JPH0134261B2 - - Google Patents
Info
- Publication number
- JPH0134261B2 JPH0134261B2 JP13281281A JP13281281A JPH0134261B2 JP H0134261 B2 JPH0134261 B2 JP H0134261B2 JP 13281281 A JP13281281 A JP 13281281A JP 13281281 A JP13281281 A JP 13281281A JP H0134261 B2 JPH0134261 B2 JP H0134261B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- abd
- sulfur
- weight
- copolymer
- 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.)
- Expired
Links
- 229920001577 copolymer Polymers 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 11
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- NMQQBXHZBNUXGJ-SNAWJCMRSA-N [(1e)-buta-1,3-dienyl] acetate Chemical compound CC(=O)O\C=C\C=C NMQQBXHZBNUXGJ-SNAWJCMRSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 238000004073 vulcanization Methods 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- -1 vinylidene norbornene Chemical compound 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 3
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-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
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- VKFXRBZSVGYYSA-UHFFFAOYSA-N 3-ethyl-1,1-dimethylthiourea Chemical compound CCNC(=S)N(C)C VKFXRBZSVGYYSA-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- YEQPPBCBKNMCKW-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethyl 2-chloroacetate Chemical compound C1C2C(COC(=O)CCl)CC1C=C2 YEQPPBCBKNMCKW-UHFFFAOYSA-N 0.000 description 1
- ILDJIOMGFNISQQ-UHFFFAOYSA-N 6-(benzylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound SC1=NC(S)=NC(NCC=2C=CC=CC=2)=N1 ILDJIOMGFNISQQ-UHFFFAOYSA-N 0.000 description 1
- KRBGYJXDLGSDEX-UHFFFAOYSA-N 6-(diethylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCN(CC)C1=NC(=S)NC(=S)N1 KRBGYJXDLGSDEX-UHFFFAOYSA-N 0.000 description 1
- RTKOEICSBRVMIY-UHFFFAOYSA-N 6-(dimethylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CN(C)C1=NC(S)=NC(S)=N1 RTKOEICSBRVMIY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OAQBFYNZVHHSCE-UHFFFAOYSA-N S(OC)OC.[Na] Chemical compound S(OC)OC.[Na] OAQBFYNZVHHSCE-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- OFHMODDLBXETIK-UHFFFAOYSA-N methyl 2,3-dichloropropanoate Chemical compound COC(=O)C(Cl)CCl OFHMODDLBXETIK-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Description
本発明は1−アセトキシ−1,3−ブタジエン
重合体または1−アセトキシ−1,3−ブタジエ
ンおよびこれと共重合可能な単体量との共重合体
の加硫組成物に関する。
1−アセトキシ−1,3−ブタジエン(以下1
−ABDと略称する)の重合体または共重合体は
ラジカル重合により得ることができる。しかしな
がらこの1−ABDの重合体または共重合体の性
状についてはほとんど知られていない。
本発明者らは1−ABDの重合体または共重合
体の性状について研究した結果、1−ABDの重
合体または共重合体は硫黄および/または含硫黄
有機化合物により容易に加硫され、しかもこの加
硫組成物は優れた耐油性を有し、且つ優れた諸特
性を有することを見出した。
また、アクリル酸エステルを主成分とする共重
合体はアクリルゴムとして知られており一般に耐
熱性耐油性のすぐれた弾性を有する共重合体であ
るが、共重合体分子主鎖に二重結合を有しないた
め一般には架橋させるために架橋点となる活性基
を有する単量体を共重合させたものがよく知られ
ている。これらの架橋点となる単量体成分として
は従来、2−クロロエチルビニルエーテル、ビニ
ルクロロアセテート、アリルクロロアセテート、
ビニルベンジルクロライド、5−クロロアセトキ
シメチル−2−ノルボルネンなどのごときハロゲ
ン系単量体、あるいはアリルグリシジルエーテ
ル、グリシジルアクリレート、グリシジルメタク
リレートなどのごときエポキシ系単量体が多く用
いられている。これらの共重合体は一般に架橋剤
として、アミン類、アンモニウム塩類、金属セツ
ケン−硫黄などを用いて架橋が行なわれている
が、架橋速度が遅く、最適な物性を得るために
は、架橋後に極めて長時間の熱処理を必要とす
る。またこれらの架橋剤の中でアミン類、アンモ
ニウム塩類などを使用した場合、混錬、架橋時に
悪臭ガスの発生などの衛生面の問題があり、また
得られた架橋組成物についても医薬用、食品用な
どの用途には使用できないという欠点を有する。
更に架橋用単量体としてハロゲン系化合物を使用
した場合、架橋時に金型を腐食させたり得られた
架橋組成物と接する金属を腐食させたりする欠点
を有する。
これらの欠点を改良するために、ジシクロペン
ダジエン、メチルシクロペンタジエン、エチリデ
ンノルボルネン、ビニリデンノルボルネン、ブタ
ジエン、イソプレン、アリルアクリレート、2−
ブテニルアクリレート、トリアリルイソシアヌレ
ートなどを架橋用単量体としてアクリル酸エステ
ルと共重合させたものが既に知られているが、単
量体によつては、共重合し難いものであつたり、
架橋が極めて遅かつたり、架橋後の物性が実用化
に程遠いものであつたりするほか、アクリル酸エ
ステルを主成分とする共重合体の特徴である耐油
性が悪化するなどの欠点があつた。
本発明者らはこのようなアクリル酸エステルを
主成分とする共重合体において1−ABDを共重
合した共重合体は硫黄加硫が極めて短時間で可能
であり、しかも加硫組成物は、耐油性がさらに改
善されるなど、すぐれた諸特性を有するものであ
ることをも見出した。
本発明は上記の知見に基づくものであり、本発
明は1−ABDの重合体または−10〜60℃でラジ
カル重合開始剤の存在下重合させた1−ABDの
重合体または1−ABDおよびこれと共重合可能
な少なくとも1種の共役ジエンおよび/またはエ
チレン性不飽和化合物との共重合体に硫黄およ
び/または含硫黄有機化合物を配合してなる極め
て優れた耐油性を有する1−ABDの重合体また
は共重合体(以下(共)重合体と略称する)の加
硫組成物を提供するものである。
本発明に使用する(共)重合体の単量体である
1−ABDはパラジウムなど貴金属触媒の存在下
でブタジエンをアセトキシ化するが、クロトンア
ルデヒドを無水酢酸およびアルカリ金属酢酸塩の
存在下で加熱することによつて得られる。これら
の反応によつて得られた1−ABDはシス体とト
ランス体の混合物であるが、本発明に用いる
(共)重合体の単量体はシス体、トランス体単独
でも、これらを任意に混合した混合物であつても
よい。また不都合にならない程度の不純物を含ん
でいても差し支えない。
本発明に使用される1−ABDと共重合可能な
単量体は、(共)重合体の機械的特性などを改良
するために用いるものでありアルキルアクリレー
ト、アルキルメタクリレート、アクリロニトリ
ル、メタクリロニトリル、酢酸ビニル、スチレ
ン、アクリルアミド、塩化ビニリデンの如きエチ
レン性不飽和化合物、ブタジエン、イソプレンの
如き共役ジエンなどが挙げられ、これらの中の1
種または2種以上が用いられる。
本発明に使用する(共)重合体の1−ABDの
共重合量は好ましくは0.5重量%以上である。従
つて1−ABDと共重合可能な単量体の好ましい
共重合量は0〜99.5重量%である。1−ABDの
共重合量が0.5重量%未満では1−ABDを共重合
することによる効果を十分に発揮することができ
ない。また1−ABDの共重合量が70重量%以上
の場合は特にすぐれた耐油性を示す加硫組成物を
得ることができる。
また耐熱性、耐油性および加硫性のすぐれたア
クリル酸エステルを主成分とする共重合体を得る
ための単量体の共重合量は、好ましくは1−
ABD0.5〜70重量%、アクリル酸エステル30〜
99.5重量%およびこれらと共重合可能な単量体0
〜30重量%である。この場合のアクリル酸エステ
ルとはアルキル基が1〜8個の炭素原子を有する
アルキルアクリレートであり、メチルアクリレー
ト、エチルアクリレート、プロピルアクリレー
ト、ブチルアクリレート、アミルアクリレート、
ヘキシルアクリレート、シクロヘキシルアクリレ
ート、オクチルアクリレートなどを例示すること
ができ、特に好ましいのはアルキル基が2〜4個
の炭素原子を有するアルキルアクリレートであ
り、エチルアクリレート、プロピルアクリレー
ト、ブチルアクリレートなどを例示することがで
きる。
本発明に使用する(共)重合体は1−ABDま
たは1−ABDとこれと共重合可能な単量体を通
常使用されるラジカル重合開始剤を用いて乳化重
合、懸濁重合、溶液重合、塊状重合などの重合様
式で容易に製造される。重合は−10〜60℃、好ま
しくは0〜60℃の温度で回分重合、連続重合で行
なうことができる。
本発明の加硫組成物は前記の(共)重合体に加
硫系として硫黄および/または含硫黄有機化合物
を配合し加硫してなるものであり、本発明の加硫
組成物はジエン系ゴムなみの加硫速度を有し、耐
油性が優れ且つ諸特性に優れた加硫組成物であ
る。
加硫に用いられる含硫黄有機化合物としては通
常ゴムの加硫に用いられる加硫剤、加硫促進剤の
中で硫黄を含有している化合物であり、例えば2
−メルカプトベンゾチアゾール、2−メルカプト
ベンゾチアゾールの亜鉛塩、ジベンゾチアジルジ
スルフイドなどのチアゾール系化合物、N−シク
ロヘキシル−2−ベンゾチアジルスルフエンアミ
ド、N,N−ジシクロヘキシル−2−ベンゾチア
ジルスルフエンアミド、N−オキシエチレン−2
−ベンゾチアジルスルフエンアミドなどのスルフ
エンアミド系化合物、チオカルバニド、ジオルト
トリルチオ尿素、2−メルカプトイミダゾリンジ
ブチルチオ尿素、ジメチルエチルチオ尿素などの
チオ尿素化合物、テトラメチルチウラムモノスル
フイド、テトラメチルチウラムジスルフイド、テ
トラエチルチウラムジスルフイド、ジペンタメチ
レンチウラムテトラスルフイド、ジペンタメチレ
ンチウラムヘキサスルフイドなどのチウラム系化
合物、ジエチルジチオカルバミン酸亜鉛、ジメチ
ルジチオカルバミン酸亜鉛、ジメチルジチオカル
バミン酸銅、エチルフエニルジチオカルバミン酸
亜鉛などのジチオカルバメート系化合物、2−ジ
メチルアミノ−4,6−ジメルカプト−s−トリ
アジン、2−ジエチルアミノ−4,6−ジメルカ
プト−s−トリアジン、2−ブチルアミノ−4,
6−ジメルカプト−s−トリアジン、2−ベンジ
ルアミノ−4,6−ジメルカプト−s−トリアジ
ン、2,4,6−トリメルカプト−s−トリアジ
ンなどのトリアジン化合物、その他のモルホリン
ジスルフイド、4,4′−ジチオモルホリンなどが
挙げられ、これらは単独または2種以上を組みあ
わせて使用することができる。硫黄および/また
は含硫黄有機化合物の使用量としては、本発明で
使用する(共)重合体100重量部に対して硫黄分
として0.1〜10重量部使用するのが好ましく、特
に好ましくは0.2〜5重量部であり、さらに好ま
しくは0.5〜3重量部である。使用量が0.1重量部
未満では加硫速度が極めて遅く且つ加硫組成物と
して充分満足し得る物性が得られない。また10重
量部を超えると耐熱性が極めて悪くなる。
本発明の加硫組成物は硫黄以外に、他種類の重
合体または共重合体や一般にゴム用配合剤として
用いられるスコーチ防止剤、活性剤、老化防止
剤、可塑剤、素錬り促進剤、粘着付与剤、軟化
剤、補強剤、発泡剤、滑剤、着色剤、充填剤など
を必要に応じて添加配合されていてもよい。また
金属化合物、特にZn、Cd、Fe、Sn、Cu、Sr、
Ca、Pb、Ba、Mgなどの酸化物、水酸化物、炭
酸塩、有機カルボン酸塩は加硫速度を早めるのに
効果的であり、とくにこの中でも酸化亜鉛、一酸
化鉛、鉛丹、炭酸鉛、ステアリン酸亜鉛、酸化マ
グネシウムが効果的であり、(共)重合体100重量
部に対して1〜5重量部配合されているのが好ま
しい。なお、本発明の加硫組成物の加硫条件は特
に限定するものではなく、通常の加硫条件を用い
ることができる。
かくして得られた加硫組成物は、優れた耐油性
を有する加硫組成物であり、このような性能を必
要とする多くの分野での用途に有用である。かか
る用途としてはガスケツト、ホース、コンベアベ
ルトバツキング、ホイルシール、バルブシートお
よびこれらの類似品など種々のゴム状製品が挙げ
られる。
次に実施例を挙げて本発明を詳しく説明する。
実施例 1〜5
容器500c.c.のガラス製耐圧ビンに窒素下、第1
表に示す単量体100g、ドデシルベンゼンスルフ
オン酸ソーダ6g、水200g、エチレンジアミン
四酢酸ナトリウム0.1g、硫酸第1鉄0.1g、ナト
リウムホルムアルデヒドスルホキシレート0.1g、
パラメンタンヒドロペルオキシド1.0gを仕込み
10℃で15時間重合させた。その後N,N−ジエチ
ルヒドロキシルアミン1.0gをいれて停止させた。
すべて凝固物のないエマルジヨンが得られ、こ
のエマルジヨンを3のメタノール中に撹拌下滴
下して(共)重合体を析出させたのち、この
(共)重合体をメタノールで充分に洗剰し50℃真
空下乾燥させた。重合の結果を第1表に示した。
なお数平均分子量は実施例1は26000、実施例
2は57000、実施例3は74000、実施例4は50000、
実施例5は80000であつた。
ここで数平均分子量は重合体または共重合体に
適した溶媒、例えばアセトン、テトラヒドロフラ
ンなどに溶解して、GPCにより測定したもので
あり、数平均分子量の標準サンプルとしてのポリ
スチレンより換算して求める。
The present invention relates to a vulcanized composition of a 1-acetoxy-1,3-butadiene polymer or a copolymer of 1-acetoxy-1,3-butadiene and an amount of a monomer copolymerizable therewith. 1-acetoxy-1,3-butadiene (hereinafter referred to as 1
-ABD) polymers or copolymers can be obtained by radical polymerization. However, little is known about the properties of this 1-ABD polymer or copolymer. As a result of research on the properties of 1-ABD polymers or copolymers, the present inventors found that 1-ABD polymers or copolymers are easily vulcanized by sulfur and/or sulfur-containing organic compounds, and that 1-ABD polymers or copolymers are easily vulcanized by sulfur and/or sulfur-containing organic compounds. It has been found that the vulcanized composition has excellent oil resistance and various excellent properties. In addition, copolymers containing acrylic acid ester as the main component are known as acrylic rubbers, and are generally heat-resistant, oil-resistant, and highly elastic copolymers, but they contain double bonds in the main chain of the copolymer molecules. Generally, it is well known to copolymerize monomers with active groups that serve as crosslinking points for crosslinking. Conventionally, monomer components serving as these crosslinking points include 2-chloroethyl vinyl ether, vinyl chloroacetate, allyl chloroacetate,
Halogen monomers such as vinylbenzyl chloride and 5-chloroacetoxymethyl-2-norbornene, and epoxy monomers such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate are often used. These copolymers are generally crosslinked using amines, ammonium salts, metal sulfur, etc. as a crosslinking agent, but the crosslinking speed is slow, and in order to obtain optimal physical properties, extremely high temperatures are required after crosslinking. Requires long heat treatment. Furthermore, when amines, ammonium salts, etc. are used among these crosslinking agents, there are hygiene problems such as generation of foul-smelling gas during kneading and crosslinking, and the resulting crosslinked compositions are also used for pharmaceutical and food purposes. It has the disadvantage that it cannot be used for other purposes.
Furthermore, when a halogen compound is used as a crosslinking monomer, it has the disadvantage that it corrodes the mold during crosslinking or corrodes the metal in contact with the resulting crosslinked composition. In order to improve these drawbacks, dicyclopendadiene, methylcyclopentadiene, ethylidene norbornene, vinylidene norbornene, butadiene, isoprene, allyl acrylate, 2-
Copolymerization of butenyl acrylate, triallyl isocyanurate, etc. with acrylic acid esters as crosslinking monomers is already known, but some monomers are difficult to copolymerize.
In addition to the fact that crosslinking was extremely slow and the physical properties after crosslinking were far from practical, they also had drawbacks such as deterioration in oil resistance, which is a characteristic of copolymers whose main component is acrylic ester. The present inventors have found that a copolymer containing 1-ABD as a main component of such an acrylic ester can be sulfur-cured in an extremely short time, and that the vulcanization composition is It has also been found that it has various excellent properties such as further improved oil resistance. The present invention is based on the above findings, and the present invention relates to a polymer of 1-ABD or a polymer of 1-ABD polymerized at -10 to 60°C in the presence of a radical polymerization initiator, or a polymer of 1-ABD and the like. A 1-ABD polymer having extremely excellent oil resistance, which is made by blending sulfur and/or a sulfur-containing organic compound with a copolymer of at least one conjugated diene and/or ethylenically unsaturated compound copolymerizable with The present invention provides a vulcanized composition of a polymer or copolymer (hereinafter abbreviated as (co)polymer). 1-ABD, the monomer of the (co)polymer used in the present invention, acetoxylates butadiene in the presence of a noble metal catalyst such as palladium, while crotonaldehyde is heated in the presence of acetic anhydride and alkali metal acetate. obtained by doing. 1-ABD obtained by these reactions is a mixture of cis and trans forms, but the monomers of the (co)polymer used in the present invention may be cis or trans forms alone, or they may be optionally mixed. It may be a mixed mixture. Further, it may contain impurities to the extent that it does not cause any inconvenience. The monomers copolymerizable with 1-ABD used in the present invention are used to improve the mechanical properties of the (co)polymer, and include alkyl acrylate, alkyl methacrylate, acrylonitrile, methacrylonitrile, Examples include ethylenically unsaturated compounds such as vinyl acetate, styrene, acrylamide, and vinylidene chloride, and conjugated dienes such as butadiene and isoprene.
A species or two or more species may be used. The copolymerized amount of 1-ABD in the (co)polymer used in the present invention is preferably 0.5% by weight or more. Therefore, the preferred copolymerization amount of the monomer copolymerizable with 1-ABD is 0 to 99.5% by weight. If the copolymerization amount of 1-ABD is less than 0.5% by weight, the effect of copolymerizing 1-ABD cannot be sufficiently exhibited. Furthermore, when the copolymerization amount of 1-ABD is 70% by weight or more, a vulcanized composition exhibiting particularly excellent oil resistance can be obtained. Furthermore, the amount of copolymerized monomers is preferably 1-
ABD0.5~70% by weight, acrylic ester 30~
99.5% by weight and 0 monomers copolymerizable with these
~30% by weight. The acrylic esters in this case are alkyl acrylates in which the alkyl group has 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Examples include hexyl acrylate, cyclohexyl acrylate, octyl acrylate, etc. Particularly preferred are alkyl acrylates in which the alkyl group has 2 to 4 carbon atoms, and examples include ethyl acrylate, propyl acrylate, butyl acrylate, etc. Can be done. The (co)polymer used in the present invention is emulsion polymerization, suspension polymerization, solution polymerization of 1-ABD or 1-ABD and a monomer copolymerizable with it using a commonly used radical polymerization initiator. It is easily produced by polymerization methods such as bulk polymerization. The polymerization can be carried out at a temperature of -10 to 60°C, preferably 0 to 60°C, by batch polymerization or continuous polymerization. The vulcanized composition of the present invention is obtained by blending sulfur and/or a sulfur-containing organic compound as a vulcanization system with the above-mentioned (co)polymer and vulcanizing it. It is a vulcanized composition that has a vulcanization rate comparable to that of rubber, excellent oil resistance, and excellent various properties. The sulfur-containing organic compound used for vulcanization is a compound containing sulfur among the vulcanizing agents and vulcanization accelerators normally used for vulcanizing rubber, such as 2
- Thiazole compounds such as mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazylsulfenamide, N,N-dicyclohexyl-2-benzothiazyl Sulfenamide, N-oxyethylene-2
-Sulfenamide compounds such as benzothiazylsulfenamide, thiocarbanides, diorthotolylthiourea, 2-mercaptoimidazoline dibutylthiourea, thiourea compounds such as dimethylethylthiourea, tetramethylthiuram monosulfide, tetramethylthiuram Disulfide, thiuram compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, ethylph Dithiocarbamate compounds such as zinc enyldithiocarbamate, 2-dimethylamino-4,6-dimercapto-s-triazine, 2-diethylamino-4,6-dimercapto-s-triazine, 2-butylamino-4,
Triazine compounds such as 6-dimercapto-s-triazine, 2-benzylamino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto-s-triazine, other morpholine disulfides, 4,4 '-dithiomorpholine and the like can be used alone or in combination of two or more. The amount of sulfur and/or sulfur-containing organic compound used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the (co)polymer used in the present invention. Parts by weight, more preferably 0.5 to 3 parts by weight. If the amount used is less than 0.1 part by weight, the vulcanization rate will be extremely slow and the vulcanized composition will not have sufficiently satisfactory physical properties. Moreover, if it exceeds 10 parts by weight, heat resistance becomes extremely poor. In addition to sulfur, the vulcanized composition of the present invention may contain other types of polymers or copolymers, scorch inhibitors, activators, anti-aging agents, plasticizers, smelting accelerators, etc., which are generally used as compounding agents for rubber. Tackifiers, softeners, reinforcing agents, foaming agents, lubricants, colorants, fillers, etc. may be added and blended as necessary. Also metal compounds, especially Zn, Cd, Fe, Sn, Cu, Sr,
Oxides, hydroxides, carbonates, and organic carboxylates such as Ca, Pb, Ba, and Mg are effective in accelerating the vulcanization rate. Among these, zinc oxide, lead monoxide, red lead, and carbonate are particularly effective. Lead, zinc stearate, and magnesium oxide are effective, and are preferably blended in an amount of 1 to 5 parts by weight per 100 parts by weight of the (co)polymer. Note that the vulcanization conditions for the vulcanization composition of the present invention are not particularly limited, and normal vulcanization conditions can be used. The vulcanized composition thus obtained has excellent oil resistance and is useful in many fields requiring such performance. Such applications include a variety of rubber-like products such as gaskets, hoses, conveyor belt bagging, foil seals, valve seats, and the like. Next, the present invention will be explained in detail with reference to Examples. Examples 1 to 5 The first container was placed in a 500 c.c. glass pressure bottle under nitrogen.
100 g of the monomer shown in the table, 6 g of sodium dodecylbenzenesulfonate, 200 g of water, 0.1 g of sodium ethylenediaminetetraacetate, 0.1 g of ferrous sulfate, 0.1 g of sodium formaldehyde sulfoxylate,
Prepare 1.0g of paramenthane hydroperoxide
Polymerization was carried out at 10°C for 15 hours. Thereafter, 1.0 g of N,N-diethylhydroxylamine was added to stop the reaction. An emulsion free of any coagulum was obtained, and this emulsion was dropped into the methanol from step 3 under stirring to precipitate the (co)polymer. The (co)polymer was thoroughly washed with methanol and heated to 50°C. Dry under vacuum. The polymerization results are shown in Table 1. The number average molecular weights are 26,000 for Example 1, 57,000 for Example 2, 74,000 for Example 3, 50,000 for Example 4,
In Example 5, it was 80,000. Here, the number average molecular weight is measured by GPC after dissolving the polymer or copolymer in a suitable solvent such as acetone or tetrahydrofuran, and is determined by converting it from polystyrene as a standard sample of number average molecular weight.
【表】
得られた(共)重合体を第2表の配合処方によ
り50℃でロールにて混練し配合物を得た。ついで
160℃で20分間のプレス加硫を行なつた。50℃で
いずれも弾性のある加硫組成物が得られた。[Table] The obtained (co)polymer was kneaded with a roll at 50°C according to the formulation shown in Table 2 to obtain a blend. Then
Press vulcanization was performed at 160°C for 20 minutes. All elastic vulcanized compositions were obtained at 50°C.
【表】
実施例 6
実施例1〜3で得られた加硫組成物をJIS K−
6301に従つてトルエン/インオクタン混合溶液に
150℃70時間浸漬したのちの体積増加率を測定し
た。
その結果を第1図に示した。
この結果から1−ABDの(共)重合体加硫組
成物は、耐油性に優れた組成物であることがわか
る。
実施例 7〜10
実施例1の重合体を第3表の配合処方により、
160℃での加硫挙動をキユラストメータ(日本合
成ゴム(株)製)で調べた結果を第2図に示す。[Table] Example 6 The vulcanized compositions obtained in Examples 1 to 3 were tested according to JIS K-
Toluene/in-octane mixed solution according to 6301
The volume increase rate was measured after immersion at 150°C for 70 hours. The results are shown in Figure 1. This result shows that the 1-ABD (co)polymer vulcanized composition is a composition with excellent oil resistance. Examples 7 to 10 The polymer of Example 1 was mixed according to the formulation shown in Table 3.
Figure 2 shows the results of examining the vulcanization behavior at 160°C using a Cyulastometer (manufactured by Japan Synthetic Rubber Co., Ltd.).
【表】
実施例11〜18および比較例1
容量500c.c.のガラス製耐圧ビンに窒素下、第4
表に示す単量体100g、ドデシルベンゼンスルフ
オン酸ナトリウム6g、水200g、エチレンジア
ミン四酢酸ナトリウム0.1g、硫酸第1鉄0.1g、
ナトリウムホルムアルデヒドスルホキシレート
0.1g、パラメンタンヒドロペルオキシド1.0gを
仕込み、10℃で15時間重合させた。
その後N,N−ジエチルヒドロキシルアミン
1.0gをいれて重合を停止させた。
すべて凝固物のほとんどないエマルジヨンが得
られ、このエマルジヨンを3のメタノール中に
撹拌下滴下して共重合体を析出させたのち、この
共重合体をメタノールで充分に洗剰し、50℃真空
下乾燥させた。
結果を第4表に示した。[Table] Examples 11 to 18 and Comparative Example 1 A glass pressure bottle with a capacity of 500 c.c.
100 g of the monomer shown in the table, 6 g of sodium dodecylbenzenesulfonate, 200 g of water, 0.1 g of sodium ethylenediaminetetraacetate, 0.1 g of ferrous sulfate,
sodium formaldehyde sulfoxylate
0.1 g of p-menthane hydroperoxide and 1.0 g of para-menthane hydroperoxide were added, and polymerization was carried out at 10° C. for 15 hours. Then N,N-diethylhydroxylamine
1.0 g was added to stop the polymerization. An emulsion with almost no coagulates was obtained, and this emulsion was added dropwise to the methanol in Step 3 under stirring to precipitate the copolymer.The copolymer was thoroughly washed with methanol, and then the copolymer was washed thoroughly with methanol. Dry. The results are shown in Table 4.
【表】
得られた共重合体を第5表の配合処方により50
℃のロールにて混練し配合物を得た。ついで160
℃20分間のプレス加硫を行なつた。いずれも弾性
のある加硫組成物が得られた。
このうち実施例14および比較例1の加硫組成物
については、JIS K−6301に準じて物性を測定し
た。
結果を第6表に示した。[Table] The obtained copolymer was mixed according to the formulation shown in Table 5.
A blend was obtained by kneading with a roll at ℃. Then 160
Press vulcanization was performed at ℃ for 20 minutes. In all cases, elastic vulcanized compositions were obtained. Among these, the physical properties of the vulcanized compositions of Example 14 and Comparative Example 1 were measured according to JIS K-6301. The results are shown in Table 6.
【表】【table】
【表】【table】
【表】
実施例 19
実施例11〜13の加硫組成物をJIS K−6301に従
つてトルエン/イソオクタン混合溶液に150℃70
時間浸漬したのちの体積増加率を測定しその結果
を第3図に示した。
この結果から1−ABDの共重合量が多くなる
ほど加硫組成物の耐油性が大きく改善されている
ことがわかる。
実施例 20〜23
実施例12の共重合体を、第7表の配合により、
160℃での加硫挙動をキユラストメータ(日本合
成ゴム(株)製)で調べた結果を第4図に示す。[Table] Example 19 The vulcanized compositions of Examples 11 to 13 were added to a toluene/isooctane mixed solution at 150°C and 70°C according to JIS K-6301.
The volume increase rate after soaking for a period of time was measured and the results are shown in FIG. This result shows that the oil resistance of the vulcanized composition is greatly improved as the amount of copolymerized 1-ABD increases. Examples 20 to 23 The copolymer of Example 12 was mixed according to the formulation shown in Table 7.
Figure 4 shows the results of examining the vulcanization behavior at 160°C using a Cyulastometer (manufactured by Japan Synthetic Rubber Co., Ltd.).
【表】【table】
【表】
実施例24〜25 比較例2
容量500c.c.のガラス製耐圧ビンに窒素下、第8
表に示す単量体100g、アルキルベンゼンスルフ
オン酸ソーダ2.5g、水200g、リン酸カリウム
0.3g、第3級ドデシルメルカプタン0.3g、硫酸
第1鉄0.003g、エチレンジアミン四酢酸ナトリ
ウム0.006g、ナトリウムホルムアルデヒドスル
ホキシレート0.01g、パラメンタンヒドロペルオ
キシド0.01gを仕込み30℃で6時間重合させた。
その後N,N−ジエチルヒドロキシルアミン0.05
gをいれて停止させた。重合転化率はいずれもほ
ぼ80%であつた。
このエマルジヨンを塩化カルシウム1%溶液で
凝固させて100℃熱風乾燥させた。重合の結果を
第8表に示した。[Table] Examples 24-25 Comparative Example 2 A glass pressure bottle with a capacity of 500 c.c.
100g of the monomer shown in the table, 2.5g of sodium alkylbenzenesulfonate, 200g of water, potassium phosphate
0.3 g of tertiary dodecyl mercaptan, 0.003 g of ferrous sulfate, 0.006 g of sodium ethylenediaminetetraacetate, 0.01 g of sodium formaldehyde sulfoxylate, and 0.01 g of paramenthane hydroperoxide, and polymerized at 30°C for 6 hours.
Then N,N-diethylhydroxylamine 0.05
I turned on g and stopped it. The polymerization conversion rate was approximately 80% in all cases. This emulsion was coagulated with a 1% calcium chloride solution and dried with hot air at 100°C. The polymerization results are shown in Table 8.
【表】
得られた共重合体を第9表の配合処方により
100℃でロールに混練し、配合物を得た。ついで
155℃15分間のプレス加硫を行なつた。[Table] The obtained copolymer was mixed according to the formulation shown in Table 9.
A blend was obtained by kneading in a roll at 100°C. Then
Press vulcanization was performed at 155°C for 15 minutes.
【表】
得られた加硫組成物の物性およびJIS K6301−
12による3号オイルで120℃7時間浸漬したのち
の体積増加率を第10表に示す。[Table] Physical properties of the obtained vulcanized composition and JIS K6301-
Table 10 shows the volume increase rate after immersion in No. 3 oil according to No. 12 at 120°C for 7 hours.
【表】
実施例 26
容量500c.c.のガラス製耐圧ビンに窒素下でブタ
ジエン60g、スチレン30g、1−ABD10g、水
200g、樹脂酸石ケン5g、硫酸第1鉄0.02g、
アルキルナフタレンスルホン酸ソーダ0.15g、エ
チレンジアミンテトラアセテート0.1g、ナトリ
ウムジメチルスルホキシレート0.1g、クメンハ
イドロパーオキサイド0.1g、第3級ドデシルメ
ルカプタン0.3gを仕込み5℃で重合し転化率60
%で重合停止剤を添加した。このエマルジヨンを
メタノールで凝固した後50℃で真空乾燥させブタ
ジエン64重量%、スチレン24重量%、1−
ABD12重量%の共重合体を得た。
得られた共重合体を第11表の配合処方によりバ
ンバリーミキサーおよびロールにより混練し、加
硫組成物の300%の引張り応力および引張り強さ
を測定した所各々142Kg/cm2、310Kg/cm2であつ
た。[Table] Example 26 In a glass pressure-resistant bottle with a capacity of 500 c.c., 60 g of butadiene, 30 g of styrene, 10 g of 1-ABD, and water were added under nitrogen.
200g, resin acid soap 5g, ferrous sulfate 0.02g,
0.15 g of sodium alkylnaphthalene sulfonate, 0.1 g of ethylene diamine tetraacetate, 0.1 g of sodium dimethyl sulfoxylate, 0.1 g of cumene hydroperoxide, and 0.3 g of tertiary dodecyl mercaptan were charged and polymerized at 5°C with a conversion rate of 60.
% of polymerization terminator was added. This emulsion was coagulated with methanol and then dried under vacuum at 50°C, containing 64% by weight of butadiene, 24% by weight of styrene, and 1-
A copolymer containing 12% by weight of ABD was obtained. The obtained copolymer was kneaded using a Banbury mixer and rolls according to the formulation shown in Table 11, and the tensile stress and tensile strength at 300% of the vulcanized composition were measured to be 142 Kg/cm 2 and 310 Kg/cm 2 , respectively. It was hot.
【表】【table】
第1図および第3図は本発明の加硫組成物の体
積増加率のグラフであり、第2図および第4図は
本発明の実施例の(共)重合体の加硫挙動を示す
グラフである。
FIGS. 1 and 3 are graphs of the volume increase rate of the vulcanized composition of the present invention, and FIGS. 2 and 4 are graphs showing the vulcanization behavior of the (co)polymer of the example of the present invention. It is.
Claims (1)
合させた1−アセトキシ−1,3−ブタジエンの
重合体または1−アセトキシ−1,3−ブタジエ
ンおよびこれと共重合可能な少なくとも1種の共
役ジエンおよび/またはエチレン性不飽和化合物
との共重合体に、硫黄および/または含硫黄有機
化合物を配合してなる1−アセトキシ−1,3−
ブタジエン(共)重合体の加硫組成物。1 A polymer of 1-acetoxy-1,3-butadiene or 1-acetoxy-1,3-butadiene polymerized at -10 to 60°C in the presence of a radical polymerization initiator and at least one species copolymerizable therewith. 1-acetoxy-1,3- made by blending sulfur and/or a sulfur-containing organic compound with a copolymer with a conjugated diene and/or an ethylenically unsaturated compound
Vulcanized composition of butadiene (co)polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13281281A JPS5834836A (en) | 1981-08-26 | 1981-08-26 | Vulcanizable composition of 1-acetoxy-1,3-butadiene (co) polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13281281A JPS5834836A (en) | 1981-08-26 | 1981-08-26 | Vulcanizable composition of 1-acetoxy-1,3-butadiene (co) polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5834836A JPS5834836A (en) | 1983-03-01 |
JPH0134261B2 true JPH0134261B2 (en) | 1989-07-18 |
Family
ID=15090150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13281281A Granted JPS5834836A (en) | 1981-08-26 | 1981-08-26 | Vulcanizable composition of 1-acetoxy-1,3-butadiene (co) polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5834836A (en) |
-
1981
- 1981-08-26 JP JP13281281A patent/JPS5834836A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5834836A (en) | 1983-03-01 |
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