CN118221861A - Polyolefin copolymers, curable compositions and articles comprising the same, and uses thereof - Google Patents
Polyolefin copolymers, curable compositions and articles comprising the same, and uses thereof Download PDFInfo
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- CN118221861A CN118221861A CN202211648955.9A CN202211648955A CN118221861A CN 118221861 A CN118221861 A CN 118221861A CN 202211648955 A CN202211648955 A CN 202211648955A CN 118221861 A CN118221861 A CN 118221861A
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- Prior art keywords
- polyolefin copolymer
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- curable composition
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 103
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 150000001993 dienes Chemical group 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 239000004711 α-olefin Substances 0.000 claims abstract description 8
- NWNPESVXYXCGLH-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2C=CC1(C=C)C2 NWNPESVXYXCGLH-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 150000002978 peroxides Chemical class 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 12
- 239000004606 Fillers/Extenders Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012936 vulcanization activator Substances 0.000 claims description 6
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical group C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 238000007906 compression Methods 0.000 abstract description 6
- 230000006835 compression Effects 0.000 abstract description 6
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 19
- 229920001971 elastomer Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003921 oil Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920002943 EPDM rubber Polymers 0.000 description 9
- -1 methyltetraindene Chemical compound 0.000 description 8
- 239000004636 vulcanized rubber Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 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 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 1
- ZTJHDEXGCKAXRZ-FNORWQNLSA-N (3e)-octa-1,3,7-triene Chemical compound C=CCC\C=C\C=C ZTJHDEXGCKAXRZ-FNORWQNLSA-N 0.000 description 1
- TVEFFNLPYIEDLS-VQHVLOKHSA-N (4e)-deca-1,4,9-triene Chemical compound C=CCCC\C=C\CC=C TVEFFNLPYIEDLS-VQHVLOKHSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 description 1
- KWPNNZKRAQDVPZ-UHFFFAOYSA-N 1,3-bis(2-methylphenyl)thiourea Chemical compound CC1=CC=CC=C1NC(=S)NC1=CC=CC=C1C KWPNNZKRAQDVPZ-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- FGKIZAATMHLTKO-UHFFFAOYSA-N 1-(diaminomethylideneamino)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1NC(=N)NNC(N)=N FGKIZAATMHLTKO-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JDICEKWSLNPYSN-UHFFFAOYSA-N 2-(2,4-dinitrophenyl)-1,3-benzothiazole-4-thiol Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1C1=NC2=C(S)C=CC=C2S1 JDICEKWSLNPYSN-UHFFFAOYSA-N 0.000 description 1
- DOMHCBYZLIWUHE-UHFFFAOYSA-N 2-(chloromethyl)-3-prop-1-en-2-ylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(=C)C)C2CCl DOMHCBYZLIWUHE-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- IOHAVGDJBFVWGE-UHFFFAOYSA-N 2-ethylidene-3-propan-2-ylidenebicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=C(C)C IOHAVGDJBFVWGE-UHFFFAOYSA-N 0.000 description 1
- SLQMKNPIYMOEGB-UHFFFAOYSA-N 2-methylhexa-1,5-diene Chemical compound CC(=C)CCC=C SLQMKNPIYMOEGB-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- TXLINXBIWJYFNR-UHFFFAOYSA-N 4-phenylpyridine-2-carbonitrile Chemical compound C1=NC(C#N)=CC(C=2C=CC=CC=2)=C1 TXLINXBIWJYFNR-UHFFFAOYSA-N 0.000 description 1
- ZVQPLXXHYUUJRX-UHFFFAOYSA-N 5-but-3-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCC=C)CC1C=C2 ZVQPLXXHYUUJRX-UHFFFAOYSA-N 0.000 description 1
- UZOALLLGRUBVIH-UHFFFAOYSA-N 5-hept-5-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCC=CC)CC1C=C2 UZOALLLGRUBVIH-UHFFFAOYSA-N 0.000 description 1
- UWAQOKCAUJGLQO-UHFFFAOYSA-N 5-hex-5-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCC=C)CC1C=C2 UWAQOKCAUJGLQO-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- XHBNZTYPSQZAIY-UHFFFAOYSA-N 5-oct-7-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCC=C)CC1C=C2 XHBNZTYPSQZAIY-UHFFFAOYSA-N 0.000 description 1
- RZTQYTKFARGVKP-UHFFFAOYSA-N 5-pent-4-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC=C)CC1C=C2 RZTQYTKFARGVKP-UHFFFAOYSA-N 0.000 description 1
- UAKPCRIFCXQISY-UHFFFAOYSA-N 5-prop-2-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC=C)CC1C=C2 UAKPCRIFCXQISY-UHFFFAOYSA-N 0.000 description 1
- KUFDSEQTHICIIF-UHFFFAOYSA-N 6-methylhepta-1,5-diene Chemical compound CC(C)=CCCC=C KUFDSEQTHICIIF-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- MOBBTBPTKFERRY-UHFFFAOYSA-N 8,14-dimethylheptadeca-1,7,14-triene Chemical compound CCC=C(C)CCCCCC(C)=CCCCCC=C MOBBTBPTKFERRY-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- PVMNBWXRCLEDCL-UHFFFAOYSA-N acetaldehyde;aniline Chemical compound CC=O.NC1=CC=CC=C1 PVMNBWXRCLEDCL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- UAGGVDVXSRGPRP-UHFFFAOYSA-N diethylcarbamothioic s-acid Chemical compound CCN(CC)C(S)=O UAGGVDVXSRGPRP-UHFFFAOYSA-N 0.000 description 1
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
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- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- ILSQBBRAYMWZLQ-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2SC(SN(C(C)C)C(C)C)=NC2=C1 ILSQBBRAYMWZLQ-UHFFFAOYSA-N 0.000 description 1
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- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 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
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- PZKZVLYBWITYEF-UHFFFAOYSA-L zinc;n,n-diethylcarbamothioate Chemical compound [Zn+2].CCN(CC)C([O-])=S.CCN(CC)C([O-])=S PZKZVLYBWITYEF-UHFFFAOYSA-L 0.000 description 1
- LAGTXXPOZSLGSF-UHFFFAOYSA-L zinc;n-butyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCCCN(C([S-])=S)C1=CC=CC=C1.CCCCN(C([S-])=S)C1=CC=CC=C1 LAGTXXPOZSLGSF-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
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides polyolefin copolymers, curable compositions and articles comprising the same, and uses thereof. The polyolefin copolymer comprises 60 to 75wt% ethylene units; 18.2 to 39.4wt% of alpha-olefin units; 0.1 to 0.8wt% of vinyl-norbornene units; and 0.5 to 6wt% of another non-conjugated diene unit; the above weight percentages are based on the total weight of the polyolefin copolymer, wherein the polyolefin copolymer comprises from 1 to 2 units of said vinyl-norbornene units per polymer molecular chain; the polyolefin copolymer produces a heat absorption of melting enthalpy of 25J/g to 45J/g at from 20 ℃ to complete melting; and the polyolefin copolymer has a weight average molecular weight in the range of 70kg/mol to 200 kg/mol. By the polyolefin copolymer, the curable composition and article comprising the same and the use thereof of the present invention, a remarkable increase in crystallization properties, branching properties and curability is achieved, and the curable composition prepared from the polyolefin copolymer of the present invention has excellent mechanical properties and compression set properties.
Description
Technical Field
The present invention relates to the field of polymers, in particular to polyolefin copolymers, curable compositions and articles comprising the same and uses thereof.
Background
Polyolefin rubber is an ethylene- α -olefin-diene elastomer, particularly an ethylene-propylene-diene copolymer (EPDM), which is considered as an excellent general-purpose elastomer that can be widely used. EPDM grades are composed of ethylene and propylene repeat units, with a smaller amount of non-conjugated diene units to introduce unsaturation and thereby promote crosslinking of the polymer chains. EPDM is a rubber that does not have any unsaturation in the polymer backbone and thus has excellent resistance to oxygen, ozone, heat and UV radiation compared to polydiene rubbers. EPDM rubber is therefore used in outdoor and high temperature applications such as automotive sealing systems, building and construction window gaskets, roofing rolls, coolant hoses, rubber belts and cables. EPDM rubbers are well suited for extrusion applications such as higher hardness cable compounds and extruded profiles for automotive and construction purposes.
However, EPDM rubbers still have disadvantages in practical use, such as poor tensile strength and tear strength, and insufficient elasticity. In the prior art, the properties of EPDM rubbers are generally improved by adjusting the content or type of individual units in the EPDM.
In JP 2006228462a an oil-free EPDM for cable applications is described having a low mooney viscosity with a monomeric ethylene/propylene and a non-conjugated diene component, wherein the non-conjugated diene component comprises 1,4 hexadiene, hexadiene or 5-ethylidene-2-norbornene. In this EPDM, the ethylene and ENB contents were 51 wt% and 8.1 wt%, respectively. However, the above-mentioned ethylene and ENB contents do not provide the desired polymer strength, and a high ENB content will limit heat resistance. Therefore, the prepared oil-free EPDM shows lower mechanical properties and unfavorable heat resistance.
In US 5763533, EPDM polymers are included as VNB units of the non-conjugated diene component, which EPDM polymers are used for the preparation of filled cable compounds. However, according to the disclosure in US 5763533, the EPDM polymer prepared has poor extrusion properties and mechanical properties, and it is necessary to blend the EPDM polymer with a polyolefin in the preparation of a filled cable compound in order to improve the extrusion and mechanical properties of the composition.
Thus, in order to solve the aforementioned problems, there is still a need for EPDM polymers having both mechanical and elastic properties.
Disclosure of Invention
The main object of the present invention is to provide a polyolefin copolymer, a curable composition and article comprising the same and uses thereof, to solve the problem that the rubber composition of the prior art cannot have excellent mechanical properties and elastic properties at the same time.
In order to achieve the above object, according to one aspect of the present invention, there is provided a polyolefin copolymer characterized by comprising: 60 to 75wt% ethylene units; 18.2 to 39.4wt% of alpha-olefin units; 0.1 to 0.8wt% of vinyl-norbornene units; and 0.5 to 6wt% of another non-conjugated diene unit; the above weight percentages are based on the total weight of the polyolefin copolymer, wherein the polyolefin copolymer comprises 1 to 2 units of vinyl-norbornene units per polymer molecular chain; the polyolefin copolymer produces a heat absorption of melting enthalpy of 25J/g to 45J/g at from 20 ℃ to complete melting; and the polyolefin copolymer has a weight average molecular weight in the range of 70kg/mol to 200 kg/mol.
Further, in the above polyolefin copolymer, another non-conjugated diene unit comprises any one of ethylidene norbornene units, dicyclopentadiene units and 1, 4-hexadiene units or any combination thereof; preferably, the other non-conjugated diene unit is an ethylidene norbornene unit.
Further, in the above polyolefin copolymer, the α -olefin unit comprises propylene, 1-butene, 1-pentene or 1-hexene.
Further, in the above polyolefin copolymer, the melting peak temperature of the polyolefin copolymer is between 35℃and 55 ℃.
Further, in the above polyolefin copolymer, the polyolefin copolymer has a branching level of 10 degrees to 20 degrees.
Further, among the above polyolefin copolymers, the polyolefin copolymer has a mooney viscosity of 15 to 35MU measured according to ISO 289.
According to still another aspect of the present invention, there is provided a curable composition characterized by comprising: the polyolefin copolymers described hereinbefore according to the invention, and a curing agent.
Further, in the above curable composition, the amount of the curing agent is 0.1 to 15 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, the amount of the curing agent is 0.5 to 5 parts by weight.
Further, in the above curable composition, the curable composition further comprises an extender oil in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, the amount of the extender oil is 8 to 10 parts by weight.
Further, in the above curable composition, the curing agent contains a sulfur-based curing agent and/or a peroxide-based curing agent.
Further, in the above curable composition, the curable composition further comprises one or any combination of a vulcanization accelerator, a vulcanization activator, an oxide co-agent, a filler, and a processing aid.
According to yet another aspect of the present invention, there is provided an article comprising the cured product of the curable composition described previously.
Further, in the above article, the article is a cable.
According to a further aspect of the present invention there is provided the use of a polyolefin copolymer or curable composition for the preparation of a cable.
By the polyolefin copolymer, the curable composition and article comprising the same and the use thereof of the present invention, a remarkable increase in crystallization properties, branching properties and curability is achieved, and the curable composition prepared from the polyolefin copolymer of the present invention has excellent mechanical properties and compression set properties.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As explained in the background, in the prior art, it is generally employed to modify the content or type of individual units in EPDM to improve the properties of the EPDM rubber, however, the mechanical properties and elastic properties of the resulting EPDM rubber still do not meet the production process requirements of the downstream product. Thus, there is still a need for further improvements in EPDM rubbers. In view of the problems in the prior art, according to one exemplary embodiment of the present application, there is provided a polyolefin copolymer comprising: 60 to 75wt% ethylene units; 18.2 to 39.4wt% of alpha-olefin units; 0.1 to 0.8wt% of vinyl-norbornene units; and 0.5 to 6wt% of another non-conjugated diene unit; the above weight percentages are based on the total weight of the polyolefin copolymer in which the polyolefin copolymer contains 1 to 2 units of vinyl-norbornene units per polymer molecular chain; the polyolefin copolymer produces a heat absorption of melting enthalpy of 25J/g to 45J/g at from 20 ℃ to complete melting; and the polyolefin copolymer has a weight average molecular weight in the range of 70kg/mol to 200 kg/mol.
In the art, it is common to increase the crystallinity of EPDM by increasing the content of ethylene units, thereby providing EPDM rubber with improved mechanical strength. However, after extensive experimentation by the inventors of the present invention, it has surprisingly been found that the desired high compound modulus or improved mechanical strength in the finished EPDM rubber cannot be achieved by simply increasing or limiting the ethylene content to a certain range. The inventors found that crystallinity above room temperature is a sufficient requirement for high vulcanized rubber strength. In the prior art, the crystallinity of polymers is typically determined using Differential Scanning Calorimetry (DSC). During a temperature sweep, as described, for example, in standard GB/T19466.3, the temperature is first raised at a rate of 20 ℃/min to about 30 ℃ above the melt extrapolation end temperature to eliminate the heat history; preserving heat for 5min; cooling at a rate of 20 ℃/min until the crystallization temperature is about 50 ℃ below the desired crystallization temperature; preserving heat for 5min; then a second temperature increase was performed at a rate of 20 c/min and recorded, heating to about 30 c above the extrapolated termination temperature. However, in the present invention, without being bound by theory, it is assumed that the copolymer of the present invention will recombine its crystals within a short period of storage and that the different types of crystals will reach an equilibrium state. This equilibrium state will represent a polymer state when used for example in cable insulation compounds. It has been found that the shape analysis of the melting endotherm obtained by DSC correlates with the expected intensity of the vulcanized rubber. Specifically, the area under the melting endotherm, which starts at about 20 ℃ until it is completely melted, is related to the mechanical properties of the rubber (such as the green strength) and the modulus of the cured vulcanized rubber. After a certain period of storage, the reorganization of the crystals represents the material properties in actual use. Therefore, the melting peak temperature of the first scan (temperature rising rate of 10K/min) in DSC scan can be used as an index of the type of crystal formed. Crystals with low peak melting temperatures are smaller and therefore they do not contribute much to strength compared to larger crystals that melt at higher temperatures. Based on the theory described above, in the present invention, the degree of crystallization of the copolymer is characterized by the heat absorption enthalpy of the melt (first scan, a rate of temperature rise of 10K/min) generated from 20℃to complete melting. The polyolefin copolymers of the invention produce a heat absorption enthalpy of fusion in the range of 25J/g to 45J/g at temperatures from 20℃to complete fusion. Meanwhile, the melting peak temperature of the polyolefin copolymer at the time of conducting DSC first scanning is between 35℃and 55 ℃.
In some embodiments of the invention, the content of ethylene units in the polyolefin copolymer is in the range of 60wt% to 75wt%, based on the total weight of the polyolefin copolymer. Within the above range, the polyolefin copolymer can exhibit an effective curing property during the curing process for producing a vulcanized rubber, and maintain good compression set characteristics. In addition, the polyolefin copolymer of the present invention exhibits significantly increased crystallization properties in combination with the heat absorption enthalpy of fusion of the polyolefin copolymer in the range of 25J/g to 45J/g, and thus gives the vulcanized rubber prepared from the polyolefin copolymer of the present invention excellent mechanical properties.
In some embodiments of the invention, the content of ethylene units in the polyolefin copolymer may be within the following ranges for the different examples: 60wt% to 75wt%, 60wt% to 74wt%, 60wt% to 73wt%, 60wt% to 72wt%, 60wt% to 71wt%, 60wt% to 70wt%, 60wt% to 69wt%, 60wt% to 68wt%, 60wt% to 67wt%, 60wt% to 66wt%, 60wt% to 65wt%, 61wt% to 75wt%, 62wt% to 75wt%, 63wt% to 75wt%, 64wt% to 75wt%, 65wt% to 75wt%, 66wt% to 75wt%, 67wt% to 75wt%, 68wt% to 75wt%, 69wt% to 75wt%, 70wt% to 75wt%.
In some embodiments of the invention, for the different examples, the melting enthalpy of heat absorption generated by the polyolefin copolymer from 20 ℃ to complete melting may be in the following range: 25J/g to 45J/g, 26J/g to 44J/g, 27J/g to 43J/g, 28J/g to 42J/g, 26J/g to 41J/g, 27J/g to 40J/g, 28J/g to 39J/g, 29J/g to 38J/g, 30J/g to 37J/g, 31J/g to 36J/g, 32J/g to 35J/g, 25J/g to 40J/g, 25J/g to 35J/g, 25J/g to 30J/g, 30J/g to 45J/g, 35J/g to 45J/g, 40J/g to 45J/g.
In the polyolefin copolymers of the present invention, the non-conjugated diene can promote the formation of a rubber network by providing crosslinking sites for the vulcanization system. While high levels of non-conjugated dienes are advantageous for rapid curing, extremely high levels will deteriorate the heat aging resistance of the vulcanizate. The optional non-conjugated diene unit may be selected from the group consisting of: 1, 4-hexadiene, 1, 6-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-1, 6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetraindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2, 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, 2-norbornadiene, 1,3, 7-octatriene, and 1,4, 9-decatriene; 5-vinyl-2-norbornene; 5- (2-propenyl) -2-norbornene; 5- (3-butenyl) -2-norbornene; 5- (4-pentenyl) -2-norbornene; 5- (5-hexenyl) -2-norbornene; 5- (5-heptenyl) -2-norbornene; 5- (7-octenyl) -2-norbornene; 5-methylene-2-norbornene; 6, 10-dimethyl-1, 5, 9-undecyltriene; 5, 9-dimethyl-1, 4, 8-decyltriene; 4-ethylene-8-methyl-1, 7-nonadiene; 13-ethyl-9-methyl-1,9,12-pentadecyltriene; 5,9, 13-trimethyl-1, 4,8, 12-tetradecadiene; 8,14,16-trimethyl-1,7,14-hexadecatriene and 4-ethylene-12-methyl-1, 11-pentadecadiene. Among the various optional non-conjugated diene monomers mentioned above, the most commonly used monomers are Ethylidene Norbornene (ENB), dicyclopentadiene (DCPD) and 1, 4-Hexadiene (HD); of these, ethylidene norbornene is most preferred.
The polyolefin copolymer of the invention comprises from 0.5 to 6wt% of another non-conjugated diene unit, based on the total weight of the polyolefin copolymer. Since the content of non-conjugated diene units will affect the number of crosslinking sites that the compound can provide during curing, the content of another non-conjugated diene unit within the above range will effectively promote the formation of a rubber network. In some embodiments of the invention, for the different examples, the content of another non-conjugated diene unit in the polyolefin copolymer may be within the following ranges: 0.5wt% to 6.0wt%, 0.6wt% to 5.5wt%, 0.7wt% to 5.0wt%, 0.8wt% to 4.5wt%, 0.9wt% to 4.0wt%, 1.0wt% to 3.5wt%, 1.1wt% to 3.0wt%, 1.2wt% to 2.5wt%, 1.3wt% to 2.0wt%, 1.4wt% to 1.5wt%, 0.5wt% to 5.5wt%, 0.5wt% to 5.0wt%, 0.5wt% to 4.5wt%, 0.5wt% to 4.0wt%, 0.5wt% to 3.5wt%, 0.5wt% to 3.0wt%, 0.5wt% to 2.5wt%, 0.5wt% to 2.0wt%, 1.0wt% to 6.0wt%, 1.5wt% to 6.0wt%, 2.0wt% to 6.0wt%, 0.5wt% to 6.5 wt%, 0.5wt% to 6.0wt%, 0.5wt% to 4.0wt% to 3.0wt% or 0.5wt% to 3.0wt% to 4.5wt% of the base.
For use in cable insulation compounds, curing is generally carried out using peroxide-based curing agents or sulfur-based curing agents. Efficient curing is required to maintain good compression set characteristics, especially at high temperatures, which is quite common for applications. A sufficiently high crosslink density can protect the insulating compound from thermal deformation. In addition, there is a need for a fast cure in cable insulation compounds that allows for fast production of cables with high yields and short economically viable process lengths. A high ethylene content is beneficial for peroxide curing, and in addition, in non-conjugated diene monomers, the inventors propose to incorporate a certain amount of vinyl-norbornene (VNB) units per polymer chain, taking into account their terminal unsaturation, to provide a high cure response. Thus, the polymers of the invention are preferably characterized by terminal unsaturated units distributed along the polymer chain (backbone), in an amount of 1 to 2 units per polymer chain. In alternative embodiments, curing may also be performed by using ionizing radiation (such as an electron beam source).
The number of VNBs contained per polymer chain in the polyolefin copolymer of the invention can be calculated by the following formula 1:
vnb= ([ VNB ] ×10×polymer Mn)/120 g/mol (formula 1) for each chain,
Wherein "[ VNB ]" is the mass fraction of VNB (gVNB/100 g polymer). The polymer Mn is the number average molecular weight of the polymer in kg/mol as determined by GPC. The number average molecular weight represents the number of polymer chains in the sample. 120g/mol is the molecular weight of VNB. The number of VNB units per chain is then directly related to the number of crosslinks in the rubber network.
In some embodiments of the invention, the content of vinyl-norbornene units in the polyolefin copolymer may be within the following ranges for the different examples: 0.1wt% to 0.8wt%, 0.2wt% to 0.8wt%, 0.3wt% to 0.8wt%, 0.4wt% to 0.8wt%, 0.5wt% to 0.8wt%, 0.6wt% to 0.8wt%, 0.1wt% to 0.7wt%, 0.1wt% to 0.6wt%, 0.1wt% to 0.5wt%, 0.1wt% to 0.4wt% or 0.1wt% to 0.3wt%.
The polyolefin copolymers in the present application have a weight average molecular weight in the range of at least 70kg/mol to 200kg/mol as measured by high temperature GPC. For the different embodiments, the weight average molecular weight of the polyolefin copolymer may be in the following range: 70kg/mol to 200kg/mol, 80kg/mol to 200kg/mol, 90kg/mol to 200kg/mol, 100kg/mol to 200kg/mol, 120kg/mol to 200kg/mol, 140kg/mol to 200kg/mol, 160kg/mol to 200kg/mol, 70kg/mol to 180kg/mol, 70kg/mol to 160kg/mol, 70kg/mol to 140kg/mol, 70kg/mol to 120kg/mol, 70kg/mol to 100kg/mol, 80kg/mol to 180kg/mol, 90kg/mol to 160kg/mol or 100kg/mol to 140kg/mol.
The polyolefin copolymers of the invention are long chains with a certain degree of branching. In the present invention, Δδ (in degrees) is used to represent the degree of long chain branching of the polyolefin copolymer, Δδ being the difference between the phase angle δ with a frequency of 0.1rad/s and the phase angle δ with a frequency of 100 rad/s. The phase angle delta of the present invention is determined by Dynamic Mechanical Spectroscopy (DMS) at 125 ℃. This amount Δδ is a measure of the amount of long chain branching structure present in the polymer and has been described in detail in h.c. booij, kautschuk+ Gummi Kunststoffe, volume 44, phase 2, pages 128-130, which is incorporated herein by reference. In some embodiments of the invention, a suitable range of Δδ is 10 degrees to 20 degrees, preferably 10 degrees to 15 degrees.
Examples of the α -olefin contained in the polyolefin copolymer of the present invention may be propylene, 1-butene, 1-pentene or 1-hexene, and preferably, the α -olefin is propylene.
The polyolefin copolymers of the present invention can also provide excellent extrudability and low compound viscosity to allow for the rapid and cost effective production of cables and profiles. The prior art generally uses the addition of plasticizers to the compounds to reduce their viscosity, however, the use of plasticizers is avoided because they are themselves highly volatile and harmful to the human body and the environment. In the field of application, the Mooney viscosity of polyolefin rubbers and their molecular weight must be sufficiently low to achieve low rubber compound viscosities. The polyolefin copolymer of the present invention can achieve a desired low viscosity because of having a low weight average molecular weight. In some embodiments of the invention, the polyolefin copolymer has a mooney viscosity between 15MU and 35MU (measured as ML 1+4, 125 ℃) measured according to ISO289, more preferably between 15MU and 30MU measured according to ISO 289.
According to another exemplary embodiment of the present invention, a curable composition is provided comprising the polyolefin copolymer of the present invention described previously, and a curing agent. Since the curable composition of the present invention comprises the polyolefin copolymer of the present invention, it exhibits excellent curing properties, and the resulting cured composition maintains good compression set characteristics and mechanical properties.
In some embodiments of the present invention, the curing agent that may be used comprises a sulfur-based curing agent and/or a peroxide-based curing agent. In the case of using a sulfur-based curing agent, it contains sulfur, 4' -dithiodimorpholine, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide (TMTD), or tetraethylthiuram disulfide (TETD). Among the sulfur-based curing agents that can be used, those that do not release nitrosamines are preferred. In the case of vulcanization using sulfur as a curing agent, sulfur is preferably used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, or even more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the polyolefin copolymer.
In the case of peroxide-based curing agents, they comprise dicumyl peroxide (DCP), 2, 5-di (t-butylperoxy) -2, 5-dimethyl-hexane (DTBPH), di (t-butylperoxyisopropyl) benzene (DTBPIB), 2, 5-di (benzoylperoxy) -2, 5-dimethylhexane, 2,5- (t-butylperoxy) -2, 5-dimethyl-3-hexyne (DTBPHY), di-t-butyl peroxide and di-t-butyl peroxide-3, 5-trimethylcyclohexane (DTBTCH) or mixtures of these peroxides. Among the above curing agents, sulfur, TMTD, TETD, DCP, DTBPH, DTBPIB, DTBPHY and DTBTCH are preferable. In the case of using the peroxide-based curing agent, the peroxide-based curing agent is used in an amount of usually 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyolefin copolymer. The choice of peroxide depends on the available curing temperature and the time available for the curing process. The above-described peroxide which is easy to use is used in the curable composition of the present invention, and thus the curing process can be performed at a temperature between 140 ℃ and 180 ℃ and within 5 to 20 minutes.
In a further embodiment of the present invention, the curable composition may further comprise an extender oil. Extender oils are petroleum-based softeners that are conventionally used in the production of rubber articles. Examples of extender oils are paraffinic, naphthenic and aromatic extender oils obtained by purification of the high boiling fraction of petroleum and further processing if necessary. The curable composition of the present invention is preferably free of extender oil or, alternatively, the amount of extender oil is from 1 to 20 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, the amount of the extender oil is 8 to 10 parts by weight.
In some embodiments of the present invention, the curable composition further comprises one or any combination of a vulcanization accelerator, a vulcanization activator, an oxide co-agent, a filler, and a processing aid. In embodiments where sulfur is used as the curative, sulfur may be used as the curative in combination with one or more vulcanization accelerators and one or more vulcanization activators.
Examples of vulcanization accelerators are N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2- (2, 4-dinitrophenyl) mercaptobenzothiazole, 2- (2, 6-diethyl-4-morpholino) benzothiazole, dibenzothiazyl disulfide, diphenylguanidine, triphenylguanidine, di-o-tolylguanidine, o-tolylbiguanidine, diphenylguanidine-phthalate, acetaldehyde-aniline reaction product, butyraldehyde-aniline condensate, cyclohexamethylene tetramine, aldol amine, 2-mercaptoimidazoline, diphenylthiourea, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea, tetramethylthiuram monosulfide, TMTD, TETD, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-N-butylthiocarbamate, zinc ethylphenyl dithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, diethylthiocarbamate, zinc and zinc tellurium. In embodiments comprising a vulcanization accelerator, the vulcanization accelerator is preferably used in an amount of 0.1 to 10 parts by weight, even more preferably 0.2 to 5 parts by weight, especially 0.25 to 2 parts by weight, based on 100 parts by weight of the polyolefin copolymer.
Examples of vulcanization activators are metal oxides such as magnesium oxide and zinc oxide, and stearic acid or reaction products such as zinc stearate; among them, zinc oxide combined with stearic acid is preferable. The vulcanization activator is generally used in an amount of 0.5 to 10 parts by weight, preferably in an amount of 0.5 to 5 parts by weight, based on 100 parts by weight of the polyolefin copolymer.
When one or more peroxide-based curing agents are used as curing agents, peroxide coagents may be used. Examples of peroxide coagents of the present invention are cyanurate compounds such as triallyl cyanurate and triallyl isocyanurate, (meth) acrylate compounds such as trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate, zinc dimethacrylate and zinc diacrylate; divinylbenzene; para-quinone dioxime; m-phenylene bismaleimide; (high vinyl) polybutadiene; and combinations thereof. The peroxide coagent may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, it may be used in an amount of 0.25 to 2.5 parts by weight.
When a sulfur-based curing agent and a peroxide-based curing agent are used as the curing agent of the curable composition of the present invention at the same time, the mixed curing system of the present invention is obtained. These cure systems combine the high heat resistance properties typically used for peroxide curing with very good final properties such as stretch and tear and the excellent dynamic and fatigue properties typically associated with sulfur cure systems. In this case, the sulfur-based curing agent is used in an amount of 0.05 to 1.0 parts by weight, preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the polyolefin copolymer.
In addition, the curable composition of the present invention may further comprise an optional filler component. The filler is preferably used in an amount of 20 to 150 parts by weight based on 100 parts by weight of the polyolefin copolymer. The filler may be carbon black and/or inorganic fillers conventionally used in rubber, such as silica, calcium carbonate, talc and clay. In the case of cable compounds, it is preferred to use inorganic fillers to provide good insulation properties and to reduce moisture penetration. The inorganic filler may be surface treated with, for example, a suitable silane, and the silane may be incorporated into the sizing formulation. Preferably, calcined clay or other calcined aluminosilicates are selected.
In addition, in further embodiments, the curable compositions of the present invention may further comprise a co-agent that promotes the formation of a rubber network, such as triallyl isocyanurate, triallyl cyanurate, multifunctional acrylates and methacrylates, low molecular weight vinyl polybutadiene, or bismaleimides. Details regarding coagents for peroxide curing can be found in S.K.Hennig, international electric wire and cable monograph conference record (Proceedings ofInternational Wire and Cable Symposium) (2007), 56 th, 587-593.
Other additives may also be used in other embodiments of the invention. Optional other additives include, but are not limited to: antioxidants such as those from BASF1076. UV stabilizers, partitioning agents or processing aids for processing of the curable composition, such as talc or metal salts, such as, for example, zinc stearate, magnesium stearate or calcium stearate, will remain in the curable composition after manufacture. The curable composition may also contain other additives such as drying agents (e.g., calcium oxide), tackifiers (e.g., resins), binders, pigments, processing aids (e.g., oil gums, fatty acids, stearates, polyethylene glycol or diethylene glycol), antioxidants, heat stabilizers (e.g., poly-2, 4-trimethyl-1, 2-dihydroquinoline or zinc 2-mercaptobenzoxazole), UV stabilizers, antiozonants, foaming agents, and mold release additives. For cable applications, paraffin wax may be added, and linear low density polyethylene may be added as a processing aid.
The method for producing the polyolefin copolymer of the present invention is known and is not particularly limited. The polyolefin copolymers of the invention can be produced by slurry, solution or gas phase polymerization processes using, for example, conventional vanadium-based catalysts, metallocene or post-metallocene catalysts. Suitable methods and catalysts are known in the literature.
Methods of preparing the curable compositions of the present invention are known, for example, the methods may include:
(i) Kneading the non-oil-filled polyolefin copolymer, and optionally a vulcanizing agent, a filler, or other components mentioned in the present invention, with a conventional kneader (such as an open roll mill, an internal mixer, a kneader, and an extruder) to obtain a mixed product, and
(Ii) The resultant kneaded product was vulcanized (cured, crosslinked) under heating.
The above-described methods may be performed in one or more steps, and such steps are also known to those skilled in the art.
According to another exemplary embodiment of the present invention, an article is provided comprising the cured product of the curable composition of the present invention. The article of the invention is preferably a cable.
According to another exemplary embodiment of the present invention, there is provided the use of the polyolefin copolymer or the curable composition of the present invention for the preparation of a cable.
Examples
Example 1
Preparation of polyolefin copolymers
The polymerization is carried out in a solution polymerization plant reactor. The mixed hexane was used as a solvent for the polymerization reaction. The solvent, ethylene, propylene, vinyl-norbornene, ethylidene-norbornene, and hydrogen feed streams are purified by contacting with various absorption media to remove impurities detrimental to the polymerization catalyst, such as water, oxygen, dienes, alkynes, and various polar compounds. The process is continuous in all feed streams. The impurity-removed solvent, ethylene, propylene, vinyl-norbornene, ethylidene norbornene and hydrogen, trioctylaluminum, triisobutylaluminum and butylated hydroxytoluene were premixed and the premix was pre-cooled before being fed to the polymerization reactor. The solution containing the catalyst compound 19 and the triphenyl-carbonium tetra-perfluorophenyl-borate as disclosed in WO 2005/090418 was fed separately to the reactor. The hydrogen content was adjusted to achieve the desired polymer mooney viscosity as given in table 1. Mooney viscosity was measured by ISO 289-1:2015. The polymerization reaction is carried out adiabatically, without external cooling or evaporative cooling being applied. Continuously discharging the resulting polymer solution via a discharge line, into which is introduced1076. The polymer is treated by continuous stripping in several vessels with appropriate steam feeds and temperature/pressure profiles. The final polyolefin copolymer is obtained after continuous dehydration in an extruder. The amounts of the components used in this example 1 are shown in table 1 below.
Examples 2 to 15
Examples 2-15 were prepared according to the procedure of example 1, with the differences shown in table 1 below.
Comparative examples 1 to 3
Comparative examples 1-3 were prepared according to the procedure of example 1, with the differences shown in table 1 below.
TABLE 1
The branching level (delta value), the heat absorption enthalpy of crystallization melt generated from 20 ℃ to the time when the crystallization was completely melted, and the melting peak temperature of the polyolefin copolymers of examples 1 to 15 and comparative examples 1 to 3 were measured by the method described in the foregoing of the present invention. The number of vinyl-norbornene units contained in each polymer molecular chain is calculated by the formula 1 described in the present invention. The experimental results and the calculation results are shown in table 2 below.
TABLE 2
As can be seen from the above table, the polyolefin copolymer of the present invention has a higher heat absorption of melting enthalpy than comparative examples 1 and 2, and the number of vinyl-norbornene units (VNB) contained in each polymer molecular chain is between 1.0 and 2.0, and thus the resulting polyolefin copolymer has a good degree of crystallization, and a large number of crosslinkable sites exist on the polymer chain, so that it can exhibit excellent curing properties during the subsequent curing. In contrast, comparative example 3 has excessively high heat absorption enthalpy (higher than the range of 25J/g to 45J/g of the present invention) in the melt and has a low VNB content, and thus has poor curability.
Example 16
Preparation of rubber composition
The polyolefin copolymer prepared in example 3, the filler and the processing aid were fed together into an internal mixer (GK1.5E1 of Harburg-Freudenberger Maschinenbau GmbH) having a ram pressure of 7 bar, a rotation speed of 45rpm, a filling factor of 72%, and a mixing time of 4 minutes. The amounts and types of polyolefin copolymer, filler and processing aid are shown in Table 3 below. Then, the mixture was further subjected to an open mill having a diameter of 200mm, wherein the rotation speed of the open mill was 20rpm, the roll temperature was 40℃and the roll speed ratio was 1.2, and a peroxide-based curing agent was added thereto. Vulcanizing at 180 ℃ for 10 minutes to obtain vulcanized rubber. The resulting vulcanized rubber was prepared into test pieces having thicknesses of 2mm and 6 mm.
TABLE 3 Table 3
The parts in the above table are based on 100 parts by weight of the polyolefin copolymer.
Comparative examples 4 to 6
Test pieces of vulcanized rubbers of comparative examples 4 to 6 were prepared in the same manner as in example 16 except that the polyolefin copolymers used were the polyolefin copolymers prepared in comparative examples 1 to 3 of the present invention, respectively.
The vulcanized rubber test pieces of example 16 and comparative examples 4 to 6 were tested using the methods listed in the following Table 4.
TABLE 4 Table 4
| Modulus, MDR rheometer | ISO 6502-3:2018 |
| Tear resistance | ISO 34-2:2015 |
| Tensile Strength | ISO 37:2017,2 test specimen |
| Compression set | ISO 815-1:2019 method A, type B |
| Gravey die extrusion test | ASTM D2230-17 |
The experimental results are shown in table 5 below.
TABLE 5
As can be seen from the above experimental results, example 16 of the present invention (comprising the polyolefin copolymer of example 3 of the present invention) has a melting heat absorption enthalpy in the range of 25J/g to 45J/g, and thus, it has a higher degree of crystallization, so that the prepared rubber composition has significantly increased mechanical strength and modulus, and the most excellent cured state, as compared with comparative examples 4 to 6.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A polyolefin copolymer comprising:
60 to 75wt% ethylene units;
18.2 to 39.4wt% of alpha-olefin units;
0.1 to 0.8wt% of vinyl-norbornene units; and
0.5 To 6wt% of another non-conjugated diene unit;
the weight percentages are based on the total weight of the polyolefin copolymer,
Wherein the polyolefin copolymer comprises 1 to 2 units of the vinyl-norbornene unit per polymer molecular chain;
the polyolefin copolymer produces a heat absorption enthalpy of fusion of 25J/g to 45J/g at a temperature of from 20 ℃ to complete fusion; and
The polyolefin copolymer has a weight average molecular weight in the range of 70kg/mol to 200 kg/mol.
2. The polyolefin copolymer of claim 1, wherein the another non-conjugated diene unit comprises any one of ethylidene norbornene units, dicyclopentadiene units, and 1, 4-hexadiene units, or any combination thereof; preferably, the other non-conjugated diene unit is an ethylidene norbornene unit.
3. The polyolefin copolymer of claim 1, wherein the α -olefin units comprise propylene, 1-butene, 1-pentene, or 1-hexene.
4. The polyolefin copolymer of claim 1, wherein the polyolefin copolymer has a melting peak temperature between 35 ℃ and 55 ℃.
5. The polyolefin copolymer of claim 1, wherein the polyolefin copolymer has a branching level of from 10 degrees to 20 degrees.
6. The polyolefin copolymer of claim 1, wherein the polyolefin copolymer has a mooney viscosity of 15 to 35MU measured according to ISO 289.
7. A curable composition comprising:
the polyolefin copolymer according to any one of claims 1 to 6, and
And (3) a curing agent.
8. The curable composition according to claim 7, wherein the amount of the curing agent is 0.1 to 15 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, the amount of the curing agent is 0.5 to 5 parts by weight.
9. The curable composition of claim 7, further comprising an extender oil in an amount of from 1 to 20 parts by weight based on 100 parts by weight of the polyolefin copolymer; preferably, the amount of the filling oil is 8 to10 parts by weight.
10. The curable composition according to claim 7, wherein the curing agent comprises a sulfur-based curing agent and/or a peroxide-based curing agent.
11. The curable composition of claim 7, further comprising one or any combination of a vulcanization accelerator, a vulcanization activator, an oxide co-agent, a filler, and a processing aid.
12. An article comprising a cured product of the curable composition of any one of claims 7 to 11.
13. The article of claim 12, which is a cable.
14. Use of the polyolefin copolymer of any of claims 1 to 6 or the curable composition of any of claims 7-11 for the preparation of a cable.
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