CN1059538A - The composition that contains chlorination ethylene-propylene analog copolymer - Google Patents
The composition that contains chlorination ethylene-propylene analog copolymer Download PDFInfo
- Publication number
- CN1059538A CN1059538A CN 91109754 CN91109754A CN1059538A CN 1059538 A CN1059538 A CN 1059538A CN 91109754 CN91109754 CN 91109754 CN 91109754 A CN91109754 A CN 91109754A CN 1059538 A CN1059538 A CN 1059538A
- Authority
- CN
- China
- Prior art keywords
- weight
- propylene
- chlorination
- ethylene
- ethylene chloride
- 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.)
- Withdrawn
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- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 217
- 229920001577 copolymer Polymers 0.000 title claims abstract description 187
- 239000000203 mixture Substances 0.000 title claims abstract description 92
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical class C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000005864 Sulphur Substances 0.000 claims abstract description 36
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 62
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 54
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 239000011593 sulfur Substances 0.000 claims description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 29
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 28
- 229910000765 intermetallic Inorganic materials 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000002052 molecular layer Substances 0.000 claims 1
- 238000005987 sulfurization reaction Methods 0.000 abstract description 30
- -1 sulphur carbamide compounds Chemical class 0.000 abstract description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000460 chlorine Substances 0.000 abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 abstract description 20
- 239000007900 aqueous suspension Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 58
- 238000000034 method Methods 0.000 description 39
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- 238000004073 vulcanization Methods 0.000 description 24
- 238000004132 cross linking Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 239000004709 Chlorinated polyethylene Substances 0.000 description 13
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000004700 high-density polyethylene Substances 0.000 description 12
- 239000011133 lead Substances 0.000 description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 12
- 238000010583 slow cooling Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229920001903 high density polyethylene Polymers 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 8
- 230000008569 process Effects 0.000 description 8
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- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000007033 dehydrochlorination reaction Methods 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 7
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
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- 244000043261 Hevea brasiliensis Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
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- 230000000996 additive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical class ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
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- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical class [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 3
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- 229910052725 zinc Inorganic materials 0.000 description 3
- ALOXZVMUNXFRFJ-UHFFFAOYSA-N 1,2-dichloroethane;prop-1-ene Chemical group CC=C.ClCCCl ALOXZVMUNXFRFJ-UHFFFAOYSA-N 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-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
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- HXKCUQDTMDYZJD-UHFFFAOYSA-N Methyl selenac Chemical compound CN(C)C(=S)S[Se](SC(=S)N(C)C)(SC(=S)N(C)C)SC(=S)N(C)C HXKCUQDTMDYZJD-UHFFFAOYSA-N 0.000 description 2
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- 125000003710 aryl alkyl group Chemical group 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- PYSZASIZWHHPHJ-UHFFFAOYSA-L calcium;phthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O PYSZASIZWHHPHJ-UHFFFAOYSA-L 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SMEDVXJKKOXLCP-UHFFFAOYSA-N cyamelide Chemical compound N=C1OC(=N)OC(=N)O1 SMEDVXJKKOXLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000010586 diagram Methods 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
- JQVDAXLFBXTEQA-UHFFFAOYSA-O dibutylazanium Chemical compound CCCC[NH2+]CCCC JQVDAXLFBXTEQA-UHFFFAOYSA-O 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- RLULIUSIDLLCSW-UHFFFAOYSA-N diethylcarbamothioylsulfanylselanyl n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)S[Se]SC(=S)N(CC)CC RLULIUSIDLLCSW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- UVOFGKIRTCCNKG-UHFFFAOYSA-N dimethylazanium;n,n-dimethylcarbamodithioate Chemical compound C[NH2+]C.CN(C)C([S-])=S UVOFGKIRTCCNKG-UHFFFAOYSA-N 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WHDGWKAJBYRJJL-UHFFFAOYSA-K ferbam Chemical compound [Fe+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S WHDGWKAJBYRJJL-UHFFFAOYSA-K 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 210000003953 foreskin Anatomy 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- QGTHALAWFUFVCU-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;lead(2+) Chemical compound [Pb+2].CN(C)C([S-])=S.CN(C)C([S-])=S QGTHALAWFUFVCU-UHFFFAOYSA-L 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
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- LPXPSTWBTULMJE-UHFFFAOYSA-N n-phenylbutan-1-imine Chemical compound CCCC=NC1=CC=CC=C1 LPXPSTWBTULMJE-UHFFFAOYSA-N 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 229940038597 peroxide anti-acne preparations for topical use Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- TVPFLPJBESCUKI-UHFFFAOYSA-M potassium;n,n-dimethylcarbamodithioate Chemical compound [K+].CN(C)C([S-])=S TVPFLPJBESCUKI-UHFFFAOYSA-M 0.000 description 1
- 238000009747 press moulding Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003921 pyrrolotriazines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012261 resinous substance Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- QRCJOCOSPZMDJY-UHFFFAOYSA-N valnoctamide Chemical compound CCC(C)C(CC)C(N)=O QRCJOCOSPZMDJY-UHFFFAOYSA-N 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
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
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Abstract
The ethylene-propylene analog copolymer made it to contact with chlorine in aqueous suspension carry out two sections or three sections chlorinations, make ethylene chloride-propylene copolymers, but mix sulphur carbamide compounds in this multipolymer, also can mix dithiocar-bamate or mercapto-triazine compounds as required, thereby can be made into sulfuration composition with good rerum natura, also can mix organo-peroxide, thereby can be made into crosslinkable composite with good rerum natura.
Description
The present invention relates to method by in aqueous suspension, making the chlorination of ethylene-propylene analog copolymer produce ethylene chloride-propylene copolymers, more particularly, the present invention relates to the production method of ethylene chloride-propylene copolymers, ethylene chloride-propylene copolymer wherein, not only have good thermotolerance and winter hardiness, oil-proofness is also very outstanding, and has good weathering resistance and ozone resistance, not only can be crosslinked, and can more easily vulcanize.
The invention still further relates to ethylene chloride-propylene copolymers composition with outstanding sulfuration or bridging property, more particularly, relate to by (A) ethylene chloride-propylene copolymers, (B) thiourea, (C) sulphur and/or sulfur donor and (D) sour accepting agent metallic compound the ethylene chloride-propylene copolymers composition that according to circumstances also has (E) dithiocar-bamate or mercapto-triazine compounds to form.This composition not only has outstanding sulfuration, and has good flexibility and compressive permanent strain, and has outstanding thermotolerance.
In addition, the invention still further relates to have outstanding bridging property by (A) ethylene chloride-propylene copolymers and (G) ethylene chloride-propylene copolymers composition of forming of organo-peroxide, said composition not only has outstanding bridging property, and have good flexibility and compressive permanent strain, and has outstanding thermotolerance.
As everyone knows, ethylene chloride-propylene copolymers generally has outstanding oil-proofness, flame retardancy etc., therefore as coating, tackiness agent (disclosing communique 59-122503 number referring to Japanese Patent).But, chlorination method as the ethylene-propylene analog copolymer, be that the ethylene-propylene analog copolymer is not being contained in the fs in water Jie method of clouding agent in being lower than under 50 ℃ (for example 20～45 ℃), chlorination is to 20%(weight) degree of (for example 2～15%(weight), be warmed up to the temperature (for example 70～100 ℃) that is higher than 50 ℃ in subordinate phase, under this temperature, make its chlorination to cl content be 18% or higher (weight) 18～50%(weight for example)) degree.In addition, also proposed the ethylene-propylene analog copolymer for example is dissolved in the tetracol phenixin equal solvent, in solution, made its chlorating method in comparatively high temps (below 150 ℃).But, in this method, exist vapour pressure height, and require the high-temperature pressure-proof reactor, and generate the relatively poor problem of thermostability of polymkeric substance owing to the solvent of reaction system.On the one hand, in above-mentioned water Jie method under the chlorating situation, when existing chlorination after washing muriate, problems such as muriate caking.
Because chlorinatedpolyethylene, especially amorphism chlorinated polyethylene rubber shape material is chemical saturated structures, and be chloride polymer substance, so its cross-linking agent (sulfide) has good rerum natura, for example weathering resistance, flame retardancy, resistance to chemical reagents, electrology characteristic and thermotolerance.Therefore, it can be configured as electric wire foreskin, electric component, flexible pipe, material of construction, bicycle assembly parts, wrapping material, thin plate etc., be used for the wide industrial field.
But,, close structure for aforesaid chemistry is full, and be difficult to make its sulfuration as vulcanizing agent with sulphur or sulfur donor because this chlorinatedpolyethylene is different from conventional rubber (for example, being the rubber of main component with the divinyl).For this reason, employing generally uses organo-peroxide to carry out crosslinked method as linking agent.But, after extrusion molding, under the crosslinked situation of the vulcanizing boiler that uses the ordinary rubber industry member to use, be difficult to make the cross-linking agent that obtains suitably crosslinked flexible pipe, plate, pipe etc., therefore there are the relatively poor problems such as tensile strength, thermotolerance of the cross-linking agent that obtains.
For these reasons, propose use sulphur or sulfur donor and carried out sulfurized method (for example, in open communique 55-71742 number of Japanese Patent, describing).In addition, the suggestion of the inventor's a part may be by at first making sulphur and/or sulfur donor and thiourea, dithiocarbamic acid metal-salt and as the magnesium oxide and/or the plumbous oxide fusion of sour accepting agent, vulcanize, and can obtain having the sulfuration chlorinatedpolyethylene based composition (disclosing communique 61-209244 number) of outstanding various mechanical property (as tensile strength) referring to Japanese Patent.
But this composition can be clear that by the vulcanization curve in the comparison diagram 1, exist because sulfuration property not necessarily meets the demands, and flexibility and compressive permanent strain are not enough, and the inferior problem of thermotolerance.
On the one hand, use organo-peroxide to carry out crosslinked method, though can obtain having the composition of outstanding thermotolerance and compressive permanent strain, but this composition is for the goods that require high heat resistance, high compression permanent strain, because cross-linking efficiency is poor, the problem that existence a large amount of organo-peroxides of needs and linking agent and the cost that links therewith raise.
Therefore, the object of the present invention is to provide a kind of production method of ethylene chloride-propylene copolymers, there is not the shortcoming in the above-mentioned prior art in ethylene chloride-propylene copolymers wherein, not only has outstanding thermotolerance and winter hardiness, and have good oil-proofness, weathering resistance and an ozone resistance, and chlorination at a lower temperature, and the muriate that obtains does not lump, and not only can be crosslinked, and can vulcanize with sulphur or sulfocompound (emitting the compound of sulphur) with organo-peroxide.
Another object of the present invention is to provide desired in a kind of ethylene chloride-propylene copolymers field, not only has fabulous sulfuration, and have outstanding mechanical characteristics (as pull resistance and compressive permanent strain), and the good ethylene chloride-propylene copolymers composition of thermotolerance.
A further object of the present invention is to provide a kind of and not only has outstanding mechanical characteristics such as high heat resistance, a high compression permanent strain by what add also that a spot of organo-peroxide obtains, and can also satisfy the ethylene chloride-propylene copolymers composition of desired characteristic cheaply under the situation.
According to the present invention, provide a kind of ethylene-propylene analog copolymer that makes in aqueous suspension, to contact the method for producing ethylene chloride-propylene copolymers with chlorine, the propylene content of ethylene-propylene analog copolymer wherein is 15～40%(weight), melting index is (according to ASTM D1238, condition L measures, to call MFR in the following text) be 0.01～0.5 gram/10 minutes, fusion peak value (measuring with difference formula scanning calorimeter (DSC)) is more than 80 ℃, degree of crystallinity with X-ray measuring is more than 3%, the molecular weight distribution index of measuring with permeation chromatography (GPC) is the Mw(weight-average molecular weight)/the Mn(number-average molecular weight)＞4, and mooney viscosity (ML
1+4, 100 ℃) and be 10～180, this method comprises:
In the fs, than low 25 ℃ at least of the fusing points of ethylene-propylene analog copolymer, but be higher than under 50 ℃ the temperature, make its chlorination to 20～60% of perchlorizing amount.
In subordinate phase, be higher than in the above-mentioned fs chlorination temperature more than 10 ℃, but be lower than in the temperature range of 5～15 ℃ of this ethylene-propylene copolymer fusing points, at least 30% of the remaining chlorination amount of chlorination, and make the chlorination amount reach 60～90% of perchlorizing amount in this stage, and
In the phase III, be lower than this ethylene-propylene analog copolymer fusing point but be higher than in the temperature range of (fusing point-2 ℃), carry out remaining chlorination, make cl content reach 20～45%(weight), and mooney viscosity (ML
1+4, 100 ℃) and be 10～150.
A kind of production method of ethylene chloride-propylene copolymers also is provided according to the present invention, and this method comprises after the above-mentioned fs (20～60% chlorination),
In subordinate phase, temperature of reaction system is raised to than under high 1～7 ℃ temperature of this ethylene-propylene analog copolymer fusing point, under this temperature, do not import chlorine, make its slow cooling 10～60 minutes,
In the phase III, in the temperature of 2～25 ℃ of the fusing points that is lower than this ethylene-propylene polymkeric substance, particularly be lower than under the temperature of 30～60 ℃ of fusing points of this multipolymer, carry out remaining chlorination.
According to the present invention, also provide a kind of after the chlorination of above-mentioned fs, in subordinate phase, be higher than above-mentioned fs chlorination temperature more than 10 ℃, carry out remaining chlorating production method but be lower than in the temperature range of 5～15 ℃ of fusing points of this ethylene-propylene analog copolymer.
A kind of ethylene chloride of being made up of following component-propylene copolymers composition also is provided according to the present invention:
(A) 100 weight parts passes through that to make propylene content be 15～40%(weight), melting index (MFR) is that the fusion peak value that 0.01～5.0 gram/10 minutes, difference formula scanning calorimeter (DSC) are measured is more than 80 ℃, with the degree of crystallinity of X-ray measuring be more than 3%, with molecular weight distribution index Mw/ Mn＞4 and the mooney viscosity (ML of permeation chromatography mensuration
1+4, 100 ℃) be that the cl content that 10～180 ethylene-propylene analog copolymer chlorination obtains is 20～45%(weight) and mooney viscosity (ML
1+4, 100 ℃) and be ethylene chloride-propylene copolymers of 10～150,
(B) thiourea of the general formula of 1.0～10.0 weight parts shown in following (I) formula,
(in the formula, R and R
1Can be the same or different, be carbonatoms 18 alkyl at the most)
(C) sulphur of 0.1～10.0 weight part and/or sulfur donor,
(D) metallic compound of the conduct of 1.0～15.0 weight parts acid accepting agent, and, according to circumstances also have:
(E) dithiocar-bamate of 0.05～5.0 weight part or
(F) the mercapto-triazine compounds of the logical formula II of 0.01～2.0 weight part.
(R in the formula
2Expression sulfydryl or amino)
According to the present invention, also provide a kind of composition that (G) organo-peroxide of fusion 0.1～10.0 weight part forms in the above-mentioned ethylene chloride-propylene copolymers (A) of 100 weight parts.
The vulcanization curve figure that Fig. 1 measures for the disk mobilometer that uses each plate (composition) that obtains according to reference example 1 and reference example 2.Among this figure, the longitudinal axis is represented torque (kgcm), and transverse axis is represented curing time.In addition, a-1 and b-1 are the vulcanization curve of each composition of making by reference example 1 and reference example 2 respectively.
The cross-linking curve figure that Fig. 2 measures for the disk mobilometer that uses each composition that makes according to embodiment IV-1 and IV-5 and comparative example IV-1 and IV-8.In the figure, the longitudinal axis is represented torque (kgcm), and transverse axis is represented crosslinking time (branch).In addition, a-2, b-2 c-2, d-2 represent the cross-linking curve of the composition that makes according to embodiment IV-1, embodiment IV-5, comparative example IV-1 and comparative example IV-8 respectively.
The cross-linking curve figure that Fig. 3 measures for the disk mobilometer that uses each composition that obtains according to embodiment V-1 and V-2 and comparative example V-1 and V-9.Among this figure, the longitudinal axis is represented torque (kgcm), and transverse axis is represented crosslinking time.And a-3, b-3, c-3, d-3 represent the cross-linking curve of each composition of obtaining by embodiment V-1, embodiment V-2, comparative example V-1 and comparative example V-9 respectively.
Fig. 4 is for using the cross-linking curve figure that measures with the disk mobilometer of each composition of obtaining according to embodiment VI-1 and VI-3 and comparative example VI-1 and comparative example VI-11.The longitudinal axis is represented torque (kgcm) among this figure, and transverse axis is represented crosslinking time.And a-4, b-4, c-4, d-4 represent the cross-linking curve of the composition that obtains according to embodiment VI-1, embodiment VI-3, comparative example VI-1 and comparative example VI-11 respectively.
Fig. 5 is for using according to embodiment VII-1 and VII-4 and comparing VII-2 and the cross-linking curve figure of the disk mobilometer mensuration of each composition that VII-9 obtains.And a-5, b-5, c-5, d-5 represent the cross-linking curve of the composition that obtains according to embodiment VII-1, embodiment VII-4, comparative example VII-2 and comparative example VII-9 respectively.
Below, the present invention is specifically described.
(1) ethylene-propylene analog copolymer
When producing ethylene chloride of the present invention-propylene copolymers, the propylene content of raw material ethylene-propylene analog copolymer is 15～40(weight) %, 18～40(weight) % is better, 20～38(weight) % is good especially.
Using propylene content less than 15%(weight) ethylene-propylene copolymer when carrying out chlorination, the caoutchouc elasticity of the ethylene chloride-propylene copolymers that obtains is poor, not equal to goods are to be plastic-like.On the other hand, use propylene content to surpass 40%(weight) ethylene-propylene analog copolymer when carrying out chlorination, it is big that the particle of the ethylene chloride-propylene copolymers that obtains during chlorination becomes since in reaction system caking and unsatisfactory.
In addition, the MFR of this ethylene-propylene analog copolymer was generally 0.01～0.5 gram/10 minutes, and better good especially was 0.05～5.0 gram/10 minutes to 0.02～5.0 gram in/10 minutes.Using MFR to carry out under the chlorating situation less than/10 minutes ethylene-propylene analog copolymer of 0.010 gram, the processibility of the ethylene chloride-propylene copolymers that obtains is bad.On the other hand, when using MFR to carry out chlorination above/10 minutes ethylene-propylene analog copolymer of 5.0 grams, the reaction efficiency when producing owing to ethylene chloride-propylene copolymers is extremely low, and muriatic caking is serious, and unsatisfactory.
Have, this ethylene-propylene analog copolymer is generally more than 80 ℃ with the fusion peak value that DSC measures, and is preferably 80～125 ℃ again, and best is 85～125 ℃.When producing less than 80 ℃ ethylene-propylene analog copolymer with above-mentioned fusion peak value, it is block that product becomes, and can not obtain uniform muriate, and unsatisfactory.
Have, this ethylene-propylene analog copolymer is generally more than 3% with the degree of crystallinity of X-ray measuring, is preferably 3～50% again, and good especially is 3～45%.When producing less than 3% multipolymer with above-mentioned degree of crystallinity, it is block that product becomes, and can not obtain even muriate, and unsatisfactory.
Have, this ethylene-propylene analog copolymer is with molecular weight distribution index Mw/ Mn＞4 that GPC measures again, be preferably 8 or be lower than 8 since this index 4 when following, the muriatic processibility that obtains is bad, so unsatisfactory.
Mooney viscosity (the ML of this ethylene-propylene analog copolymer is arranged again
1+4, 100 ℃) and be 10～180, be preferably 10～170, good especially is 10～150.If when making mooney viscosity less than 10 ethylene-propylene analog copolymer chlorination, muriatic caking is serious in the chlorination process.On the other hand, when using mooney viscosity to be higher than 180 ethylene-propylene copolymer,, lack caoutchouc elasticity, and be plastic-like though the muriatic mechanical characteristics that obtains is very outstanding.
This ethylene-propylene analog copolymer is to obtain by each scope of using so-called Z-type catalyst to make ethene and copolymerization of propylene reach aforesaid propylene content, MFR and mooney viscosity, is material can industrial production, that utilize in many-side.
Ethylene chloride-propylene copolymers of the present invention can be produced by two sections or three-stage process chlorination of the present invention by making above-mentioned ethylene-propylene analog copolymer.
(2) first chlorination processs
According to first chlorination process of the present invention, in aqueous suspension, carry out fs and subordinate phase chlorination.When in this aqueous suspension, carrying out chlorination, make particulate state or pulverous above-mentioned ethylene-propylene analog copolymer outstanding turbid in water medium.For keeping this water to hang turbid state, preferably add a spot of emulsifying agent, clouding agent.At this moment, as required, also can add free radical generating agents such as benzoyl peroxide, Diisopropyl azodicarboxylate and hydrogen peroxide, the defoamer of light silicone oil etc. and so on and other additive.
(2-1) fs chlorination
Chlorination in fs is to carry out under the temperature of 25 ℃ of the fusing points that is lower than used ethylene-propylene analog copolymer at least.Especially, wish under the temperature that is lower than 30～60 ℃ of this multipolymer fusing points, to carry out.Carry out under the chlorating situation under the temperature that is lower than 25 ℃ of this multipolymer fusing points at least, the particle in the reaction does not lump, and can easily carry out follow-up subordinate phase chlorination.On the other hand, carry out under the chlorating situation under being lower than less than 25 ℃ temperature, particle lumps easily in the reaction, and reaction is difficult to proceed, and the chlorination degree of the resultant that obtains distributes also inhomogeneous.Chlorination in this fs is carried out being higher than under 50 ℃ the temperature.
In addition, in this fs, 20～60% the chlorination that total chlorination amount is carried out in requirement (for example, in that to produce cl content is 30%(weight) the situation of ethylene chloride-propylene copolymers of the present invention under, must produce cl content in this fs is 8～20%(weight) ethylene chloride-propylene copolymers), it is special that what wish is to carry out 20～55% chlorination.In this stage, carry out chlorination if less than 20% o'clock of perchlorizing amount, in follow-up subordinate phase chlorination reaction, the particulate caking takes place easily.
On the one hand, when the chlorination that surpasses 60%, owing to carry out inhomogenous chlorination, so the thermotolerance of the resultant that obtains and very poor in processability.
Carry out like this carrying out the chlorination of subordinate phase under the following conditions after the fs chlorination, then carry out the chlorination of phase III, just can produce ethylene chloride-propylene copolymers of the present invention.When the chlorination from the fs carries out the transition to the subordinate phase chlorination, the condition that can change in the reactor used in the chlorination of fs is carried out the chlorination of subordinate phase, also the aqueous suspension that contains chlorination ethylene-propylene analog copolymer by the chlorination production of fs can be moved on in another reactor that is controlled in advance under the subordinate phase chlorization condition.
(2-2) subordinate phase chlorination
The subordinate phase chlorination can be by being higher than the fs chlorination temperature more than 10 ℃, carries out chlorination under the temperature range of 5～15 ℃ of ethylene-propylene analog copolymer fusing points of use and finish and be lower than.Especially, hope be that the subordinate phase chlorination is being higher than the fs chlorination temperature more than 10 ℃, carry out but be lower than in the temperature range of 5～10 ℃ of this multipolymer fusing points.
Carry out under the subordinate phase chlorating situation being lower than under the temperature of this multipolymer fusing point below 5 ℃, generate the chlorination degree that does not have homogeneous and distribute, and its processibility and thermotolerance are very poor.On the other hand, be lower than under the used temperature of multipolymer fusing point more than 15 ℃, carrying out under the subordinate phase chlorating situation, the chlorination degree that resultant does not have homogeneous distributes, and its processibility and thermotolerance are very poor.
In above-mentioned fs and subordinate phase, require the 80～90%(carry out the chlorination amount to be preferably 65～90%, good especially is 70～90%) chlorination.For example in that to produce cl content be 30%(weight) the situation of ethylene chloride-propylene copolymers of the present invention under, it is desirable in fs and subordinate phase, producing chloride rate is 21～27%(weight) (it is desirable to 24～27%(weight)) ethylene chloride-propylene copolymers.Have again, require in this subordinate phase, to carry out the chlorination of perchlorizing amount at least 30%.When chlorination in this stage less than the perchlorizing amount 30% the time, when carrying out follow-up phase III chlorination, the heterogeneity chlorination takes place, and makes the thermotolerance of the resultant (ethylene chloride-propylene copolymers) that obtains inferior.And when this subordinate phase surpasses 90% chlorination of perchlorizing amount, because the resultant caking, and unsatisfactory.
Finish like this after the chlorination of subordinate phase,, just can produce ethylene chloride-propylene copolymers of the present invention by carrying out the phase III chlorination under the following conditions.When carrying out the transition to the phase III chlorination from the subordinate phase chlorination, the condition that can change in the reactor used in the subordinate phase chlorination is carried out the phase III chlorination, also the aqueous suspension that contains the ethylene chloride-propylene copolymers that is produced by the subordinate phase chlorination can be transferred in another reactor that is controlled in advance under the phase III chlorization condition, be carried out the phase III chlorination.
(2-3) phase III chlorination
Chlorination in this phase III can be by being lower than used ethylene-propylene analog copolymer fusing point, finishes but be not less than at least 10% the chlorination of carrying out the perchlorizing amount in the temperature range of fusing point-2 ℃.In being lower than the temperature range of this multipolymer fusing point more than 2 ℃, when carrying out the phase III chlorination, distribute because resultant does not have the chlorination degree of homogeneous, and its thermotolerance is very poor, so unsatisfactory.On the other hand, when carrying out chlorination under being higher than the temperature of this melting point polymer, resultant lumps easily, and its very poor in processability.In addition, if when surpassing 10% chlorination of perchlorizing amount in the phase III, can not get having desirable elastomeric muriate, its flexibility, thermotolerance and thermostability are all relatively poor.
In the chlorination of above fs to phase III, chlorine can use separately with gaseous state, perhaps uses with suitable inert gas dilution.Chlorine under this situation is introduced to press and is generally 5 kg/cm
2Below.Can reduce the understanding chlorating by the weight of measuring the chlorine of supplying with and carry out situation, can understand chlorination degree by the amount of measuring the hydrogenchloride that generates.This is to also being same in other following method.
(3-1) subordinate phase slow coolingization
According to other method of the present invention, after the fs of above-mentioned (2-1) chlorination, carry out slow coolingization and chlorination.
Slow coolingization in the subordinate phase can be raised to the temperature that is higher than 1-7 ℃ of this ethylene-propylene analog copolymer fusing point by the temperature that makes reaction system, does not introduce chlorine under this temperature, and its slow cooling was finished in 10-60 minute.Especially, wish under the temperature that is higher than 1-6 ℃ of this ethylene-propylene analog copolymer fusing point (best is 1-5 ℃), to carry out.Have, the needed time of slow cooling is generally 10-60 minute, is preferably 10-50 minute again, and best is 10-40 minute.When slow coolingization had been lower than ethylene-propylene analog copolymer fusing point and carries out under less than 1 ℃ temperature, the resultant (ethylene chloride-propylene copolymers) that obtains by chlorination in the following phase III did not have the chlorination degree of homogeneous.On the other hand, when under the temperature that is higher than 7 ℃ of this multipolymer fusing points, carrying out,, and can not obtain good goods because the resultant that obtains by the chlorination of carrying out the follow-up phase III is easy to caking.Have, when carrying out less than 10 minutes slow cooling, because slow cooling is insufficient, and the ethylene chloride-propylene copolymers that finally obtains is bad again.On the other hand, when the slow cooling that surpasses 60 minutes, not only can not further improve the ethylene chloride-propylene copolymers that finally obtains, and because the problem on the cost, and impracticable.
(3-2) phase III chlorination
The chlorination of phase III can be finished by carry out remaining chlorination under the temperature that is lower than 2-25 ℃ of employed ethylene-propylene analog copolymer fusing point.Especially, wish under the temperature that is lower than 2-23 ℃ of this multipolymer fusing point, to carry out, and under the temperature that is lower than 2-20 ℃ of this multipolymer fusing point, carry out best.If the ethylene-propylene analog copolymer fusing point that uses is not when carrying out chlorination under 2 ℃ the temperature,, and can not obtain good goods because resultant easily lumps in being lower than this phase III chlorination.On the other hand, when being lower than the temperature of this multipolymer fusing point more than 25 ℃ and carrying out chlorination, the chlorination skewness one of the ethylene chloride-propylene copolymers that obtains, and can not obtain having outstanding stable on heating resultant.
According to the present invention, can also be by as previously mentioned, in the chlorination (2-1) of fs afterwards, carry out the subordinate phase chlorination under the following conditions and produce ethylene chloride-propylene copolymers of the present invention.When the chlorination from the fs carries out the transition to the chlorination of subordinate phase, the condition in reactor used that can change in the fs chlorination is carried out the chlorination of subordinate phase, also can carry out chlorination in another reactor under being controlled at the subordinate phase chlorization condition in advance.
(4) subordinate phase chlorination
The subordinate phase chlorination can be by being higher than the fs chlorination temperature more than 10 ℃, carries out remaining chlorination in the temperature range of 5-15 ℃ of ethylene-propylene analog copolymer fusing point of use and finish but be lower than.Especially, wish to be higher than the fs chlorination temperature more than 10 ℃, carry out but be lower than in the temperature range of 5-10 ℃ of this multipolymer fusing point.Carrying out under the subordinate phase chlorating situation under the low scope more than 5 ℃ than this multipolymer fusing point, resultant does not have uniform chlorine and distributes, and its processibility and thermotolerance are very poor.On the other hand, under the situation when under low temperature more than 15 ℃, carrying out this chlorination, distribute, and its processibility and thermotolerance are very poor because resultant does not have uniform chlorine than this multipolymer fusing point in stage, and unsatisfactory.
Ethylene chloride-the propylene copolymers that will make with above-mentioned each method, remove the hydrochloric acid, emulsifying agent etc. of attachment removal by washing after, drying can be produced ethylene chloride-propylene copolymers of the present invention.
(5) rerum natura of ethylene chloride-propylene copolymers, mechanical characteristics etc.
The chloride rate of the ethylene chloride-propylene copolymers that obtains like this is a 20-45%(weight), be preferably 20～42%(weight), best is 25～42%(weight).If the chloride rate of this ethylene chloride-propylene copolymers is less than 20%(weight) time, existing problems aspect recovery and the refining ethylene chloride-propylene copolymers that obtains, and it also lacks resistivity against fire.On the one hand, when chloride rate surpasses 45%(weight) time, the ethylene chloride-propylene copolymers of generation, by having reduced thermostability and thermotolerance significantly, and unsatisfactory.
The mooney viscosity of the ethylene chloride-propylene copolymers that more than obtains is determined as the 10-150 point with big garden tube (Large Roter) down at 100 ℃, is preferably 10～120 points, and best is 15～100 points.
In addition, the melting index of ethylene chloride-propylene copolymers of the present invention (is pressed ASTM D 1238,180 ℃ of temperature, loading is measured down for 21.6 kilograms, to call FR in the following text) be generally 1～100 gram/10 minutes, be preferably 3～50 grams/10 minutes, best is 5～30 grams/10 minutes.
The representative characteristic of ethylene chloride-propylene copolymers of the present invention is as follows.
Density is 1.00～1.30 gram/cubic centimetres, and in the tension test of measuring according to ASTM D530～60T, fracture tensile strength is 5～7 kilograms/square centimeter, and extension at break is 800～2500%, and hardness (Shore-A) is 30～70.
(6) mix manufacturing process
When ethylene chloride of the present invention-propylene copolymers hybrid shaping, generally also can in used ethylene chloride-propylene, add lubricant, tinting material, charged preventor, weighting agent and the additive of stablizer of oxygen, light and heat and so on is cooperated with it.The ethylene chloride of all right mixed universal, styrene butadiene class copolymer rubber, acrylonitrile-butadiene class copolymer rubber, with ethene and propylene is the binary or the terpolymer rubber of main component, chloroprene class rubber, chlorosulfonated polyethylene rubber shape material, the rubber rubber-like substance of butadiene homopolymerization rubber and natural rubber and so on, and polyvinyl chloride, with ethene and/or propylene is the olefine kind resin of main component, with the methyl methacrylic acid ester is the methyl methylacrylic acid esters resin of main component, the arborescens thing of graft polymerization thing that the graft polymerization of at least a material of the ethylene compounds of acrylonitrile-styrene copolymerized resin and methyl iso-butylene phenolic ester and so on obtains and so on.
When producing these compositions, cooperation wherein (mixing) method can be used this technical field mixing machine commonly used, as open type cylinder, dry-mixed machine, closed mixing roll and kneader, mixes.In these blending meanss,, can adopt these two or more methods (for example, after mixing with dry-mixed machine earlier, the mixture that obtains being used form cylinder blended method again) for obtaining the more composition of homogeneous.In these blending meanss, when mixed chlorinated ethylene-propylene analog copolymer and rubber, mixing temperature is 30～120 ℃, is generally 50～100 ℃.Particularly when mixing, owing to the cohesive force of rubber is generated heat, so it is desirable to mixing temperature is controlled at below 150 ℃.In addition, when mixed chlorinated ethylene-propylene analog copolymer and resinous substance, it is desirable to more than their melt temperature, but in the scope below 180 ℃, carry out.
Normally used extrusion moulding machine, injection molding forming in forming mill such as ordinary rubber industry and the resin industry with ethylene chloride-propylene copolymers of the present invention and their composition, compressing forming machine and rolling press re-use after being configured as desired shape.In addition, under the situation of the ethylene chloride-propylene copolymers that only is shaped, its forming temperature is 70～130 ℃, is generally 90～120 ℃.
(7) sulfuration composition of the present invention
(A) ethylene chloride-propylene copolymers
Produce with aforesaid method as ethylene chloride-propylene copolymers that (A) composition of the present composition uses.
(B) thiourea
Used thiourea is stated as above-mentioned general formula (I) and is shown among the present invention.
Alkyl wherein is selected from alkyl, cycloalkyl, aryl and the aralkyl, can provide methyl, propyl group, butyl, cyclohexyl, phenmethyl as concrete example.
As such thiourea, can provide N, N '-diphenyl thiourea, N, N '-diethyl thiourea, N, N '-two support thiocarbamide, N, N '-dibutyl thiourea, N, N '-dilauryl thiocarbamide etc.Especially, N, N '-diethyl thiourea is the most suitable.
(C) sulphur and sulfur donor
In the sulphur and sulfur donor as (C) composition use among the present invention, sulfur donor is meant the compound that can emit sulphur at comparatively high temps (general 50～200 ℃) down.The typical example of this sulfur donor is in the material of record in the 19th and 57 page of " brief guide, rubber moulding mixture compounding chemicals " (ラ バ-ダ ィ ジ ェ ス ト society sheet, 1974 distribution), has the above polysulfide bonded material of disulphide.
In these sulfur donors, tetramethyl-thiuram disulfide, curing two pentamethylene thiurams, four sulfurations, two pentamethylene thiurams are arranged as representative.In these sulfur donors, good especially is the compound (as four sulfurations, two pentamethylene thiurams) of emitting sulphur in 100～200 ℃ of scopes.In addition, the sulphur compound of putting down in writing in the 3rd～5 page in the above-mentioned publication also usually uses as sulfur donor.The representative of this sulphur compound has sulfur monochloride, sulfur dichloride, sulfuration morpholine and curing alkylphenol.
Have, the typical example of the sulphur that uses among the present invention is recorded in the 1st～3 page of above-mentioned publication again.Its typical example has powder sulphur, sulfuration, sedimentation sulphur, sulfoid and surface treatment sulphur.
(D) metallic compound
The sour accepting agent metallic compound that (D) composition uses as in the present invention has oxide compound, oxyhydroxide, carbonate, carboxylate salt, silicate, borate and the phosphite of periodic table of elements II family metal and oxide compound, subcarbonate, alkali formula carboxylate salt, alkali formula phosphite, alkali acid sulphite and three subsulphates of periodic table of elements IV a family metal.
The typical example of this metallic compound has magnesium oxide, magnesium hydroxide, magnesiumcarbonate, hydrated barta, barium carbonate, calcium oxide (unslaked lime), calcium hydroxide (slaked lime), lime carbonate, Calucium Silicate powder, calcium stearate, calcium phthalate, phosphorous acid magnesium, phosphorous acid calcium, stannic oxide, yellow lead oxide, red lead, white lead, dibasic lead phthalate, two white lead carbonates, lead stearate, alkali formula Lead Phosphite, Dibasic (Coated), alkali formula phosphorous acid tin, basic lead sulfite, tribasic lead sulfate etc.
The median size of this metallic compound is generally 0.1～100 micron, is preferably 0.2～100 micron, and good especially is 0.5～50 micron.If use flat about particle diameter to be lower than 0.1 micron metallic compound, disperse when mixing, exist problem in the processing.On the other hand, when using particle diameter to surpass 100 microns metallic compound,, the secondary aggegation is difficult to make its homodisperse owing to taking place easily.
When producing ethylene chloride of the present invention-propylene copolymers composition, not only can be by in ethylene chloride-propylene copolymer, sneaking into above thiourea, sulphur and/or sulfur donor and sour accepting agent metal oxide is sneaked into the purpose metal oxide, and can in them, further sneak into other vulcanization accelerator.
(E) dithiocar-bamate
As the compound of dithiocar-bamate shown in following general formula (III) of (E) composition use among the present invention,
In (III) formula, R
3And R
4Can be the same or different, perhaps can mutually combine circlewise.R
3And R
4Be the alkyl of 18 carbon atoms at the most.As what this alkyl can provide alkyl, cycloalkyl, aryl and aralkyl arranged.In addition, M be metal (as, tellurium, selenium, sodium, potassium, lead, copper, zinc, iron, bismuth, cadmium, cobalt, magnesium, manganese) and amine (as dimethylamine, diethylamine, dibutylamine, N, N '-dimethyl urotropin, piperidines, pipecoline), X is 1～4 integer.
As having that the typical example of this dithiocar-bamate can provide: Sodium dimethyldithiocarbamate 40min, Thiocarb, di-n-butyl dithiocarbamate sodium, pentamethylene thiocarbamate sodium, potassium dimethyldithiocarbamate, second, n-butyl dithiocarbamate potassium, lead dimethyl dithiocarbamate, pentamethylene thiocarbamate lead, ethylphenyl dithiocarbamate lead, ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocaarbamate, the bibenzyl zinc dithiocarbamate, N-pentamethylene thiocarbamate zinc, zinc-ethylphenyl dithiocarbamate, Selenium dimethyl dithiocarbamate, selenium diethyl dithiocarbamate, tellurium diethyl dithiocarbamate, cadmium diethyl dithiocarbamate, pentamethylene dithiocarbamic acid cadmium, cupric dimethyldithiocarbamate, ferric dimethyl dithiocarbamate, bismuth dimethyl dithiocarbamate.The N of dimethyl dithiocarbamic acid Dimethyl Ammonium, dibutyl dithiocaarbamate dibutyl ammonium, diethyldithiocar bamic acid dihexyl ammonium, dibutyl dithiocaarbamate, N '-dimethyl ammonioformaldehyde salt, pentamethylene dithiocarbamic acid piperidines, methyl pentamethylene dithiocarbamic acid pipecoline.
(F) mercapto-triazine compounds
The mercapto-triazine compounds that uses as (F) composition is the material that is used as vulcanizing agent or vulcanization accelerator in the rubber industry field in the present invention, shown in above-mentioned general formula (II).
In above-mentioned (II) formula, R
2In amino can be to have the amino that carbonatoms is at most 20 alkyl.
As having that the typical example of this mercapto-triazine compounds can provide: 1,3, oneself is amino-3 for 5-trithio cyanuric acid, 1-two, 5-diethyl mercapto-triazine, 1-diethylin-3,5-dimercapto triazine, 1-hexamethylene amino-3,5-dimercapto triazine etc.This compound write up is in No. 99, the open communique 59-100 of Japanese Patent.
(X) other vulcanization accelerator
Arbitrarily used in the present invention other vulcanization accelerator is for being widely used as the compound of vulcanization accelerator in the ordinary rubber industrial circle.What their typical example can provide has: the guanidine compound of di-o-tolylguanidine etc.; Aldehyde-the amine and the aldehyde-ammoniac compounds of the condenses of the reactant of acetaldehyde-aniline, the condenses of butyraldehyde-aniline, butyraldehyde-butylamine, (ring) vulkacit H, aldamine etc.; The thiazoles and the imidazolines of the hexamethylene ammonium salt of the sodium salt of 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, N cyclohexyl 2 benzothiazole sulfenamide, 2-mercaptoimidazoline (ethylene thiourea) etc.; The thiourea of diethyl thiourea, di-o-tolyl-thiourea etc.; The thiuram compound of tetramethylthiuram monosulfide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, four sulfurations, two pentamethylene thiurams etc.; The dithiocarbamate(s) compound of Sodium dimethyldithiocarbamate 40min, di-n-butyl dithiocarbamate sodium, Selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, piperidines pentamethylene dithiocar-bamate etc.; The cellulose xanthate compounds of dibutyl xanthogenic acid zinc, Good-Rite Nix etc.; The mixed accelerators of mixture, heterogeneous ring compound and the guanidine derivative of mixture, tetramethyl-thiuram disulfide and the mercaptobenzothiazole of mixture, ziram and the tetramethyl-thiuram disulfide of mixture, mercaptobenzothiazole and the dithiocar-bamate of mercaptobenzothiazole and (ring) vulkacit H and the mixing resultant of amine etc.; And other promotor of pyrrolotriazine derivatives etc.In addition, be recorded in day disclosure communique 59-15440 number as the typical example of nucleophilic reagent and vulcanization accelerator as the Phosphorus compound of the aminated compounds of record in the 64th page to the 67th page in above-mentioned publication and record in the 64th page to the 170th page of above-mentioned publication.
(8) proportion of composing
Proportion of composing with respect to other component of 100 weight part ethylene chloride-propylene copolymers (A) is as follows.
Thiourea (B) is 1.0～10.0 weight parts, with 2.0～10.0 weight parts for well, 3.0～10.0 weight parts preferably.If the proportion of composing of thiourea is limit less than it, the sulfuration of the composition that makes will be insufficient.On the other hand, the cooperation ratio surpasses the upper limit, can not further improve sulfuration.
The proportion of composing of sulphur and sulfur donor (C), its total amount are 0.1～10.0 weight part, with 0.1～7.0 weight part for well, 0.2～7.0 weight part preferably.If its insufficient total amount 0.1 weight part of the proportion of composing of sulphur and sulfur donor then can not get the good composition of the property vulcanized.On the other hand, if proportioning surpasses 10.0 weight parts, not only the property vulcanized can not further improve, and the caoutchouc elasticity of sulfide also can reduce.
The proportion of composing of metallic compound (D) is 1.0～15.0 weight parts, and for well, the best is 3.0～12.0 weight parts with 2.0～15.0 weight parts.If the proportion of composing of metallic compound (D) is less than 1.0 weight parts, dehydrochlorination reaction can take place in ethylene chloride-propylene class co-polymer.On the other hand, if proportioning surpasses 15.0 weight parts, not only can not further prevent dehydrochlorination reaction, processibility also can degenerate, thereby the sulfide rubber intensity that makes will reduce.
The proportion of composing of dithiocar-bamate (F) is 0.05～5.0 weight part, and for well, 0.1～4.0 weight part is best with 0.1～5.0 weight part.The proportion of composing of dithiocar-bamate is during less than 0.05 weight part, and the cure efficiency of the composition that makes is poor, and the improved effect of compressive permanent strain etc. is poor.On the other hand, if proportioning surpasses 5.0 weight parts, in the shaping thing of the composition that makes phenomenon of deflation is arranged not only, Combination and plasticity also descend.
The proportion of composing of mercapto-triazine compounds (F) is 0.01～2.0 weight part with 0.02～1.5 weight part for well, and the best is 0.1～1.2 weight part.When the mercapto-triazine compounds is lower than 0.01 weight part, be difficult to the crosslinked so that crosslinked tension of control.On the other hand, proportioning is if surpass 2.0 weight parts, and the tearing property of the cross-linking agent that then makes in high temperature is poor, thereby bad.
In addition, when adding other vulcanization accelerator (X) except that above-mentioned, its proportioning mostly is 10.0 weight parts most.
(9) blending means, vulcanization process, forming method etc.
The even fusion of above material can be made the present invention's composition, also can add various additives, the weighting agent that as in the rubber industry, uses, plasticizer, to oxygen, ozone, heat and light (ultraviolet ray) stable stablizer, lubricant and tinting material etc. according to the application target of composition.In addition, also can cooperate with general chlorinatedpolyethylene, styrene butadiene class copolymer rubber, the acrylonitrile-butadiene copolymer rubber is the binary of main component or the rubber of terpolymer rubber, chloroprene class rubber, chlorosulfonated polyethylene rubber shape thing, butadiene homopolymerization rubber and natural rubber and so on ethene and propylene.
In order to make the present invention's composition, can adopt the mixing of carrying out usually in the rubber industry.When making said composition, it is very important that ethylene chloride-propylene class concurrent mixture does not vulcanize this in essence.Therefore, mix generally and can under room temperature to 100 ℃, carry out.
With the composition that obtains thus, with general single-lead-screw extruding briquetting machine in the ordinary rubber industry, injection moulding forming machine, compacting shape machine etc. are made desirable shape.
Sulfuration is normally carried out in the moulding process in 100～200 ℃ of temperature ranges, or by vapor can, airbath heating.Curing time is different with curing temperature. but be generally 0.5～120 minute.
(10) bridging property ethylene chloride-propylene copolymers composition
According to another embodiment of the present invention, can be provided at the crosslinkable composite that mixes organo-peroxide (G) in above-mentioned ethylene chloride-propylene copolymers (A).
There is no particular limitation to the organo-peroxide that uses among the present invention, but be that 120 ℃ material is an ideal with decomposition temperature (transformation period is 1 minute a temperature), the best more than 140 ℃.Typical example as best organo-peroxide; can exemplify peroxidation 1; 1-pair-tertiary butyl, peroxidation 3; 3; the ketone of 5-trimethyl-cyclohexane and so on, 2,5-dimethylhexane-2, the hydroperoxide of 5-dihydro-peroxidase and so on, 2; 5-dimethyl-2, the dialkyl peroxide of the diacyl peroxide of the peroxidation ethene of 5-ditertiary butyl peroxide and so on, benzoyl superoxide and so on and dicumyl peroxide and so on.
In addition, also can mix in the General Purpose Rubber field the multi-functional material of the triaryl cyanurate that uses as crosslinking coagent and triaryl isocyanurate and so on.
Owing to mixed the mercapto-triazine compounds, then can improve the tear strength of composition under comparatively high temps.This mercapto-triazine compounds uses as vulcanizing agent or vulcanization accelerator in rubber industry, represents with above-mentioned general formula (II).
When making the present invention's composition, also can mix the following metallic compound of use as the sour accepting agent that prevents dehydrochlorination.
The blending ratio of organo-peroxide is 0.1～10.0 weight part, with 0.5～10.0 weight part for well, 0.5～8.0 weight part preferably.During with respect to organo-peroxide proportioning less than 0.1 weight part of 100 weight part ethylene chloride-propylene copolymers, can not obtain the good composition of mechanical characteristics, and in case surpass 10.0 weight parts, then can problem be arranged at aspects such as flexibilities.
When mixing mercapto-triazine, with respect to 100 weight part ethylene chloride-propylene copolymers, its blending ratio mostly is 2 most.0 weight part wishes 0.01～2。0 weight part, for well, the best is 0.1～1.2 weight part with 0.02～1.5 weight part.If with respect to 100 weight part ethylene chloride-propylene copolymers, blended mercapto-triazine amount surpasses 2.0 weight parts, and bridging property reduces.
During mixed-metal compounds, its blending ratio generally mostly is most 15.0 weight parts, and for well, hope is 2.0～15.0 weight parts with 1.0～15.0 weight parts, and 3.0～12.0 weight parts are best.If combined amount surpasses 15.0 weight part not only can not further prevent dehydrochlorination reaction, and processibility also can variation, and then the rubbery intensity of the cross-linking agent that makes will reduce.
When making composition of the present invention, its mixing (mixing) method can adopt the general form cylinder that uses in this technical field, the mixing machine of dry-mixed machine, closed muller and kneading machine and so on.In order to obtain more uniform composition, can in these blending meanss, adopt two or more method (after for example mixing with dry-mixed machine in advance, its mixture being carried out the blended method with the open type cylinder again).In these blending meanss, if will implement under higher temperature when fusion is mixed, part or all of the ethylene chloride-propylene copolymers of use is crosslinked sometimes, therefore is necessary usually implementing below 70 ℃.
When making bridging property ethylene chloride of the present invention-propylene class copolymer composition, also can be blended in the additive that adds in the chlorinatedpolyethylene of common usefulness, for example the stablizer of lubricant, tinting material, charged preventor, weighting agent and antioxygen, light and heat etc.In addition, also can mix chlorinatedpolyethylene with common usefulness, styrene butadiene class copolymer rubber, acrylonitrile-butadiene class copolymer rubber, be the binary of main component or terpolymer rubber, chloroprene class rubber, chlorosulfonated polyethylene rubber shape thing, the rubber of butadiene homopolymerization rubber and natural rubber and so on ethene and propylene.
Composition of the present invention also can adopt the shaper of the normally used single-lead-screw extruding briquetting machine of ordinary rubber industry, injection mould shaper, compacting shape machine and rolling press moulding and so on to make it to form the form of dust seal.While can also adopt interpolation ethylene chloride-propylene copolymers or above-mentioned various groups to close thing And and carry out the general crosslinked method of making forming composition in the rubber technology field in addition, just can adopt and make method ， And crosslinked and that moulding is carried out simultaneously can adopt the shaper of calendering formation machine and so on to make it to form desirable shape.
Ethylene chloride-propylene copolymers that the present invention makes can prove absolutely that not only the common chlorinatedpolyethylene of its sulfuration propertyization is good by Fig. 1～Fig. 5, also has following effect.
(1) ozone resistance is good.
(2) rebound resilience is good.
(3) flame retardancy is good.
(4) weathering resistance and weather resistance are good.
(5) resistance to breakage and other physical strength are all fine.
(6) oil-proofness is good.
(7) thermotolerance and low temperature properties are good.
(8) binding property is good.
Ethylene chloride-propylene copolymers of the present invention has above-mentioned various excellent characteristic, therefore can utilize widely.Below enumerate the typical application example.
(1) by carrying out the resin fusion with polypropylene, acrylonitrile-butadiene-styrene ternary copolymerized resin (ABC resin), high density polyethylene(HDPE), new LDPE (film grade), ethylene chloride resin etc., not only can improve the flame retardancy of these resins, can also improve its mechanical characteristics (for example, shock-resistance).
(2) by sneaking into the difficult burning agent of general use, then can make harder nonflammable material utilization.
(3) the various parts of using on the automobile.
(4) coating material of electric wire.
(5) jointing material.
(6) parts of electronics, electric installation etc.
Can bring into play following effect by the composition that the present invention makes.
(1) physical strength (as tensile strength) is good.
(2) dimensional precision of forming composition is good.
(3) resistance to chemical reagents, weathering resistance are good.
(4) compressive permanent strain is good.
(5) bridging property of cross-linking agent is good.
(6) thermotolerance is good.
Embodiment and comparative example
Embodiment, comparative example and reference example below are shown, so that illustrate in greater detail the present invention, but Fan Wei And of the present invention is not limited to these embodiment.
In following embodiment, measure its rerum natura with following method.
Tensile strength: ASTM D530-60T(tensile strength: 500
The mm/ branch)
Elongation: ASTM D530-60T
Compressive permanent strain: ASTM D395(A method)
Mooney viscosity: 100 ℃ of preheatings 1 of ASTM D927-57T(temperature
Minute, big rotating cylinder (Lanre Rotor uses, the value after 4 minutes) thermotolerance: ASTMD573-53
Resistance to breakage: ASTM D624-54(B method)
Melting index (MFR): ASTM D1238(condition L)
Melting index (FR): 180 ℃ of ASTM D1238(temperature, lotus
Weigh 21.6kg）
Hardness: ASTM D676-59T
Test film
The dumb-bell(dumb-bell shape) test film: ASTM D412-61T
Thickness: ASTM D-15
Embodiment I-1
80 premium on currency of in the autoclave of 100 liters of glass inner-linings, packing into, the propylene content of 80 gram sodium laurates and 10 kilograms is a 22(weight) %, mooney viscosity (MI
α+4, 100 ℃) be 115 ethylene-propylene analog copolymer (MFR1.0 gram/10 minutes, 120 ℃ of fusing points, degree of crystallinity 5.1%, Mw/Mn=5.0, hereinafter referred to as " EPR(I-I) ") limit stirs, and carries out chlorination in 50～90 ℃ of temperature ranges, reaches 18 until the chloride rate of this multipolymer.2(weight) %(fs chlorination).Then making reaction system be warming up to 105～115 ℃ ， And, to carry out chlorination in this temperature range be 27 up to chloride rate.1(weight) %(subordinate phase chlorination).In 118～120 ℃ of temperature ranges, carry out chlorination subsequently and reach 30.2(weight up to chloride rate) %(phase III chlorination), thereby make ethylene chloride-propylene copolymers (to call " CLEPR(I-A) " in the following text).
Embodiment I-2
Carry out the fs chlorination with embodiment I-1 similarity condition.Then reaction system is warming up to 105～115 ℃, carrying out chlorination at this temperature Fan Fannei is 36 until chlorinity.1(weight) %(subordinate phase chlorination).In 118～120 ℃ of temperature ranges, carry out chlorination subsequently and reach 41 until chloride.1(weight) %(phase III chlorination), thus make ethylene chloride-propylene copolymers (hereinafter referred to as " CLEPR(I-B) ").
Embodiment I-3
Adopting propylene content is 24.5(weight) %, mooney viscosity (ML
1+4, 100 ℃) and be 34.1 ethylene-propylene analog copolymer (MFR:4.8g/10 branch, degree of crystallinity: Mw/Mn=7 3.5%.5, fusing point: 80 ℃) to replace the EPR(I-1 of use in the embodiment I-1).And carries out the fs chlorination and reaches 17.6(weight until chlorinity in 50～55 ℃ of temperature ranges) %.Then, in 65～75 ℃ temperature range, carry out the subordinate phase chlorination and reach 26 until chlorinity.8(weight) %.And then, in 78～80 ℃ temperature range, carry out chlorination (phase III chlorination), be 31.3(weight thereby make chlorinity) ethylene chloride-propylene copolymers of % (hereinafter referred to as " CLEPR(I-C) ").
Comparative example I-1
Removing and adopting propylene content is 31.8(weight) %, mooney viscosity (ML
1+4, 100 ℃) and be 58.7 ethylene-propylene analog copolymer (MFR:8.2g/10 branch, degree of crystallinity: 2.5%，Mw/Mn＝3。8, fusing point: 35 ℃) to replace the EPR(I-1 of use in the embodiment I-1) outside, other conditions are all identical with embodiment I-1, carry out the fs to the phase III chlorination.Chlorinity in the ethylene chloride-propylene copolymers that makes (hereinafter referred to as " CLEPR(I-D) ") is 30.3(weight) %.
Comparative example I-2～I-7
With the EPR(I of using in the embodiment I-1-1), in the temperature shown in the table I-1, carry out chlorination until reaching the chlorinity shown in the table I-1, thereby implement fs chlorination separately.Subsequently, (subordinate phase chlorination) ， And makes muriate each muriate that so obtains to be carried out chlorination immediately in the temperature range shown in the table I-1.And then, shown in table I-1, carry out chlorination (phase III chlorination) like that, thereby make ethylene chloride-propylene copolymers with the chlorinity shown in the table I-1.
In comparative example I-1, produce agglomerate in the fs chlorination process of I-2 and I-5, thereby can not get good goods.The skewness that chlorine in the subordinate phase chlorination process of comparative example I-3, occurs.In the comparative example I-4, in the subordinate phase chlorination process, produce agglomerate, and the skewness of chlorine, thereby can not obtain good ethylene chloride-propylene copolymers.
The various rerum naturas of each ethylene chloride-propylene copolymers that embodiment I-1 to I-3 and routine I-6 and I-7 made are measured.It the results are shown in table I-2.
Reference example
The sulfuration of ethylene chloride-propylene copolymers that the present invention is made and general commercially available chlorinatedpolyethylene compares research.
Reference example 1
In 100(weight) mix magnesium oxide 10 weight parts that receive as acid in part CLEPR(I that makes by embodiment I-1-A), as carbon black (asahi carbon system, the SRF of weighting agent
#50, mean particle size 90nm) 50 weight parts are as trioctyl trimellitate 30 weight parts of plasticizer, as sulphur 0.5 weight part of vulcanizing agent and as the diethyl thiourea 4 of vulcanization accelerator.5 weight parts, at room temperature the type of service cylinder makes them fully mix clock And making in 20 fens in flakes.
Reference example 2
Remove to adopt that pre-molecular weight is about 200,000, density is 0.The outstanding turbid method of the high density polyethylene(HDPE) water of 95 gram/square centimeters makes it the mooney viscosity (MS that chlorination makes
1+4, 100 ℃) and be 70, chlorinity is 30.3(weight) the CLEPR(I-1 of the chlorinatedpolyethylene of % to replace using in the embodiment I-1), other are all identical with reference example 1, mix and practice the And making in flakes.
With reference example I (a-1) and the reference example 2(b-1 that makes thus) each sheet material be that 165 ℃ and angle are to observe its sulfided state with the rheological test machine under the conditions of 3 degree in temperature.Their vulcanization curve is shown in Fig. 1.
Embodiment II-1
The propylene content of 80 gram sodium laurates and 10 kilograms of packing in the autoclave of 100 liters of glass inner-linings is a 22(weight) %, and mooney viscosity (ML
1+4, 100 ℃) and be 115 ethylene-propylene analog copolymer (MFR1.The 0g/10 branch, degree of crystallinity 6.2%, Mw/Mn=6.1,120 ℃ of fusing points, hereinafter referred to as " EPR(II-1) ", stirring And carries out chlorination and reaches 18 until the chlorinity of this multipolymer in 50～90 ℃ temperature range.2(weight) %(fs chlorination).Reaction system is warming up to 121～125 ℃ subsequently, does not feed chlorine in this temperature range, And carries out 30 minutes slow cooling (subordinate phase slow cooling).Then, make the reaction system cooling in 95～118 ℃ temperature range, carry out chlorination and reach 30 until chlorinity.4(weight) %(phase III chlorination), thus make ethylene chloride-propylene copolymers (hereinafter referred to as " CLEPR(II-A) ").
Embodiment II-2
Use propylene content to be 24.5(weight) %, and mooney viscosity is (ML
14, 100 ℃) and be 34 ethylene-propylene analog copolymer (MFR4.8g/10 branch, degree of crystallinity 3.2%, Mw/Mn=5.2,80 ℃ of fusing points) EPR(II-1 to replace using in the embodiment II-1), in temperature is 50～55 ℃ scope, carry out the fs chlorination equally with embodiment II-1.The muriatic chlorinity that obtains in this stage is 18.2(weight) %.Subsequently, this reaction system is heated up, in 85～87 ℃ temperature range, carry out the subordinate phase slow cooling equally) with embodiment II-1.Then, with reaction system cooling, carrying out the phase III chlorination in 55～78 ℃ temperature range is 30.5(weight until chlorinity) %, thus make ethylene chloride-propylene copolymers (hereinafter referred to as " CLEPR(II-B) ").
Embodiment II-3
Use the EPR(II of using in the embodiment II-1-1), carrying out the fs chlorination with embodiment II-1 the same terms is 21 until chlorinity.5(weight) %.Subsequently, carrying out subordinate phase slow cooling and phase III chlorination equally with embodiment II-1, is 40 thereby make chlorinity.3(weight) ethylene chloride-propylene copolymers of % (hereinafter referred to as CLEPR(II-C)).
Comparative example II-1
Removing and using propylene content is 31.8(weight) %, mooney viscosity (ML
1+4100 ℃) be 58.7(weight) the ethylene-propylene analog copolymer of % (MFR:8.2 gram/10 minutes, degree of crystallinity: 2.5%, Mw/Mn=3.8,35 ℃ of fusing points) the EPR(II-1 to replace using in the embodiment II-1), carry out fs chlorination and subordinate phase chlorination (not implementing the subordinate phase slow cooling) equally with embodiment II-1.The ethylene chloride that makes-propylene class interpolymer (to call " CLEPR(II-D " in the following text), chlorinity be 31.5(weight) %.
Comparative example II-2～II-7
With the EPR(II of using in the embodiment II-1-1) in the temperature range of table shown in the II-1, carry out chlorination until reaching the chlorinity shown in the table II-1, thus implement fs chlorination separately.Subsequently, each muriate that so obtains is carried out subordinate phase And immediately and then carry out chlorination (phase III chlorination) in the temperature range shown in the table II-1 in the temperature range shown in the table II-1, thereby make ethylene chloride-propylene copolymer with the chlorinity shown in the table II-1.
1) chlorinity of each the ethylene chloride-propylene copolymer after the phase III chlorination
In comparative example II-1, in the fs chlorination of II-2 and II-5, can not obtain good goods owing to lump; And in the subordinate phase chlorination of comparative example II-3 and II-4, though do not lump the chlorine skewness.
Carry out the characteristic measurement of various ethylene chloride-propylene copolymers of being obtained by embodiment II-1 to II-3 and comparative example II-6 and II-7, it the results are shown in table II-2.
Embodiment III-1
80 premium on currency of packing in the autoclave of 100 liters glass inner-linings, the propylene content of 80 gram sodium laurates and 10 kilograms is 22 weight %, and mooney viscosity (ML
1+4100 ℃) be 115 ethylene-propylene analog copolymer (MFR:1.0 gram/10 minutes, fusing point: 120 ℃, degree of crystallinity: 6.2%, Mw/Mn=6.1, to call " EPR(III-1) " in the following text), on one side stir, on one side in carry out under 50-90 ℃ the cl content of chlorination until this polymkeric substance be 18.2 weight % till (fs chlorination).Then reaction system is warming up to 105-115 ℃, and in this temperature range, carries out chlorination (subordinate phase chlorination) till cl content reaches 31.3 weight %, thereby make ethylene chloride-propylene copolymers (calling " CLEPR(III-A) " in the following text).
Embodiment III-2
The heavy % of the cl content chlorination to 40.1 of last gained ethylene chloride-propylene copolymers in making embodiment III-1 and, with embodiment III-1 similarity condition under carry out chlorination, thereby make ethylene chloride-propylene copolymers (calling " CLEPR(III-B) " in the following text).
Embodiment III-3
Removing and adopting propylene content is 24.5 weight %, and mooney viscosity (ML
1+4100 ℃) be 34 ethylene-propylene analog copolymer (MFR:4.8 gram/10 minutes, degree of crystallinity 3.2%, Mw/Mn=5.2, fusing point: 80 ℃) replace EPR(III-1 used in the embodiment III-1) outside, carry out the fs chlorination equally with embodiment III-1 in 50-55 ℃ of temperature range, obtaining muriatic cl content in this stage is 18.2(weight) %.Then reaction system is heated up, come to carry out in the temperature range chlorination till cl content is 31.3 weight % at 65-75 ℃, thereby make ethylene chloride-propylene copolymers (to call " CLEPR(III-C " in the following text)).
Comparative example III-1
Removing and adopting propylene content is 31.8% weight %, and mooney viscosity (ML
1+4, 100 ℃) and be outside 58.7 ethylene-propylene analog copolymer (MFR:8.2 gram/10 minutes, degree of crystallinity: 2.5%, Mw/Mn=3.8, fusing point: the 35 ℃) class, carry out the chlorination of fs and subordinate phase equally with embodiment III-1.Obtain ethylene chloride-propylene copolymers thus and (call that " cl content of CLEPR(III-D) is 31.3 weight % in the following text.
Comparative example III-2～III-5
Will be in the used EPR(III-1 of embodiment III-1) in the temperature range shown in the table III-1, carry out chlorination and make it reach the cl content shown in III-1 table, carry out fs chlorination separately.The various muriates that will obtain are thus subsequently carrying out chlorination (subordinate phase chlorination) in the temperature range shown in the table III-1 immediately, thereby make the ethylene chloride-propylene copolymers with cl content shown in the table III-1.
1) cl content of each the chlorinatedpolyethylene-propylene copolymer after the subordinate phase chlorination
In the fs chlorination of comparative example III-1 and III-5, lump, and the chlorine skewness; And in the chlorination of the fs of comparative example III-2, also luming, and chlorine skewness.And also can luming in the subordinate phase chlorination of comparative example III-3 and III-4, and chlorine skewness.
Measure the rerum natura that embodiment III-1 to III-3 and comparative example III-2 obtains various ethylene chloride alkene-propylene copolymers, it the results are shown in table III-2.
Used ethylene chloride-propylene copolymers, thiourea, sulphur and sulfur donor in following examples and comparative example, the different sorts of metallic compound and other vulcanization accelerator with transitivity like following.
((A) ethylene chloride-propylene copolymers)
As what the ethylene-propylene analog copolymer used is to add the propylene content 22 weight % and the mooney viscosity (ML of the aqueous suspensions shape of 10Kg
1+4100 ℃) 115 ethylene-propylene analog copolymer (MFR:1.0g/10 minute, degree of crystallinity: 6.2%, Mw/Mn=6.1,120 ℃ of fusing points, call " (EPR(IV-1) " in the following text), stir on one side then, in 50-90 ℃ under carry out chlorination so that in multipolymer cl content 18.2 weight %(fs chlorinations on one side).Then reaction system is warming up to 121-125 ℃, stop to import chlorine afterwards and slow coolingization 30 minutes (subordinate phase slow coolingization) in this temperature range, chlorination is carried out so that cl content reaches 30.4 weight %(phase III chlorinations in reaction system cooling back under 95-118 ℃), obtain mooney viscosity (ML
14, 100 ℃) ethylene chloride-propylene copolymers of 42.0 (FR 10.0g/10 minute, call in the following text " the CLEPR(IV-A) "); And with the aforementioned EPR(IV-1 of above-mentioned same adding 10Kg) 10Kg, stir on one side then, on one side under 50-90 ℃, carry out chlorination so that in this multipolymer cl content reach 18.2 weight %(fs chlorinations).Then again reaction system is warming up to 105-115 ℃ and in this temperature range, carry out chlorination so that cl content reaches 27.1 weight %(subordinate phase chlorinations).Under 118-120 ℃, carry out chlorination again afterwards so that cl content reaches 30.2 weight %(phase III chlorinations), mooney viscosity (ML
1+4, 100 ℃) ethylene chloride alkene-propylene copolymers of 61 (FR 11.0g/10 minute, call in the following text " the CLEPR(IV-B) ").
((B) thiourea)
Use diethyl thiourea (to call " FUR " in the following text) and diethylene thiocarbamide (calling " 2,2 " in the following text) as thiourea.
((C) sulphur and sulfur donor)
What use as sulphur is powdery sulphur (more than particle diameter 200 orders, to call " S " in the following text), and what adopt as sulfur donor is four sulfuration two pentamethylene thiurams (to call " TRA " in the following text).
((D) metallic compound)
What adopt as metallic compound is that median size is that the red lead of 1.5 microns of 1.0 microns magnesium oxide (calling " MgO " in the following text) and median sizes (is called " Pb in the following text
3O
4").
((E) other vulcanization accelerator)
Adopt tetramethyl-thiuram disulfide (to call " TT " in the following text) as other vulcanization accelerator.
Embodiment IV-1～IV-7, comparative example IV-1～IV-7
The mixture of various combined amount shown in the table IV-1 and kind was mixed 20 minutes so that its slabbing thing with the form cylinder down in room temperature (about 20 ℃).With the various flap compacting shape machines that obtain, make its sulfuration under the pressure of 160 ℃ temperature and 200 kilograms/square centimeter make sulfide in 30 minutes.Again the sulfur product that obtains is carried out tensile strength, elongation, hardness and compressive permanent strain test, it the results are shown in the table IV-2.Use is vulcanized test by the flap that the form cylinder obtains, and it the results are shown in the 2nd figure.
Comparative example IV-8
About 200,000 except adopting by predetermined molecular weight, and density 0.950g/cm
3High density polyethylene(HDPE) carry out chlorination with the outstanding turbid method of water and mooney viscosity (MS
1+4, 100 ℃) 70 and the chlorinatedpolyethylene of cl content 30.3 weight % replace used CLEPR(IV in the embodiment IV-1-A) and outer, mix equally with embodiment IV-1 and make its slabbing.Gained flap and embodiment IV-1 are vulcanized equally and made sulfide.Afterwards gained sulfide is carried out tensile strength, elongation, hardness and compressive permanent strain test, it the results are shown in table IV-2.Vulcanize test equally with embodiment IV-1 again, it the results are shown among Fig. 2.
When sulfuration desalination acid taking place in comparative example IV-3 and the IV-5, and can not form sheet sulfide.
Embodiment IV-1 and IV-5 and comparative example IV-1 and IV-8 obtain the cross-linking curve of composition (product mixes) respectively with α-2, b-2, and c-2 and d-2 are shown among Fig. 2.
As can be seen, the sulfuration ethylene chloride-propylene copolymers composition that makes by the present invention is not only at tensile strength (T from the result of above embodiment and comparative example
B) and the compression set aspect have superiority, and also can find out from flow curve and can make excellent vulcanization curve.
Table IV-2
| Embodiment or comparative example number | T B（Kg/cm 2) | E B（％） | Hardness | Compressive permanent strain (%) |
| EXAMPLE IV-1 " IV-2 " IV-3 " IV-4 " IV-5 " IV-6 " IV-7 Comparative Example I V-1 " IV-2 " IV-4 " IV-6 " IV-7 " IV-8 | 200 212 220 222 212 210 208 142 102 124 123 184 232 | 500 500 520 525 535 530 510 720 920 880 890 500 590 | 59 57 58 56 56 57 56 55 56 55 56 69 85 | 31.0 30.8 33.4 31.6 30.0 31.4 34.2 62.4 92.4 79.2 80.2 41.0 58.2 |
The kind separately of the used ethylene chloride-propylene copolymers of following examples and comparative example, thiourea, dithiocar-bamate, sulfuration and sulfur donor, metallic compound and other vulcanization accelerator with transitivity like following.
((A) ethylene chloride-propylene copolymers)
Be that the propylene content that adds the outstanding turbid shape of water of 10Kg is 22 weight % and mooney viscosity (ML as what the ethylene-propylene analog copolymer used
1+4100 ℃) 115 ethylene-propylene analog copolymer (MFR1.0g/10 minute, degree of crystallinity 5.1%, Mw/Mn=5.0,120 ℃ of fusing points, call " EPR(V-1) " in the following text), stir on one side then, on one side under 50-90 ℃, carry out chlorination so that in this multipolymer cl content reach 18.2 weight %(fs chlorinations).Then reaction system is warming up to 121-125 ℃, stops to import chlorine afterwards and slow coolingization 30 minutes (subordinate phase slow coolingization) in this temperature range.Chlorination is carried out so that cl content reaches 30.4 weight %(phase III chlorinations in reaction system cooling back under 95-118 ℃), the mooney viscosity (ML that obtains
1+4, 100 ℃) ethylene chloride-propylene copolymers of 42.0 (FR10.0g/10 minute, call in the following text " the CLEPR(V-A) "); And with the aforementioned EPR(V-1 of above-mentioned same adding 10Kg), stir on one side then, on one side under 50-90 ℃, carry out chlorination so that in this multipolymer cl content reach 18.2 weight %(fs chlorinations).Then again reaction system is warming up to 105-115 ℃ and in this temperature range, carry out chlorination so that cl content reaches 27.1 weight %(subordinate phase chlorinations).Under 118-120 ℃, carry out chlorination afterwards so that cl content reaches 30.2 weight %(phase III chlorinations), obtain mooney viscosity (ML
1+4, 100 ℃) ethylene chloride-propylene copolymers of 61 (FR 11.0g/10 minute, call in the following text " CLEPR(V-B) ").
((B) thiourea)
Adopt diethyl thiourea (calling " EUR " in the following text) and diethylene thiocarbamide (to call " 2,2 " in the following text) as thiourea.
((C) curing carbaminate)
Adopt pentamethylene thiocarbamate sodium (to call " PMTC " in the following text) as dithiocar-bamate.
((D) sulphur and sulfur donor)
What adopt as sulphur is powdery sulphur (more than particle diameter 200 orders, to call " S " in the following text), and what adopt as sulfur donor is four sulfuration two pentamethylene thiurams (to call " TRA " in the following text).
((E) metallic compound)
What adopt as metallic compound is that the red lead of 1.5 microns of the magnesium oxide (to call " MgO " in the following text) of 1.0 microns of median sizes and median sizes is (to call " Pb in the following text
3O
4").
((F) other vulcanization accelerator)
In addition, adopt tetramethyl-thiuram disulfide (to call " TT " in the following text) as other vulcanization accelerator.
Embodiment V-1～V-7, comparative example V-1～V-8
The mixture of combined amount shown in the table V-1 and kind was formed flap in 20 minutes following the mixing with the form cylinder of room temperature (about 20 ℃).Using compacting shape machine then is that 160 ℃ and pressure are 200Kg/cm in temperature
2Under the condition flap that obtains was vulcanized 30 minutes, thereby make sulfide.Sulfide to gained carries out tensile strength, elongation, hardness and compressive permanent strain test then, and it the results are shown in table V-2.Use the flap of gained to vulcanize test with the open type cylinder, it the results are shown among Fig. 3.
Table V-2
| Embodiment or comparative example number | T B（Kg/cm 2) | E B（％） | Hardness | Compressive permanent strain (%) |
| EXAMPLE V-1 " V-2 " V-3 " V-4 " V-5 " V-6 " V-7 comparative example V-1 " V-2 " V-3 " V-5 " V-7 " V-8 " V-9 | 190 202 180 192 200 192 195 200 152 141 155 145 220 190 | 390 360 400 395 395 393 395 500 660 780 680 760 390 400 | 60 59 58 59 59 59 60 59 56 56 56 57 65 90 | 30.0 30.1 31.2 30.8 31.0 30.4 31.0 31.0 52.4 63.4 72.4 70.0 38.0 35.2 |
Comparative example V-9
About 200,000 except using predetermined molecular weight, density 0.950g/cm
3High density polyethylene(HDPE) carry out chlorination by the outstanding turbid method of water and mooney viscosity (MS
1+4, 100 ℃) 70 and cl content 30.3(weight) chlorinatedpolyethylene of % replaces used CLEPR(V in the embodiment V-1-A) and outer, mix equally so that its slabbing with embodiment V-1.The flap that obtains is vulcanized equally with embodiment V-1 again and make sulfide.Afterwards the gained sulfur product is carried out tensile strength, elongation, hardness and compressive permanent strain test, it the results are shown in the table V-2.Simultaneously, vulcanize test equally with embodiment V-1.It the results are shown among Fig. 3.
Dehydrochlorination takes place, and can not form sheet sulfide in comparative example V-4 and V-6 when sulfuration.
The cross-linking curve of the composition (product mixes) that is obtained by embodiment V-1 and V-2 and comparative example V-1 and V-9 is shown among Fig. 3 with a-3, b-3, c-3 and d-3 respectively.
The kind separately of used ethylene chloride-propylene copolymers, thiourea, mercapto-triazine compounds, sulphur and sulfur donor, metallic compound and other vulcanization accelerator and rerum natura such as following in following examples and comparative example.
((A) ethylene chloride-propylene copolymers)
As what the ethylene-propylene analog copolymer used be, the outstanding turbid shape of water of adding 10Kg
Propylene content 22% and mooney viscosity (ML
1+4100 ℃) 115 ethylene-propylene analog copolymer (MFR 1.0g/ minute, degree of crystallinity 5.1%, Mw/Mn=5.0,120 ℃ of fusing points, call " EPR(VI-1) " in the following text), stir on one side then, on one side under 50-90 ℃, carry out chlorination so that in this multipolymer cl content reach 18.2 weight %(fs chlorinations).Then reaction system is warming up to 121-125 ℃, stops to import chlorine afterwards and slow coolingization 30 minutes (subordinate phase slow coolingization) in this temperature range.Chlorination is carried out so that cl content reaches 30.4 weight %(phase III chlorinations in reaction system cooling back under 95-118 ℃), the mooney viscosity (ML that obtains
1+4100 ℃) ethylene chloride-propylene copolymers of 42.0 (FR10.0g/10 minute, call " CLEPR(VI-A) " in the following text) and with the aforementioned EPR(VI-1 of above-mentioned same adding 10Kg), stir on one side then, on one side under 50-90 ℃, carry out chlorination so that in this multipolymer cl content reach 18.2 weight %(fs chlorinations).Then again reaction system is warming up to 105-115 ℃ and in this temperature range, carry out chlorination so that cl content reaches 27.1 weight %(subordinate phase chlorinations).Under 118-120 ℃, carry out chlorination again afterwards so that cl content reaches 30.4 weight %(phase III chlorinations), obtain mooney viscosity (ML
1+4, 100 ℃) ethylene chloride-propylene copolymers of 61 (FR 11.0g/10 minute, call in the following text " the CLEPR(VI-B) ").
((B) thiourea)
Use diethyl thiourea (to call " EUR " in the following text) and diethylene thiocarbamide (to call " 2,2 " in the following text) as thiourea.
((C) mercapto-triazine compounds)
((D) sulphur and sulfur donor)
What adopt as sulphur is powdery sulphur (more than 200 orders of powder footpath, to call " S " in the following text), and what adopt as sulfur donor is four sulfuration two pentamethylene thiurams (to call " TRA " in the following text).
((E) metallic compound)
What adopt as metallic compound is that the red lead of 1.5 microns of the magnesium oxide (to call " MgO " in the following text) of 1.0 microns of median sizes and median sizes is (to call " Pb in the following text
3O
4").
((F) other vulcanization accelerator)
In addition, other vulcanization accelerator adopts tetramethyl-thiuram disulfide (to call " TT " in the following text).
Embodiment VI-1～VI-7, comparative example VI-1～VI-10
The mixture of combined amount shown in the table VI-1 and kind was made flap in 20 minutes following the mixing with the open type cylinder of room temperature (about 20 ℃).Making compressing forming machine then is that 160 ℃ and pressure are 200Kg/cm in temperature
2Condition under with flap sulfuration 30 minutes, thereby make sulfide.Afterwards gained sulfide is carried out tensile strength, elongation, hardness and compressive permanent strain test, it the results are shown in the table VI-2.Use the gained flap to vulcanize test in the open type cylinder, it the results are shown among Fig. 4.
Table VI-2
| Embodiment or comparative example number | T B（Kg/cm 2) | E B（％） | Hardness | Compressive permanent strain (%) |
| Example VI-1 " VI-2 " VI-3 " VI-4 " VI-5 " VI-6 " VI-7 comparative example VI-1 " VI-2 " VI-3 " VI-4 " VI-5 " VI-7 " VI-9 " VI-10 " VI-11 | 192 190 206 191 196 191 197 200 196 162 163 162 150 152 200 240 | 350 360 330 320 350 320 320 500 620 690 695 780 820 890 500 420 | 63 62 63 62 61 62 61 59 58 59 58 58 58 59 59 87 | 28.5 27.0 27.5 25.4 28.0 24.8 25.4 31.0 52.0 53.6 51.6 62.5 82.4 88.6 31.2 30.6 |
Comparative example VI-11
About 200,000 except using predetermined molecular weight, and density 0.950g/cm
3The high density polyethylene(HDPE) mooney viscosity (MS that its chlorination obtained with the outstanding turbid method of water-based
1+4, 100 ℃) and be 70, and cl content is that the chlorinatedpolyethylene of 30.3 weight % is to replace being made of mixing flap equally with embodiment VI-1 outside the used CLEPR(VI in the embodiment VI-1-A).The gained flap is vulcanized equally with embodiment VI-1 again and make sulfide.Afterwards gained sulfide is carried out tensile strength, elongation, hardness and compressive permanent strain test, the results are shown in the table VI-2.Vulcanize test equally with embodiment VI-1.It the results are shown among Fig. 4.
When sulfuration dehydrochlorination taking place in comparative example VI-6 and the VI-8, and can not form sheet sulfide.
The cross-linking curve of the composition (product mixes) that is obtained by embodiment VI-1 and VI-3 and comparative example VI-1 and VI-11 is shown in Figure 4 with a-4, b-4, c-4 and d-4 respectively.
The kind separately of the ethylene chloride-propylene copolymers that uses in following examples and comparative example, organo-peroxide, crosslinking coagent and mercapto-triazine compounds is as described below with transitivity.
((A) ethylene chloride-propylene copolymers)
Be that the propylene content that adds 10 kilograms the outstanding turbid state of water is 22%, mooney viscosity (ML as what ethylene chloride-propylene copolymers used
1+4100 ℃) be 115 ethylene-propylene analog copolymer (MFR1.0g/ minute, degree of crystallinity 5.1%, Mw/Mn=5.0,120 ℃ of fusing points, call in the following text " EPR(VII-1) "), stir on one side, on one side reach 18.2(weight carrying out chlorination cl content in this multipolymer under 50-90 ℃) %(fs chlorination), then reaction system is warming up to 121-125 ℃, stop to lead to chlorine and slow cooling 30 minutes (subordinate phase slow coolingization) in this temperature range afterwards, again chlorination carried out in reaction system cooling back under 95-118 ℃ and reach 30.4(weight up to cl content) %(phase III chlorination), the mooney viscosity (ML that obtains
1+4100 ℃) be ethylene chloride-propylene copolymers of 42.0 (FR10.0g/10 minute, call " CLEPR(VII-A) " in the following text) and with the aforesaid EPR(VII-1 of above-mentioned same adding 10Kg), stir on one side, carrying out chlorination under 50-90 ℃ reaches 18.2(weight up to the cl content of this multipolymer on one side) %(fs chlorination), then again reaction system is warming up to 105-115 ℃ and in this temperature range, carry out chlorination up to making cl content reach 27.1 weight %(subordinate phase chlorinations), under 118-120 ℃, carry out chlorination subsequently and reach 30.2(weight up to cl content) chlorination of %(subordinate phase, the mooney viscosity (ML that obtains
1+4, 100 ℃) and be ethylene chloride-propylene copolymers of 61 (FR11.0g/10 minute, call " CLEPR(VII-B) " in the following text).
((B) organo-peroxide)
Use dicumyl peroxide (to call " DCP " in the following text) as organo-peroxide.
((C) crosslinking coagent)
Use cyamelide triallyl (to call " TAIC " in the following text) as crosslinking coagent.
((D) mercapto-triazine compounds)
((E) metallic compound)
What use as metallic compound is that the red lead of 1.5 microns of the magnesium oxide (to call " MgO " in the following text) of 1.0 microns of median sizes and median sizes is (to call " Pb in the following text
3O
4").
Embodiment VII-1～VII-6, comparative example VII-1～VII-8
The mixture of combined amount shown in the table VII-1 and kind was made sheet in 20 minutes following the mixing with the open type cylinder of room temperature (about 20 ℃).Using compressing forming machine then is that 160 ℃ and pressure are 200Kg/cm in temperature
2Under made flap sulfuration 30 minutes, thereby make sulfide.Afterwards the gained sulfur product is carried out tensile strength, elongation, hardness and compression strain-gauge test forever, it the results are shown in the table VII-2 and with the open type cylinder gained sheet is vulcanized test with material, and it the results are shown among Fig. 5.
Comparative example VII-9
Remove to use predetermined molecular weight for about 200,000, density is 0.950g/cm
3The outstanding turbid method of high density polyethylene(HDPE) water carry out the mooney viscosity (MS that chlorination obtains
1+4, 100 ℃) be 70 and cl content be 30.3(weight) chlorinatedpolyethylene of % replaces mixing equally so that its slabbing with embodiment VII-A outside the CLEPR(VII used in the embodiment VII-1-A).To obtain flap and embodiment VII-1 vulcanizes equally and makes sulfide.Subsequently gained sulfide is carried out tensile strength, elongation, hardness and compressive permanent strain test, it the results are shown in the table VII-2.Equally it is vulcanized test with embodiment VII-1.It the results are shown among Fig. 4.
Dehydrochlorination takes place, and can not form the sheet cross-linking agent in comparative example VII-4 and VII-5 when sulfuration.
Cross-linking curve by embodiment VII-1 and VII-4 and comparative example VII-1 and VII-9 resulting composition (product mixes) is shown among Fig. 5 with a-5, b-5, c-5 and d-5 respectively.
As can be seen, the composition of the bridging property ethylene chloride-propylene copolymers that makes by the present invention is not only at tensile strength (T from the result of above embodiment and comparative example
B) and the compressive permanent strain aspect have superiority, and also can make excellent cross-linking curve from the mobilometer curve.
Claims (4)
1, the composition of ethylene chloride-propylene copolymers of forming by (A), (B), (C), (D), wherein,
(A) be to be 20-38 (weight) % with propylene content, melting index is 0.01-5.0 gram/10 minutes, the fusion peak value of measuring with difference formula scanning calorimeter (DSC) is more than 80 ℃, with the degree of crystallinity of X-ray measuring be 3% or more than, the molecular layer distribution index of measuring with permeation chromatography (GPC) is Mw/ Mn＞4, mooney viscosity (ML
1+4, 100 ℃) and to make chloride rate be 20～45 (weight) % for the ethylene-propylene analog copolymer of 10-180 carries out chlorination, mooney viscosity
(ML
1+4, 100 ℃) and be ethylene chloride-propylene copolymer of 10-150, its amount is 100 weight parts,
(B) being the thiourea of general formula (I) expression, is 1.0～10.0 weight parts.
(in the formula, R and R
1Can be identical also can be different, be that carbonatoms mostly is 18 alkyl most)
(C) being sulphur and/or sulfur donor, is 0.1～10.0 weight part,
(D) being metallic compound as sour accepting agent, is 1.0～15.0 weight parts.
2, the ethylene chloride of forming by (A), (B), (C), (D), (E)-propylene copolymers composition, wherein,
(A) be to be 20-38(weight with containing the propylene amount) %, melting index is 0.01-5.0 gram/10 minutes, the fusion peak value of measuring with difference formula scanning calorimeter (DSC) is more than 80 ℃, with the degree of crystallinity of X-ray measuring be 3% or more than, the molecular weight distribution index of measuring with permeation chromatography is Mw/ Mn＞4, mooney viscosity (ML
1+4, 100 ℃) be that to carry out the chloride rate that chlorination makes be 20-45(weight for 10～180 ethylene-propylene analog copolymer) %, mooney viscosity (ML
1+4, 100 ℃) and be ethylene chloride-propylene copolymer of 10-150, its amount is 100 weight parts,
(B) being the thiourea that logical formula I is represented, is 1.0～10.0 weight parts,
(in the formula, R and R
1Can be identical, also can be different, be that amount of carbon atom mostly is 18 alkyl most),
(C) being sulphur and/or sulfur donor, is 0.1～10.0 weight part,
(D) be metallic compound, be the 1.0-15.0 weight part as sour accepting agent,
(E) being dithiocar-bamate, is 0.05～5.0 weight part.
3, the ethylene chloride of forming by (A), (B), (C), (D), (E), (F)-propylene copolymers composition, wherein,
(A) be to be the 20-38(weight part with containing the propylene amount, melting index is 0.01～5.0 gram/10 minutes, the fusion peak value of measuring with difference formula scanning calorimeter (DSC) is more than 80 ℃, with X-ray measuring come degree of crystallinity be 3% or more than, the molecular weight distributing index of measuring with permeation chromatography (GPC) is Mw/ Mn＞4, mooney viscosity (ML
1+4, 100 ℃) and for carrying out chlorination, the ethylene-propylene analog copolymer of 10-180 makes, chloride rate is a 20-45(weight) %, mooney viscosity (ML
1+4, 100 ℃) and be ethylene chloride-propylene copolymers of 10-150, its amount is 100 weight parts,
(B) being the thiourea that logical formula I is represented, is 1.0～10.0 weight parts,
(in the formula, R and R
1Can be identical also can be different, be that carbonatoms mostly is 18 alkyl most),
(C) being sulphur and/or sulfur donor, is 0.1～10.0 weight part,
(D) being metallic compound as sour accepting agent, is 1.0～15.0 weight parts,
(E) be dithiocar-bamate, be the 0.05-5.0 weight part,
(F) be the mercapto-triazine compounds that logical formula II is represented, be the 0.01-2.0 weight part,
(in the formula, R
2Expression sulfydryl or amino).
4, by (A) and ethylene chloride-propylene copolymers composition of (G) forming, wherein,
(A) be to be 20-38(weight with propylene content) %, melting index is 0.01～5.0 gram/10 minutes, the fusion peak value of measuring with difference formula scanning calorimeter (DSC) is more than 80 ℃, with the degree of crystallinity of X-ray measuring be 3% or more than, with molecular weight distribution index Mw/ Mn＞4 that permeation chromatography (GPC) is measured, mooney viscosity (ML
1+4, 100 ℃ is that 10～180 ethylene-propylene analog copolymer carries out chlorination to make chloride rate be 20-45(weight) and %, mooney viscosity (ML
1+4, 100 ℃) and be ethylene chloride-propylene copolymers of 10-150, its amount is 100 weight parts,
(G) being organo-peroxide, is 0.1～10.0 weight part.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP273000/86 | 1986-11-18 | ||
| JP273002/86 | 1986-11-18 | ||
| JP27004/86 | 1986-11-18 | ||
| JP300160/86 | 1986-12-18 | ||
| JP300159/86 | 1986-12-18 | ||
| JP300161/86 | 1986-12-18 | ||
| JP65806/87 | 1987-03-23 | ||
| CN87107853A CN1016429B (en) | 1986-11-18 | 1987-11-18 | Production method of chlorinated ethylene-propylene copolymer |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107853A Division CN1016429B (en) | 1986-11-18 | 1987-11-18 | Production method of chlorinated ethylene-propylene copolymer |
| CN87107853 Division | 1987-11-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059538A true CN1059538A (en) | 1992-03-18 |
| CN1019581B CN1019581B (en) | 1992-12-23 |
Family
ID=4816265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109754 Expired CN1019581B (en) | 1987-11-18 | 1987-11-18 | Chlorinated ethylene-propylene copolymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019581B (en) |
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1987
- 1987-11-18 CN CN 91109754 patent/CN1019581B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1019581B (en) | 1992-12-23 |
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