JP7419762B2 - Graft copolymer, modified halogenated polyolefin composition containing the same, and method for producing the same - Google Patents
Graft copolymer, modified halogenated polyolefin composition containing the same, and method for producing the same Download PDFInfo
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- JP7419762B2 JP7419762B2 JP2019208683A JP2019208683A JP7419762B2 JP 7419762 B2 JP7419762 B2 JP 7419762B2 JP 2019208683 A JP2019208683 A JP 2019208683A JP 2019208683 A JP2019208683 A JP 2019208683A JP 7419762 B2 JP7419762 B2 JP 7419762B2
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- Japan
- Prior art keywords
- halogenated polyolefin
- carboxylic acid
- polyolefin composition
- weight
- acrylonitrile
- 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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- 229920000098 polyolefin Polymers 0.000 title claims description 118
- 239000000203 mixture Substances 0.000 title claims description 93
- 229920000578 graft copolymer Polymers 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 acrylic compound Chemical class 0.000 claims description 54
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 52
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 33
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229920002681 hypalon Polymers 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000007906 compression Methods 0.000 description 38
- 230000006835 compression Effects 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 36
- 238000004073 vulcanization Methods 0.000 description 35
- 238000012360 testing method Methods 0.000 description 31
- 239000000295 fuel oil Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 23
- 230000035699 permeability Effects 0.000 description 23
- 238000009472 formulation Methods 0.000 description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 241001441571 Hiodontidae Species 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 13
- 238000005660 chlorination reaction Methods 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 235000010269 sulphur dioxide Nutrition 0.000 description 8
- 235000019398 chlorine dioxide Nutrition 0.000 description 7
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound 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
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002635 aromatic organic solvent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
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- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- CTPYJEXTTINDEM-UHFFFAOYSA-N 1,2-bis(1-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOCC(C)C1=CC=CC=C1C(C)COOC(C)(C)C CTPYJEXTTINDEM-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical class CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- HXQWFROUEVBXFE-UHFFFAOYSA-N 1,2-dichloro-3,4-difluorobenzene Chemical compound FC1=CC=C(Cl)C(Cl)=C1F HXQWFROUEVBXFE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、グラフト共重合体及びこれを含有する変性ハロゲン化ポリオレフィン組成物並びにその製造方法に関するものであり、より詳しくは、ハロゲン化ポリオレフィンにグラフト鎖が結合したグラフト共重合体であって、前記グラフト鎖がアクリロニトリルと、アクリル系化合物と、カルボン酸又はカルボン酸無水物を含有する不飽和単量体との共重合体であるグラフト共重合体及びこのグラフト共重合体を含有する変性ハロゲン化ポリオレフィン組成物に関するものである。 The present invention relates to a graft copolymer, a modified halogenated polyolefin composition containing the same, and a method for producing the same, and more specifically, a graft copolymer in which a graft chain is bonded to a halogenated polyolefin, A graft copolymer in which the graft chain is a copolymer of acrylonitrile, an acrylic compound, and an unsaturated monomer containing carboxylic acid or carboxylic acid anhydride, and a modified halogenated polyolefin containing this graft copolymer. The present invention relates to a composition.
ハロゲン化ポリオレフィンは、クロロスルホン化ポリエチレンや塩素化ポリエチレン等の総称であり、優れた耐熱性、耐候性、耐オゾン性、耐薬品性及び明色性を有することから、各種ホースやホースのカバー材、電線被覆材、パッキン、ガスケット、ロール及びエスカレーターの手摺等の各種用途に使用されている。また、クロロスルホン化ポリエチレンや塩素化ポリエチレン等は塩素基を含有することから、天然ゴム、スチレン・ブタジエンゴム及びエチレン・プロピレン系ゴム等の汎用ゴムと比べて耐油性が良好であり、耐油性が要求されるホースやチューブ等にも多く使用されている。 Halogenated polyolefin is a general term for chlorosulfonated polyethylene, chlorinated polyethylene, etc., and has excellent heat resistance, weather resistance, ozone resistance, chemical resistance, and bright color, so it is used as a material for covering various hoses and hoses. It is used for various purposes such as wire sheathing, packing, gaskets, rolls, and escalator handrails. In addition, since chlorosulfonated polyethylene and chlorinated polyethylene contain chlorine groups, they have better oil resistance than general-purpose rubbers such as natural rubber, styrene-butadiene rubber, and ethylene-propylene rubber. It is also widely used in required hoses and tubes.
ハロゲン化ポリオレフィンの耐油性を向上する方法としては、ハロゲン量を増大させることが知られているが、この方法で耐油性を向上した場合、得られるハロゲン化ポリオレフィンのガラス転移温度が高くなり、室温付近での硬さが増大し、ゴム材料としての特性を失ってしまう問題が生じる。そのため、各種ホース用途分野に於いてはハロゲン量増大による耐油性の向上には限界があり、高度な耐油性が要求される用途に対しては好ましい方法とは言えない。 It is known that increasing the amount of halogen is a method for improving the oil resistance of halogenated polyolefins, but when oil resistance is improved by this method, the glass transition temperature of the resulting halogenated polyolefins becomes higher and room temperature A problem arises in that the hardness increases in the vicinity and the properties of the rubber material are lost. Therefore, in various hose application fields, there is a limit to the improvement in oil resistance by increasing the amount of halogen, and this method cannot be said to be preferable for applications that require a high degree of oil resistance.
また、ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物等の共グラフト反応により耐油性を大きく改良した変性ハロゲン化ポリオレフィン組成物が得られる（例えば、特許文献１，２参照。）が、ホース部品やシール部品等に必要不可欠な圧縮永久歪み性が損なわれる。比較的低価格で、耐油性と圧縮永久歪み性のバランスを兼ね備えたゴム材料が望まれている。 Furthermore, modified halogenated polyolefin compositions with significantly improved oil resistance can be obtained by co-grafting acrylonitrile and acrylic compounds onto halogenated polyolefins (see, for example, Patent Documents 1 and 2); Compression set properties, which are indispensable for such processes, are impaired. There is a need for a rubber material that is relatively inexpensive and has a good balance of oil resistance and compression set.
本発明はこの問題点に鑑みてなされたものであり、その目的は、ハロゲン化ポリオレフィンの持つ良好な圧縮永久歪み性を損なうことなく、耐油性が大きく改良された変性ハロゲン化ポリオレフィン組成物を提供するものである。 The present invention was made in view of this problem, and its purpose is to provide a modified halogenated polyolefin composition that has significantly improved oil resistance without impairing the good compression set properties of halogenated polyolefin. It is something to do.
本発明者は、このような背景の下、上記課題を解決するため鋭意検討した結果、ハロゲン化ポリオレフィンの持つ良好な圧縮永久歪み性を損なうことなく耐油性が改良されたゴム組成物が得られるに至ったものである。すなわち、本発明の各態様は以下に示す［１］～［９］である。
［１］ ハロゲン化ポリオレフィンにグラフト鎖が結合したグラフト共重合体であって、前記グラフト鎖がアクリロニトリルと、アクリル系化合物と、カルボン酸又はカルボン酸無水物を含有する不飽和単量体（以下、カルボン酸含有化合物という）との共重合体（以下、カルボン酸含有共重合体という）であるグラフト共重合体。
［２］ ［１］記載のグラフト共重合体、及びハロゲン化ポリオレフィンに結合していないカルボン酸含有共重合体を含有することを特徴とする変性ハロゲン化ポリオレフィン組成物。
［３］ グラフト共重合体中のカルボン酸含有共重合体と、ハロゲン化ポリオレフィンと結合していないカルボン酸含有共重合体の合計の含有率が２０重量％から７５重量％の範囲であり、カルボン酸含有共重合体中のアクリロニトリルとアクリル系化合物由来の成分の重量比率が３／９７～７０／３０の範囲であることを特徴とする［２］に記載の変性ハロゲン化ポリオレフィン組成物。
［４］ カルボン酸又はカルボン酸無水物の含有率が１重量％から７重量％の範囲であることを特徴とする［２］又は［３］に記載の変性ハロゲン化ポリオレフィン組成物。
［５］ ハロゲン化ポリオレフィンがクロロスルホン化ポリエチレンであることを特徴とする［２］～［４］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［６］ アクリル系化合物がアクリル酸２－メトキシエチルであることを特徴とする［２］～［５］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［７］ カルボン酸無水物が無水マレイン酸であることを特徴とする［２］～［６］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［８］ ［２］～［７］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫物。
［９］ 溶剤に溶解したハロゲン化ポリオレフィン溶液に、アクリロニトリル、アクリル系化合物、及びカルボン酸含有化合物を、ラジカル開始剤を用いてグラフト反応することを特徴とする［２］～［７］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物の製造法。
Against this background, the inventors of the present invention made extensive studies to solve the above problems, and as a result, it was possible to obtain a rubber composition with improved oil resistance without impairing the good compression set properties of halogenated polyolefins. This is what led to this. That is, each aspect of the present invention is [1] to [9] shown below.
[1] A graft copolymer in which a graft chain is bonded to a halogenated polyolefin, wherein the graft chain is an unsaturated monomer containing acrylonitrile, an acrylic compound, and a carboxylic acid or a carboxylic acid anhydride (hereinafter referred to as (hereinafter referred to as a carboxylic acid-containing copolymer).
[2] A modified halogenated polyolefin composition comprising the graft copolymer according to [1] and a carboxylic acid-containing copolymer that is not bonded to a halogenated polyolefin.
[3] The total content of the carboxylic acid-containing copolymer and the carboxylic acid-containing copolymer not bonded to the halogenated polyolefin in the graft copolymer is in the range of 20% to 75% by weight, The modified halogenated polyolefin composition according to [2], wherein the weight ratio of the acrylonitrile to the component derived from the acrylic compound in the acid-containing copolymer is in the range of 3/97 to 70/30.
[4] The modified halogenated polyolefin composition according to [2] or [3], wherein the content of carboxylic acid or carboxylic acid anhydride is in the range of 1% by weight to 7% by weight.
[5] The modified halogenated polyolefin composition according to any one of [2] to [4], wherein the halogenated polyolefin is chlorosulfonated polyethylene.
[6] The modified halogenated polyolefin composition according to any one of [2] to [5], wherein the acrylic compound is 2-methoxyethyl acrylate.
[7] The modified halogenated polyolefin composition according to any one of [2] to [6], wherein the carboxylic acid anhydride is maleic anhydride.
[8] A vulcanized product obtained by vulcanizing the modified halogenated polyolefin composition according to any one of [2] to [7].
[9] Any one of [2] to [7], characterized in that acrylonitrile, an acrylic compound, and a carboxylic acid-containing compound are subjected to a graft reaction with a halogenated polyolefin solution dissolved in a solvent using a radical initiator. A method for producing a modified halogenated polyolefin composition as described in .
以下、本発明について詳細に説明する。 The present invention will be explained in detail below.
本発明の一態様である変性ハロゲン化ポリオレフィン組成物は、ハロゲン化ポリオレフィンに、アクリロニトリル、アクリル系化合物、カルボン酸含有化合物を共グラフトすることにより得ることができる。変性ハロゲン化ポリオレフィン組成物には、ハロゲン化ポリオレフィンにグラフト鎖としてカルボン酸含有共重合体が結合したグラフト共重合体と、ハロゲン化ポリオレフィンに結合していないカルボン酸含有共重合体を含有する。 The modified halogenated polyolefin composition, which is one embodiment of the present invention, can be obtained by co-grafting acrylonitrile, an acrylic compound, and a carboxylic acid-containing compound onto a halogenated polyolefin. The modified halogenated polyolefin composition contains a graft copolymer in which a carboxylic acid-containing copolymer is bonded to a halogenated polyolefin as a graft chain, and a carboxylic acid-containing copolymer not bonded to the halogenated polyolefin.
また、本発明の一態様であるグラフト共重合体は、得られた変性ハロゲン化ポリオレフィン組成物から分別により得ることができる。 Further, the graft copolymer which is one embodiment of the present invention can be obtained by fractionation from the obtained modified halogenated polyolefin composition.
ハロゲン化ポリオレフィンとしては、原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化して得られるハロゲン化ポリオレフィンが例示できる。また、必要に応じて臭素やフッ素を含有したハロゲン化ポリオレフィンも使用可能である。原料であるポリオレフィンには、例えば、ポリエチレン、ポリプロピレン等が挙げられ、ポリエチレンとしては、高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、フッ素含有ポリエチレン等が挙げられる。これらを単独または併用して用いることができるが、良好な物理特性と耐油性を両立させるためには、高密度ポリエチレン（ＨＤＰＥ）が好ましい。 Examples of the halogenated polyolefin include halogenated polyolefins obtained by chlorinating or chlorinating and chlorosulfonating a raw material polyolefin. Further, halogenated polyolefins containing bromine or fluorine can also be used if necessary. Examples of the raw material polyolefin include polyethylene, polypropylene, etc. Polyethylene includes high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). ), fluorine-containing polyethylene, etc. Although these can be used alone or in combination, high density polyethylene (HDPE) is preferred in order to achieve both good physical properties and oil resistance.
原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化する反応を行う際、溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系有機溶剤や、モノクロロベンゼン、ジクロロベンゼン、フロロベンゼン、ジクロロジフロロベンゼン、四塩化炭素、クロロホルム、１，１－ジクロロエタン、１，２－ジクロロエタン、１，１，１－トリクロロエタン、１，１，２－トリクロロエタン、テトラクロロエタン、トリクロロフロロエタン等の塩素系有機溶剤が挙げられ、これらを単独または２種類以上を併用して用いることができるが、塩素化反応に対し不活性な塩素系有機溶剤のみの使用が好ましい。 When carrying out the reaction of chlorinating or chlorinating and chlorosulfonating the raw material polyolefin, the solvent may be an aromatic organic solvent such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, or dichlorobenzene. Chlorinated organic solvents such as fluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane, etc. Although these can be used alone or in combination of two or more types, it is preferable to use only a chlorinated organic solvent that is inert to the chlorination reaction.
ポリオレフィンの塩素化、または塩素化及びクロロスルホン化を行う反応工程はラジカル発生剤を触媒として、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリルを、溶剤に溶解または懸濁したポリオレフィンと反応させる。また、臭素化のために塩素の一部又は全部を臭素に変更することも可能である。クロロスルホン化反応を行う場合には必要に応じて助触媒としてピリジン、キノリン等のアミノ化合物が添加させる。反応温度は塩素化反応、または塩素化反応及びクロロスルホン化反応が進行する範囲であれば特に限定するものではなく、例えば４０～１５０℃であり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには好ましくは６０～１３０℃の範囲である。反応圧力は塩素化反応、または塩素化反応及びクロロスルホン化反応が進行する範囲であれば特に限定するものではなく、例えば、０～１．０ＭＰａであり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには好ましくは０～０．７ＭＰａである。 The reaction process of chlorinating polyolefin, or chlorinating and chlorosulfonating, uses a radical generator as a catalyst, and uses chlorine, chlorine and sulfur dioxide gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfur dioxide gas and sulfuryl chloride, React with polyolefin dissolved or suspended in a solvent. It is also possible to change some or all of the chlorine to bromine for bromination. When carrying out the chlorosulfonation reaction, an amino compound such as pyridine or quinoline is added as a co-catalyst if necessary. The reaction temperature is not particularly limited as long as the chlorination reaction, or the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, 40 to 150°C. In order for the sulfonation reaction to proceed, the temperature is preferably in the range of 60 to 130°C. The reaction pressure is not particularly limited as long as the chlorination reaction, or the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, 0 to 1.0 MPa. In order for the chlorosulfonation reaction to proceed, the pressure is preferably 0 to 0.7 MPa.
原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化する反応を行う際に使用するラジカル発生剤は、塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するものであれば特に限定するものではなく、例えば、アゾ系化合物、有機過酸化物等が挙げられる。アゾ系化合物としては、例えば、α，α‘－アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等が挙げられ、有機過酸化物としては、例えば、過酸化ベンゾイル、過酸化アセチル、過酸化ｔ－ブチル、過安息香酸ｔ－ブチル等が挙げられる。取り扱い上安定性が高いため、好ましくはアゾ系化合物であり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには、特に好ましくはα，α‘－アゾビスイソブチロニトリルである。 The radical generator used when carrying out the reaction of chlorinating the raw material polyolefin, or chlorinating and chlorosulfonating, is particularly limited as long as the chlorinating reaction, or the chlorinating reaction and chlorosulfonating reaction proceeds. For example, azo compounds, organic peroxides, etc. may be mentioned. Examples of azo compounds include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and organic peroxides. Examples include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, t-butyl perbenzoate, and the like. Azo compounds are preferred because they are highly stable in handling, and α,α'-azobisisobutylene is particularly preferred in order for the chlorination reaction, or the chlorination reaction and chlorosulfonation reaction, to proceed appropriately. It's lonitrile.
塩素化、または塩素化及びクロロスルホン化を行う反応工程における、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリルとラジカル発生剤を添加する際の添加方法は、塩素化反応、または塩素化及びクロロスルホン化反応が進行すれば特に限定されないが、明色性のためにはラジカル発生剤を加える前に、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリル等を先に添加するのが好ましい。反応工程終了時にはラジカル発生剤の添加停止後、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリル等の添加を停止するのが好ましく、これらの添加方法は単独または併用しても良い。 Addition when adding chlorine, or chlorine and sulfur dioxide gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfur dioxide gas, sulfuryl chloride, and a radical generator in the reaction process of chlorination or chlorination and chlorosulfonation. The method is not particularly limited as long as the chlorination reaction or chlorination and chlorosulfonation reaction progresses, but for brightness, before adding the radical generator, chlorine, chlorine and sulfur dioxide gas, or chlorine and chloride gas It is preferable to add sulfuryl, sulfuryl chloride alone, chlorine, sulfur dioxide gas, sulfuryl chloride, etc. first. At the end of the reaction step, after stopping the addition of the radical generator, it is preferable to stop the addition of chlorine, chlorine and sulfur dioxide gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfur dioxide gas and sulfuryl chloride, etc., and how to add these. may be used alone or in combination.
変性ハロゲン化ポリオレフィン組成物の製造に用いられるハロゲン化ポリオレフィンの塩素量は特に制限はないが、耐油性や機械特性を考慮し、１５．０～４５．０重量％の範囲が好ましく、更に低温性を考慮した場合、２０．０～４０．０重量％の範囲であることが好ましい。ハロゲン化ポリオレフィンが、ポリオレフィンを塩素化及びクロロスルホン化によって得られるクロロスルホン化ポリエチレンである場合の硫黄量は特に制限はないが、０．１～３．０重量％の範囲が好ましい。 The amount of chlorine in the halogenated polyolefin used to produce the modified halogenated polyolefin composition is not particularly limited, but in consideration of oil resistance and mechanical properties, it is preferably in the range of 15.0 to 45.0% by weight, and furthermore, In consideration of this, it is preferably in the range of 20.0 to 40.0% by weight. When the halogenated polyolefin is chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonating a polyolefin, the amount of sulfur is not particularly limited, but is preferably in the range of 0.1 to 3.0% by weight.
ハロゲン化ポリオレフィンに共グラフトする不飽和単量体としては、アクリロニトリル、アクリル系化合物及びカルボン酸含有化合物が用いられる。 As the unsaturated monomer to be cografted to the halogenated polyolefin, acrylonitrile, an acrylic compound, and a carboxylic acid-containing compound are used.
アクリル系化合物としては、アクリロイル基又はメタクリロイル基を含有する化合物であれば制限されず、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ｎ－オクタデシル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル等のアクリル酸エステル、（メタ）アクリル酸２，２，２－トリフルオロエチル等のフッ素含有（メタ）アクリル酸系化合物、アクリル酸グリシジル、４－ヒドロキシブチルアクリル酸グリシジルエーテル、メタクリル酸グリシジル等を例示することができ、これらは単独あるいは２種類以上併用しても良いが、良好な物理特性及び耐油性を維持するためには、アクリル酸メチル、アクリル酸エチル、アクリル酸２－メトキシエチル、アクリル酸ｎ－ブチルをそれぞれ単独あるいは併用することが望ましい。 The acrylic compound is not limited as long as it contains an acryloyl group or a methacryloyl group, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate. 2-ethylhexyl acrylate, n-pentyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, n-octadecyl (meth)acrylate, 2-methoxy (meth)acrylate Ethyl, acrylic esters such as 2-ethoxyethyl (meth)acrylate, fluorine-containing (meth)acrylic acid compounds such as 2,2,2-trifluoroethyl (meth)acrylate, glycidyl acrylate, 4-hydroxy Examples include butyl acrylic acid glycidyl ether, glycidyl methacrylate, etc., and these may be used alone or in combination of two or more types, but in order to maintain good physical properties and oil resistance, methyl acrylate, acrylic acid glycidyl ether, etc. It is desirable to use ethyl acrylate, 2-methoxyethyl acrylate, and n-butyl acrylate alone or in combination.
カルボン酸含有化合物としては、アクリル酸、メタクリル酸、エチルアクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステル、無水マレイン酸、無水イタコン酸等を例示することができ、これらは単独あるいは２種類以上併用しても良いが、良好な圧縮永久歪み性及び耐油性を発現するためには、無水マレイン酸を使用することが望ましい。 Examples of carboxylic acid-containing compounds include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, itaconic acid monoalkyl ester, and maleic anhydride. , itaconic anhydride, etc. These may be used alone or in combination of two or more types, but in order to express good compression set properties and oil resistance, it is preferable to use maleic anhydride. desirable.
また、上記不飽和単量体は、アクリロニトリル、アクリル系化合物及びカルボン酸含有化合物以外に、変性ハロゲン化ポリオレフィンとしての特性を損なわない範囲で、その他の単量体を含有していても良く、例えばメチルビニルケトン等のアルキルビニルケトン化合物、ビニルエチルエーテル等のアルキルビニルエーテル化合物、アリルメチルエーテル等のアリルエーテル化合物、スチレン、α－メチルスチレン、クロロスチレン、ビニルトルエン、ビニルナフタレン等のビニル芳香族化合物、メタクリロニトリル等のビニルニトリル化合物、酢酸ビニル、クロロ酢酸ビニル、アクリルアミド、プロピレン、ブタジエン、イソプレン、ペンタジエン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、プロピオン酸ビニル等を例示することができる。これらの上記単量体としては、グラフト重合に用いる総不飽和単量体中の２０重量％以下の割合で加えることが好ましい。 In addition, the unsaturated monomers may contain other monomers in addition to acrylonitrile, acrylic compounds, and carboxylic acid-containing compounds as long as they do not impair the properties of the modified halogenated polyolefin, such as Alkyl vinyl ketone compounds such as methyl vinyl ketone, alkyl vinyl ether compounds such as vinyl ethyl ether, allyl ether compounds such as allyl methyl ether, vinyl aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, Examples include vinyl nitrile compounds such as methacrylonitrile, vinyl acetate, vinyl chloroacetate, acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, etc. . These monomers are preferably added in an amount of 20% by weight or less based on the total unsaturated monomers used for graft polymerization.
本発明の特徴は、アクリロニトリル、アクリル系化合物及びカルボン酸含有化合物を共グラフト反応によりハロゲン化ポリオレフィンに導入させることで、圧縮永久歪み性と耐油性に優れるグラフト重合体および変性ハロゲン化ポリオレフィン組成物を得ることが出来る点である。 A feature of the present invention is to introduce acrylonitrile, an acrylic compound, and a carboxylic acid-containing compound into a halogenated polyolefin through a co-graft reaction, thereby creating a graft polymer and a modified halogenated polyolefin composition with excellent compression set properties and oil resistance. This is something that can be achieved.
変性ハロゲン化ポリオレフィン組成物中の、ハロゲン化ポリオレフィンと結合していないカルボン酸含有共重合体及びグラフト共重合体中のカルボン酸含有共重合体の合計の含有率は、ハロゲン化ポリオレフィン組成物としての特性を維持しつつ、優れた圧縮永久歪み特性と耐油性を両立させるためには２０重量％から７５重量％の範囲であることが好ましい。さらに好ましくは、４０重量％から７５重量％の範囲である。残りの成分は、グラフト共重合体中のハロゲン化ポリオレフィンに由来する成分である。 The total content of the carboxylic acid-containing copolymer not bonded to the halogenated polyolefin and the carboxylic acid-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is as follows: In order to achieve both excellent compression set properties and oil resistance while maintaining properties, the content is preferably in the range of 20% by weight to 75% by weight. More preferably, it is in the range of 40% to 75% by weight. The remaining components are components derived from the halogenated polyolefin in the graft copolymer.
変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないカルボン酸含有共重合体及びグラフト共重合体中のカルボン酸含有共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重合比率は３／９７～７０／３０の範囲であることが好ましく、更に１０／９０～５０／５０の範囲、特に１５／８５～４０／６０の範囲であることがより好ましい。 The polymerization ratio of the acrylonitrile and acrylic compound-derived components contained in the carboxylic acid-containing copolymer that is not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the carboxylic acid-containing copolymer in the graft copolymer is The range is preferably from 3/97 to 70/30, more preferably from 10/90 to 50/50, particularly preferably from 15/85 to 40/60.
変性ハロゲン化ポリオレフィン組成物中のカルボン酸含有化合物の含有率は１重量％から７重量％の範囲であることが好ましい。カルボン酸含有化合物は、当該の変性ハロゲン化ポリオレフィン組成物に於いて架橋点として作用するものであり、変性ハロゲン化ポリオレフィン組成物中のカルボン酸の重量比率が１重量％以上であれば、十分な架橋構造を形成することでき、得られる変性ハロゲン化ポリオレフィン加硫物は圧縮永久歪み性、耐油性に優れる。一方、変性ハロゲン化ポリオレフィン組成物中のカルボン酸含有化合物の重量比率が７重量％以下であれば、過度な架橋構造の形成することなく、得られる変性ハロゲン化ポリオレフィン加硫物の硬さが高くなることや破断伸びが極端に低下する問題が発生しない。優れた圧縮永久歪み特性と耐油性、加硫物特性が要求される場合には、変性ハロゲン化ポリオレフィン組成物中のカルボン酸含有化合物の重量比率は１重量％から５重量％以下の範囲がより好ましい。 The content of the carboxylic acid-containing compound in the modified halogenated polyolefin composition is preferably in the range of 1% to 7% by weight. The carboxylic acid-containing compound acts as a crosslinking point in the modified halogenated polyolefin composition, and if the weight ratio of carboxylic acid in the modified halogenated polyolefin composition is 1% by weight or more, sufficient A crosslinked structure can be formed, and the resulting modified halogenated polyolefin vulcanizate has excellent compression set properties and oil resistance. On the other hand, if the weight ratio of the carboxylic acid-containing compound in the modified halogenated polyolefin composition is 7% by weight or less, the hardness of the obtained modified halogenated polyolefin vulcanizate is high without forming an excessive crosslinked structure. There are no problems such as excessive breakage or an extreme decrease in elongation at break. When excellent compression set properties, oil resistance, and vulcanizate properties are required, the weight ratio of the carboxylic acid-containing compound in the modified halogenated polyolefin composition is preferably in the range of 1% to 5% by weight. preferable.
本発明の一態様である変性ハロゲン化ポリオレフィン組成物の製造法としては、本発明の変性ハロゲン化ポリオレフィン組成物が得られる方法であれば特に制限はない。例えば、ハロゲン化ポリオレフィンを溶剤に溶解、または押出し機などを用いて撹拌しながら、一括または連続でアクリロニトリル、アクリル系化合物、及びカルボン酸含有化合物を添加して、ラジカル開始剤によりグラフト重合し、所定の重合転化率に達したところで、必要により酸化防止剤を添加し、溶剤または未反応の不飽和単量体を洗浄、減圧除去し、乾燥すること等によって、本発明の変性ハロゲン化ポリオレフィン組成物を得ることができる。 The method for producing the modified halogenated polyolefin composition, which is one embodiment of the present invention, is not particularly limited as long as the modified halogenated polyolefin composition of the present invention can be obtained. For example, a halogenated polyolefin is dissolved in a solvent, or acrylonitrile, an acrylic compound, and a carboxylic acid-containing compound are added all at once or continuously while stirring using an extruder, and graft polymerization is carried out using a radical initiator to achieve a desired amount. When a polymerization conversion rate of can be obtained.
共グラフト反応工程を均一な溶液状態で行うためには、原料であるハロゲン化ポリオレフィンと単量体、及び得られる変性ハロゲン化ポリオレフィン組成物が可溶な溶剤を用いることが好ましい。溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系有機溶剤や、モノクロロベンゼン、ジクロロベンゼン、フロロベンゼン、ジクロロジフロロベンゼン、四塩化炭素、クロロホルム、１，１－ジクロロエタン、１，２－ジクロロエタン、１，１，１－トリクロロエタン、１，１，２－トリクロロエタン、テトラクロロエタン、トリクロロフロロエタン等の塩素系有機溶剤が挙げられ、これらを単独または２種類以上を併用して用いることができる。 In order to carry out the co-grafting reaction step in a uniform solution state, it is preferable to use a solvent in which the halogenated polyolefin and monomer as raw materials and the resulting modified halogenated polyolefin composition are soluble. Examples of solvents include aromatic organic solvents such as benzene, toluene, and xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, Examples include chlorinated organic solvents such as 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, and trichlorofluoroethane, and these can be used alone or in combination of two or more.
ラジカル開始剤としては、パーオキサイド類やアゾ化合物等を用いることができる。パーオキサイド類としては、メチル―エチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、アセチルアセトンパーオキサイド等のケトンパーオキサイド類、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ジ（ｔ－ブチルパーオキシ）ブタン、ｎ－ブチル－４，４－ジ（ｔ－ブチルパーオキシ）吉草酸等のパーオキシケタール類、ｐ－メンタン－ハイドロパーオキサイド、ジイソプロピルベンゼン－ハイドロパーオキサイド、１，１，３，３－テトラメチルブチル－ハイドロパーオキサイド、クメン－ハイドロパーオキサイド、ｔ－ブチル－ハイドロパーオキサイド等のハイドロパーオキサイド類、ジ（２－ｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミル－パーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチル－クミル－パーオキサイド、ジ－ｔ－ヘキシル－パーオキサイド、ジ－ｔ－ブチル－パーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン－３等のジアルキルパーオキサイド類、ジイソブチリル－パーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキサイド、ジラウロイル－パーオキサイド、ジコハク酸－パーオキサイド、ジベンゾイル－パーオキサイド、ジ（４－メチルベンゾイル）パーオキサイド等のジアジルパーオキサイド類、ジ－ｎ－プロピル－パーオキシジカーボネート、ジイソプロピル－パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチル－パーオキシジカーボネート等のパーオキシジカーボネート類、クミル－パーオキシネオデカン酸、１，１，３，３－テトラメチルブチル－パーオキシネオデカン酸、ｔ－ヘキシル－パーオキシネオデカン酸、ｔ－ブチル－パーオキシネオデカン酸、ｔ－ブチル－パーオキシネオヘプタン酸、ｔ－ヘキシル－パーオキシピバル酸、ｔ－ブチル－パーオキシピバル酸、１，１，３，３－テトラメチルブチル－パーオキシ－２－エチルヘキサン酸、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、ｔ－ヘキシル－パーオキシ－２－エチルヘキサン酸、ｔ－ブチル－パーオキシ－２－エチルヘキサン酸、ｔ－ヘキシル－パーオキシ－イソプロピル－モノカーボネート、ｔ－ブチル－パーオキシ－マレイン酸、ｔ－ブチル－パーオキシ－３，５，５－トリメチルヘキサン酸、ｔ－ブチル－パーオキシラウリン酸、ｔ－ブチルーパーオキシイソプロピルーモノカーボネート、ｔ－ブチル－パーオキシ－２－エチルヘキシル－モノカーボネート、ｔ－ヘキシル－パーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシアセテート、ｔ－ブチル－パーオキシベンゾエート等のパーオキシエステル類が挙げられる。アゾ化合物としては、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、４，４’－アゾビス（４－シアノバレリン酸）、２，２’－アゾビス（２，４，４－トリメチルペンタン）、２，２’－アゾビス｛２－メチル－ｎ－［１，１’－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド｝、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジハイドロクロライド、２，２’－アゾビス［２－（イミダゾリン－２－イル）プロパン］ジサルフェートジハイドレート、２，２’－アゾビス｛２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン｝ジハイドロクロライド、２，２’－アゾビス（１－イミノ－１－ピロリジノ－２－メチルプロパン）ジハイドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）ジハイドロクロライド、２，２’－アゾビス［ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］テトラハイドレート等が挙げられる。これらのラジカル開始剤は、単独または併用して用いることができ、場合によっては、硫酸第一鉄等の第一鉄塩、ハイドロサルファイトナトリウム、アスコルビン酸、エリソルビン酸、アニリン、ｎ－ブチルアルデヒドアミン、三級アミン等の還元剤を添加してグラフト重合を行うこともできる。 As the radical initiator, peroxides, azo compounds, etc. can be used. Examples of peroxides include ketone peroxides such as methyl-ethylketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butyl). peroxyketals such as cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl-4,4-di(t-butylperoxy)valeric acid, p-menthane-hydroper oxide, di(2-t -butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl-cumyl-peroxide, di-t-hexyl-peroxide , di-t-butyl-peroxide, dialkyl peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisobutyryl-peroxide, di(3,5,5 - diazyl peroxides such as trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di-n-propyl peroxide Peroxydicarbonates such as carbonate, diisopropyl-peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di-sec-butyl-peroxydicarbonate, etc. cumyl-peroxyneodecanoic acid, 1,1,3,3-tetramethylbutyl-peroxyneodecanoic acid, t-hexyl-peroxyneodecanoic acid, t-butyl-peroxyneodecanoic acid, t-butyl-peroxy Neoheptanoic acid, t-hexyl-peroxypivalic acid, t-butyl-peroxypivalic acid, 1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoic acid, 2,5-dimethyl-2,5-di( 2-ethylhexanoylperoxy)hexane, t-hexyl-peroxy-2-ethylhexanoic acid, t-butyl-peroxy-2-ethylhexanoic acid, t-hexyl-peroxy-isopropyl-monocarbonate, t-butyl-peroxy -Maleic acid, t-butyl-peroxy-3,5,5-trimethylhexanoic acid, t-butyl-peroxylauric acid, t-butyl-peroxyisopropyl monocarbonate, t-butyl-peroxy-2-ethylhexyl-monocarbonate Peroxy esters such as carbonate, t-hexyl-peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, and t-butyl-peroxybenzoate are listed. It will be done. Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2- methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, dimethyl-2,2'-azobis(2-methyl propionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis{2-methyl-n-[1 , 1'-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis[ 2-(imidazolin-2-yl)propane] disulfate dihydrate, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-azobis(1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[n- (2-carboxyethyl)-2-methylpropionamidine]tetrahydrate and the like. These radical initiators can be used alone or in combination, and in some cases, ferrous salts such as ferrous sulfate, sodium hydrosulfite, ascorbic acid, erythorbic acid, aniline, n-butyraldehyde amine, etc. Graft polymerization can also be carried out by adding a reducing agent such as a tertiary amine or the like.
上述の不飽和単量体及びラジカル開始剤の添加方法としては特に制限はなく、共グラフト反応の初期段階に一括で添加する方法、一部の不飽和単量体及び／またはラジカル開始剤を共グラフト反応の初期段階で添加し、残りの不飽和単量体及び／またはラジカル開始剤を連続注入する方法、すべての不飽和単量体及び／またはラジカル開始剤を連続注入する方法が挙げられる。 There are no particular restrictions on the method of adding the unsaturated monomer and radical initiator, and there are methods such as adding them all at once in the initial stage of the co-grafting reaction, and adding some of the unsaturated monomers and/or radical initiator together. Examples include a method in which it is added at the initial stage of the graft reaction and the remaining unsaturated monomers and/or radical initiator are continuously injected, and a method in which all unsaturated monomers and/or radical initiators are continuously injected.
また、共重合体の分子量を調整するため、及び分子間架橋を抑制するため、共グラフト反応時に分子量調節剤を添加しても良い。分子量調節剤としては、例えば、ジイソプロピルキサントゲンジスルフィド、ジエチルキサントゲンジスルフィド、ジエチルチウラムジスルフィド、２，２’－ジチオプロピオン酸、３，３’－ジチオプロピオン酸、４，４’－ジチオジブラン酸、２，２’－ジチオビス安息香酸などのジスルフィド類、ｎ－ドデシルメルカプタン、オクチルメルカプタン、ｔ－ブチルメルカプタン、チオグリコール酸、チオリンゴ酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、チオサリチル酸、３－メルカプト安息香酸、チオマレイン酸無水物、ジチオマレイン酸、チオグルタール酸、システイン、ホモシステイン、６－メルカプトテトラゾール酢酸、３－メルカプト－１－プロパンスルホン酸等のメルカプタン類、ジフェニルエチレン、ｐ－クロロジフェニルエチレン、ｐ－シアノジフェニルエチレン、α－メチルスチレンダイマー、ベンジルジチオベンゾエート、有機テルル化合物、硫黄等が挙げられ、これらを単独または併用して用いることができる。 Furthermore, in order to adjust the molecular weight of the copolymer and to suppress intermolecular crosslinking, a molecular weight regulator may be added during the cograft reaction. Examples of the molecular weight regulator include diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, 2,2'-dithiopropionic acid, 3,3'-dithiopropionic acid, 4,4'-dithiodibranic acid, 2,2' - Disulfides such as dithiobisbenzoic acid, n-dodecylmercaptan, octylmercaptan, t-butylmercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, Mercaptans such as thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazole acetic acid, 3-mercapto-1-propanesulfonic acid, diphenylethylene, p-chlorodiphenylethylene, p-cyanodiphenyl Examples include ethylene, α-methylstyrene dimer, benzyl dithiobenzoate, organic tellurium compounds, sulfur, and the like, and these can be used alone or in combination.
酸化防止剤としては特に限定するものではなく、ポリマーの酸化防止剤として一般に利用されているもので、例えば２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、２，２－ビス〔｛［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］オキシ｝メチル］プロパン－１，３－ジオール、１，３－ビス［３－（ｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－５－メチル－ヒドロキシフェニル）プロピオネート］、１，６－ヘキサンジオール－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリン）－１，３，５－トリアジン、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサメチレンビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマイド）、３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジルホスホネート－ジエチルエステル、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレート、２，４－ビス［（オクチルチオ）メチル］－オルト－クレゾール、イソオクチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、３，９－ビス〔２－［３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）－プロピオニオキシ］－１，１－ジメチルエチル〕－２，４，８，１０－テトラオキサスピロ［５・５］ウンデカン等のフェノール系酸化防止剤、２，２－ヒドロキシ－５－メチルフェニル－ベンゾトリアゾール、４，４’－ビス－（２，２－ジメチルベンジル）ジフェニルアミン、ビス（１，２，２，５，６－ペンタメチル－４－ピペリジル）デカンジオナート等のアミン系酸化防止剤、ジラウリルー３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリルー３，３’－ジチオプロピオネート、ペンタエリスリチル－テトラキス（３－ラウリルチオプロピオネート）ジトリデシル－３，３’－チオジプロピオネート、２－メルカプトベンズイミダゾール等の硫黄系酸化防止剤、トリスノニルフェニルホスファイト、トリフェニルホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト等のリン系酸化防止剤、２，２，６，６－テトラメチルピペリジン－１－オキシル等の安定ラジカル系酸化防止剤等が挙げられる。 The antioxidant is not particularly limited, and it includes those commonly used as antioxidants for polymers, such as 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'- Methylenebis(4-ethyl-6-t-butylphenol), 2,2-bis[{[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]oxy}methyl]propane-1,3 -diol, 1,3-bis[3-(t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3- (3-t-butyl-5-methyl-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4 -bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylaniline)-1,3,5-triazine, pentaerythrityl-tetrakis[3-(3,5-di -t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t -butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3 , 5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 2,4-bis[(octylthio)methyl]-ortho-cresol, isooctyl-3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-[3-(3-t-butyl- Phenolic antioxidants such as 4-hydroxy-5-methylphenyl)-propionioxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 2, 2-Hydroxy-5-methylphenyl-benzotriazole, 4,4'-bis-(2,2-dimethylbenzyl)diphenylamine, bis(1,2,2,5,6-pentamethyl-4-piperidyl)decandionate Amine-based antioxidants such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-dithiopropionate, pentaerythrityl-tetrakis (3- laurylthiopropionate) ditridecyl-3,3'-thiodipropionate, sulfur-based antioxidants such as 2-mercaptobenzimidazole, trisnonylphenylphosphite, triphenylphosphite, tris(2,4-di- Examples include phosphorus-based antioxidants such as t-butylphenyl) phosphite, and stable radical-based antioxidants such as 2,2,6,6-tetramethylpiperidine-1-oxyl.
共グラフト反応の反応温度及び反応圧力は特に限定するものではないが、反応温度は５０～１５０℃、反応圧力は０～１．０ＭＰａの範囲が好ましい。 The reaction temperature and reaction pressure of the co-grafting reaction are not particularly limited, but the reaction temperature is preferably in the range of 50 to 150°C and the reaction pressure is in the range of 0 to 1.0 MPa.
反応終了後、メタノール等の不溶性溶剤による析出、ドラムドライヤー、ベント付押出し機等を用いた濃縮、乾燥により、目的とする変性ハロゲン化ポリオレフィン組成物が得られる。 After the reaction is completed, the desired modified halogenated polyolefin composition is obtained by precipitation with an insoluble solvent such as methanol, concentration using a drum dryer, vented extruder, etc., and drying.
また、反応終了後の溶液を、アセトン等のグラフト共重合体が不溶で、カルボン酸含有共重合体が可溶な溶剤に添加することによって、グラフト共重合体を分別し、これを乾燥することにより、ハロゲン化ポリオレフィンに結合していないカルボン酸含有共重合体を含有しない、グラフト共重合体を得ることが可能である。 Alternatively, the graft copolymer can be separated by adding the solution after the reaction to a solvent such as acetone in which the graft copolymer is insoluble and the carboxylic acid-containing copolymer is soluble, and then dried. Accordingly, it is possible to obtain a graft copolymer that does not contain a carboxylic acid-containing copolymer that is not bonded to a halogenated polyolefin.
本発明のグラフト共重合体及び変性ハロゲン化ポリオレフィン組成物は加硫物として使用される。変性ハロゲン化ポリオレフィン組成物の加硫物を得る方法としては、グラフト共重合体又は変性ハロゲン化ポリオレフィン組成物と各種配合剤をロール又はバンバリーミキサー等で配合又は混練した後、プレス加硫、蒸気加硫、高周波（ＵＨＦ）加硫あるいは電子線加硫等が行われる。加硫温度は特に制限はないが、好ましくは１２０～２２０℃、より好ましくは１５０～１７０℃であり、加硫時間は好ましくは３０秒～１時間、より好ましくは５分～４０分である。また、一次加硫した後に、加硫物の内部まで確実に加硫させるために、二次加硫を行うことが好ましい。二次加硫は加熱方法、加熱温度、形状などにより異なるが、加熱温度は好ましくは１２０～２００℃で、加熱時間は好ましくは１２時間～３６時間行う。加熱方法はオーブン加熱等を適宜選択すればよい。各種配合剤としては加硫剤、加硫促進剤、受酸剤、可塑剤、補強剤、充填剤、加工助剤、老化防止剤等が挙げられ、必要に応じて用いられる。 The graft copolymer and modified halogenated polyolefin composition of the present invention are used as vulcanizates. As a method for obtaining a vulcanized product of a modified halogenated polyolefin composition, the graft copolymer or modified halogenated polyolefin composition and various compounding agents are blended or kneaded using a roll or a Banbury mixer, and then press vulcanization or steam vulcanization is performed. Vulcanization, high frequency (UHF) vulcanization, electron beam vulcanization, etc. are performed. The vulcanization temperature is not particularly limited, but is preferably 120 to 220°C, more preferably 150 to 170°C, and the vulcanization time is preferably 30 seconds to 1 hour, more preferably 5 minutes to 40 minutes. Furthermore, after primary vulcanization, it is preferable to perform secondary vulcanization in order to ensure that the inside of the vulcanizate is vulcanized. The secondary vulcanization differs depending on the heating method, heating temperature, shape, etc., but the heating temperature is preferably 120 to 200°C, and the heating time is preferably 12 to 36 hours. As the heating method, oven heating or the like may be selected as appropriate. Various compounding agents include vulcanizing agents, vulcanization accelerators, acid acceptors, plasticizers, reinforcing agents, fillers, processing aids, anti-aging agents, etc., which are used as necessary.
加硫剤としては、硫黄等の無機系加硫剤、チウラムポリスルフィド類、ジチオカルバミン酸塩類、オキシム類、ニトロソ化合物、有機過酸化物、ジアミン化合物等の有機系加硫剤が挙げられる。このうち良好な加工性や力学物性、圧縮永久歪み性を損なうことなく、耐油性を改良させるためには、融点が１２０℃以下の芳香族ジアミンであることが望ましい。芳香族ジアミン化合物ではなく、脂肪族ジアミン化合物を使用した場合には、焼けによる硬化が発生する。 Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur, and organic vulcanizing agents such as thiuram polysulfides, dithiocarbamates, oximes, nitroso compounds, organic peroxides, and diamine compounds. Among these, aromatic diamines with a melting point of 120° C. or lower are desirable in order to improve oil resistance without impairing good processability, mechanical properties, and compression set properties. When an aliphatic diamine compound is used instead of an aromatic diamine compound, hardening due to burning occurs.
加硫促進剤としては、チオウレア類、グアニジン類、チアゾール類、スルフェンアミド類、チウラム類、ジチオカルバミン酸塩類、キサントゲン酸塩類等が挙げられる。このうち良好な加工性や力学物性、圧縮永久歪み性を損なうことなく、耐油性を改良させるためには、グアニジン塩であることが望ましい。 Examples of the vulcanization accelerator include thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, and the like. Among these, guanidine salts are preferred in order to improve oil resistance without impairing good processability, mechanical properties, and compression set properties.
受酸剤としては、酸化マグネシウム、酸化亜鉛、ハイドロタルサイト、エポキシ樹脂等が挙げられる。このうち良好な加工性や力学物性、圧縮永久歪み性を損なうことなく、耐油性を改良させるためには、エポキシ樹脂であることが望ましい。 Examples of the acid acceptor include magnesium oxide, zinc oxide, hydrotalcite, and epoxy resin. Among these, epoxy resins are preferred in order to improve oil resistance without impairing good processability, mechanical properties, and compression set properties.
可塑剤としては、鉱物油系軟化剤、植物油系軟化剤、合成軟化剤、合成可塑剤等が挙げられる。 Examples of the plasticizer include mineral oil softeners, vegetable oil softeners, synthetic softeners, and synthetic plasticizers.
補強材としては、カーボンブラック、ホワイトカーボン等が挙げられる。 Examples of reinforcing materials include carbon black and white carbon.
充填剤としては、炭酸カルシウム類、塩基性炭酸マグネシウム類、珪酸及び珪酸塩類等が挙げられる。 Examples of fillers include calcium carbonates, basic magnesium carbonates, silicic acid and silicates.
加工助剤としては脂肪酸類、脂肪酸エステル類、脂肪酸金属塩類、炭化水素系ワックス等が挙げられる。 Examples of processing aids include fatty acids, fatty acid esters, fatty acid metal salts, and hydrocarbon waxes.
老化防止剤としては、アミン系老化防止剤、フェノール系老化防止剤、硫黄系老化防止剤、リン系老化防止剤、ワックス類等が挙げられる。 Examples of anti-aging agents include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents, and waxes.
本発明の変性ハロゲン化ポリオレフィン組成物は、混練り機によって混練後に目的に応じた形状に成形加工することで、成形加硫物を得ることができる。変性ハロゲン化ポリオレフィン組成物のムーニー粘度（ＭＬ（１＋４）１００℃）は、加工性を考慮すると、１０～１２０であることが好ましく、２０～１００であることがより好ましい。また、クロロスルホン化ポリオレフィン組成物のレオメータ加硫試験（１６０℃、４５分間）の最大トルク値（ＭＨ）は、加工性を考慮すると、１５～２００ｄＮｍであることが好ましく、２０～１５０ｄＮｍであることがより好ましい。尚、ムーニー粘度、最大トルク値（ＭＨ）は後述する通り、ＪＩＳ－Ｋ ６３００（２０１２年度版）に基づいて測定される値である。 The modified halogenated polyolefin composition of the present invention can be kneaded with a kneader and then molded into a desired shape to obtain a molded vulcanizate. The Mooney viscosity (ML(1+4) 100°C) of the modified halogenated polyolefin composition is preferably 10 to 120, more preferably 20 to 100, in consideration of processability. In addition, the maximum torque value (MH) of the rheometer vulcanization test (160°C, 45 minutes) of the chlorosulfonated polyolefin composition is preferably 15 to 200 dNm, and preferably 20 to 150 dNm, considering processability. is more preferable. Note that the Mooney viscosity and maximum torque value (MH) are values measured based on JIS-K 6300 (2012 edition), as described below.
本発明の変性ハロゲン化ポリオレフィン組成物を用いることで、良好な圧縮永久歪み性と優れた耐油性を有する加硫ゴムを得ることができる。 By using the modified halogenated polyolefin composition of the present invention, a vulcanized rubber having good compression set properties and excellent oil resistance can be obtained.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited only to these examples.
尚、以下の実施例等で用いた値は、以下の測定法で行ったものである。
（１）原料ゴム組成
＜不飽和単量体の転化率＞
不飽和単量体の転化率は、反応終了後の溶液を少量採取し、未反応の不飽和単量体量をガスクロマトグラフィー（ＧＣ－２０２５、島津製作所製）を用いて測定することにより求めた。
Note that the values used in the following Examples and the like were determined by the following measurement method.
(1) Raw rubber composition <Conversion rate of unsaturated monomer>
The conversion rate of unsaturated monomers is determined by collecting a small amount of the solution after the reaction is completed and measuring the amount of unreacted unsaturated monomers using gas chromatography (GC-2025, manufactured by Shimadzu Corporation). Ta.
＜カルボン酸含有共重合体の含有率＞
変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないカルボン酸含有共重合体及びグラフト共重合体中のカルボン酸含有共重合体の合計の含有率は、原料であるハロゲン化ポリオレフィン重量と、不飽和単量体の仕込み量と各不飽和単量体の転化率より求めた不飽和単量体重量から算出した。
<Content of carboxylic acid-containing copolymer>
The total content of the carboxylic acid-containing copolymer that is not bonded to the halogenated polyolefin and the carboxylic acid-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is the halogenated polyolefin raw material. It was calculated from the weight of the polyolefin, the amount of unsaturated monomer charged, and the weight of unsaturated monomer determined from the conversion rate of each unsaturated monomer.
含有率＝｛反応した不飽和単量体重量／（ハロゲン化ポリオレフィン重量＋反応した不飽和単量体重量）｝×１００
＜共重合体中のアクリロニトリルとアクリル系化合物とカルボン酸含有化合物の重量比率＞
変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないカルボン酸含有共重合体及びグラフト共重合体中のカルボン酸含有共重合体に含まれるアクリロニトリル、アクリル系化合物、カルボン酸含有化合物由来の成分の重量比率は、不飽和単量体の重合率より算出した
アクリロニトリル重量比率
＝（反応したアクリロニトリル重量／反応した不飽和単量体重量）×１００
アクリル系化合物重量比率
＝（反応したアクリル系化合物重量／反応した不飽和単量体重量）×１００
カルボン酸含有化合物重量比率
＝（反応したカルボン酸含有化合物重量／反応した不飽和単量体重量）×１００
（２）コンパウンド特性
＜ムーニースコーチ試験＞
クロロスルホン化ポリオレフィン組成物（未加硫物）をＪＩＳ－Ｋ ６２９９（２０１２年度版）に従い、混練りを行い、得られたコンパウンドのムーニー粘度（ＭＬ（１＋４）１００℃）をＪＩＳ－Ｋ ６３００（２０１２年度版）に従い測定した。
＜レオメータ加硫試験＞
ＡＬＰＨＡ ＴＥＣＨＮＯＬＯＧＩＥＳ社製ＲＵＢＢＥＲ ＰＲＯＣＥＳＳ ＡＮＡＬＹＺＥＲ ＲＰＡ ２０００を用いて１６０℃、４５分間の測定を実施し、ＪＩＳ Ｋ ６３００（２０１２年度版）に従い、最大トルク値（ＭＨ）と９０％加硫時間（Ｔｃ９０）を求めた。
（３）加硫ゴム物性
＜常態物性（加硫ゴム特性）＞
クロロスルホン化ポリオレフィン組成物（未加硫物）をＪＩＳ－Ｋ ６２９９（２０１２年度版）に従い混練りを行い、得られたサンプルを厚み２ｍｍの金型にて加硫を行った。その後、硬さ（ＨＳ）はＪＩＳ－Ｋ ６２５３に準拠してデュロメーター硬さ計を用いて２３℃にて測定した。引張強さ（ＴＢ）、破断時伸び（ＥＢ）、１００％引張応力（Ｍ１００）はＪＩＳ－Ｋ ６２５１（２０１２年度版）に従い、引張速度５００ｍｍ／ｍｉｎ、２３℃の条件にて評価した。
＜高温圧縮永久歪み＞
高温圧縮永久歪みは、ＪＩＳ Ｋ６２６２（２０１２年度版）に従い、大型試験片による２５％圧縮にて１２０℃で７２時間の条件で熱老化することにより算出した。
＜耐油性評価＞
内径１００ｍｍ、深さ５０ｍｍの淵付きアルミ製試験容器にトルエン／イソオクタン／エタノール＝４０／４０／２０体積％の燃料油を７５ｍｌ入れ、得られた厚さ２ｍｍの加硫物シートで蓋をするように締め具で固定した。これを４０℃恒温槽内に、加硫ゴムシート側が下になるように、カップをふせて静置した。恒温槽に入れる前のカップ全体の重量と７２時間後のカップ全体の重量より燃料油の透過量を求めた。燃料油透過量、燃料油が接液している加硫物シートの面積、加硫物シートの厚みと透過時間より燃料油透過係数を求めた。燃料油透過係数が小さいほど、耐油性に優れている。
Content rate = {weight of reacted unsaturated monomer/(weight of halogenated polyolefin + weight of reacted unsaturated monomer)}×100
<Weight ratio of acrylonitrile, acrylic compound, and carboxylic acid-containing compound in the copolymer>
Acrylonitrile, acrylic compound, and carboxylic acid contained in the carboxylic acid-containing copolymer that is not bonded to the halogenated polyolefin and the carboxylic acid-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition The weight ratio of the components derived from the compound was calculated from the polymerization rate of the unsaturated monomer.Acrylonitrile weight ratio = (Reacted acrylonitrile weight/Reacted unsaturated monomer weight) x 100
Acrylic compound weight ratio = (weight of reacted acrylic compound/weight of reacted unsaturated monomer) x 100
Weight ratio of carboxylic acid-containing compound = (weight of reacted carboxylic acid-containing compound/weight of reacted unsaturated monomer) x 100
(2) Compound properties <Mooney scorch test>
The chlorosulfonated polyolefin composition (unvulcanized product) was kneaded according to JIS-K 6299 (2012 edition), and the Mooney viscosity (ML (1 + 4) 100°C) of the obtained compound was determined according to JIS-K 6300 ( 2012 edition).
<Rheometer vulcanization test>
Measurement was performed at 160°C for 45 minutes using RUBBER PROCESS ANALYZER RPA 2000 manufactured by ALPHA TECHNOLOGIES, and the maximum torque value (MH) and 90% vulcanization time (Tc90) were determined according to JIS K 6300 (2012 edition). Ta.
(3) Vulcanized rubber physical properties <Normal physical properties (vulcanized rubber properties)>
A chlorosulfonated polyolefin composition (unvulcanized product) was kneaded in accordance with JIS-K 6299 (2012 edition), and the resulting sample was vulcanized in a mold with a thickness of 2 mm. Thereafter, the hardness (HS) was measured at 23° C. using a durometer hardness tester in accordance with JIS-K 6253. Tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K 6251 (2012 edition) at a tensile speed of 500 mm/min and at 23°C.
<High temperature compression set>
High-temperature compression set was calculated according to JIS K6262 (2012 edition) by heat aging at 120° C. for 72 hours under 25% compression using a large test piece.
<Oil resistance evaluation>
Pour 75 ml of fuel oil containing toluene/isooctane/ethanol = 40/40/20% by volume into an aluminum test container with an inner diameter of 100 mm and a depth of 50 mm, and cover with the resulting 2 mm thick vulcanizate sheet. It was fixed with a fastener. This was placed in a constant temperature bath at 40° C. with the cup covered so that the vulcanized rubber sheet side was facing down. The amount of fuel oil permeated was determined from the weight of the entire cup before placing it in the thermostatic bath and the weight of the entire cup 72 hours later. The fuel oil permeation coefficient was determined from the amount of fuel oil permeation, the area of the vulcanizate sheet in contact with the fuel oil, the thickness of the vulcanizate sheet, and the permeation time. The smaller the fuel oil permeability coefficient, the better the oil resistance.
実施例、比較例で使用した配合剤の内容は、以下の通りである。 The contents of the compounding agents used in the Examples and Comparative Examples are as follows.
ハロゲン化ポリオレフィン：ＴＯＳＯ－ＣＳＭ ＴＳ－８３０（東ソー（株）製）
受酸剤１：エポミックＲ－１４０（三井化学（株）製）
受酸剤２：酸化マグネシウム（協和化学工業（株）製 キョーワマグ＃１５０）
加工助剤：スプレンダーＲ－３００（花王（株）製）
カーボンブラック：シーストＳ（東海カーボン（株）製）
可塑剤：アジピン酸エーテルエステル系可塑剤ＲＳ－１０７（（株）ＡＤＥＫＡ社製）
加硫剤１：４，４’－メチレンジアニリン（和光（株）製）（融点：９２℃）
加硫剤２：パークミルＤ－４０（ジクミルパーオキサイドの４０重量％希釈品）（日油（株）製）
グアニジン系加硫促進剤１：ノクセラーＰＲ（ジカテコールボレートのジ－ｏ－トリルグアニジン塩）（大内新興化学工業（株）製）
チウラム系加硫促進剤２：ノクセラーＴＲＡ（ジペンタメチレンチウラムテトラスルフィド）（大内新興化学工業（株）製）
加硫助剤：トリアリルイソシアヌレート（三菱ケミカル（株）製 ＴＡＩＣ Ｍ－６０）
ペンタエリスリトール（多価アルコール）：ノイライザーＰ（日本合成化学工業（株）製）
実施例１
窒素雰囲気下４リットルのガラスフラスコにハロゲン化ポリオレフィン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル６２．７ｇ、アクリル酸２－メトキシエチル１７０．７ｇ、無水マレイン酸２２．５ｇを添加し、１，１，２－トリクロロエタン１４４ｇにラジカル開始剤（日油（株）製 パーロイルＯＰＰ（ジ－２－エチルヘキシル－パーオキシジカーボネート））２．９ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。
Halogenated polyolefin: TOSO-CSM TS-830 (manufactured by Tosoh Corporation)
Acid acceptor 1: Epomic R-140 (manufactured by Mitsui Chemicals, Inc.)
Acid acceptor 2: Magnesium oxide (Kyowa Mag #150 manufactured by Kyowa Chemical Industry Co., Ltd.)
Processing aid: Splendor R-300 (manufactured by Kao Corporation)
Carbon black: Seast S (manufactured by Tokai Carbon Co., Ltd.)
Plasticizer: Adipic acid ether ester plasticizer RS-107 (manufactured by ADEKA Co., Ltd.)
Vulcanizing agent 1: 4,4'-methylene dianiline (manufactured by Wako Co., Ltd.) (melting point: 92°C)
Vulcanizing agent 2: Permil D-40 (40% dicumyl peroxide diluted product) (manufactured by NOF Corporation)
Guanidine-based vulcanization accelerator 1: Noxela PR (di-o-tolyl guanidine salt of dicatecol borate) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
Thiuram-based vulcanization accelerator 2: Noxela TRA (dipentamethylenethiuram tetrasulfide) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)
Vulcanization aid: triallyl isocyanurate (TAIC M-60 manufactured by Mitsubishi Chemical Corporation)
Pentaerythritol (polyhydric alcohol): Neulyser P (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.)
Example 1
150 g of halogenated polyolefin and 2.0 kg of 1,1,2-trichloroethane were placed in a 4-liter glass flask under a nitrogen atmosphere, the interior of the flask was purged with nitrogen, and the flask was heated to 110° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65°C, 62.7 g of acrylonitrile, 170.7 g of 2-methoxyethyl acrylate, and 22.5 g of maleic anhydride were added, and a radical initiator (NOF) was added to 144 g of 1,1,2-trichloroethane. A solution containing 2.9 g of perloyl OPP (di-2-ethylhexyl peroxydicarbonate) manufactured by Co., Ltd. was added dropwise over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried in a drum drier to obtain a modified halogenated polyolefin composition.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。表１に示す処方１の配合処方に従い、変性ハロゲン化ポリオレフィン組成物１００重量部にエポミックＲ－１４０を１５重量部、加工助剤２重量部、カーボンブラック３０重量部、可塑剤１０重量部、４，４’－メチレンジアニリン２重量部、ノクセラーＰＲ１重量部をオープンロール混練機を用いて添加し、未加硫物を得た。その未加硫物のムーニースコーチ試験、レオメータ加硫試験を実施し、これらの結果を表２に示す。また、得られた未加硫物を加硫プレスにより１６０℃、３０分間の一次加硫、及び加熱オーブンによる１５０℃、２４時間の二次加硫を実施し、加硫物を得た。得られた加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性を測定し、これらの評価結果を表２に示す。表２から、高温圧縮永久歪みが３４％であり良好であった。また、燃料油透過係数が１５４ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 30/70. According to the formulation of Formulation 1 shown in Table 1, 100 parts by weight of the modified halogenated polyolefin composition, 15 parts by weight of Epomic R-140, 2 parts by weight of processing aid, 30 parts by weight of carbon black, 10 parts by weight of plasticizer, 4 , 2 parts by weight of 4'-methylene dianiline, and 1 part by weight of Noxeler PR were added using an open roll kneader to obtain an unvulcanized product. The unvulcanized product was subjected to a Mooney scorch test and a rheometer vulcanization test, and the results are shown in Table 2. Further, the obtained unvulcanized product was subjected to primary vulcanization at 160°C for 30 minutes using a vulcanization press, and secondary vulcanization at 150°C for 24 hours using a heating oven to obtain a vulcanized product. The normal physical properties, high temperature compression set, and fuel oil permeation resistance of the obtained vulcanizate were measured, and the evaluation results are shown in Table 2. From Table 2, the high temperature compression set was 34%, which was good. Further, the fuel oil permeability coefficient was 154 mg·mm/(cm 2 ·day), which was good.
実施例２
不飽和単量体の仕込み量を、アクリロニトリル６２．７ｇ、アクリル酸２－メトキシエチル１７０．７ｇ、無水マレイン酸１１．３ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 2
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amounts of unsaturated monomers were changed to 62.7 g of acrylonitrile, 170.7 g of 2-methoxyethyl acrylate, and 11.3 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２９／７１であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが３８％であり良好であった。また、燃料油透過係数が１６０ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 29/71. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 38%, which was good. Further, the fuel oil permeability coefficient was 160 mg·mm/(cm 2 ·day), which was good.
実施例３
不飽和単量体の仕込み量を、アクリロニトリル６２．７ｇ、アクリル酸２－メトキシエチル１７０．７ｇ、無水マレイン酸５．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 3
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amounts of unsaturated monomers were changed to 62.7 g of acrylonitrile, 170.7 g of 2-methoxyethyl acrylate, and 5.6 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２８／７２であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが４３％であり良好であった。また、燃料油透過係数が１６９ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 28/72. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 43%, which was good. Further, the fuel oil permeability coefficient was 169 mg·mm/(cm 2 ·day), which was good.
実施例４
不飽和単量体の仕込み量を、アクリロニトリル５３．６ｇ、アクリル酸２－メトキシエチル１５１．６ｇ、無水マレイン酸１０．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 4
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amounts of unsaturated monomers were changed to 53.6 g of acrylonitrile, 151.6 g of 2-methoxyethyl acrylate, and 10.8 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は１９／８１であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが３９％であり良好であった。また、燃料油透過係数が１８８ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 19/81. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 39%, which was good. Further, the fuel oil permeability coefficient was 188 mg·mm/(cm 2 ·day), which was good.
実施例５
不飽和単量体の仕込み量を、アクリロニトリル６４．３ｇ、アクリル酸２－メトキシエチル１８６．９ｇ、無水マレイン酸１１．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 5
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amount of unsaturated monomers charged was changed to 64.3 g of acrylonitrile, 186.9 g of 2-methoxyethyl acrylate, and 11.6 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３８／６２であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが３７％であり良好であった。また、燃料油透過係数が１４９ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 38/62. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 37%, which was good. Further, the fuel oil permeability coefficient was 149 mg·mm/(cm 2 ·day), which was good.
実施例６
不飽和単量体の仕込み量を、アクリロニトリル３１．２ｇ、アクリル酸２－メトキシエチル８９．３ｇ、無水マレイン酸８．９ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 6
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amount of unsaturated monomers charged was changed to 31.2 g of acrylonitrile, 89.3 g of 2-methoxyethyl acrylate, and 8.9 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は２９重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが３６％であり良好であった。また、燃料油透過係数が１６４ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 29% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 29% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 30/70. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 36%, which was good. Further, the fuel oil permeability coefficient was 164 mg·mm/(cm 2 ·day), which was good.
実施例７
不飽和単量体の仕込み量を、アクリロニトリル１０９．１ｇ、アクリル酸２－メトキシエチル３２８．１ｇ、無水マレイン酸１５．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Example 7
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amounts of unsaturated monomers were changed to 109.1 g of acrylonitrile, 328.1 g of 2-methoxyethyl acrylate, and 15.6 g of maleic anhydride. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は６０重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２８／７２であった。実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表２に示す。表２から、高温圧縮永久歪みが４１％であり良好であった。また、燃料油透過係数が１６２ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、良好であった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 60% by weight, and the acrylonitrile-2-methoxyethyl acrylate - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 28/72. In the same manner as in Example 1, an unvulcanized product and a vulcanized product were obtained according to the formulation of Formulation 1. Table 2 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. From Table 2, the high temperature compression set was 41%, which was good. Further, the fuel oil permeability coefficient was 162 mg·mm/(cm 2 ·day), which was good.
比較例１
不飽和単量体の仕込み量を、アクリロニトリル５７．４ｇ、アクリル酸２－メトキシエチル１６９．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Comparative example 1
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1, except that the amounts of unsaturated monomers charged were changed to 57.4 g of acrylonitrile and 169.8 g of 2-methoxyethyl acrylate.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体（カルボン酸含有共重合体）含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－無水マレイン酸共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２７／７３であった。実施例１と同様に処方１の配合処方に従い、未加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果を表３に示す。表３から、未加硫物の最大トルク値（ＭＨ）が低く、加硫プレスによる成型時に発砲が生じ、加硫シートが得られなかった。 The acrylonitrile-2-methoxyethyl acrylate-maleic anhydride copolymer (carboxylic acid-containing copolymer) content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of acrylonitrile-2-methoxyethyl acrylate was 44% by weight. - The acrylonitrile/2-methoxyethyl acrylate ratio of the maleic anhydride copolymer was 27/73. An unvulcanized product was obtained in the same manner as in Example 1 according to the formulation of Formulation 1. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product. From Table 3, the maximum torque value (MH) of the unvulcanized product was low, foaming occurred during molding with a vulcanization press, and a vulcanized sheet could not be obtained.
比較例２
比較例１で得られた変性ハロゲン化ポリオレフィン組成物と同一の変性ハロゲン化ポリオレフィン組成物を使用した。４，４’－メチレンジアニリン２重量部、ノクセラーＰＲ１重量部の代わりに、処方２の配合処方に従い、ノクセラーＴＲＡ２重量部、ノイライザーＰ３重量部を用いた以外は実施例１と同様に未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表３に示す。表３から高温圧縮永久歪みが５８％であり、実施例１より圧縮永久歪み性が劣る結果であった。
Comparative example 2
The same modified halogenated polyolefin composition as the modified halogenated polyolefin composition obtained in Comparative Example 1 was used. Unvulcanized in the same manner as in Example 1, except that 2 parts by weight of Noxeler TRA and 3 parts by weight of Neulyser P were used in accordance with the formulation 2 instead of 2 parts by weight of 4,4'-methylene dianiline and 1 part by weight of Noxeler PR. and a vulcanizate were obtained. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. Table 3 shows that the high temperature compression set was 58%, which was inferior to Example 1.
比較例３
比較例１で得られた変性ハロゲン化ポリオレフィン組成物と同一の変性ハロゲン化ポリオレフィン組成物を使用した。エポミックＲ－１４０を１５重量部、４，４’－メチレンジアニリン２重量部、ノクセラーＰＲ１重量部の代わりに、処方３の配合処方に従い、キョーワマグ＃１５０を１５重量部、パークミルＤ－４０を６重量部、トリアリルイソシアヌレート７重量部を用いた以外は実施例１と同様に未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表３に示す。表３から高温圧縮永久歪みが５４％であり、実施例１より圧縮永久歪み性が劣る結果であった。
Comparative example 3
The same modified halogenated polyolefin composition as the modified halogenated polyolefin composition obtained in Comparative Example 1 was used. Instead of 15 parts by weight of Epomic R-140, 2 parts by weight of 4,4'-methylene dianiline, and 1 part by weight of Noxela PR, according to the formulation 3, 15 parts by weight of Kyowa Mag #150 and 6 parts by weight of Percmil D-40 were added. An unvulcanized product and a vulcanized product were obtained in the same manner as in Example 1 except that 7 parts by weight of triallyl isocyanurate were used. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. Table 3 shows that the high temperature compression set was 54%, which was inferior to Example 1.
比較例４
不飽和単量体の仕込み量を、アクリロニトリル６３．０ｇ、アクリル酸２－メトキシエチル１５８．９ｇ、メタクリル酸グリシジル１３．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。
Comparative example 4
A modified halogenated polyolefin composition was prepared in the same manner as in Example 1, except that the amounts of unsaturated monomers were changed to 63.0 g of acrylonitrile, 158.9 g of 2-methoxyethyl acrylate, and 13.8 g of glycidyl methacrylate. Obtained.
得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は４４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３１／６９であった。４，４’－メチレンジアニリン２重量部、ノクセラーＰＲ１重量部の代わりに、処方２の配合処方に従い、ノクセラーＴＲＡ２重量部、ノイライザーＰ３重量部を用いた以外は実施例１と同様に未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表３に示す。表３から高温圧縮永久歪みが５５％であり、実施例１より圧縮永久歪み性が劣る結果であった。 The acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of the obtained modified halogenated polyolefin composition was 44% by weight, and the content of the acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer The acrylonitrile/2-methoxyethyl acrylate ratio was 31/69. An unvulcanized product was prepared in the same manner as in Example 1, except that 2 parts by weight of Noxeler TRA and 3 parts by weight of Neulyser P were used in place of 2 parts by weight of 4,4'-methylene dianiline and 1 part by weight of Noxeler PR according to the formulation 2. and a vulcanizate were obtained. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. Table 3 shows that the high temperature compression set was 55%, which was inferior to Example 1.
比較例５
ハロゲン化ポリオレフィンを変性せずに使用した以外は、実施例１と同様に処方１の配合処方に従い、未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表３に示す。表３から燃料油透過係数が２５８ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、実施例１より耐燃料油透過性が劣る結果であった。
Comparative example 5
An unvulcanized product and a vulcanized product were obtained in the same manner as in Example 1, except that the halogenated polyolefin was used without modification. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. Table 3 shows that the fuel oil permeability coefficient was 258 mg·mm/(cm 2 ·day), which was inferior to Example 1 in terms of fuel oil permeability.
比較例６
ハロゲン化ポリオレフィンを変性せずに使用した。４，４’－メチレンジアニリン２重量部、ノクセラーＰＲ１重量部の代わりに、処方２の配合処方に従い、ノクセラーＴＲＡ２重量部、ノイライザーＰ３重量部を用いた以外は実施例１と同様に未加硫物と加硫物を得た。得られた未加硫物のムーニースコーチ試験、レオメータ加硫試験の結果と加硫物の常態物性、高温圧縮永久歪み、耐燃料油透過性の評価結果を表３に示す。表３から燃料油透過係数が２６６ｍｇ・ｍｍ／（ｃｍ２・ｄａｙ）であり、実施例１より耐燃料油透過性が劣る結果であった。
Comparative example 6
The halogenated polyolefin was used without modification. Unvulcanized in the same manner as in Example 1, except that 2 parts by weight of Noxeler TRA and 3 parts by weight of Neulyser P were used in accordance with the formulation 2 instead of 2 parts by weight of 4,4'-methylene dianiline and 1 part by weight of Noxeler PR. and a vulcanizate were obtained. Table 3 shows the results of the Mooney scorch test and rheometer vulcanization test of the obtained unvulcanized product, and the evaluation results of the normal physical properties, high temperature compression set, and fuel oil permeability of the vulcanized product. Table 3 shows that the fuel oil permeability coefficient was 266 mg·mm/(cm 2 ·day), which was inferior to Example 1 in terms of fuel oil permeability.
Claims (5)
前記グラフト共重合体がクロロスルホン化ポリエチレンにグラフト鎖が結合し、グラフト鎖がアクリロニトリルと、アクリル系化合物と、カルボン酸又はカルボン酸無水物を含有する不飽和単量体（以下、カルボン酸含有化合物という）との共重合体（以下、カルボン酸含有共重合体という）であり、前記アクリル系化合物がアクリル酸メチル、アクリル酸エチル、アクリル酸２－メトキシエチル、アクリル酸ｎ－ブチルの単独あるいは併用であり、
カルボン酸含有化合物の含有率が１重量％から７重量％の範囲である、
変性ハロゲン化ポリオレフィン組成物。 A modified halogenated polyolefin composition comprising a graft copolymer and a carboxylic acid-containing copolymer not bonded to chlorosulfonated polyethylene, the composition comprising:
The graft copolymer has a graft chain bonded to chlorosulfonated polyethylene, and the graft chain is an unsaturated monomer containing acrylonitrile, an acrylic compound, and a carboxylic acid or carboxylic acid anhydride (hereinafter referred to as a carboxylic acid-containing compound). ) (hereinafter referred to as carboxylic acid-containing copolymer), and the acrylic compound is methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, or n-butyl acrylate alone or in combination. and
The content of the carboxylic acid-containing compound is in the range of 1% to 7% by weight,
Modified halogenated polyolefin composition .
いないカルボン酸含有共重合体の合計の含有率が２０重量％から７５重量％の範囲であり
、カルボン酸含有共重合体中のアクリロニトリルとアクリル系化合物由来の成分の重量比
率が３／９７～７０／３０の範囲であることを特徴とする請求項１に記載の変性ハロゲン
化ポリオレフィン組成物。 The total content of the carboxylic acid-containing copolymer and the carboxylic acid-containing copolymer not bonded to the halogenated polyolefin in the graft copolymer is in the range of 20% by weight to 75% by weight, and the carboxylic acid-containing copolymer The modified halogenated polyolefin composition according to claim 1, wherein the weight ratio of acrylonitrile and components derived from the acrylic compound in the polymer is in the range of 3/97 to 70/30.
硫物。 A vulcanizate obtained by vulcanizing the modified halogenated polyolefin composition according to any one of claims 1 to 3 .
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