler | 20 |
| Paraplex G62 | Epoxy soybean oil | Softening agent | 11 |
| TOTM | Trioctyl trimellitate | Softening agent | 11 |
| Nordel IP NDR-125 | Ethylene-propylene-diene trimer-42.5 % ethene, 0.5% diene | Polymer/plasticizer | 20 |
| Vulcup 40KE | 2,2 '-two (t-butylperoxy diisopropyl benzenes) | Vulcanizing agent | 4.5 |
| Trigonox29-40B-PD | 1-1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane | Vulcanizing agent | 0.15 |
| Ricon 152 DLC 70％ | Be dispersed in 1 on the Calucium Silicate powder, 2-is poly- | Coagent | 8 |
| Divinyl | |||
| TAC DLC-A | Triallyl cyanurate | Coagent | 4.5 |
| Vanax MBM | N, N '-m-phenylene dimaleimide | Coagent | 0.75 |
| Add up to | 283.90 |
When making high heat-resistant rubber comosition and testing, obtain following data:
Table 4
| Component | Chemical name | Component function | Embodiment A |
| WSA-M96D26-A | |||
| Tensile strength, pound (1305 minutes) | 1790 | ||
| Elongation, % (110% minute) | 230 | ||
| Durometer, (65-80) | 78 | ||
| 125 ℃ following 70 hours, 65% maximum | 42.8 | ||
| Tensile strength changes, % (10% maximum) | 10 | ||
| Elongation change, % (40% maximum) | -21 | ||
| Changes in hardness, pts (+10pts.) | 7 | ||
| Ozone, D518-99 handled 24 hours | By | ||
From top data obviously high as can be seen heat-proof chlorinated polyethylene rubber combination little variation is all arranged on every attribute, for example, 150 ℃ of test tensile strength elongation and hardness of 168 hours down.
Though provided preferred plan and preferred embodiment according to patent law, scope of the present invention is not limit by it, is only defined by appended claim.
Claims (28)
- But 1 vulcanizate compositions comprises:The chlorinatedpolyethylene elastomerics of at least a chloride about 25 weight %～about 50 weight %, the elastomeric total amount of described one or more chlorinatedpolyethylenees is 70 weight parts;At least a mooney viscosity is that about 10～about 25 ethylene-acrylic acid elastomerics and/or at least a mooney viscosity are about polyacrylic acid elastomerics of 10～about 70, described one or more ethylene-acrylic acid elastomericss and/or described at least a polyacrylic acid elastomerics with respect to the elastomeric total amount of described one or more chlorinatedpolyethylenees of 70 weight parts be about 5～about 49 weight parts andOptional at least a chloride about 25 weight %～about 45 weight %, the chlorosulfonated polyethylene of the about 0.25 weight % of sulfur-bearing～about 2.0 weight %, described at least a chlorosulfonated polyethylene is about 5～about 49 weight parts with respect to the elastomeric total amount of described one or more chlorinatedpolyethylenees of 70 weight parts.
- But 2, vulcanizate compositions as claimed in claim 1, the content of chlorine is about 30 weight %～about 45 weight % in the wherein said chlorinated polyethylene composition.
- But 3, vulcanizate compositions as claimed in claim 2, the elastomeric mooney viscosity of wherein said ethylene-acrylic acid is about 13～about 19, the elastomeric mooney viscosity of described polyacrylic acid be about 25～about 55, described ethylene-acrylic acid elastomerics and/or the elastomeric amount of described polyacrylic acid are about 5～about 40 weight parts.
- But 4, vulcanizate compositions as claimed in claim 3 comprises the carbon black with respect to about 50～about 300 weight parts of described one or more chlorinatedpolyethylene elastomericss of 70 weight parts; With softening agent with respect to about 1～about 60 weight parts of described one or more chlorinatedpolyethylene elastomericss of 70 weight parts.
- But 5, vulcanizate compositions as claimed in claim 4, the content of chlorine is about 36 weight %～about 42 weight % in the wherein said chlorinatedpolyethylene elastomerics, wherein said ethylene-acrylic acid elastomerics and/or the elastomeric amount of polyacrylic acid are about 25～about 35 weight parts, wherein said sooty amount is about 100～about 250 weight parts, and the amount of described softening agent is about 7～about 50 weight parts.
- But 6, vulcanizate compositions as claimed in claim 5, comprise chloride about 25 weight %～about 45 weight %, the chlorosulfonated polyethylene elastomer of the about 0.25 weight % of sulfur-bearing～2 weight %, wherein chlorosulfonated polyethylene is about 10～about 40 weight parts with respect to the elastomeric amount of described chlorinatedpolyethylene of 70 weight parts.
- 7, the vulcanizate compositions of claim 1.
- 8, the vulcanizate compositions of claim 3, wherein vulcanizing agent contains superoxide.
- 9, the vulcanizate compositions of claim 5, wherein vulcanizing agent contains superoxide.
- 10, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 7.
- 11, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 8.
- 12, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 9.
- 13, a kind of sebific duct of anti-transmission fluid or flexible pipe, it contains the composition of claim 7.
- 14, a kind of sebific duct of anti-transmission fluid or flexible pipe, it contains the composition of claim 9.
- 15, a kind of high heat-resistant rubber comosition comprises:The chlorinated polyethylene rubber of at least a chloride about 20 weight %～about 45 weight %, the total amount of described one or more chlorinated polyethylene rubbers is 70 weight parts;At least a octene content is the ethylene-octene copolymer of about 25 weight %～about 55 weight %, and described one or more ethylene-octene copolymers are about 5～about 49 weight parts with respect to the elastomeric amount of described one or more chlorinatedpolyethylenees of 70 weight parts;At least a mooney viscosity is that about 10～about 25 ethylene-acrylic acid elastomerics and/or at least a mooney viscosity are about polyacrylic acid elastomerics of 10～about 70, described one or more ethylene-acrylic acid elastomericss and/or described at least a polyacrylic acid elastomerics with respect to the elastomeric total amount of described one or more chlorinatedpolyethylenees of 70 weight parts be about 5～about 49 weight parts andOne or more EPDM rubber, the amount of therein ethylene repeating unit is about 30 weight %～about 70 weight %, the amount of diene repeat units is about 0.1 weight %～about 8 weight %, and wherein said EPDM rubber phase is about 10～about 50 weight parts for the elastomeric amount of described one or more chlorinatedpolyethylenees of 70 weight parts.
- 16, as the high heat-resistant rubber comosition of claim 15, wherein said ethylene-acrylic acid elastomerics and/or the elastomeric amount of described polyacrylic acid are about 5～about 35 weight parts.
- 17, as the high heat-resistant rubber comosition of claim 16, the elastomeric mooney viscosity of wherein said ethylene-acrylic acid is about 13～about 19, the elastomeric mooney viscosity of wherein said polyacrylic acid be about 25～about 55, wherein comprise with respect to the antioxidant of about 0.1～about 4 weight parts of described one or more chlorinated polyethylene rubbers of 70 weight parts with respect to the carbon black of about 40～about 200 weight parts of described one or more chlorinatedpolyethylene elastomericss of 70 weight parts.
- 18, as the high heat-resistant rubber comosition of claim 17, wherein said chlorinatedpolyethylene elastomerics comprises the chlorine of about 25 weight %～about 40 weight %, the amount of octene is about 35 weight %～about 45 weight % in the wherein said ethylene-octene copolymer, the amount of wherein said antioxidant is about 0.5～about 2 weight parts, and described sooty amount is about 70～about 150 weight parts.
- 19, as the high heat-resistant rubber comosition of claim 18, the amount of wherein said EPDM rubber is about 12～about 35 weight parts, wherein the amount at ethylene repeating unit described in the described EPDM is about 35 weight %～about 60 weight %, and wherein the amount of diene repeat units is about 0.2 weight %～about 2 weight %; The amount of wherein said ethylene-octene copolymer is about 10～about 20 weight parts; And wherein said ethylene-acrylic acid elastomerics and/or the elastomeric amount of described polyacrylic acid are about 10～about 30 weight parts.
- 20,, comprise chloride about 25 weight %～about 45 weight % of about 5～about 49 weight parts, the chlorosulfonated polyethylene elastomer of the about 0.25 weight % of sulfur-bearing～2 weight % as the high heat-resistant rubber comosition of claim 19.
- 21, the high heat-resistant rubber comosition of sulfurized claim 15.
- 22, the high heat-resistant rubber comosition of the sulfuration of claim 17, wherein said vulcanizing agent is a superoxide.
- 23, the high heat-resistant rubber comosition of the sulfuration of claim 19, wherein said vulcanizing agent is a superoxide.
- 24, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 21.
- 25, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 22.
- 26, a kind of sebific duct, flexible pipe or sealing member, it contains the composition of claim 23.
- 27, a kind of transmission fluid sebific duct or sealing member, it contains the composition of claim 21.
- 28, a kind of transmission fluid sebific duct or sealing member, it contains the composition of claim 23.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956875A (en) * | 2010-09-16 | 2011-01-26 | 广东美的电器股份有限公司 | Aluminum-rubber composite tube of air conditioner |
| CN102443218A (en) * | 2011-09-23 | 2012-05-09 | 郑勇 | Thermoplastic rubber composition and preparation method thereof |
| CN104987583A (en) * | 2015-07-17 | 2015-10-21 | 连云港德翔新材料有限公司 | Ethylene-octene copolymer high performance composite material and preparation method thereof |
| CN107778641A (en) * | 2017-10-31 | 2018-03-09 | 青岛三祥科技股份有限公司 | Rubber composition for automobile cooling pipe and preparation method thereof |
| CN109776978A (en) * | 2019-01-25 | 2019-05-21 | 临朐县恒信橡塑制品厂 | Melt modification POE/CPE/EPDM flame-resistant sealing material and preparation method thereof |
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2006
- 2006-05-30 CN CN 200610106030 patent/CN101081915A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101956875A (en) * | 2010-09-16 | 2011-01-26 | 广东美的电器股份有限公司 | Aluminum-rubber composite tube of air conditioner |
| CN102443218A (en) * | 2011-09-23 | 2012-05-09 | 郑勇 | Thermoplastic rubber composition and preparation method thereof |
| CN102443218B (en) * | 2011-09-23 | 2013-12-25 | 郑勇 | Thermoplastic rubber composition and preparation method thereof |
| CN104987583A (en) * | 2015-07-17 | 2015-10-21 | 连云港德翔新材料有限公司 | Ethylene-octene copolymer high performance composite material and preparation method thereof |
| CN107778641A (en) * | 2017-10-31 | 2018-03-09 | 青岛三祥科技股份有限公司 | Rubber composition for automobile cooling pipe and preparation method thereof |
| CN109776978A (en) * | 2019-01-25 | 2019-05-21 | 临朐县恒信橡塑制品厂 | Melt modification POE/CPE/EPDM flame-resistant sealing material and preparation method thereof |
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