CN116162300A - Ethylene resin composition and molded article - Google Patents
Ethylene resin composition and molded article Download PDFInfo
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- CN116162300A CN116162300A CN202211488729.9A CN202211488729A CN116162300A CN 116162300 A CN116162300 A CN 116162300A CN 202211488729 A CN202211488729 A CN 202211488729A CN 116162300 A CN116162300 A CN 116162300A
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- resin composition
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- density polyethylene
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000005977 Ethylene Substances 0.000 title claims abstract description 115
- 239000011342 resin composition Substances 0.000 title claims abstract description 106
- 238000010828 elution Methods 0.000 claims abstract description 66
- 238000009826 distribution Methods 0.000 claims abstract description 38
- 238000005259 measurement Methods 0.000 claims abstract description 33
- 229920001684 low density polyethylene Polymers 0.000 claims description 73
- 229920001903 high density polyethylene Polymers 0.000 claims description 60
- 239000004700 high-density polyethylene Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 238000005194 fractionation Methods 0.000 claims description 17
- 229920001184 polypeptide Polymers 0.000 claims description 9
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 9
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 description 133
- 239000004702 low-density polyethylene Substances 0.000 description 71
- 229920000642 polymer Polymers 0.000 description 55
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 49
- 238000004519 manufacturing process Methods 0.000 description 48
- -1 silk Substances 0.000 description 32
- 239000003054 catalyst Substances 0.000 description 29
- 238000005227 gel permeation chromatography Methods 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 22
- 238000004898 kneading Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000008188 pellet Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000012986 chain transfer agent Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012968 metallocene catalyst Substances 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 241000251468 Actinopterygii Species 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 3
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 3
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 3
- SCUPJVKZFHVSDD-UHFFFAOYSA-N 2-methylpentan-2-yl 3,3-dimethylbutaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CC(C)(C)C SCUPJVKZFHVSDD-UHFFFAOYSA-N 0.000 description 3
- YMMLZUQDXYPNOG-UHFFFAOYSA-N 2-methylpentan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)CCCCCC(C)(C)C YMMLZUQDXYPNOG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 3
- PRIFGVOVRHAALC-UHFFFAOYSA-N tert-butyl 3,3-dimethylbutaneperoxoate Chemical compound CC(C)(C)CC(=O)OOC(C)(C)C PRIFGVOVRHAALC-UHFFFAOYSA-N 0.000 description 3
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- IOCYQQQCJYMWDT-UHFFFAOYSA-N (3-ethyl-2-methoxyquinolin-6-yl)-(4-methoxycyclohexyl)methanone Chemical compound C=1C=C2N=C(OC)C(CC)=CC2=CC=1C(=O)C1CCC(OC)CC1 IOCYQQQCJYMWDT-UHFFFAOYSA-N 0.000 description 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-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
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- SZVMZLJAAGWNPG-UHFFFAOYSA-N 1-tert-butylperoxyoctane Chemical compound CCCCCCCCOOC(C)(C)C SZVMZLJAAGWNPG-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- 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 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- IISCRELTMNKFMH-UHFFFAOYSA-N 2-methoxypropan-2-yl 2-methoxypropan-2-yloxycarbonyloxy carbonate Chemical compound COC(C)(C)OC(=O)OOC(=O)OC(C)(C)OC IISCRELTMNKFMH-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
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- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- DFSWNYUWLQKNQP-UHFFFAOYSA-N [Ti].CC=CC=C Chemical compound [Ti].CC=CC=C DFSWNYUWLQKNQP-UHFFFAOYSA-N 0.000 description 1
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- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZRDRRLQUBZPUOP-UHFFFAOYSA-N trichloro(hydroxy)silane Chemical compound O[Si](Cl)(Cl)Cl ZRDRRLQUBZPUOP-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C08L2207/00—Properties characterising the ingredient of the composition
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Abstract
The invention provides an ethylene resin composition and a molded body. An ethylene resin composition satisfying the conditions (A) to (E). < condition (A) > MFR 1.0g/10 min to 20.0g/10 min. < Condition (B) > Density is 920kg/m 3 ～960kg/m 3 . Condition (C) > in the elution temperature-elution amount curve obtained by TREF of CFC, at least one peak exists in the range of 60 ℃ or more and 80 ℃ or less, and at least one peak exists in the range of more than 80 ℃ and 100 ℃ or less. Condition (D) > the molecular weight distribution of the component eluted at a temperature showing the peak with the largest elution amount in the range of 60 ℃ to 80 ℃ inclusive in CFC measurement is 9 to 100 inclusive. < condition (E) > inThe GPC chart of the component eluted at 70℃in the CFC measurement shows that the molecular weight in terms of the fraction is 10 6 A ratio X of an area of g/mol or more to a total area of 10 in terms of a molecular weight 5 The ratio X/Y of the area of g/mol or more to the total area is 0.05 to 0.50.
Description
Technical Field
The present invention relates to an ethylene resin composition and a molded article.
Background
The ethylene resin composition is molded by various molding methods and is used for various applications, and the required properties are different depending on the molding method and the application.
Typical applications of the ethylene resin composition include films. Specifically, a surface protective film for an optical member or the like is known. The surface protective film is required to be clean, in which fish eyes (hereinafter sometimes referred to as "FE") are small and contamination by bleeding of low molecular weight components of the vinyl resin composition as a raw material is small, so as not to damage an object to be protected.
The FE refers to a small spherical foreign matter or a defective structure existing in the film.
The reasons for FE are largely classified into an unmelted resin component and a foreign matter component, and most of the reasons for FE are unmelted resin components.
The unmelted resin component is produced due to insufficient melting in the granulation step of the high-density polyethylene, or is produced due to mixing of a component having a viscosity (molecular weight) different from that of the base resin, a gel component, an oxidatively degraded resin, or a different resin.
The foreign matter component is produced by mixing chips (paper, silk, fiber, etc.) of the packaging material, dust, etc. into any one of the raw material resin production process, bagging and conveying process, and film forming process.
As a method for producing the above-described ethylene resin composition with reduced FE, for example, a method of mixing high-density polyethylene with low-density polyethylene is known. Patent documents 1 and 2 disclose techniques in which FE can be reduced by mixing a small amount of low-density polyethylene with high-density polyethylene. Patent document 3 discloses a clean polyethylene for a surface protective film, which is obtained by mixing a high-density polyethylene having a small low molecular weight component with a low-density polyethylene, has a small FE and is excellent in stain resistance.
Patent documents 4 and 5 disclose a method for producing a high-quality surface protective film having FE and little foreign matter by mounting a sintered filter having a filtration performance of 10 μm to 100 μm on an extruder, specifically, a method for producing a high-quality surface protective film by mounting the sintered filter at an outlet of an extruder for granulating or an extruder for film forming in a process for producing polyolefin.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2017-193661
Patent document 2: international publication No. 2021/014984
Patent document 3: japanese patent No. 6243195
Patent document 4: japanese patent No. 4426441
Patent document 5: international publication No. 2021/070672
Disclosure of Invention
Problems to be solved by the invention
In the case of carrying out resin extrusion by mounting a sintered filter at the outlet of an extruder as described above, if foreign matter, FE, or the like is contained in the resin as a raw material, clogging occurs, and a differential pressure increases with time, and a step of replacing or cleaning the sintered filter is required. Therefore, a clean ethylene resin composition which is less likely to cause pressure increase in the extrusion step using a sintered filter, that is, is less likely to cause FE trapped in the sintered filter, particularly FE derived from crosslinked gel or oxidation degradation products, and less likely to cause dust, catalyst residues and other foreign matters is preferable as a raw material for the surface protective film.
However, patent documents 1 to 5 describe evaluation of the contamination properties by low molecular weight components, although the number of FE having a diameter of 100 μm or more is described, the following problems are presented: in the case of performing the extrusion step using the sintered filter, the pressure increase of the sintered filter, that is, the fine foreign matter which can be trapped by the sintered filter, is not evaluated, and there is room for improvement from the viewpoint of obtaining a clean surface protective film.
Accordingly, in view of the above problems of the prior art, an object of the present invention is to provide an ethylene resin composition having less FE, capable of effectively suppressing the pressure increase caused by clogging when a resin extrusion process is performed using a sintered filter, and excellent in film formation stability.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems of the prior art, and as a result, have found that an ethylene resin composition having specific properties as shown below can solve the above-described problems of the prior art, and have completed the present invention.
Namely, the present invention is as follows.
[1]
An ethylene resin composition satisfying the following conditions (A) > < conditions (E) >.
Condition (A) >, a method of producing a polypeptide
The melt flow rate under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less.
< condition (B) >)
Density of 920kg/m 3 Above 960kg/m 3 The following is given.
Condition (C) >, a method of producing a polypeptide
In an elution temperature-elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatograph (CFC), at least one peak having a peak top is present in a range of 60 ℃ or more and 80 ℃ or less, and at least one peak having a peak top is present in a range of 80 ℃ or more and 100 ℃ or less.
Condition (D) >
The peak having the largest elution amount obtained in the CFC measurement at 60 ℃ or more and 80 ℃ or less has a molecular weight distribution of the component eluted at a temperature at which the peak is shown, of 9 to 100.
Condition (E) >, a method of producing a polypeptide
In the GPC chart obtained by GPC measurement of the component eluted at 70℃in the CFC measurement, the molecular weight was 10 in terms of the molecular weight 6 A ratio X of an area of g/mol or more to a total area of 10 in terms of a molecular weight 5 The ratio X/Y of the area of g/mol or more to the total area ratio Y is 0.05 or more and 0.50 or less.
[2]
The ethylene resin composition according to the above [1], wherein the peak having the largest elution amount in the range of 80℃or more and 100℃or less in the CFC measurement has a molecular weight distribution of components eluted at a temperature at which the peak is exhibited of 4.0 to 20 g/mol inclusive and a weight average molecular weight of 60000g/mol to 200000g/mol inclusive.
[3]
The ethylene resin composition according to the above [1] or [2], wherein the mass ratio of the component eluted in the Temperature Rising Elution Fractionation (TREF) at 60℃to 80℃is 10% to 90% by mass based on the total amount eluted.
[4]
As described above [1]]～[3]The ethylene resin composition according to any one of the preceding claims, wherein the ethylene resin composition has a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following is a mixture of high pressure process low density polyethylenes.
[5]
A molded article of the ethylene resin composition according to any one of the above [1] to [4 ].
[6]
The molded article according to [5], wherein the molded article is a film.
Effects of the invention
According to the present invention, there can be provided an ethylene resin composition having a small FE, particularly a small FE derived from an oxidatively degraded resin or a crosslinked gel, capable of effectively suppressing the pressure increase caused by clogging when a resin extrusion process is performed using a sintered filter, and excellent in film formation stability.
Drawings
FIG. 1 is a GPC chart showing that the molecular weight in terms of the GPC chart obtained by GPC measurement of components eluted at 70℃in CFC measurement is 10 6 A ratio X of the area of g/mol or more to the total area and a reduced molecular weight of 10 5 Schematic diagram of an example of the ratio Y of the area of g/mol or more to the total area.
Detailed Description
Hereinafter, a mode for carrying out the invention of the present application (hereinafter referred to as "the present embodiment") will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following. The present invention can be implemented by various modifications within the scope of the gist.
[ ethylene resin composition ]
The ethylene resin composition of the present embodiment satisfies the following < condition (A) > < condition (E) >.
Condition (A) >, a method of producing a polypeptide
The melt flow rate under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less.
< condition (B) >)
Density of 920kg/m 3 Above 960kg/m 3 The following is given.
Condition (C) >, a method of producing a polypeptide
In an elution temperature-elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatograph (CFC), at least one peak having a peak top is present in a range of 60 ℃ or more and 80 ℃ or less, and at least one peak having a peak top is present in a range of 80 ℃ or more and 100 ℃ or less.
Condition (D) >
The peak having the largest elution amount obtained in the CFC measurement at 60 ℃ or more and 80 ℃ or less has a molecular weight distribution of the component eluted at a temperature at which the peak is shown, of 9 to 100.
Condition (E) >, a method of producing a polypeptide
In the GPC chart obtained by GPC measurement of the component eluted at 70℃in the CFC measurement, the molecular weight was 10 in terms of the molecular weight 6 A ratio X of an area of g/mol or more to a total area of 10 in terms of a molecular weight 5 The ratio X/Y of the area of g/mol or more to the total area ratio Y is 0.05 or more and 0.50 or less.
With the above configuration, an ethylene resin composition having a small FE content, particularly a small FE content derived from an oxidatively degraded resin or a crosslinked gel, which can effectively suppress the pressure rise due to clogging of the sintered filter when the sintered filter is used in the extrusion step of the ethylene resin composition, and which has excellent film formation stability, can be obtained.
The ethylene resin composition of the present embodiment preferably satisfies the following conditions (F) >, and (G) >. Thus, it is possible to obtain an ethylene resin composition which can suppress the occurrence of FE, is excellent in suppression of pressure increase due to clogging of a sintered filter when the sintered filter is used in an extrusion step, and is excellent in film formation stability.
< condition (F) >)
The peak having the largest elution amount in the range of 80 ℃ or higher and 100 ℃ or lower in the CFC measurement has a molecular weight distribution of components eluted at a temperature at which the peak is shown, of 4.0 to 20 inclusive and a weight average molecular weight of 60000g/mol to 200000g/mol inclusive.
Condition (G) >
The mass ratio of the components eluted in the Temperature Rising Elution Fractionation (TREF) at 60 to 80 ℃ inclusive is 10 to 90 mass% of the total elution amount.
The ethylene resin composition of the present embodiment preferably contains a polyethylene selected from the group consisting of high-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene and other special ultra-low-density polyethylene.
Among them, the ethylene resin composition of the present embodiment preferably contains a resin having a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following heightsLow density polyethylene by compression. Such an ethylene resin composition tends to further decrease FE.
Here, the "high pressure method" refers to a process for producing a low density polyethylene by radical polymerization in the presence of a peroxide at a polymerization temperature of 150 ℃ or higher and a polymerization pressure of 100MPa or higher.
The polyethylene contained in the ethylene resin composition of the present embodiment may be an ethylene homopolymer, a copolymer of ethylene and an α -olefin, or two or more (co) polymers.
The method for producing polyethylene is not particularly limited, and any of conventionally used methods such as a solution method, a high-pressure bulk method, a gas method, and a slurry method can be applied.
(melt flow Rate (MFR) at 190 ℃ C. Under a load of 2.16 kg)
As shown in the above-mentioned < condition (A) > the ethylene resin composition of the present embodiment has an MFR of 1.0g/10 min or more and 20.0g/10 min or less under a load of 2.16kg at 190 ℃. Preferably 2.0g/10 min or more and 18.0g/10 min or less, more preferably 3.0g/10 min or more and 15.0g/10 min or less.
When the MFR is 1.0g/10 min or more, film breakage of a film obtained using the ethylene resin composition of the present embodiment can be suppressed.
When the MFR is 200g/10 minutes or less, necking in the molding step using the ethylene resin composition of the present embodiment can be suppressed.
The MFR of the ethylene resin composition can be controlled by adjusting the polymerization conditions, and the MFR of the ethylene resin composition can be controlled within the above-mentioned numerical range by adjusting the selection of the kind of raw materials and the mixing ratio.
(Density)
The ethylene resin composition of the present embodiment has a density of 920kg/m 3 Above 960kg/m 3 The following is given. Preferably 922kg/m 3 Above and 958kg/m 3 Hereinafter, more preferably 925kg/m 3 Above and 955kg/m 3 The following are the following。
When the density is 920kg/m 3 As described above, the heat resistance and stiffness of the film obtained by using the ethylene resin composition of the present embodiment are improved.
When the density is 960kg/m 3 In the following, the strand stability in the production of pellets using the ethylene resin composition of the present embodiment is improved, and the film shaking in the film formation can be reduced.
The density of the ethylene resin composition of the present embodiment is measured in accordance with JIS K7112, specifically, by the method described in examples described later.
The density of the vinyl resin composition can be controlled by adjusting the polymerization conditions, and the density of the vinyl resin composition can be controlled within the above-mentioned numerical range by adjusting the selection of the kind of raw materials and the mixing ratio.
(elution temperature-elution amount Curve obtained by CFC measurement)
In the elution temperature-elution amount curve of the ethylene resin composition of the present embodiment obtained by Temperature Rising Elution Fractionation (TREF) as measured by cross-fractionation chromatography (CFC), at least one peak having a peak top is present in a range of 60 ℃ or more and 80 ℃ or less, and at least one peak having a peak top is present in a range of 80 ℃ or more and 100 ℃ or less.
Here, the term "cross-fractionation chromatography (CFC)" refers to a device in which a temperature rising elution fractionation unit (hereinafter also referred to as "TREF unit") for performing crystallization fractionation and a gel permeation chromatography unit (hereinafter also referred to as "GPC unit") for performing molecular weight fractionation are combined, and the TREF unit and the GPC unit are directly connected to each other to enable analysis of the correlation between the composition distribution and the molecular weight distribution.
The elution amount and the elution accumulation amount of the ethylene resin composition at each temperature can be obtained by measuring an elution temperature-elution amount curve by the TREF unit as described below. First, a column containing a filler was heated to 140℃and a sample solution was prepared by dissolving an ethylene resin composition in o-dichlorobenzene, and the sample solution (for example, 20mg/20 mL) was introduced and held for 120 minutes.
Then, the temperature was lowered to 40℃at a cooling rate of 0.5℃per minute, whereby the samples were sequentially deposited on the filler surface.
The temperature was maintained at 40℃for 20 minutes, and then the column temperature was successively increased at a rate of 20℃per minute. First, the temperature was raised from 40℃to 60℃at 10℃intervals, from 60℃to 69℃at 3℃intervals, from 69℃to 100℃at 1℃intervals, and from 100℃to 120℃at 10℃intervals.
After holding at each temperature for 21 minutes, the temperature was raised, and the concentration of the sample (polyethylene) eluted at each temperature was measured.
That is, the "each temperature" means all temperatures (40 ℃, 50 ℃, 60 ℃, 63 ℃, 66 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, … …, 98 ℃, 99 ℃, 100 ℃, 110 ℃, 120 ℃) at which the temperature is raised from 40 ℃ to 60 ℃, from 60 ℃ to 69 ℃ at 3 ℃ and from 69 ℃ to 100 ℃ at 1 ℃ and from 100 ℃ to 120 ℃ at 10 ℃ intervals ". Each of these temperatures was maintained for 21 minutes, and then samples at each temperature were collected and the concentration was measured.
Then, the elution temperature-elution amount curve was measured from the elution amount (% by mass) of the sample (ethylene-based resin composition) and the value of the in-column temperature (. Degree. C.) at that time, thereby obtaining the elution amounts at the respective temperatures.
(molecular weight distribution Mw/Mn of component eluted at low-temperature peak temperature)
In the ethylene resin composition of the present embodiment, the molecular weight distribution of the component eluted at the temperature at which the peak is detected (hereinafter referred to as "low-temperature peak temperature") by GPC measurement is 9 to 100, with respect to the peak having the largest elution amount obtained in the range of 60 ℃ to 80 ℃ in CFC detection.
The lower limit of the molecular weight distribution is preferably 10 or more, more preferably 11 or more. The upper limit value is preferably 90 or less, and more preferably 80 or less.
The molecular weight distribution is represented by Mw/Mn, which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, and the molecular weight distribution of each component eluted at each temperature of 40℃to 120℃can be obtained by the measurement of the CFC.
The molecular weight distribution of the component eluted at the low-temperature peak temperature indicates the molecular weight distribution of the component having low crystallinity in the ethylene resin composition, that is, the degree of long-chain branching in the low-density component. The molecular weight distribution of the component eluted at the low-temperature peak temperature tends to show a value equivalent to the molecular weight distribution of the low-density component contained in the ethylene resin composition. However, when a highly-supported polymer is contained, the highly-branched component and the low-molecular-weight component are eluted simultaneously, and therefore, the polymer tends to exhibit a value significantly larger than the molecular weight distribution of the low-density component contained in the vinyl resin composition, which is measured by GPC.
When the molecular weight distribution of the component eluted at the low-temperature peak temperature is 9 or more, since the component contains a highly branched polymer, stress due to the entanglement effect of the long-chain branched component in the kneading step by an extruder acts, and FE derived from the unmelted resin or the crosslinked gel tends to be sufficiently reduced. In addition, foreign matter such as a catalyst carrier tends to be crushed.
When the molecular weight distribution of the component eluted at the low-temperature peak temperature is 100 or less, there is a tendency that the component does not contain a low-molecular weight component which is a cause of contamination with an adherend or an ultrahigh-molecular weight component which is a cause of FE.
The molecular weight distribution of the component eluted at the low temperature peak temperature can be controlled within the above numerical range by adjusting the polymerization conditions of the low density polyethylene component, for example, polymerization temperature, polymerization pressure, polymerization initiator species, presence or absence of chain transfer agent, reactor species, but is not particularly limited. Specifically, it is effective to use a peroxide ester as a peroxide having high reactivity as a polymerization initiator and to adjust the polymerization pressure to 200MPa or less. Further, polymerization is carried out under forced stirring while controlling the polymerization pressure and the polymerization temperature to appropriate values without adding a chain transfer agent, and thus a polymer having a broad molecular weight distribution tends to be produced.
(GPC measurement of component eluted at 70 ℃ C.)
In the GPC chart of the component eluted at 70℃obtained by CFC measurement of the ethylene resin composition of the present embodiment, the molecular weight in terms of the molecular weight is 10 6 A ratio X of an area of g/mol or more to a total area of 10 in terms of a molecular weight 5 The ratio X/Y of the area of g/mol or more to the total area ratio Y is 0.05 or more and 0.50 or less. Preferably from 0.06 to 0.45, more preferably from 0.07 to 0.40.
The component eluted at 70℃obtained by CFC measurement is also a component having low crystallinity in the ethylene resin composition, and Y represents a component having a molecular weight of 10 in terms of molecular weight 5 The ratio of the polymer having long chain branches of g/mol or more, X represents a molecular weight of 10 in terms of molecular weight, which is particularly large in the polymer having long chain branches 6 A ratio of the polymer to the polymer of g/mol or more.
FIG. 1 shows a GPC chart showing that the molecular weight in terms of the GPC chart obtained by GPC measurement of components eluted at 70℃by CFC measurement is 10 6 A ratio X of the area of g/mol or more to the total area and a reduced molecular weight of 10 5 Schematic diagram of an example of the ratio Y of the area of g/mol or more to the total area.
Therefore, X/Y represents the proportion of a long-chain branched polymer having a larger molecular weight among the long-chain branched polymers, and the X/Y is 0.05 or more, and tends to be as follows: in the kneading step by an extruder, stress due to entanglement effect of the long-chain branched component acts, FE derived from the unmelted resin or the crosslinked gel is sufficiently reduced, and foreign matter such as the catalyst carrier is crushed. Further, since the component having a large number of branches elutes from 70 ℃ which is a relatively low temperature, the processability of the film formation is improved, and a film having less film unevenness tends to be formed.
X/Y is 0.50 or less, and the molecular weight in terms of FE or dispersion failure is 10 6 The proportion of the ultrahigh molecular weight component of g/mol or more tends to be sufficiently reduced.
X/Y can be adjusted within the above range by controlling the polymer branching structure of the low density component.
Polymers of low density composition are typically produced by high pressure processes. In order to control the branched structure of the polymer, there is no particular limitation, and it is effective to adjust the polymerization conditions such as polymerization temperature, polymerization pressure, chain transfer agent, and kind of polymerization initiator.
The chain transfer agent is not particularly limited, and various physical properties can be adjusted by stopping radicals in the growing polymer using hydrocarbon compounds such as propane, propylene, butane, and the like. Since a polymer having a higher polymerization degree is produced by polymerization without using a chain transfer agent, the polymer tends to be easily obtained as a long chain branch.
By selecting an organic peroxide having high reactivity, for example, a peroxyester (specifically, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3, 5, 6-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropylcarbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, etc.) as a polymerization initiator, a long chain branch formation reaction can be promoted.
In addition, in order to control X/Y as described above, it is effective to control the branched structure of the polymer of the low-density component more precisely. For example, by adjusting the temperature of the polymer immediately after the discharge from the polymerization reactor and the temperature of the raw material ethylene gas supplied to the polymerization reactor, the branched structure of the polymer of the low-density component can be controlled more precisely.
Since the decomposition of the polymer produced, particularly the decomposition of the branching point, is easily affected by the temperature of the polymer immediately after the discharge from the polymerization reactor, the branching structure of the polymer of the low-density component can be precisely controlled by appropriately adjusting the temperature. For example, by setting the temperature of the polymer immediately after discharge from the polymerization reactor to 180℃or lower, decomposition of the polymer can be suppressed.
The temperature of the polymer immediately after discharge from the polymerization reactor generally shows a temperature in the vicinity of the polymerization temperature, but can be controlled by, for example, jacket cooling of a pipe immediately after the polymerization reactor with water vapor or warm water.
The temperature of ethylene supplied to the polymerization reactor affects the branched structure of the polymer, and for example, the lower the temperature of ethylene supplied to the polymerization reactor, the easier the polymerization reaction proceeds, and in particular, the greater the temperature difference between the temperature of ethylene supplied to the polymerization reactor and the polymerization temperature, the higher the polymerization degree of the polymer is produced at the initial stage of the reaction. For example, by lowering the temperature at which ethylene is supplied, a polymer having a high degree of polymerization is produced in the initial stage of the reaction, whereby the polymer having a high degree of polymerization is introduced as long chain branches in the subsequent branch formation reaction, and thus a polymer having strong entanglement is formed. The ethylene temperature supplied to the polymerization reactor is heated by the heat released from the polymerization reactor, but can be controlled by, for example, jacket cooling the pipe immediately before the polymerization reactor with cold water. For example, when the difference between the polymerization temperature and the temperature at which ethylene is supplied is 180℃or more, a polymer having a high degree of polymerization is easily introduced as a branched chain.
(molecular weight distribution and weight average molecular weight of component eluted at high temperature peak temperature)
The ethylene resin composition of the present embodiment is preferably: the peak having the largest elution amount in the CFC measurement in the range of 80 ℃ or higher and 100 ℃ or lower has a molecular weight distribution of 3.5 to 20.0 inclusive and a weight average molecular weight of 60000g/mol to 200000g/mol inclusive, which is a component eluted at a temperature at which the peak is shown (hereinafter referred to as "high temperature peak temperature"). The molecular weight distribution is preferably 4.0 to 20.0, more preferably 4.5 to 18.0, and still more preferably 5.0 to 15.0. The weight average molecular weight is preferably 65000g/mol or more and 180000g/mol or less, more preferably 70000g/mol or more and 160000g/mol or less.
The molecular weight distribution and weight average molecular weight of the component eluted at the high temperature peak temperature represent the molecular weight distribution and weight average molecular weight of the high density component contained in the ethylene resin composition. Therefore, the molecular weight distribution and weight average molecular weight of the component eluted at the high temperature peak temperature tend to show values equivalent to those of the molecular weight distribution and weight average molecular weight of the high-density component contained in the ethylene resin composition.
The molecular weight distribution and weight average molecular weight of the high-density component can be controlled by adjusting the type of catalyst and the polymerization conditions at the time of polymerization to obtain the high-density component, but the physical properties of the polymer and the state of catalyst residues can be controlled by adjusting these conditions. For example, when a ziegler-type catalyst is used as a catalyst having a low reaction rate and the polymerization temperature is set to 70 ℃ or lower, the molecular weight distribution is controlled to 3.5 or higher and the weight average molecular weight is controlled to 60000g/mol or higher, whereby the raw material monomer permeates into the catalyst carrier and the polymer sufficiently grows from the inside of the carrier, the catalyst carrier is easily crushed, and the occurrence of abnormal high molecular weight components can be suppressed, and thus FE tends to be reduced. In general, the polymerization production tends to be lowered by lowering the reaction temperature, but the polymer properties can be controlled within a range not greatly impairing the production by controlling the reaction temperature to 60 ℃ or higher and 70 ℃ or lower. On the other hand, for example, in the case of using spherical silica having a particle diameter of about 1 μm to about 20 μm as a catalyst carrier, the catalyst carrier is not easily broken, and when a sintered filter is used in the resin extrusion step, there is a high possibility of clogging, which is not preferable. In addition, even with a catalyst carrier that is difficult to crush, the pressure increase tends to be slightly reduced by setting the particle diameter to be equal to or less than the filtration accuracy of the filter.
When the molecular weight distribution of the component eluted at the high temperature peak temperature is 3.5 or more and the weight average molecular weight is 60000g/mol or more, the reaction rate becomes sufficiently slow, so that the catalyst carrier tends to be easily crushed, clogging of the filter is reduced in the film forming step, and FE can be effectively reduced, which is preferable. The component eluted at the high temperature peak temperature has a molecular weight distribution of 20.0 or less and a weight average molecular weight of 200000g/mol or less, and thus tends to contain no abnormal high molecular weight component and to decrease FE, which is preferable.
(the mass ratio of the components eluted in the range of 60 ℃ to 80 ℃ inclusive)
The mass ratio of the component eluted in the range of 60 ℃ to 80 ℃ with respect to the ethylene resin composition of the present embodiment, which is calculated from the elution temperature-elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of CFC measurement, is preferably 10% by mass to 90% by mass of the total elution amount, more preferably 15% by mass to 85% by mass of the total elution amount, and still more preferably 20% by mass to 80% by mass of the total elution amount.
The total elution amount refers to the total area of the elution temperature-elution amount curve in the range of 40 to 120 ℃.
The mass ratio of the components eluted at 60℃or more and 80℃or less tends to be substantially equal to the mass ratio of the low-density components contained in the vinyl resin composition, i.e., the long-chain branched polymers.
The following effects are exhibited by the mass ratio of the components eluted in the range of 60 ℃ to 80 ℃ inclusive being 10% by mass or more of the total elution amount: in the kneading step by an extruder, stress due to entanglement effect of the long-chain branched component acts, FE derived from the unmelted resin or the crosslinked gel is sufficiently reduced, and the stability of film formation using the ethylene resin composition of the present embodiment is improved, and foreign matter such as a catalyst carrier is crushed, so that it is preferable.
The mass ratio of the components eluted in the range of 60 ℃ to 80 ℃ is preferably 90 mass% or less of the total elution amount, since the low-density component and the high-density component are well dispersed and FE is reduced without causing uneven physical properties at the time of film formation using the ethylene resin composition of the present embodiment.
The mass ratio of the components eluted at 60 ℃ or more and 80 ℃ or less can be controlled within the above numerical range by adjusting the amount of the low-density component in the ethylene resin composition, and for example, the content of the high-pressure low-density polyethylene can be controlled to 20 mass% or more and 80 mass% or less in the ethylene resin composition.
[ molded article ]
The molded article of the present embodiment is a molded article of the ethylene resin composition of the present embodiment, and examples thereof include films. When the film is a multilayer film, the ethylene resin composition of the present embodiment may be used for the outermost layer or the intermediate layer.
[ method for producing vinyl resin composition ]
The method for producing the ethylene resin composition of the present embodiment is not particularly limited, and it can be produced, for example, by melt-kneading a high-density polyethylene (a) and a high-pressure low-density polyethylene (B).
Here, the high-density polyethylene means a polyethylene having a density of 942kg/m 3 The polyethylene resin above, low-density polyethylene means a polyethylene having a density of 930kg/m 3 The following polyethylene resins.
Examples of the melt kneader used in the kneading operation include a single screw extruder, a twin screw extruder, a vented extruder, and a tandem extruder.
The high-density polyethylene (a) can be produced by, for example, a continuous slurry polymerization method. The catalyst used in the production is not particularly limited, and for example, a metallocene catalyst, a Ziegler-Natta catalyst, a Phillips catalyst, or the like can be used. The use of a Ziegler-Natta catalyst having a low reaction rate is preferable because the catalyst carrier can be easily crushed. In general, the physical properties of the high-density polyethylene (a) can be controlled by adjusting the comonomer concentration and the hydrogen concentration in addition to the polymerization temperature, the polymerization pressure, and the catalyst type. When a large amount of comonomer is added, the density is reduced, and thus adjusted to an appropriate comonomer concentration.
In the case where the high-density polyethylene (a) and the high-pressure process low-density polyethylene (B) described later are copolymers of ethylene and other comonomers, examples of the comonomers include: a compound selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, styrene, and derivatives thereof; a cyclic olefin having 3 to 20 carbon atoms selected from the group consisting of cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1, 4,5, 8-dimethylene-1, 2,3, 4a,5,8 a-octahydronaphthalene; the linear, branched or cyclic diene having 4 to 20 carbon atoms selected from the group consisting of 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 7-octadiene and cyclohexadiene, but is not limited thereto. Propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like are particularly preferable.
The polymerization temperature of the high-density polyethylene (a) is preferably 30 ℃ or higher and 100 ℃ or lower, and the polymerization temperature is 30 ℃ or higher, whereby an industrially more efficient production can be achieved, while the polymerization temperature is 100 ℃ or lower, whereby a more stable operation can be continuously performed. In particular, it is preferable to control the temperature to 60 ℃ or higher and 70 ℃ or lower because the productivity is not impaired, and the pulverization of the catalyst carrier and the production of FE can be suppressed.
The polymerization pressure in the process for producing the high-density polyethylene (a) is usually preferably not less than normal pressure and not more than 2MPa, more preferably not less than 0.1MPa and not more than 1.5MPa, still more preferably not less than 0.1MPa and not more than 1.0 MPa.
The molecular weight of the high-density polyethylene (a) can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature, as described in the specification of german patent application publication No. 3127133. The molecular weight of the high-density polyethylene (a) can be controlled within an appropriate range by adding hydrogen as a chain transfer agent to the polymerization system.
Examples of the solvent separation method include decantation, centrifugation, and filter filtration, and more preferably centrifugation with good separation efficiency of the ethylene polymer from the solvent.
The polyethylene powder obtained is preferably classified by a sieve immediately before granulation to remove powder having a particle size of 100 μm or less. Since the polymer having a small powder particle size has low activity and contains a large amount of catalyst residues, the removal of the polymer having a small powder particle size can reduce the pressure increase when using a sintered filter in the extrusion step using the finally obtained ethylene resin composition.
The polyethylene powder is pelletized by a single screw extruder, a twin screw extruder, an exhaust extruder, a tandem extruder, etc. The type of extruder and the number of extrusion times are not particularly limited, and kneading is preferably performed by a twin-screw extruder.
The high-pressure low-density polyethylene (B) can be obtained, for example, by radical polymerization of ethylene in an autoclave or tubular reactor, but is not particularly limited.
In the case of using an autoclave type reactor, the polymerization conditions for the high-pressure low-density polyethylene (B) may be set to a temperature of 200 to 300℃and a polymerization pressure of 100 to 250MPa in the presence of a peroxide, while in the case of using a tubular reactor, the polymerization conditions for the high-pressure low-density polyethylene (B) may be set to a polymerization peak temperature of 180 to 400℃and a polymerization pressure of 100 to 400MPa in the presence of a peroxide.
The physical properties of the resulting high-pressure low-density polyethylene (B) can be controlled by adjusting the polymerization temperature and polymerization pressure as described above, and adjusting the type of peroxide and the presence or absence of a chain transfer agent as described below.
The peroxide is not particularly limited, and examples thereof include: methyl ethyl ketone peroxide, ketone peroxide (specifically, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) octane, n-butyl 4, 4-bis (t-butylperoxy) valerate, 2-bis (t-butylperoxy) butane, etc.), hydroperoxides (specifically, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1, 3-tetramethylbutyl hydroperoxide, etc.), dialkyl peroxides (specifically, di-t-butyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-di (t-butylperoxy) -3-hexyne, etc.), diacyl peroxide (specifically, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, 3, 5-trimethylhexanoyl peroxide, benzoyl peroxide, etc.), peroxydicarbonates (specifically, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, etc.), and the like, bis (3-methyl-3-methoxybutyl) peroxydicarbonate, diallyl peroxydicarbonate, and the like), peroxyesters (specifically, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3, 5, 6-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, and the like), acetyl cyclohexyl sulfonyl peroxide, t-butyl peroxyallylcarbonate, and the like.
In particular, long-chain branching reaction is promoted by selecting a peroxide having high reactivity, for example, a peroxyester (specifically, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-3, 5, 6-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropylcarbonate, cumyl peroxyoctoate, t-hexyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxyneohexanoate, t-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, etc.), and is therefore preferable.
The chain transfer agent is not particularly limited, and various physical properties can be adjusted by stopping radicals of the growing polymer by using hydrocarbon compounds such as propane, propylene, butane, and the like. The polymerization is preferably carried out without using a chain transfer agent, because a polymer having a larger degree of polymerization and more long chain branches is produced.
Further, since the temperature of ethylene supplied to the polymerization reactor and the temperature of the polymer immediately after the discharge from the polymerization reactor affect the branched structure of the polymer, it is preferable to control the temperature difference between the temperature of ethylene supplied to the polymerization reactor and the polymerization temperature to 180 ℃ or more and the temperature of the polymer immediately after the discharge from the polymerization reactor to 180 ℃ or less by the method of jacket-cooling the pipe immediately before the polymerization reactor and the pipe immediately after the polymerization reactor with cold water as described above.
(additive)
The ethylene resin composition, each component as a raw material, and the molded article of the present embodiment may further contain additives such as an antioxidant, a light stabilizer, a slip agent, a filler, and an antistatic agent.
Examples
Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples.
The measurement method and evaluation method of each physical property and characteristic are described below.
[ method for measuring physical Properties ]
((physical Property 1) Melt Flow Rate (MFR) at 190 ℃ C., load of 2.16 kg)
The ethylene resin compositions and raw materials obtained in examples and comparative examples were numbered D by JIS K7210: 1999 (temperature=190 ℃, load=2.16 kg) the melt flow rate (g/10 min) was measured.
((physical Property 2) Density)
The ethylene resin compositions and raw materials obtained in examples and comparative examples were prepared by the method of JIS K7112: 1999. density (kg/m) was measured by the Density gradient tube method (23 ℃ C.) 3 )。
(Property 3) Mw, mn, mw/Mn in GPC measurement
The low density polyethylene (B) produced as described below was subjected to Gel Permeation Chromatography (GPC) measurement using GPC-IR manufactured by Polymer Char company and IR5 manufactured by Polymer Char company as a detector.
To 20mg of the low-density polyethylene (B), 15mL of o-dichlorobenzene as a mobile phase was added and stirred at 150℃for 1 hour, thereby preparing a sample solution, which was flowed at a flow rate of 1.0 mL/min. As a column, UT-807 (1) manufactured by Showa electric Co., ltd. And GMHHR-H (S) HT (2) manufactured by Tosoh Co., ltd., were used in series, and the measurement was performed under the conditions of a column temperature of 140℃and a sample dissolution time of 90 minutes.
The ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) as determined by GPC was used as the molecular weight distribution.
The molecular weight calibration was performed at 12 points in the range of 1050 to 2060000 in terms of Mw (molecular weight) of standard polystyrene manufactured by Tosoh corporation, and the Mw of each standard polystyrene was multiplied by a coefficient of 0.43 to obtain a molecular weight in terms of polyethylene, and a calibration straight line was prepared from the graph of the elution time and the molecular weight in terms of polyethylene, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined.
(Property 4) elution temperature-elution amount curve, number of elution peaks, mass ratio of component eluted in a range of 60 ℃ to 80 ℃ inclusive to total elution amount in Cross Fractionation Chromatography (CFC) measurement, mw/Mn of component eluted at a temperature of peak having the largest elution amount obtained in a range of 60 ℃ to 80 ℃ inclusive, weight average molecular weight Mw and weight average molecular weight Mw of component eluted at a temperature of peak having the largest elution amount in a range of 80 ℃ to 100 ℃ inclusive Molecular weight distribution Mw/Mn, calculated molecular weight of component eluted at 70℃was 10 6 The ratio X of the above area to the total area of GPC chart was 10 in terms of molecular weight 5 The ratio X/Y of the above ratio Y of the area to the total area)
For each of the ethylene resin compositions obtained in examples and comparative examples, CFC measurement was carried out using an Automated 3D analyzer CFC-2 manufactured by Polymer Chur Co.
As a TREF column, a stainless steel microsphere column (outer diameter 3/8 inch. Times.length 150 mm) was used. As GPC columns, 1 GPC UT-807 manufactured by Shodex corporation and 2 GMHHR-H (S) HT manufactured by Tosoh Co., ltd.) were used in total of 3.
As an eluent, o-dichlorobenzene (for high performance liquid chromatography) was flowed at a flow rate of 1.0 mL/min.
The column containing the filler was heated to 140℃and 20mL of a sample solution (sample concentration: 1.0 g/mL) obtained by dissolving the ethylene resin composition in o-dichlorobenzene was introduced and kept for 120 minutes.
Then, the temperature of the column was lowered to 40℃at a lowering rate of 0.5℃per minute, and then kept for 20 minutes. In this step, the sample is deposited on the filler surface.
Then, the temperature of the column was adjusted as follows.
First, the temperature was raised to 50℃and maintained at 50 ℃. Then, the temperature was raised to 60℃and maintained at 60 ℃. Then, the temperature is raised and maintained at 5℃intervals from 60℃to 75℃and at 3℃intervals from 75℃to 90℃and at 1℃intervals from 90℃to 110℃and at 5℃intervals from 110℃to 120 ℃. The temperature was raised at a rate of 20 ℃/min in each heating process, and the temperature was maintained at each holding temperature for 21 minutes.
The concentration (mass%) of the sample eluted during the holding for 21 minutes at each holding temperature was measured, and an elution temperature-elution amount curve was obtained from the holding temperature and the concentration of the eluted sample.
Then, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the component eluted during the holding at each holding temperature for 21 minutes were determined using a GPC column connected to a TREF column.
The mass ratio of the components eluted in the range of 60 ℃ to 80 ℃ from the number of elution peaks and the total elution amount was determined from the elution temperature-elution amount curve obtained as described above.
Further, from the GPC measurement results of the components eluted at the respective temperatures obtained as described above, the peak having the largest elution amount obtained in the range of 60 ℃ to 80 ℃ was obtained, and the molecular weight distribution Mw/Mn of the component eluted at the temperature showing the peak was obtained; for a peak having the largest elution amount obtained in a range of 80 ℃ or more and 100 ℃ or less, the weight average molecular weight Mw and the molecular weight distribution Mw/Mn of the component eluted at a temperature at which the peak is displayed; the component eluted at 70℃had a converted molecular weight of 10 6 The ratio X of the area of (g/m & gtl) or more to the total area of GPC chart is 10 in terms of molecular weight 5 A ratio X/Y of the ratio Y of the area of (g/m & gtl) or more to the total area.
In the table, the peak having the largest elution amount obtained in the range of 60 ℃ to 80 ℃ is referred to as a low temperature peak, and the peak having the largest elution amount in the range of 80 ℃ to 100 ℃ inclusive is referred to as a high temperature peak.
[ evaluation method ]
(evaluation 1) number of FE' s
The ethylene resin composition was molded using a T-die film-forming machine (HM 40N, screw diameter 40mm, die width 300mm, manufactured by North Ind Co., ltd.) at a barrel temperature of 200℃and a die temperature of 210℃with an extrusion amount of 5 kg/hr.
The film comprising the ethylene resin composition was obtained by trimming 50mm on each of both ends to a thickness of 35. Mu.m, and the film area was visually evaluated for 400cm 2 The length of the long axis is more than 0.1mm and the number N3 of FE.
The index X of the number of FEs was defined by "x=n3/(n1×a+n2×b)" using the number N1 of FEs of the high-density polyethylene (a) alone film as a raw material, the mass ratio a of the high-density polyethylene (a) when the entire ethylene resin composition was 1, the number N2 of FEs of the low-density polyethylene (B) alone film as a raw material, and the mass ratio B of the low-density polyethylene (B) when the entire ethylene resin composition was 1, and evaluated as described below.
In the case of using two or more kinds of low-density polyethylene (B), the term of the low-density polyethylene as a denominator is increased according to the number.
And (3) the following materials: 0.5 or less
O: greater than 0.5 and less than or equal to 0.7
Delta: greater than 0.7 and less than or equal to 1.0
X: greater than 1.0
((evaluation 2) the amount of FE derived from an oxidatively degraded resin or crosslinked gel)
Microscopic FT-IR measurements of cross sections were performed on 20 FE's randomly selected from the films produced in the above (evaluation 1) using a Fourier transform infrared spectrophotometer FT/IR-4000 manufactured by Japanese Spectroscopy Co., ltd and an infrared microscope IRT-3000 attached thereto.
Wherein, will be at 1700cm -1 ～1750cm -1 The fish eyes in which peaks were observed in the range of (a) were defined as fish eyes derived from an oxidatively degraded resin or a crosslinked gel, and the proportion of fish eyes derived from an oxidatively degraded resin or a crosslinked gel contained in 20 fish eyes was evaluated as described below.
And (3) the following materials: 0.1 or less
O: greater than 0.1 and less than or equal to 0.3
Delta: greater than 0.3 and less than or equal to 0.5
X: greater than 0.5
(evaluation 3) pressure boosting of sintered Filter
For each of the ethylene resin compositions obtained in examples and comparative examples, the resin pressure at the time of extrusion for 30 minutes in a single screw extruder manufactured by Toyo Seiki Seisaku Co., ltd., equipped with a metal nonwoven fabric sintered filter (NF-06T manufactured by Nippon Seisakusho Co., ltd.) having a filtration accuracy of 10 μm was measured under the following extrusion conditions.
Here, the value of the pressure increase means the difference between the resin pressure at the time of charging each of the ethylene resin compositions obtained in examples and comparative examples into a hopper and taking the start time after 3 minutes from the discharge of the ethylene resin composition as the start time, and the difference between the resin pressure at this time and the resin pressure after 30 minutes therefrom was evaluated by the following evaluation criteria.
Extrusion conditions >
And (3) an extruder: single screw extruder
Extrusion temperature: 230 DEG C
Screw rotation speed: 5rpm
And (3) a filter: NF-06T (filtration accuracy 10 μm)
Area of filter: 314mm 2
< evaluation criteria >
And (3) the following materials: less than 5MPa
O: 5MPa to less than 10MPa
Delta: 10MPa to less than 20MPa
X: 20MPa or more
((evaluation 4) Standard deviation of 20 ° gloss)
The film samples of 10 points randomly cut from the film produced in the above (evaluation 1) were measured under the condition of 20 ° incident angle according to ASTM D523 (2457) using the GLOSS METER GM-26D manufactured by the color technology research on co.
The standard deviation of the obtained gloss value was evaluated as an index of film formation stability of the film as follows.
And (3) the following materials: less than 2.0
O: 2.0 to less than 3.0
Delta: 3.0 to less than 4.0
X: 4.0 or more
[ preparation of the ingredients used in examples and comparative examples ]
(high Density polyethylene (A))
Preparation of Ziegler-Natta catalyst (a)
1000mL of a hexane solution of 2mol/L hydroxytrichlorosilane was charged into an 8L stainless steel autoclave which had been sufficiently replaced with nitrogen gas, and AlMg was added dropwise over 4 hours while stirring at 65 ℃ 5 (C 4 H 9 ) 11 (OC 4 H 9 ) 2 2550mL (equivalent to 2.68 moles of magnesium) of a hexane solution of the organomagnesium compound was shown, and then the reaction was continued while stirring at 65℃for 1 hour.
After the completion of the reaction, the supernatant was removed, and the mixture was washed with 1800mL of hexane 4 times to obtain a solid as a carrier. As a result of analysis of this solid, the amount of magnesium contained in each 1g of the solid was 8.31 mmol.
110mL of a hexane solution of 1mol/L titanium tetrachloride and 1mol/L AlMg were simultaneously added to 1970mL of a hexane slurry containing 110g of the above carrier with stirring at a temperature of 10℃for 1 hour 5 (C 4 H 9 ) 11 (OSiH) 2 110mL of a hexane solution of the organomagnesium compound shown. After the addition, the reaction was continued at 10℃for 1 hour. After the completion of the reaction, 1100mL of the supernatant was removed and washed 2 times with 1100mL of hexane, thereby preparing a Ziegler-Natta catalyst (a).
Preparation of metallocene catalyst (b-1)
Average particle diameter of 3 μm and surface area of 800m 2 The spherical silica having/g and an intraparticle pore volume of 1.5mL/g was calcined at 500℃for 5 hours under a nitrogen atmosphere to be dehydrated, thereby obtaining dehydrated silica.
The amount of surface hydroxyl groups of dehydrated silica relative to 1g of SiO 2 1.85 mmoles/g.
40g of the dehydrated silica was dispersed in 800mL of hexane in an autoclave having a capacity of 1.8L under a nitrogen atmosphere, to thereby obtain a slurry. 80mL of a hexane solution of triethylaluminum (concentration: 1 mol/L) was added to the obtained slurry while keeping at 50℃with stirring, and then, triethylaluminum was reacted with the surface hydroxyl groups of silica with stirring for 2 hours, thereby obtaining a component [ c ] containing triethylaluminum-treated silica and supernatant and in which the surface hydroxyl groups of triethylaluminum-treated silica were terminated with triethylaluminum.
Then, the supernatant in the resulting reaction mixture was removed by decantation, thereby removing unreacted triethylaluminum in the supernatant.
Then, an appropriate amount of hexane was added to obtain 880mL of hexane slurry of triethylaluminum-treated silica (component [ c ]).
On the other hand, [ (N-tert-butylamino) (tetramethyl-. Eta.5-cyclopentadienyl) dimethylsilane ]200 mmol of titanium-1, 3-pentadiene (hereinafter referred to as "titanium complex") was dissolved in 1000mL of Isopar E (trade name of hydrocarbon mixture manufactured by Exxon chemical Co., ltd., U.S.A.), and AlMg of the formula previously synthesized from triethylaluminum and dibutylmagnesium was added 6 (C 2 H 5 ) 3 (n-C 4 H 9 ) y 20mL of 1mol/L hexane solution, and then hexane was added to adjust the concentration of the titanium complex to 0.1mol/L, thereby obtaining component [ d ]]。
In addition, 5.7g of bis (hydrogenated tallow) methyl ammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as "borate compound") was added and dissolved in 50mL of toluene, to thereby obtain a 100 mmol/L toluene solution of the borate compound. To the toluene solution of the borate compound was added 5mL of a 1mol/L hexane solution of diethylaluminum ethoxide at room temperature, and then hexane was added so that the borate concentration in the solution reached 70 mmol/L. Then, the mixture was stirred at room temperature for 1 hour, thereby obtaining a reaction mixture containing a borate compound.
46mL of the reaction mixture containing a borate compound was added to 800mL of the slurry of the component [ c ] obtained above while stirring at 15℃to 20℃to support the borate compound on silica. Thus, a slurry of silica loaded with a borate compound was obtained. Then, 32mL of the above-obtained component [ d ] was added thereto, and the mixture was stirred for 3 hours to react the titanium complex with the borate compound. Thus, a supported metallocene catalyst (b-1) comprising silica and a supernatant and having a catalyst active material formed on the silica was obtained.
Preparation of metallocene catalyst (b-2)
Using a mean particle diameter of 15 μm and a surface area of 700m 2 The same procedure as for the metallocene catalyst (b-1) was carried out except that spherical silica having a intraparticle pore volume of 1.8mL/g was used as the carrier, thereby obtaining a metallocene catalyst (b-2))。
< production of high Density polyethylene (A-1) >)
A vessel-type 280L polymerization reactor equipped with a stirring device was used to conduct continuous polymerization at a polymerization temperature of 68℃under a polymerization pressure of 0.80MPa and an average residence time of 1.6 hours. Dehydrated n-hexane was supplied as a solvent at 40L/hr, the Ziegler-Natta catalyst [ a ] was supplied as a catalyst at 0.4 g/hr, and triisobutylaluminum was supplied as a liquid co-catalyst component at 24 mmol/hr in terms of Al atom. The hydrogen for adjusting the molecular weight was supplied in a manner of 40.2 mol% with respect to the gas phase concentration of ethylene and 1-butene, and 1-butene was supplied in a manner of 0.74 mol% with respect to the gas phase concentration of ethylene, thereby polymerizing ethylene and 1-butene.
The dehydrated n-hexane was supplied from the bottom of the polymerization reactor, the hydrogen gas was supplied from the middle between the liquid surface and the bottom of the polymerization reactor together with the catalyst from the catalyst introduction line for the purpose of contact with the catalyst in advance, and the ethylene was supplied from the bottom of the polymerization reactor.
The polymerization slurry in the polymerization reactor was introduced into a flash tank having a pressure of 0.08MPa and a temperature of 75 ℃ in such a manner that the liquid surface of the polymerization reactor was kept constant, and unreacted ethylene, 1-butene and hydrogen were separated.
Next, the polymerization slurry is continuously fed into a centrifuge in such a manner that the liquid surface of the polymerization reactor is kept constant, and the polymer and the solvent or the like other than the polymer are separated. The content of the solvent or the like in this case was 45%.
The separated high-density polyethylene powder was dried at 85 ℃ while blowing nitrogen. Then, the obtained powder was classified by a classifier to remove powder having a particle diameter of 100 μm or less.
Next, 300 mass ppm of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] as an antioxidant was added to the obtained powder, and melt-kneaded and pelletized at a temperature of 200℃by using a TEX-44 twin-screw extruder manufactured by Japanese Steel Co., ltd.
The density of the resulting high-density polyethylene (A-1) was 957kg/m 3 The MFR was 11.0g/10 min.
< production of high Density polyethylene (A-2) >)
The high-density polyethylene (A-2) was obtained by the same operation as in the production of the high-density polyethylene (A-1), except that the polymerization temperature was 75 ℃, the polymerization pressure was 1.0MPa, the gas phase concentration of hydrogen gas relative to ethylene was 54.3 mol%, and 1-butene was not supplied.
The density of the resulting high-density polyethylene (A-2) was 962kg/m 3 The MFR was 20.0g/10 min.
< production of high Density polyethylene (A-3) >)
The polymerization was carried out in the same manner as in the high-density polyethylene (A-1) except that the classification by the sieve was not carried out, thereby obtaining the high-density polyethylene (A-3).
The density of the resulting high-density polyethylene (A-3) was 957kg/m 3 The MFR was 11.0g/10 min.
< production of high Density polyethylene (A-4) >)
The polymerization was carried out in the same manner as in the high-density polyethylene (A-1) except that the polymerization temperature was set to 76℃and classification by a sieve was not carried out, thereby obtaining a high-density polyethylene (A-4).
The density of the resulting high-density polyethylene (A-4) was 957kg/m 3 The MFR was 12.0g/10 min.
< production of high Density polyethylene (A-5) >)
A vessel-type 280L polymerization reactor equipped with a stirring device was used to conduct continuous polymerization at a polymerization temperature of 69℃under a polymerization pressure of 0.8MPa and an average residence time of 1.6 hours. Dehydrated n-hexane was supplied as a solvent at 40L/hr, the above-mentioned supported metallocene catalyst [ b-1] was supplied as a catalyst at 1.4 mmol/hr in terms of Ti atom, and triisobutylaluminum was supplied as a liquid co-catalyst component at 20 mmol/hr in terms of Al atom. The hydrogen for adjusting the molecular weight was supplied in a manner of 0.12 mol% with respect to the gas phase concentration of ethylene and 1-butene, and 1-butene was supplied in a manner of 0.011 mol% with respect to the gas phase concentration of ethylene, thereby polymerizing ethylene and 1-butene.
The dehydrated n-hexane was supplied from the bottom of the polymerization reactor, the hydrogen gas was supplied from the middle between the liquid surface and the bottom of the polymerization reactor together with the catalyst from the catalyst introduction line for the purpose of contact with the catalyst in advance, and the ethylene was supplied from the bottom of the polymerization reactor. The polymerization slurry in the polymerization reactor was introduced into a flash tank having a pressure of 0.08MPa and a temperature of 75 ℃ in such a manner that the liquid surface of the polymerization reactor was kept constant, and unreacted ethylene, 1-butene and hydrogen were separated.
Next, the polymerization slurry is continuously fed into a centrifuge in such a manner that the liquid surface of the polymerization reactor is kept constant, and the polymer and the solvent or the like other than the polymer are separated. The content of the solvent or the like in this case was 45%.
The separated high-density polyethylene powder was dried at 85 ℃ while blowing nitrogen. The obtained powder was then classified by a classifier to remove a powder having a particle size of 100 μm or less.
The obtained high-density polyethylene powder was melt kneaded at a temperature of 200℃and pelletized using a TEX-44 twin-screw extruder manufactured by Japan Steel Co., ltd without using an additive such as a neutralizing agent or an antioxidant.
The density of the resulting high-density polyethylene (A-5) was 965kg/m 3 The MFR was 12.0g/10 min.
< production of high Density polyethylene (A-6) >)
The polymerization was carried out in the same manner as in the production method of the high-density polyethylene (A-5) except that the polymerization temperature was set to 72℃and the above-mentioned supported metallocene catalyst [ b-2] was used as a catalyst, and classification using a sieve was not carried out, whereby the high-density polyethylene (A-6) was obtained.
The density of the resulting high-density polyethylene (A-6) was 965kg/m 3 The MFR was 13.0g/10 min.
(high pressure Process Low Density polyethylene (B))
< production of Low Density polyethylene (B-1) >)
In an autoclave reactor, a polymerization temperature was 259℃and a polymerization pressure was 128.1MPa, and a low-density polyethylene (B-1) was obtained by polymerization using t-butyl peroxyacetate as a polymerization initiator.
The temperature of ethylene supplied to the polymerization reactor was adjusted to 20℃by jacket-cooling the pipe immediately before the reactor with cold water, and the temperature of the polymer immediately after discharging from the polymerization reactor was adjusted to 155℃by jacket-cooling the pipe immediately after the polymerization reactor with warm water.
The low-density polyethylene (B-1) obtained was processed into pellets with a density of 920kg/m by means of a single-screw extruder 3 The MFR was 3.0g/10 min and the Mw/Mn was 18.
< production of Low Density polyethylene (B-2) >)
The polymerization temperature was 245℃and the polymerization pressure was 170.0MPa, 18.5 mol% of the ethylene was changed to butane, the temperature of the ethylene supplied to the polymerization reactor was 83℃and the temperature of the polymer immediately after the discharge from the polymerization reactor was 215℃without performing jacket cooling of the pipe. The other conditions were the same as those of the low-density polyethylene (B-1), thereby obtaining a low-density polyethylene (B-2).
The density of the resulting low-density polyethylene (B-2) was 923kg/m 3 The MFR was 3.8g/10 min and the Mw/Mn was 13.
< production of Low Density polyethylene (B-3) >)
In a tubular reactor, the polymerization temperature was 280℃and the polymerization pressure was 240MPa, and 1.2 mol% of the ethylene raw material was changed to propylene by using tert-butyl peroxy-2-ethylhexanoate as a polymerization initiator, and polymerization was carried out to obtain a low-density polyethylene (B-3).
The temperature of ethylene supplied to the polymerization reactor was 120℃and the temperature of the polymer immediately after discharge from the polymerization reactor was 255℃without performing jacket cooling of the piping.
The density of the resulting low-density polyethylene (B-3) was 917kg/m 3 The MFR was 3.7g/10 min and Mw/Mn was 7.
< production of Low Density polyethylene (B-4) >)
The polymerization temperature was adjusted to 240℃and the polymerization pressure was adjusted to 155.2MPa, jacket cooling of the pipe at the inlet of the reactor was not performed, and the temperature of ethylene supplied to the polymerization reactor was 91 ℃. The other conditions were the same as those of (B-1), thereby obtaining a low-density polyethylene (B-4).
The density of the resulting low-density polyethylene (B-4) was 918kg/m 3 The MFR was 7.0g/10 min and the Mw/Mn was 14.
< production of Low Density polyethylene (B-5) >)
The polymerization temperature was changed to 245℃and the polymerization pressure was changed to 125.0MP, jacket cooling of the piping was not performed, the temperature of ethylene supplied to the polymerization reactor was 83℃and the temperature of the polymer immediately after discharge from the polymerization reactor was 215 ℃.
The other conditions were the same as those of (B-1), thereby obtaining low-density polyethylene (B-5).
The density of the resulting low-density polyethylene (B-5) was 918kg/m 3 The MFR was 2.0g/10 min and the Mw/Mn was 19.
< production of Low Density polyethylene (B-6) >)
The polymerization was carried out in the same manner as in the low-density polyethylene (B-1) except that the polymerization temperature was 245℃and the polymerization pressure was 170.0MPa, and 18.5 mol% of the ethylene raw material was changed to butane, thereby obtaining a low-density polyethylene (B-6).
The density of the resulting low-density polyethylene (B-6) was 922kg/m 3 The MFR was 4.0g/10 min and the Mw/Mn was 13.
< production of Low Density polyethylene (B-7) >)
The polymerization temperature was adjusted to 240℃and the polymerization pressure was adjusted to 155.2MPa, jacket cooling of the piping immediately after the reactor was not performed, and the temperature of the polymer immediately after discharge from the polymerization reactor was 218 ℃.
The other conditions were the same as those of (B-1), thereby obtaining low-density polyethylene (B-7).
The density of the resulting low-density polyethylene (B-7) was 919kg/m 3 An MFR of 8.0g/10 min, an Mw/Mn of17。
< production of Low Density polyethylene (B-8) >)
The polymerization temperature was 255℃and the polymerization pressure was 170.0MPa, 18.5 mol% of the ethylene feed was changed to butane, jacket cooling of a pipe immediately after the polymerization reactor was not performed, and the temperature of the polymer immediately after discharge from the polymerization reactor was 212 ℃.
The other conditions were the same as those of the low-density polyethylene (B-1), thereby obtaining a low-density polyethylene (B-8).
The density of the resulting low-density polyethylene (B-8) was 925kg/m 3 The MFR was 2.5g/10 min and Mw/Mn was 13.
< production of Low Density polyethylene (B-9) >)
The polymerization temperature was 250℃and the polymerization pressure was 173.0MPa, 18.5 mol% of the ethylene raw material was changed to butane, and the temperature of the ethylene gas supplied to the polymerization reactor was 87℃without performing jacket cooling of the pipe at the inlet of the polymerization reactor.
The other conditions were the same as those of the low-density polyethylene (B-1), thereby obtaining a low-density polyethylene (B-9).
The density of the resulting low-density polyethylene (B-9) was 924kg/m 3 The MFR was 6.0g/10 min and Mw/Mn was 13.
(ethylene resin composition)
Example 1 production of vinyl resin composition C-1
The high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-1) were melt-kneaded at 200℃using a single screw extruder (screw diameter: 50mm, L/D=24) manufactured by Nippon Steel Co., ltd.) so that the high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-1) were 70 mass% and 30 mass%, respectively, and pelletized.
Example 2 production of vinyl resin composition C-2
The melt-kneading was performed in the same manner as in (C-1) except that 30 mass%, 15 mass% and 55 mass% of the high-density polyethylene (A-1), the high-pressure low-density polyethylene (B-1) and the high-pressure low-density polyethylene (B-2) were used, respectively, and the pellets were obtained.
Example 3 production of vinyl resin composition C-3
The melt-kneading was performed in the same manner as in (C-1) except that 50 mass% and 40 mass% of the high-density polyethylene (A-2), 40 mass% and 10 mass% of the high-pressure low-density polyethylene (B-3) and the high-pressure low-density polyethylene (B-4) were used, respectively, and the pellets were obtained.
Example 4 production of vinyl resin composition C-4
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-2) and the high-pressure low-density polyethylene (B-4) were used in an amount of 65% by mass and 35% by mass, respectively, and the pellets were obtained.
Example 5 production of vinyl resin composition C-5
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-3) and the high-pressure low-density polyethylene (B-1) were used in an amount of 65% by mass and 35% by mass, respectively, and the pellets were obtained.
Example 6 production of vinyl resin composition C-6
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-4) and the high-pressure low-density polyethylene (B-1) were used in an amount of 65% by mass and 35% by mass, respectively, and the pellets were obtained.
Example 7 production of vinyl resin composition C-7
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-6) were used in an amount of 70% by mass and 30% by mass, respectively, and the pellets were obtained.
Example 8 production of vinyl resin composition C-8
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-5) and the high-pressure low-density polyethylene (B-1) were used in an amount of 50% by mass and 50% by mass, respectively, and the pellets were obtained.
Example 9 production of vinyl resin composition C-9
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-7) were used in an amount of 40% by mass and 60% by mass, respectively, and the pellets were obtained.
Comparative example 1 production of vinyl resin composition C-10
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-2) were used in an amount of 70% by mass and 30% by mass, respectively, and the pellets were obtained.
Comparative example 2 production of vinyl resin composition C-11
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-5) and the high-pressure low-density polyethylene (B-5) were used in an amount of 50% by mass and 50% by mass, respectively, and the pellets were obtained.
Comparative example 3 production of vinyl resin composition C-12
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-1) and the high-pressure low-density polyethylene (B-3) were used in an amount of 60% by mass and 40% by mass, respectively, and the pellets were obtained.
Comparative example 4 production of vinyl resin composition C-13
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-4) and the high-pressure low-density polyethylene (B-5) were used in an amount of 65% by mass and 35% by mass, respectively, and the pellets were obtained.
Comparative example 5 production of vinyl resin composition C-14
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-6) and the high-pressure low-density polyethylene (B-5) were used in an amount of 50% by mass and 50% by mass, respectively, and the pellets were obtained.
Comparative example 6 production of vinyl resin composition C-15
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-4) and the high-pressure low-density polyethylene (B-8) were used in an amount of 80% by mass and 20% by mass, respectively, and the pellets were obtained.
Comparative example 7 production of vinyl resin composition C-16
The melt-kneading was performed in the same manner as in (C-1) except that the high-density polyethylene (A-3) and the high-pressure low-density polyethylene (B-9) were used in an amount of 50% by mass and 50% by mass, respectively, and the pellets were obtained.
Comparative example 8 production of vinyl resin composition C-17
An ethylene resin composition (C-17) was obtained in the same manner as in example 8 described in Japanese patent No. 6912290.
Comparative example 9 production of vinyl resin composition C-18
The ethylene resin composition (C-18) was obtained in the same manner as in example 3 described in Japanese patent application laid-open No. 2018-44122.
Industrial applicability
The ethylene resin composition of the present invention is industrially useful as a raw material for, for example, a protective film in film applications where fish eye quality is particularly important.
Claims (6)
1. An ethylene resin composition satisfying the following < condition (A) > < condition (E) >:
condition (A) >, a method of producing a polypeptide
The melt flow rate of the ethylene resin composition under the conditions of 190 ℃ and a load of 2.16kg is 1.0g/10 min or more and 20.0g/10 min or less;
< condition (B) >)
The ethylene resin composition has a density of 920kg/m 3 Above 960kg/m 3 The following are set forth;
condition (C) >, a method of producing a polypeptide
In an elution temperature-elution amount curve obtained by Temperature Rising Elution Fractionation (TREF) of a cross-fractionation chromatograph (CFC), at least one peak having a peak top exists in a range of 60 ℃ or more and 80 ℃ or less, and at least one peak having a peak top exists in a range of more than 80 ℃ and 100 ℃ or less;
condition (D) >
For the peak having the largest elution amount obtained in the CFC measurement within a range of 60 ℃ to 80 ℃, the molecular weight distribution of the component eluted at a temperature at which the peak is displayed is 9 to 100 inclusive;
condition (E) >, a method of producing a polypeptide
In a GPC chart obtained by GPC measurement of the component eluted at 70℃in the CFC measurement, the molecular weight was 10 in terms of 6 A ratio X of an area of g/mol or more to a total area of 10 in terms of a molecular weight 5 The ratio X/Y of the area of g/mol or more to the total area ratio Y is 0.05 or more and 0.50 or less.
2. The vinyl resin composition according to claim 1, wherein a peak having the largest elution amount in the CFC measurement in a range of 80 ℃ or higher and 100 ℃ or lower has a molecular weight distribution of components eluted at a temperature at which the peak is displayed of 4.0 to 20 inclusive and a weight average molecular weight of 60000g/mol to 200000g/mol inclusive.
3. The ethylene resin composition according to claim 1, wherein the mass ratio of the components eluted in the Temperature Rising Elution Fractionation (TREF) range from 60 ℃ to 80 ℃ is 10% to 90% by mass based on the total amount of the components eluted.
4. The vinyl resin composition according to claim 1Wherein the ethylene resin composition has a density of 942kg/m 3 The high-density polyethylene has a density of 930kg/m 3 The following is a mixture of high pressure process low density polyethylenes.
5. A molded article comprising the ethylene resin composition according to any one of claims 1 to 4.
6. The molded article according to claim 5, wherein the molded article is a film.
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| JP7393505B2 (en) | 2023-12-06 |
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