CN1148405C - 氯丁二烯系橡胶组合物 - Google Patents
氯丁二烯系橡胶组合物 Download PDFInfo
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- CN1148405C CN1148405C CNB998153346A CN99815334A CN1148405C CN 1148405 C CN1148405 C CN 1148405C CN B998153346 A CNB998153346 A CN B998153346A CN 99815334 A CN99815334 A CN 99815334A CN 1148405 C CN1148405 C CN 1148405C
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- Prior art keywords
- chloroprene
- based rubber
- rubber composition
- sulfide
- thermotolerance
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- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 abstract description 15
- 235000019241 carbon black Nutrition 0.000 abstract description 15
- 229940105289 carbon black Drugs 0.000 abstract 1
- -1 alkali metal salt Chemical class 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 230000003712 anti-aging effect Effects 0.000 description 11
- 239000004902 Softening Agent Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 10
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000006234 thermal black Substances 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SKMUADUXCABNRO-UHFFFAOYSA-N 3-methyl-2h-1,3-thiazole Chemical compound CN1CSC=C1 SKMUADUXCABNRO-UHFFFAOYSA-N 0.000 description 1
- GVYHDVHOWAIYEH-UHFFFAOYSA-N 4-azatricyclo[5.2.2.02,6]undeca-1,6,8,10-tetraene-3,5-dione Chemical compound C1=CC2=CC=C1C1=C2C(=O)NC1=O GVYHDVHOWAIYEH-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical compound CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- DIWPZFGLTODTJM-UHFFFAOYSA-N CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC.CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC.CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC DIWPZFGLTODTJM-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- PSXFWDBXOBHGSA-UHFFFAOYSA-N benzene-1,3-dicarboxylate;dimethylazanium;hydron Chemical compound C[NH2+]C.OC(=O)C1=CC=CC(C([O-])=O)=C1 PSXFWDBXOBHGSA-UHFFFAOYSA-N 0.000 description 1
- ZRIHAIZYIMGOAB-UHFFFAOYSA-N butabarbital Chemical compound CCC(C)C1(CC)C(=O)NC(=O)NC1=O ZRIHAIZYIMGOAB-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JCYPECIVGRXBMO-FOCLMDBBSA-N methyl yellow Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1 JCYPECIVGRXBMO-FOCLMDBBSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
一种氯丁二烯系橡胶组合物,其特征在于,含有氯丁二烯橡胶、微晶内的层平面的C轴方向的平均堆积高度Lc在2nm以上的炭黑和锌粉。
Description
技术领域
本发明涉及氯丁二烯系橡胶组合物,具体地说,涉及加入了耐热性显著改善的硫化物的氯丁二烯系橡胶组合物。
背景技术
改善氯丁二烯系橡胶组合物的硫化物的耐热性的方法迄今已有多个提出。例如,日本特许公开公报1975年第87437号公开了一种在氯丁二烯橡胶中添加锌粉和水以改善耐热性的方法,日本特许公开公报1990年第34645号公开了一种添加锌粉和热炭黑以改善耐热性的方法,日本特许公开公报1991年第81350号公开了一种在氯丁二烯橡胶中添加锌粉和4,4′-(α,α-二甲基苄基)二苯胺以改善耐热性的方法。但是,在用于汽车用橡胶部件等用途时,由于对耐热性的要求已变得严格,因此,用这些公知的方法并不一定能满足耐热性要求,需要对此进行改进。
发明的公开
本发明是一种在氯丁二烯系橡胶中加入了特定炭黑和锌粉的组合物,通过加入特定炭黑和锌粉,改善氯丁二烯系橡胶组合物的硫化物的耐热性。
即,本发明者为改善氯丁二烯系橡胶组合物的硫化物的耐热性,进行了深入的研究,结果发现,将氯丁二烯系橡胶与微晶内的层平面的C轴方向的平均堆积高度Lc在2nm以上的炭黑和锌粉组合,可改善氯丁二烯系橡胶组合物的硫化物的耐热性。
下面对本发明作更详细的说明。
本发明的氯丁二烯系橡胶组合物中的氯丁二烯系橡胶以氯丁二烯橡胶为主要成分,但除此之外,视需要,还可含天然橡胶、SBR、丁基橡胶、BR、NBR、EPDM等。
本发明的氯丁二烯系橡胶是氯丁二烯的均聚物或将氯丁二烯和一种以上的可与氯丁二烯共聚的其他单体的混合物聚合而得到的共聚物(以下常称氯丁二烯系橡胶)。
可与氯丁二烯共聚的单体例如有2,3-二氯-1,3-丁二烯、1-氯-1,3-丁二烯、硫、苯乙烯、丙烯腈、异丁烯腈、异戊二烯、丁二烯和丙烯酸、甲基丙烯酸及它们的酯类等,它们可在满足本发明目的的范围内使用。
对本发明中使用的得到氯丁二烯橡胶的聚合方法无特别限定,可使用通常的聚合方法。可在常用于氯丁二烯聚合的聚合引发剂的存在下用常用的方法将氯丁二烯单体乳化聚合,得到氯丁二烯橡胶。
对实施上述乳化聚合时的乳化剂无特别限定,可使用一般用于氯丁二烯乳化聚合的乳化剂,例如,6-22个碳原子的饱和的或不饱和的脂肪酸的碱金属盐、松香酸或歧化松香酸的碱金属盐、β-萘磺酸的福尔马林缩合物的碱金属盐等。
氯丁二烯橡胶可根据分子量调节剂的种类而分成硫改性型、硫醇改性型、黄原酸改性型。硫改性型是用二硫化秋兰姆将由硫和氯丁二烯共聚而成的聚合物增塑,调整至规定的门尼粘度。硫醇改性型是用正十二烷硫醇、叔十二烷硫醇、辛硫醇等烷基硫醇类作为分子量调节剂。黄原酸改性型是用烷基黄原酸作为分子量调节剂。
本发明的氯丁二烯系橡胶可采用任一种改性型,也可采用将硫、硫醇和黄原酸加以组合而改性的氯丁二烯系橡胶。但是,硫改性型与硫醇改性型和黄原酸改性型相比,聚合物自身的耐热性差,因此,要求更好的耐热性时,最好使用硫醇改性型和黄原酸改性型。
用于黄原酸改性型的烷基黄原酸化合物的具体例子有二硫化二甲基黄原酸、二硫化二乙基黄原酸、二硫化二异丙基黄原酸、二硫化二异丁基黄原酸等。
烷基黄原酸化合物的用量根据使氯丁二烯系聚合物的分子量(或者,将聚合物分离而得到的氯丁二烯系橡胶的门尼粘度)成为合适值的要求进行确定。根据烷基的结构和目标分子量而异,相对于氯丁二烯系单体100重量份,一般为0.05-5.0重量份,最好为0.3-1.0重量份。
聚合引发剂可采用通常用于氯丁二烯乳化聚合的公知的过硫酸钾、过硫酸铵、过硫酸钠、过氧化氢、叔丁基过氧化氢等有机过氧化物类。
在本发明中,对聚合温度和单体的最终转化率无特别限定,但聚合温度以0-50℃为佳,20-50℃更佳。此外,最好使单体的最终转化率达到50-90%,在达到该转化率时添加少量聚合终止剂,终止聚合。
聚合终止剂例如可采用吩噻嗪、4-叔丁基儿茶酚、2,2-亚甲基双-4-甲基-6-叔丁基苯酚等常用的终止剂。
未反应的单体例如可用汽提法加以除去,然后,调整乳胶的pH,通过常法的冷冻凝固、水洗、热风干燥等将聚合物分离。
在本发明的氯丁二烯系橡胶组合物中掺入的炭黑可以是用热解法得到的热炭黑、乙炔黑,或者是用不完全燃烧法得到的炉黑、槽法炭黑中的任一种,但在这些炭黑中,微晶内的层平面的C轴方向的平均堆积高度Lc必须在2nm以上,2.5nm以上更佳。
优选平均粒径在60nm以下且DBP吸油量宜为100-350ml/100g(较好地为120-300ml/100g,更好地为140-300ml/100g)的炭黑。
若微晶内的层平面的C轴方向的平均堆积高度Lc小于2nm,则将氯丁二烯系橡胶组合物硫化而得到的硫化物的耐热性不足。
乙炔黑是将乙炔气体热解而得到的炭黑,已明显地结晶化且结构高度发达、吸油量大,因此,使用乙炔黑的氯丁二烯系橡胶组合物,其硫化物的耐热性改善效果大,因而也是最适宜的。
炭黑的添加量相对于氯丁二烯系橡胶100重量份,宜为10-70重量份,20-60重量份更佳。若添加量超过70重量份,则加工性能差,易出现过早硫化,而且,硫化物的脆化温度升高。而若添加量小于10重量份,则硫化物的拉伸强度和模量会下降。
本发明中使用的锌粉的粒度最好是200目以上的。锌粉的添加量相对于氯丁二烯系橡胶100重量份,宜为1-30重量份,2-20重量份更佳。若小于1重量份,则硫化物的耐热性不能充分改善,而若大于30重量份,则硫化物的机械特性会下降。
对本发明中使用的硫化剂无特别限定,最好是金属氧化物,具体例子有氧化锌、氧化镁、氧化铅、四氧化三铅、三氧化铁、二氧化钛、氧化钙等。它们也可二种以上并用。这些硫化剂的添加量相对于氯丁二烯系橡胶100重量份,最好为3-15重量份。
与下述硫化促进剂并用,可更有效地进行硫化。
硫化促进剂可以是一般用于氯丁二烯系橡胶硫化的硫脲系、胍系、秋兰姆系、噻唑系和三嗪系硫化促进剂,但以硫脲系为佳。硫脲系硫化促进剂的例子有亚乙基硫脲、二乙基硫脲、三甲基硫脲、三乙基硫脲、N,N′-二苯基硫脲等,尤以三甲基硫脲为佳。此外,也可使用3-甲基噻唑啉-2-硫酮或噻二唑与亚苯基马来酰亚胺的混合物、间苯二甲酸氢二甲铵或1,2-二巯基-1,3,4-噻二唑衍生物等硫化促进剂。这些硫化促进剂可二种以上并用。此外,还可使用过氧化物硫化系。这些硫化促进剂的添加量相对于氯丁二烯系橡胶100重量份,最好为0.5-5重量份。
在本发明的氯丁二烯系橡胶组合物中,视需要,可掺入各种添加剂,例如软化剂、增塑剂、加工助剂、防老剂、润滑剂、填充剂等。
防老剂可采用胺系、咪唑系、氨基甲酸金属盐、酚系、蜡等一般的防老剂。改善耐热性效果大的防老剂的例子有胺系的4,4′-双(α,α-二甲基苄基)二苯胺、辛基化二苯胺等。尤其是4,4′-双(α,α-二甲基苄基)二苯胺可使本发明的氯丁二烯系橡胶组合物的耐热性进一步改善。这些防老剂可单独使用,也可二种以上并用。
软化剂可采用润滑油、操作油、石蜡、液体石蜡、凡士林、石油沥青等石油系软化剂,菜籽油、亚麻仁油、蓖麻油、椰油等脂肪族系软化剂等一般的软化剂。增塑剂可采用邻苯二甲酸二辛酯、己二酸二辛酯等一般的增塑剂。不阻碍或可提高本发明的氯丁二烯系橡胶组合物的耐热性的增塑剂例如有醚·硫醚系增塑剂(如拜耳公司生产的Vulkanol OT)、植物油或酯系增塑剂、醚·硫醚系增塑剂(如旭电化工业株式会社生产的Adekacizer RS-700、RS-735等。尤其是醚·硫醚系增塑剂可在提高耐热性的同时还具有改善耐寒性的效果,且两者之间的平衡优异,因此是优选的。这些增塑剂根据所要求的特性,可单独使用,也可并用。
本发明中的橡胶组合物的混炼方法和硫化方法可以是橡胶工业常用的方法。一般地,可通过用捏和机、班伯里混炼机或滚筒等混炼机混合,加工成形成适合目的的形状,得到成形硫化物。具体地说,可将各成分在硫化温度以下的温度混炼后将该混炼物成形成各种形状并硫化。硫化时的温度和硫化时间可适当设定。硫化温度以140-190℃为宜,150-180℃更佳。
由本发明的氯丁二烯系橡胶组合物得到的硫化物除了橡胶的机械特性之外,还具有优异的耐热性、耐油性、耐寒性,因此,非常适合要求具有耐热性、耐油性和耐寒性的行李箱、软管、皮带、防振橡胶、止振材料、电线、垫圈、油封圈、填塞料等工业部件,尤其是对品质保证和耐热性要求严格的汽车用橡胶部件。
本发明的最佳实施方式
下面通过实施例对本发明作详细说明,但本发明不限于这些实施例。
实施例1-5、比较例1-4
按表1、2所示配料处方,用8英寸滚筒进行混炼,制作2.3mm厚的片材。在150℃将该片材加压硫化20分钟,得到2mm厚的硫化片材。用3号哑铃进行物性试验,拉伸试验依据JIS K6251进行,硬度依据JISK6253测定。此外,低温性评价依据JIS K6261,通过Gehman扭转试验测定,用T10(系相对于在23℃的模量的值的某一比模量达到10时的温度)表示。
耐热性系依据JIS K6257,使用在140℃的齿轮炉(gear oven)中保存9日的试验片,用上述测定方法分别进行拉伸试验和硬度测定,用拉伸强度和伸长变化率及硬度的变化量表示。
微晶内的层平面的C轴方向的平均堆积高度Lc(nm)是根据使用Cu-Kα线的X线衍射法中的(002)衍射线,按下式算出。
Lc=(180·K·λ)/(π·β·COSΘ)
K=形状因子(使用0.9)
λ=X线的波长(0.154nm)
Θ=(002)衍射线吸收带中显示极大值的角度
β=(002)衍射线吸收带中用角度表示的半峰值
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | |
氯丁二烯橡胶 1) | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
硬脂酸 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
防老剂4,4′-双(α,α-二甲基苄基)二苯胺 | 6 | - | 6 | - | 6 | 6 | 6 |
防老剂辛基化二苯胺 | - | 6 | - | 6 | - | - | - |
防老剂亚磷酸三壬基苯酯 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
氧化镁 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
乙炔黑 2) | 45 | 45 | 20 | 45 | 45 | - | - |
炭黑(MAF) 3) | - | - | - | - | - | 50 | - |
炭黑(N330:HAF) 4) | - | - | - | - | - | - | 45 |
炭黑(N880:FT) 5) | - | - | - | - | - | - | - |
Vulkanol OT 6) | 25 | 25 | - | - | - | 25 | 25 |
癸二酸二辛酯 | - | - | - | 25 | - | - | - |
邻苯二甲酸二辛酯 | - | - | - | - | 25 | - | - |
锌粉 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
氧化锌 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
亚乙基硫脲 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
二硫化四甲基秋兰姆 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
硫化物特性(硫化条件:150℃×20分钟)(常态物性)拉伸强度 (MPa)伸长 (%)硬度 (JIS-A) | 15.663057 | 15.762056 | 18.661057 | 15.560057 | 15.761057 | 18.042057 | 18.937056 |
(耐寒性:Gehman扭转试验)T10 (℃) | -45 | -45 | -37 | -49 | -43 | -44 | -44 |
(耐热性:140℃×9日)拉伸强度变化率 (%)伸长变化率 (%)硬度变化 | -14-16+17 | -16-24+22 | -12-2+15 | -17-25+24 | -18-25+23 | -22-36+28 | -19-36+29 |
表中使用的材料如下所示。
1)电气化学工业株式会社生产的巯基改性氯丁二烯(S-40V)
2)电气化学工业株式会社生产的Denka Black粒状品(Lc=3.5nm,DBP吸油量=210ml/100g)
3)东海碳株式会社生产的Sheast 116(Lc=1.8nm以下,DBP吸油量=133ml/100g)
4)东海碳株式会社生产的Sheast 3(Lc=1.8nm以下,DBP吸油量=101ml/100g)
5)旭碳株式会社生产的Asahi Thermal FT(Lc=1.8nm以下,DBP吸油量=28ml/100g)
6)拜耳(Bayer)公司(德国)生产的醚·硫醚系增塑剂
表2
实施例1 | 实施例2 | |
氯丁二烯橡胶 1) | 100 | 100 |
硬脂酸 | 0.5 | 0.5 |
防老剂4,4′-双(α,α-二甲基苄基)二苯胺 | 6 | 6 |
防老剂辛基化二苯胺 | - | - |
防老剂亚磷酸三壬基苯酯 | 2 | 2 |
氧化镁 | 4 | 4 |
乙炔黑 2) | - | 45 |
炭黑(MAF) 3) | - | - |
炭黑(N330:HAF) 4) | - | - |
炭黑(N880:FT) 5) | 85 | - |
Vulkanol OT 6) | 25 | 25 |
癸二酸二辛酯 | - | - |
邻苯二甲酸二辛酯 | - | - |
锌粉 | 5 | - |
氧化锌 | 5 | 5 |
亚乙基硫脲 | 1 | 1 |
二硫化四甲基秋兰姆 | 0.3 | 0.3 |
硫化物特性(硫化条件:150℃×20分钟)(常态物性)拉伸强度 (MPa)伸长 (%)硬度 (JIS-A) | 13.951057 | 15.763056 |
(耐寒性:Gehman扭转试验)T10 (℃) | -41 | -46 |
(耐热性:140℃×9日)拉伸强度变化率(%)伸长变化率 (%)硬度变化 | -22-31+28 | -19-29+27 |
如表1和表2所示,氯丁二烯橡胶中含有微晶内的层平面的C轴方向的平均堆积高度Lc在2nm以上的炭黑和锌粉的本发明的氯丁二烯系橡胶组合物可产生具有优异耐热性的硫化物。
Claims (3)
1.氯丁二烯系橡胶组合物,其特征在于,含有氯丁二烯橡胶、微晶内的层平面的C轴方向的平均堆积高度Lc在2nm以上的乙炔黑和锌粉。
2.如权利要求1所述的氯丁二烯系橡胶组合物,其特征在于,相对于氯丁二烯系橡胶100重量份,掺入了10-70重量份的乙炔黑和1-30重量份的锌粉。
3.硫化物,其特征在于,将权利要求1或2所述的氯丁二烯系橡胶组合物硫化而成。
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DE102007057133A1 (de) * | 2007-11-28 | 2009-06-04 | Robert Bosch Gmbh | Wischgummi für Scheibenwischer |
GB201016463D0 (en) * | 2010-09-30 | 2010-11-17 | Icon Polymer Ltd | Rubber compositions for use in tension belts |
KR101800062B1 (ko) * | 2011-03-11 | 2017-11-21 | 덴카 주식회사 | 클로로프렌 고무 조성물 및 그의 가황 고무, 및 상기 가황 고무를 이용한 고무형물, 방진 고무 부재, 엔진 마운트 및 호스 |
JP5721182B2 (ja) * | 2012-04-11 | 2015-05-20 | 国立大学法人長岡技術科学大学 | 加硫物及びその製造方法 |
WO2014041649A1 (ja) * | 2012-09-13 | 2014-03-20 | 電気化学工業株式会社 | ゴム組成物、その加硫物及び成形品 |
CN103012889B (zh) * | 2012-12-24 | 2015-05-06 | 天津市橡胶工业研究所 | 一种氯丁胶布拼接封皮用氯丁橡胶配方及制作方法 |
JP5714055B2 (ja) * | 2013-05-21 | 2015-05-07 | 株式会社ブリヂストン | ホース用ゴム組成物及びホース |
CN105911204A (zh) * | 2016-06-23 | 2016-08-31 | 福清出入境检验检疫局综合技术服务中心 | 一种橡胶及其制品中亚乙基硫脲的检测方法 |
CN107033418A (zh) * | 2017-05-10 | 2017-08-11 | 广西桂山特种橡胶制品有限公司 | 一种橡胶骨架油封及其制备方法 |
JP2022013964A (ja) * | 2018-11-09 | 2022-01-19 | デンカ株式会社 | ゴム組成物、該ゴム組成物の加硫物及び加硫成形体 |
KR20230109181A (ko) * | 2020-11-27 | 2023-07-19 | 덴카 주식회사 | 클로로프렌계 고무 조성물, 상기 클로로프렌계 고무 조성물의 가황물 및 클로로프렌계 고무 조성물의 가황 성형체 |
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JPS5747022B2 (zh) * | 1973-01-12 | 1982-10-06 | ||
JPS5135491B2 (zh) | 1973-12-08 | 1976-10-02 | ||
US4367208A (en) * | 1979-06-27 | 1983-01-04 | Columbian Chemicals Company | Process for the manufacture of battery carbon black |
JPS592451B2 (ja) * | 1980-01-30 | 1984-01-18 | 株式会社ブリヂストン | ゴム組成物 |
JPS59193284A (ja) * | 1983-04-15 | 1984-11-01 | Hitachi Ltd | 防食テ−プ |
DE3680249D1 (de) * | 1985-05-10 | 1991-08-22 | Asahi Chemical Ind | Sekundaerbatterie. |
JPH0234645A (ja) | 1988-07-22 | 1990-02-05 | Showa Electric Wire & Cable Co Ltd | 耐熱性ポリクロロプレンゴム組成物 |
JPH0643518B2 (ja) * | 1989-08-25 | 1994-06-08 | バンドー化学株式会社 | 伝動ベルト |
US5352289A (en) * | 1992-12-18 | 1994-10-04 | Cabot Corporation | Low ash carbon blacks |
TW576848B (en) * | 1998-02-19 | 2004-02-21 | Denki Kagaku Kogyo Kk | Chloroprene rubber composition |
JP3749019B2 (ja) * | 1998-05-08 | 2006-02-22 | 電気化学工業株式会社 | クロロプレン系ゴム組成物 |
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1999
- 1999-11-02 WO PCT/JP1999/006112 patent/WO2001032768A1/ja active IP Right Grant
- 1999-11-02 DE DE69930657T patent/DE69930657T8/de active Active
- 1999-11-02 EP EP99951214A patent/EP1148094B1/en not_active Expired - Lifetime
- 1999-11-02 CN CNB998153346A patent/CN1148405C/zh not_active Expired - Fee Related
- 1999-11-02 ES ES99951214T patent/ES2262343T3/es not_active Expired - Lifetime
- 1999-11-02 KR KR10-2001-7008387A patent/KR100463474B1/ko not_active IP Right Cessation
- 1999-11-02 US US09/719,536 patent/US6495625B1/en not_active Expired - Lifetime
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ES2262343T3 (es) | 2006-11-16 |
EP1148094A4 (en) | 2002-04-17 |
DE69930657T2 (de) | 2006-08-17 |
EP1148094A1 (en) | 2001-10-24 |
DE69930657T8 (de) | 2006-12-14 |
EP1148094B1 (en) | 2006-03-29 |
KR20010108061A (ko) | 2001-12-07 |
WO2001032768A1 (fr) | 2001-05-10 |
KR100463474B1 (ko) | 2005-01-07 |
US6495625B1 (en) | 2002-12-17 |
CN1332771A (zh) | 2002-01-23 |
DE69930657D1 (de) | 2006-05-18 |
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