WO2019187727A1 - 超高分子量ポリエチレンパウダー - Google Patents
超高分子量ポリエチレンパウダー Download PDFInfo
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- WO2019187727A1 WO2019187727A1 PCT/JP2019/005120 JP2019005120W WO2019187727A1 WO 2019187727 A1 WO2019187727 A1 WO 2019187727A1 JP 2019005120 W JP2019005120 W JP 2019005120W WO 2019187727 A1 WO2019187727 A1 WO 2019187727A1
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- Prior art keywords
- molecular weight
- weight polyethylene
- polyethylene powder
- less
- ultrahigh molecular
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- 239000000843 powder Substances 0.000 title claims abstract description 308
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 268
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 268
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 30
- 238000004898 kneading Methods 0.000 claims abstract description 27
- 229940057995 liquid paraffin Drugs 0.000 claims description 59
- 239000010936 titanium Substances 0.000 claims description 51
- 239000000835 fiber Substances 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- 239000012982 microporous membrane Substances 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 29
- 239000003963 antioxidant agent Substances 0.000 claims description 25
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- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 13
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 120
- 125000004432 carbon atom Chemical group C* 0.000 description 82
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- 230000000052 comparative effect Effects 0.000 description 34
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
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- 239000000377 silicon dioxide Substances 0.000 description 15
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 14
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
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- 125000003545 alkoxy group Chemical group 0.000 description 11
- 150000002902 organometallic compounds Chemical class 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- 150000003623 transition metal compounds Chemical class 0.000 description 11
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 11
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
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- 125000003118 aryl group Chemical group 0.000 description 9
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
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- 125000004122 cyclic group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
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- 229920000642 polymer Polymers 0.000 description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 239000007789 gas Substances 0.000 description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 6
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- 150000003609 titanium compounds Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 125000005916 2-methylpentyl group Chemical group 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000005336 allyloxy group Chemical group 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
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- 229910052763 palladium Inorganic materials 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
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- 150000001412 amines Chemical class 0.000 description 4
- 150000004718 beta keto acids Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
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- 125000001624 naphthyl group Chemical group 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
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- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- 229910052753 mercury Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 3
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- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 241000251511 Holothuroidea Species 0.000 description 2
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- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- DPTWZQCTMLQIJK-UHFFFAOYSA-N tris(3-methylbutyl)alumane Chemical compound CC(C)CC[Al](CCC(C)C)CCC(C)C DPTWZQCTMLQIJK-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2500/01—High molecular weight, e.g. >800,000 Da.
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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- C08L2314/02—Ziegler natta catalyst
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to ultra high molecular weight polyethylene powder.
- Ultra high molecular weight polyethylene is excellent in impact resistance and wear resistance, and is used in various fields as an engineering plastic.
- the processability of ultra-high molecular weight polyethylene is important.
- a method such as Patent Document 1 is disclosed.
- Patent Document 1 has excellent moldability while taking advantage of the original characteristics of ultrahigh molecular weight polyethylene such as high strength, abrasion resistance, lubricity, hygiene, and chemical resistance.
- an ultrahigh molecular weight polyethylene resin composition that gives a molded article excellent in appearance and mechanical strength and a method for producing the same are disclosed.
- the ultrahigh molecular weight polyethylene resin composition described in Patent Document 1 is a composition comprising an ultrahigh molecular weight polyethylene resin and a polyolefin resin other than the ultrahigh molecular weight polyethylene resin, and the appearance of only the ultrahigh molecular weight polyethylene is There is no discussion about the ease of processing and the suppression of the amount of smoke during processing.
- ultra-high molecular weight polyethylene has a much higher molecular weight than general-purpose polyethylene, it is expected that a molded product having high strength and high elasticity can be obtained if it can be highly oriented.
- the ultrahigh molecular weight polyethylene is sufficiently impregnated with the solvent before kneading.
- improvement in production efficiency of ultra high molecular weight polyethylene has been demanded, and in order to shorten the processing time, kneading occurs in a state where the ultra high molecular weight polyethylene is not sufficiently impregnated with the solvent.
- the obtained ultrahigh molecular weight polyethylene has a problem that the molecular chain is broken by the shear during kneading and high orientation is achieved, but the strength is lowered.
- the present invention has been made in view of the above problems, and provides an ultrahigh molecular weight polyethylene powder that is excellent in appearance, ease of processing, and suppression of the amount of oil smoke during processing, and has both high strength and high stretch. Objective.
- the present inventor has found that the above-mentioned problems can be solved with a predetermined ultrahigh molecular weight polyethylene powder, and has completed the present invention.
- the present invention is as follows.
- the filling, ⁇ Mv ⁇ Mv (A) ⁇ / Mv is 0.20 or less
- Ultra high molecular weight polyethylene powder Ultra high molecular weight polyethylene powder.
- Screw rotation speed is 50 rpm Under nitrogen atmosphere
- the present invention can provide an ultra-high molecular weight polyethylene powder that is excellent in appearance of a molded product, easy to process, and suppresses the amount of oily smoke during processing, and has both high strength and high stretch.
- the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to this. Various modifications are possible without departing from the scope of the invention.
- the ultrahigh molecular weight polyethylene powder (hereinafter also simply referred to as “powder”) of the present embodiment has a viscosity average molecular weight of 10 ⁇ 10 4 or more and 1000 ⁇ 10 4 or less. From the viewpoint of moldability and final physical properties, the viscosity average molecular weight is preferably in the range of 10 ⁇ 10 4 to 950 ⁇ 10 4 , more preferably in the range of 20 ⁇ 10 4 to 900 ⁇ 10 4. is there.
- the viscosity average molecular weight in this embodiment points out the value which converted the intrinsic viscosity calculated
- the ultra high molecular weight polyethylene powder of the present embodiment is preferably a powder made of an ethylene homopolymer and / or a copolymer of ethylene and an olefin copolymerizable with ethylene (hereinafter also referred to as a comonomer). .
- the olefin copolymerizable with ethylene is not particularly limited. Specifically, for example, an ⁇ -olefin having 3 to 15 carbon atoms, a cyclic olefin having 3 to 15 carbon atoms, a formula CH 2 ⁇ CHR 1 ( Wherein R 1 is an aryl group having 6 to 12 carbon atoms), and at least one selected from the group consisting of linear, branched or cyclic dienes having 3 to 15 carbon atoms. Specified comonomers. Among these, ⁇ -olefins having 3 to 15 carbon atoms are preferable.
- the ⁇ -olefin is not particularly limited, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Examples include dodecene, 1-tridecene and 1-tetradecene.
- the content of the comonomer unit in the ethylene polymer is preferably 0.01 mol% or more and 5 mol% or less, more preferably 0.01 mol%.
- the content is 2 mol% or less, more preferably 0.01 mol% or more and 1 mol% or less.
- the comonomer amount is preferably 5 mol% or less from the viewpoint of suppressing the decomposition rate.
- the viscosity average molecular weight (Mv) of the ultra high molecular weight polyethylene powder of this embodiment is 10 ⁇ 10 4 or more and 1000 ⁇ 10 4 or less, preferably 10 ⁇ 10 4 or more and 950 ⁇ 10 4 or less, more preferably 20 ⁇ 10 4 or more and 900 ⁇ 10 4 or less.
- Examples of a method for controlling the viscosity average molecular weight (Mv) within the above range include changing the polymerization temperature of the reactor when (co) polymerizing ethylene or an olefin copolymerizable with ethylene. It is done.
- the viscosity average molecular weight (Mv) tends to decrease as the polymerization temperature is increased, and tends to increase as the polymerization temperature is decreased.
- an organometallic compound species as a promoter used when polymerizing ethylene or an olefin copolymerizable with ethylene can be used. To change.
- a chain transfer agent may be added when polymerizing ethylene or an olefin copolymerizable with ethylene.
- a chain transfer agent By adding a chain transfer agent, the viscosity average molecular weight of the ultrahigh molecular weight polyethylene produced even at the same polymerization temperature tends to be low.
- [Kneading conditions] material A mixture containing 5 parts by weight of ultrahigh molecular weight polyethylene powder, 95 parts by weight of liquid paraffin, and 1 part by weight of an antioxidant when the total amount of ultrahigh molecular weight polyethylene powder and liquid paraffin is 100 parts by weight.
- . conditions The raw materials are kneaded at 130 ° C. for 30 minutes, and further kneaded at 240 ° C. for 15 minutes. The temperature increase rate from 130 ° C. to 240 ° C. is 22 ° C./min. Screw rotation speed is 50 rpm Under nitrogen atmosphere
- the liquid paraffin used in the present embodiment plays a role as a plasticizer, and can be a liquid paraffin that can form a uniform solution above the melting point of the ultra high molecular weight polyethylene powder when kneaded with the ultra high molecular weight polyethylene powder. Good.
- Nonvolatile solvent other than liquid paraffin can be used as a plasticizer.
- Nonvolatile solvents other than liquid paraffin are not particularly limited, and examples include hydrocarbons such as paraffin wax, esters such as dioctyl phthalate and dibutyl phthalate, and higher alcohols such as oleyl alcohol and stearyl alcohol. .
- the antioxidant is not particularly limited, but for example, a phenol compound or a phenol phosphate compound is preferable. Specifically, 2,6-di-t-butyl-4-methylphenol (dibutylhydroxytoluene), n-octadecyl-3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, tetrakis (Methylene (3,5-di-t-butyl-4-histaloxyhydrocinnamate)) phenolic antioxidants such as methane; 6- [3- (3-t-butyl-4-hydroxy-5-methyl Phenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine and other phenol phosphorus antioxidants; tetrakis (2,4 -Di-t-butylphenyl) -4,4'-biphenylene-di-d
- ⁇ Mv-Mv (A) ⁇ / Mv When kneaded under the above kneading conditions, the viscosity average molecular weight Mv of the ultra-high molecular weight polyethylene powder before kneading and the viscosity average molecular weight Mv (A) of the gel after kneading satisfy the following relationship.
- ⁇ Mv ⁇ Mv (A) ⁇ / Mv is 0.20 or less, more preferably 0.15 or less, still more preferably 0.10 or less, and most preferably 0.08 or less.
- the lower limit of ⁇ Mv ⁇ Mv (A) ⁇ / Mv is not particularly limited, but is preferably 0.04 or more, for example.
- the decomposition amount of the ultrahigh molecular weight polyethylene powder is suppressed (suppression of oligomer generation due to decomposition), for example, in the vicinity of the nozzle outlet during extrusion molding.
- the amount of accumulation of accumulated particles accumulation of degradation products such as oligomers
- processing becomes easy and production efficiency can be improved.
- the ultrahigh molecular weight polyethylene powder of the present embodiment contains an ultrahigh molecular weight polyethylene powder having a particle size of 212 ⁇ m or more.
- the average pore volume is 0.6 ml / g or more and the average The pore diameter is 0.3 ⁇ m or more.
- the average pore volume is preferably 0.65 ml / g or more, more preferably 0.7 ml / g or more, and the average pore diameter is preferably 0.35 ⁇ m or more, more preferably 0.4 ⁇ m or more.
- the upper limit of the average pore volume is not particularly limited, but is, for example, 3.0 ml / g or less.
- the upper limit of the average pore diameter is not particularly limited, but is 1.0 ⁇ m or less, for example.
- the average particle diameter (D50) of the ultrahigh molecular weight polyethylene powder of the present embodiment is preferably 40 ⁇ m or more and 200 ⁇ m or less, more preferably 60 ⁇ m or more and 140 ⁇ m or less, and further preferably 70 ⁇ m or more and 120 ⁇ m or less.
- the upper limit of a particle size is not specifically limited, For example, it is 710 micrometers or less.
- the present inventor found that the molecular chain entanglement of the powder having a particle size of 212 ⁇ m or more is particularly difficult to unravel, and by setting the average pore volume and the average pore diameter of the powder having a particle size of 212 ⁇ m or more to a predetermined value or higher, It was found that the molecular weight polyethylene powder was sufficiently impregnated with liquid paraffin, and the molecular chain entanglement could be solved in a short time. As a result, it is possible to drastically shorten the time required for unraveling the molecular chain by melt-kneading at a high temperature, and to suppress a decrease in strength of the molded product after heating.
- stretching can be made low by untangling a molecular chain in a short time, and high extending
- the high molecular weight polyethylene powder can be obtained, for example, by a production method described later. Specifically, the temperature of the catalyst charged into the reactor is adjusted to “polymerization temperature + 10 ° C. or higher” and polymerized rapidly. In the polymerization step, baffle plates are provided in the reactor at equal intervals of 2 or more and 6 or less to prevent uneven reaction in the system. The baffle plate is provided from the bottom of the reactor to the top of the reactor (opening).
- the length from the top of the baffle plate to the side of the reactor is 10% to 30% of the inner diameter of the reactor, and the width of the projection. Is adjusted to 10% to 30% of the circumference of the reactor.
- the average pore volume and average pore diameter of the ultrahigh molecular weight polyethylene powder can be controlled by the slurry concentration in the reactor, and can usually be increased by lowering the slurry concentration.
- the average pore volume and average pore diameter of the ultrahigh molecular weight polyethylene powder with ⁇ Mv ⁇ Mv (A) ⁇ / Mv and a particle size of 212 ⁇ m or more are specifically determined by the method described in the examples. Can be measured.
- the ultra high molecular weight polyethylene powder of the present embodiment is preferably less than 40% by mass, more preferably 35% by mass or less, when the proportion of the powder having a particle size of 53 ⁇ m or less is 100% by mass of the ultra high molecular weight polyethylene powder. More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.
- a uniform kneaded gel can be obtained by adjusting the ratio of powder having a particle size of 53 ⁇ m or less to the above range.
- the lower limit of the proportion of the powder having a particle size of 53 ⁇ m or less is not particularly limited, and is usually 0% by mass or more.
- the proportion of the powder having a particle size of 53 ⁇ m or less By setting the proportion of the powder having a particle size of 53 ⁇ m or less to be less than 40% by mass, when the ultrahigh molecular weight polyethylene powder and liquid paraffin are kneaded, the fine powder having a particle size of 53 ⁇ m or less melts before swelling. There is a tendency that the possibility of obtaining a non-uniform kneaded product (kneaded gel) by fusing powders together can be further suppressed. As a result, for example, a yarn having a uniform yarn diameter tends to be obtained when a fiber is used, and a film having a uniform film thickness is obtained when a fiber is used.
- the content of ultra-high molecular weight polyethylene powder having a particle size of 53 ⁇ m or less can be generally controlled by adjusting the size and / or amount of the catalyst carrier used for polymerization. By adjusting the size of the catalyst carrier, the particle size of the ultrahigh molecular weight polyethylene powder to be produced is controlled. Furthermore, by polymerizing using a catalyst in which catalyst carriers of various sizes are mixed, the content of the ultra-high molecular weight polyethylene powder to be produced can be controlled. Moreover, the content rate of ultra high molecular weight polyethylene powder with a particle diameter of 53 micrometers or less can also be adjusted by controlling superposition
- the drying temperature in the ultra-high molecular weight polyethylene powder drying step, the drying temperature (previous stage: 60 ° C. or more and 70 ° C. or higher) in the former stage (first half of the total drying time) and the latter stage (second half of the total drying time).
- the temperature below 70 ° C. and the subsequent stage 70 ° C. or more and 90 ° C. or less rapid drying at high temperatures is prevented, and the ultrahigh molecular weight polyethylene powder is prevented from cracking and increasing the amount of fine powder.
- the content of the ultrahigh molecular weight polyethylene powder having a particle diameter of 53 ⁇ m or less can be measured by the method described in Examples.
- the proportion of powder having a particle size of 53 ⁇ m or less is 40% by mass or more when the mass of the ultrahigh molecular weight polyethylene powder is 100% by mass, the particle size is 53 ⁇ m or less when melt kneaded while mixing with liquid paraffin. Since the fine powder melts before the powder swells and the powders are fused, a uniform gel cannot be obtained. In order to dissolve the fusion between the powders under such circumstances, it is necessary to melt and knead at a higher temperature. Even if a uniform gel can be obtained, the thermal decomposition of the ultrahigh molecular weight polyethylene powder is promoted. Therefore, there is a problem in terms of strength. However, these problems can be solved by using the ultrahigh molecular weight polyethylene powder of the present embodiment.
- the bulk density of the powder having a particle size of 212 ⁇ m or more is preferably 0.20 g / cm 3 or more and 0.60 g / cm 3 or less, more preferably 0.25 g / cm 3 or more. It is 0.55 g / cm 3 or less, more preferably 0.30 g / cm 3 or more and 0.55 g / cm 3 or less.
- the bulk density of the powder having a particle diameter of 212 ⁇ m or more By setting the bulk density of the powder having a particle diameter of 212 ⁇ m or more to 0.20 g / cm 3 or more, when the ultrahigh molecular weight polyethylene powder is aggregated, a gap where the powders are not in contact with each other can be secured to some extent. There is a tendency that the penetration of liquid paraffin into the ultrahigh molecular weight polyethylene powder can be promoted and the generation of unmelted material due to undissolved residue can be reduced.
- the bulk density of the powder having a particle size of 212 ⁇ m or more to 0.60 g / cm 3 or less when sending ultrahigh molecular weight polyethylene powder from inside the extruder hopper to the inside of the extruder, it is smooth without clogging in the hopper. Tend to be able to send out.
- the bulk density generally varies depending on the catalyst used, but can be controlled by the productivity of ultrahigh molecular weight polyethylene powder per unit catalyst.
- the bulk density of the ultrahigh molecular weight polyethylene powder can also be controlled by the polymerization temperature when polymerizing the ultrahigh molecular weight polyethylene powder, and the bulk density can be lowered by raising the polymerization temperature.
- the bulk density of the ultrahigh molecular weight polyethylene powder can be controlled by the slurry concentration in the polymerization vessel, and the bulk density can be increased by increasing the slurry concentration.
- the magnesium (Mg) content in the powder is preferably 0.1 ppm or more and 20 ppm or less, and the titanium (Ti) content is 0.1 ppm or more and 5 ppm or less.
- the aluminum (Al) content is preferably 0.5 ppm or more and 10 ppm or less, More preferably, it is 0.5 ppm or more and 7.0 ppm or less, More preferably, it is 0.5 ppm or more and 6.0 ppm or less, It is preferable that silicon (Si) content is 0.1 ppm or more and 100 ppm or less, and chlorine (Cl ) The content is preferably 1 ppm or more and 50 ppm or less.
- the ultrahigh molecular weight polyethylene powder is more excellent in thermal stability, and the long-term stability of the molded body is further improved. Moreover, it exists in the tendency which can suppress reaction with the antioxidant and heat stabilizer added at the time of a process, and can suppress coloring of the molded object by producing
- the contents of Mg, Ti, Al, Si and Cl in the ultrahigh molecular weight polyethylene powder can be controlled by the productivity of the ethylene polymer per unit catalyst.
- the productivity of the ethylene polymer can be controlled by the polymerization temperature, polymerization pressure, and slurry concentration of the reactor during production. That is, in order to increase the productivity of the ultrahigh molecular weight polyethylene powder according to the present embodiment, the polymerization temperature when polymerizing the ethylene polymer is increased, the polymerization pressure is increased, and / or the slurry concentration is increased. Can be mentioned.
- Other methods include selecting the type of promoter component when polymerizing the ethylene polymer, reducing the concentration of the promoter component, and washing the ethylene polymer with acid or alkali. It is possible to control the amount.
- the amount of Mg, Ti, Al, Si, and Cl can be measured by the method described in the examples.
- the content ratio of Mg / Ti in the powder is preferably 0.1 or more and 10 or less, more preferably 0.2 or more and 9.5 or less, and still more preferably 0. .3 or more and 9 or less.
- the content ratio of Al / Ti in the powder is preferably 0.1 or more and 20 or less, more preferably 0.1 or more and 18 or less, and still more preferably 0.15 or more and 15 or less.
- the reaction with the antioxidant and heat stabilizer added during processing can be suppressed, and the organic metal There exists a tendency which can suppress the coloring of the molded object by a complex being produced
- the content ratio of Mg / Ti 10 or less or the content ratio of Al / Ti to 20 or less, the amount of generated sea cucumber can be reduced and the generation frequency of oily smoke can be suppressed. As a result, it is possible to suppress a decrease in strength of the molded product due to thermal decomposition.
- the Ziegler-Natta catalyst is a catalyst comprising a solid catalyst component [A] and an organometallic compound component [B], and the solid catalyst component [A] can be used as an inert hydrocarbon solvent represented by the following formula 1.
- a olefin polymerization catalyst produced by reacting a soluble organomagnesium compound (A-1) with a titanium compound (A-2) represented by the following formula 2 is preferred.
- the inert hydrocarbon solvent used in the reaction between (A-1) and (A-2) is not particularly limited, and specific examples thereof include aliphatic hydrocarbons such as pentane, hexane and heptane. Aromatic hydrocarbons such as benzene and toluene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane.
- (A-1) is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent and includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds.
- the hydrocarbon group having 2 to 20 carbon atoms represented by R 2 and R 3 is not particularly limited, and is specifically an alkyl group, a cycloalkyl group or an aryl group, for example, ethyl Propyl, butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group and the like. Of these, an alkyl group is preferable.
- ⁇ >0 as the metal atom M 1 a metal atom belonging to the group consisting of Groups 12, 13, and 14 of the periodic table can be used, and examples thereof include zinc, boron, and aluminum. Of these, aluminum and zinc are preferable.
- the ratio ⁇ / ⁇ of magnesium to the metal atom M 1 is not particularly limited, but is preferably 0.1 or more and 30 or less, and more preferably 0.5 or more and 10 or less.
- R 2 and R 3 are recommended to satisfy any one of the following three groups (1), (2), and (3): .
- Group (1) At least one of R 2 and R 3 is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R 2 and R 3 have 4 to 6 carbon atoms.
- the following alkyl groups at least one of which is a secondary or tertiary alkyl group.
- Specific examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms in the group (1) include 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2 -Methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group and the like. Of these, a 1-methylpropyl group is particularly preferred.
- alkyl group having 2 or 3 carbon atoms examples include ethyl, 1-methylethyl, propyl group and the like. Of these, an ethyl group is particularly preferred.
- the alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples include butyl, pentyl, hexyl, heptyl, octyl groups and the like. Of these, butyl and hexyl groups are particularly preferable.
- the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like. It is done.
- an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable.
- organomagnesium compound can be used by diluting with an inert hydrocarbon solvent, although a small amount of Lewis basic compound such as ether, ester, amine or the like may be contained or remain in the solution. It can be used without any problem.
- Y 1 is alkoxy, siloxy, allyloxy, amino, amide, —N ⁇ C—R 4 , R 5 , —SR 6 (where R 4 , R 5, and R 6 are each independently 2 or more carbon atoms) Represents a hydrocarbon group of 20 or less), and is a ⁇ -keto acid residue.
- the hydrocarbon group represented by R 4 , R 5 and R 6 is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms. .
- Y 1 is preferably an alkoxy group or a siloxy group.
- the alkoxy group is not particularly limited. Specifically, for example, methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 1,1-dimethylethoxy, pentoxy, hexoxy, 2-methylpen Toxyl, 2-ethylbutoxy, 2-ethylpentoxy, 2-ethylhexoxy, 2-ethyl-4-methylpentoxy, 2-propylheptoxy, 2-ethyl-5-methyloctoxy, octoxy, phenoxy, naphthoxy groups Preferably there is.
- siloxy group is not particularly limited, but specifically, for example, hydrodimethylsiloxy, ethylhydromethylsiloxy, diethylhydrosiloxy, trimethylsiloxy, ethyldimethylsiloxy, diethylmethylsiloxy, triethylsiloxy group and the like are preferable. Of these, hydrodimethylsiloxy, ethylhydromethylsiloxy, diethylhydrosiloxy, and trimethylsiloxy groups are more preferable.
- the synthesis method of (A-1) is not particularly limited.
- the formula R 2 MgX 1 and the formula R 2 Mg (R 2 is as defined above, and X 1 is halogen).
- a compound represented by the or can be synthesized by reacting an organic magnesium compound and / or an organoaluminum compound having a functional group represented by Y 1.
- the order of the reaction is not particularly limited, and for example, the formula in the organomagnesium compound how will the addition of a compound represented by Y 1 -H, using any of the methods of the formula Y 1 way going adding an organic magnesium compound into a compound represented by -H, or a method of gradually adding simultaneously both be able to.
- the molar composition ratio c / ( ⁇ + ⁇ ) of Y 1 with respect to all metal atoms in (A-1) is 0 ⁇ c / ( ⁇ + ⁇ ) ⁇ 2 and 0 ⁇ c / ( ⁇ + ⁇ ) ⁇ 1. It is preferable. When the molar composition ratio of Y 1 to all metal atoms is 2 or less, the reactivity of (A-1) to (A-2) tends to be improved.
- (A-2) is a titanium compound represented by Formula 2.
- d is preferably 0 or more and 1 or less, and more preferably 0.
- the hydrocarbon group represented by R 7 in Formula 2 is not particularly limited. Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl are exemplified. And aliphatic hydrocarbon groups such as allyl groups; alicyclic hydrocarbon groups such as cyclohexyl, 2-methylcyclohexyl and cyclopentyl groups; and aromatic hydrocarbon groups such as phenyl and naphthyl groups.
- halogen represented by X 1 include chlorine, bromine, and iodine. Of these, chlorine is preferred.
- (A-2) is particularly preferably titanium tetrachloride. In this embodiment, it is possible to use a mixture of two or more compounds selected from the above.
- the reaction is preferably performed in an inert hydrocarbon solvent, and more preferably in an aliphatic hydrocarbon solvent such as hexane or heptane.
- the molar ratio of (A-1) to (A-2) in the reaction is not particularly limited, but the molar ratio of Ti atoms contained in (A-2) to Mg atoms contained in (A-1) ( Ti / Mg) is preferably 0.1 or more and 10 or less, and more preferably 0.3 or more and 3 or less.
- the reaction temperature is not particularly limited, but it is preferably in the range of ⁇ 80 ° C. to 150 ° C., more preferably in the range of ⁇ 40 ° C.
- the order of addition of (A-1) and (A-2) is not particularly limited, and (A-2) is added following (A-1).
- (A-1) is followed by (A-1) Any method of adding (A-1) and (A-2) at the same time is possible, but a method of simultaneously adding (A-1) and (A-2) is preferred.
- the solid catalyst component [A] obtained by the above reaction is used as a slurry solution using an inert hydrocarbon solvent.
- a carrier (C-3) prepared by the reaction of an organomagnesium compound (C-1) that is soluble in an inert hydrocarbon solvent and a chlorinating agent (C-2) represented by formula 4 contains formula 5
- Preferred is an olefin polymerization catalyst produced by supporting an organomagnesium compound (C-4) soluble in an inert hydrocarbon solvent represented by the formula (I) and a titanium compound (C-5) represented by the formula (6): .
- M 2 is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, and R 8 , R 9 and R 10 are each a hydrocarbon having 2 to 20 carbon atoms.
- (C-1) is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but includes all dihydrocarbylmagnesium compounds and complexes of this compound with other metal compounds Is.
- the hydrocarbon group represented by R 8 to R 9 is not particularly limited, but specifically, it is an alkyl group, a cycloalkyl group or an aryl group, for example, methyl, ethyl, propyl, butyl. , Pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl group and the like. Of these, preferably R 8 and R 9 are each an alkyl group.
- the metal atom M 2 can be a metal atom belonging to the group consisting of Group 12, Group 13, and Group 14 of the Periodic Table, and examples thereof include zinc, boron, and aluminum. Among these, aluminum and zinc are particularly preferable.
- Group (1) At least one of R 8 and R 9 is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R 8 and R 9 have 4 to 6 carbon atoms. Yes, at least one of which is a secondary or tertiary alkyl group.
- Group (3) At least one of R 8 and R 9 is a hydrocarbon group having 6 or more carbon atoms, preferably an alkyl group in which the sum of carbon atoms contained in R 8 and R 9 is 12 or more. .
- the secondary or tertiary alkyl group having 4 to 6 carbon atoms in the group (1) include, for example, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2- A methylbutyl, 2-ethylpropyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, 2-methyl-2-ethylpropyl group or the like is used. Of these, a 1-methylpropyl group is particularly preferable.
- examples of the alkyl group having 2 or 3 carbon atoms include ethyl, 1-methylethyl, and propyl groups. Among these, an ethyl group is particularly preferable. Further, the alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples include butyl, pentyl, hexyl, heptyl, octyl group and the like. Of these, butyl and hexyl groups are particularly preferable.
- the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples thereof include hexyl, heptyl, octyl, nonyl, decyl, phenyl, 2-naphthyl group and the like.
- the hydrocarbon groups an alkyl group is preferable, and among the alkyl groups, hexyl and octyl groups are particularly preferable.
- the said organomagnesium compound is used as an inert hydrocarbon solution, even if trace amount of Lewis basic compounds, such as ether, ester, an amine, are contained in this solution, it can be used without any problem.
- the hydrocarbon group represented by R 10 is preferably an alkyl group or aryl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group or aryl group having 3 to 10 carbon atoms.
- R 10 is not particularly limited.
- the synthesis method of (C-1) is not particularly limited, but the formula R 8 MgX 1 and the formula R 8 Mg (R 8 is as defined above, and X 1 is a halogen atom.) and organomagnesium compound belonging to the group consisting of the formula M 2 R 9 k and the formula M 2 R 9 (k-1 ) H (M 2, R 9 and k above meanings) with an organometallic compound belonging to the group consisting of Is reacted at a temperature of 25 ° C. or higher and 150 ° C. or lower in an inert hydrocarbon solvent, and if necessary, an alcohol having a hydrocarbon group represented by R 9 (R 9 has the above-mentioned meaning).
- a method of reacting with an alkoxymagnesium compound having a hydrocarbon group represented by R 9 and / or an alkoxyaluminum compound soluble in an inert hydrocarbon solvent is preferred.
- the order of the reaction is not particularly limited, and a method of adding alcohol to the organomagnesium compound, organomagnesium in the alcohol. Either a method of adding a compound or a method of adding both at the same time can be used.
- the reaction ratio between the organomagnesium compound soluble in the inert hydrocarbon solvent and the alcohol is not particularly limited.
- the alkoxy group-containing organomagnesium compound has an alkoxy group with respect to all metal atoms.
- the molar composition ratio g / ( ⁇ + ⁇ ) is 0 ⁇ g / ( ⁇ + ⁇ ) ⁇ 2, and preferably 0 ⁇ g / ( ⁇ + ⁇ ) ⁇ 1.
- (C-2) is represented by Formula 4, and at least one is a silicon chloride compound having a Si—H bond.
- the hydrocarbon group represented by R 11 in Formula 4 is not particularly limited, and specific examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group such as methyl, ethyl, and the like.
- an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and 1-methylethyl group is more preferable.
- H and i are numbers greater than 0 satisfying the relationship of h + i ⁇ 4, and i is preferably 2 or more and 3 or less.
- HSiCl 3 HSiCl 2 CH 3 , HSiCl 2 C 2 H 5 , HSiCl 2 (C 3 H 7 ), HSiCl 2 (2-C 3 H 7 ), HSiCl 2 (C 4 H 9 ), HSiCl 2 (C 6 H 5 ), HSiCl 2 (4-Cl—C 6 H 4 ), HSiCl 2 (CH ⁇ CH 2 ), HSiCl 2 (CH 2 C 6 H 5 ), HSiCl 2 (1-C 10 H 7 ), HSiCl 2 (CH 2 CH ⁇ CH 2 ), H 2 SiCl (CH 3 ), H 2 SiCl (C 2 H 5 ), HSiCl (CH 3 ) 2 HSiCl (C 2 H 5 ) 2 , HSiCl (CH 3 ) (2-C 3 H 7 ), HSiCl (CH 3 ) (C 6 H 5 ), HSiCl (CH 3 ) (C 6 H 5
- a silicon chloride compound comprising these compounds or a mixture of two or more selected from these compounds is used.
- HSiCl 3 , HSiCl 2 CH 3 , HSiCl (CH 3 ) 2 and HSiCl 2 (C 3 H 7 ) are preferable, and HSiCl 3 and HSiCl 2 CH 3 are more preferable.
- (C-2) is preliminarily used as an inert hydrocarbon solvent, chlorinated hydrocarbons such as 1,2-dichloroethane, o-dichlorobenzene and dichloromethane; ether-based media such as diethyl ether and tetrahydrofuran; It is preferable to use after diluting with a mixed medium. Among these, an inert hydrocarbon solvent is more preferable in terms of catalyst performance.
- the reaction ratio between (C-1) and (C-2) is not particularly limited, but the silicon atom contained in (C-2) is 0.01 mol or more and 100 mol per 1 mol of magnesium atom contained in (C-1). Or less, more preferably 0.1 mol or more and 10 mol or less.
- the reaction method of (C-1) and (C-2) is not particularly limited, and a method of simultaneous addition in which (C-1) and (C-2) are reacted while being simultaneously introduced into the reactor, A method in which (C-1) is introduced into the reactor after C-2) is charged in the reactor in advance, or (C-2) is charged into the reactor after (C-1) is charged in the reactor in advance. Any of the methods of introduction can be used. Among these, the method in which (C-1) is introduced into the reactor after (C-2) is charged into the reactor in advance is preferable.
- the carrier (C-3) obtained by the above reaction is preferably separated by filtration or decantation, and then thoroughly washed with an inert hydrocarbon solvent to remove unreacted products or by-products. .
- the reaction temperature of (C-1) and (C-2) is not particularly limited, but is preferably 25 ° C or higher and 150 ° C or lower, more preferably 30 ° C or higher and 120 ° C or lower, and 40 ° C or higher. More preferably, it is 100 ° C. or lower.
- the temperature of the reactor is adjusted to a predetermined temperature in advance and the simultaneous addition is performed in the reactor. It is preferable to adjust the reaction temperature to the predetermined temperature by adjusting the temperature to the predetermined temperature.
- the temperature of the reactor charged with the silicon chloride compound is adjusted to a predetermined temperature, and the organomagnesium It is preferable to adjust the reaction temperature to a predetermined temperature by adjusting the temperature in the reactor to a predetermined temperature while introducing the compound into the reactor.
- the temperature of the reactor charged with (C-1) is adjusted to a predetermined temperature, It is preferable to adjust the reaction temperature to a predetermined temperature by adjusting the temperature in the reactor to a predetermined temperature while introducing -2) into the reactor.
- organomagnesium compound (C-4) As (C-4), those represented by the aforementioned formula 5 (C-4) are preferable.
- the amount of (C-4) used is preferably 0.1 or more and 10 or less in terms of the molar ratio of magnesium atoms contained in (C-4) to titanium atoms contained in (C-5). More preferably, it is 5 or less.
- the temperature of the reaction between (C-4) and (C-5) is not particularly limited, but is preferably ⁇ 80 ° C. or higher and 150 ° C. or lower, more preferably ⁇ 40 ° C. or higher and 100 ° C. or lower. preferable.
- the concentration when (C-4) is used is not particularly limited, but is preferably 0.1 mol / L or more and 2 mol / L or less based on the titanium atom contained in (C-4), and 0.5 mol / L More preferably, it is 1.5 mol / L or less.
- an inert hydrocarbon solvent is preferably used for the dilution of (C-4).
- the order of addition of (C-4) and (C-5) to (C-3) is not particularly limited, and (C-5) is added following (C-4). Following (C-5) (C-4) and (C-4) and (C-5) can be added at the same time. Of these, the method of simultaneously adding (C-4) and (C-5) is preferred.
- the reaction between (C-4) and (C-5) is carried out in an inert hydrocarbon solvent, but it is preferable to use an aliphatic hydrocarbon solvent such as hexane or heptane.
- the catalyst thus obtained is used as a slurry solution using an inert hydrocarbon solvent.
- (C-5) is a titanium compound represented by Formula 6 described above.
- the hydrocarbon group represented by R 7 in Formula 6 is not particularly limited, and specific examples include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, allyl.
- An aliphatic hydrocarbon group such as a group; an alicyclic hydrocarbon group such as a cyclohexyl, 2-methylcyclohexyl, or cyclopentyl group; an aromatic hydrocarbon group such as a phenyl or a naphthyl group.
- an aliphatic hydrocarbon group is preferable.
- the halogen represented by X 1 is not particularly limited, and specific examples include chlorine, bromine, and iodine. Of these, chlorine is preferred. (C-5) selected from the above may be used singly or in combination of two or more.
- the amount of (C-5) used is not particularly limited, but is preferably 0.01 or more and 20 or less, and particularly preferably 0.05 or more and 10 or less, in terms of a molar ratio to the magnesium atom contained in the carrier (C-3).
- the reaction temperature of (C-5) is not particularly limited, but is preferably from ⁇ 80 ° C. to 150 ° C., and more preferably from ⁇ 40 ° C. to 100 ° C.
- the method for supporting (C-5) with respect to (C-3) is not particularly limited, and a method of reacting excess (C-5) with (C-3), a third method, A method of efficiently supporting (C-5) by using components may be used, but a method of supporting by (C-5) and an organomagnesium compound (C-4) is preferred.
- the organometallic compound component [B] used in this embodiment becomes a highly active polymerization catalyst by combining with the organometallic compound component [B].
- the organometallic compound component [B] is sometimes called a “promoter”.
- the organometallic compound component [B] is preferably a compound containing a metal belonging to the group consisting of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, particularly organoaluminum compounds and / or Or an organomagnesium compound is preferable.
- organoaluminum compound a compound represented by the following formula 7 is preferably used alone or in combination.
- R 12 is a hydrocarbon group having 1 to 20 carbon atoms
- Z 1 is a group belonging to the group consisting of hydrogen, halogen, alkoxy, allyloxy and siloxy groups
- j is a number of 2 to 3 .
- the hydrocarbon group having 1 to 20 carbon atoms represented by R 12 is not particularly limited.
- the hydrocarbon group is an aliphatic hydrocarbon, an aromatic hydrocarbon, or an alicyclic hydrocarbon.
- the organomagnesium compound is preferably an organomagnesium compound that is soluble in the inert hydrocarbon solvent represented by Formula 3 above.
- M 2 is a metal atom belonging to the group consisting of Groups 12, 13 and 14 of the periodic table, and R 8 , R 9 and R 10 are each a hydrocarbon having 2 to 20 carbon atoms.
- This organomagnesium compound is shown as a complex form of organomagnesium soluble in an inert hydrocarbon solvent, but encompasses all dialkylmagnesium compounds and complexes of this compound with other metal compounds. is there. ⁇ , ⁇ , e, f, g, M 2 , R 8 , R 9 , and OR 10 are as described above. However, since this organomagnesium compound preferably has higher solubility in an inert hydrocarbon solvent, ⁇ / ⁇ is preferably in the range of 0.5 to 10, more preferably a compound in which M 2 is aluminum.
- the combination ratio of the solid catalyst component and the organometallic compound component [B] is not particularly limited, but the organometallic compound component [B] is preferably 1 mmol or more and 3,000 mmol or less with respect to 1 g of the solid catalyst component.
- a metallocene catalyst As an example using a metallocene catalyst, a general transition metal compound is used. Although it does not specifically limit as a manufacturing method of a metallocene catalyst, For example, the manufacturing method of Japanese Patent 4868853 is mentioned.
- Such metallocene catalysts include two catalysts: a) a transition metal compound having a cyclic ⁇ -bonding anion ligand and b) an activator capable of reacting with the transition metal compound to form a complex that exhibits catalytic activity. Consists of ingredients.
- the transition metal compound having a cyclic ⁇ -bonding anion ligand used in the present embodiment can be represented by, for example, the following formula 8.
- L 1 is each independently ⁇ selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group.
- M 3 is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and is bonded to at least one ligand L 1 by ⁇ 5. Represents a transition metal.
- W is a divalent substituent having up to 50 non-hydrogen atoms, and is bonded to L 1 and M 3 with a valence of 1 each, whereby L 1 and M 3 Represents a divalent substituent that forms a metallocycle in cooperation with each other, and each X 2 independently represents a monovalent anionic ⁇ -bonded ligand, a divalent bond that binds to M 3 in a divalent manner.
- L 1 and M 3 Represents a divalent substituent that forms a metallocycle in cooperation with each other
- each X 2 independently represents a monovalent anionic ⁇ -bonded ligand, a divalent bond that binds to M 3 in a divalent manner.
- Up to 60 non-ionic ⁇ -bonded ligands selected from the group consisting of an anionic ⁇ -bonded ligand and a divalent anionic ⁇ -bonded ligand that binds to L 1 and M 3 each with a monovalent valence.
- each X 2 independently represents a neutral Lewis base coordinating compound having up to 40 non-hydrogen atoms
- X 3 represents a neutral Lewis base coordinating compound
- the divalent group includes a hydrocarbadiyl group having 1 to 20 carbon atoms, a halohydrocarbadiyl group having 1 to 12 carbon atoms, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, and a hydrocarbyleneamino group having 1 to 12 carbon atoms.
- k is 0 or 1
- p is 0, 1 or 2
- X 2 is a monovalent anionic ⁇ -bonded ligand, or a divalent bond bonded to L 1 and M 3
- p is 1 or more integer smaller than form oxidation number of M 3, also divalent anionic ⁇ -bound coordination which X 2 is bonded only to M 3
- p is an integer that is (j + 1) or more smaller than the formal oxidation number of M 3
- q is 0, 1 or 2.
- M 4 represents a transition metal selected from the group consisting of titanium, zirconium, nickel, and hafnium, and represents a transition metal having a formal oxidation number of +2, +3, or +4, and R 13 is independently selected.
- a substituent having up to 20 non-hydrogen atoms selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom and a composite group thereof.
- substituent R 13 is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group
- two adjacent substituents R 13 may be bonded to each other to form a divalent group. And thereby can form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring that is bonded to each of the two adjacent substituents R 13 .
- each X 4 independently represents a halide, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, a hydrocarbylamino group having 1 to 18 carbon atoms, a silyl group, or a carbon number.
- Y 2 represents —O—, —S—, —NR * — or —PR * —, wherein R * is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 carbon atom.
- R * is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or 1 carbon atom.
- Examples of the transition metal compound having a cyclic ⁇ -binding anion ligand used in the present embodiment include the following compounds.
- Zirconium-based compounds are not particularly limited. Specifically, for example, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) Zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (4,5,6,7-tetrahydro-1-indenyl
- the titanium-based compound is not particularly limited. Specifically, for example, [(Nt-butylamide) (tetramethyl- ⁇ 5 -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [( Nt-butylamido) (tetramethyl- ⁇ 5 -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamido) (tetramethyl- ⁇ 5 -cyclopentadienyl) dimethylsilane] titanium dimethyl, [( N-phenylamido) (tetramethyl- ⁇ 5 -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-benzylamido) (tetramethyl- ⁇ 5 -cyclopentadienyl) dimethylsilane] titanium dimethyl, [( N-t-butylamido) (eta 5 - cyclopentadienyl) -1,2 Ethaned
- the nickel-based compound is not particularly limited, and specifically, for example, dibromobistriphenylphosphine nickel, dichlorobistriphenylphosphine nickel, dibromodiacetonitrile nickel, dibromodibenzonitrile nickel, dibromo (1,2-bisdiphenylphosphino) Ethane) nickel, dibromo (1,3-bisdiphenylphosphinopropane) nickel, dibromo (1,1′-diphenylbisphosphinoferrocene) nickel, dimethylbisdiphenylphosphinenickel, dimethyl (1,2-bisdiphenylphosphinoethane) ) Nickel, methyl (1,2-bisdiphenylphosphinoethane) nickel tetrafluoroborate, (2-diphenylphosphino-1-phenylethyleneoxy) phenylpyridine Buckel, dichlorobistriphenylphosphine palladium, dichlorodibenzonitrile pal
- the hafnium-based compound is not particularly limited. Specifically, for example, [(Nt-butylamide) (tetramethyl- ⁇ 5-cyclopentadienyl) -1,2-ethanediyl] hafnium dimethyl, [(N -T-Butylamide) (tetramethyl- ⁇ 5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-methylamido) (tetramethyl- ⁇ 5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-phenyl Amido) (tetramethyl- ⁇ 5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(N-benzylamido) (tetramethyl- ⁇ 5-cyclopentadienyl) dimethylsilane] hafnium dimethyl, [(Nt-butylamide) ) ( ⁇ 5-Cyclopenta
- transition metal compound having a cyclic ⁇ -bonding anion ligand used in the present embodiment include “dimethyl” in the names of the zirconium-based compounds and titanium-based compounds listed above (this is , The name at the end of the name of each compound, that is, the name that appears immediately after the part of “zirconium” or “titanium”, and the name corresponding to the part of X 4 in Formula 2), for example, “ “Dichloro”, “Dibrom”, “Diiodo”, “Diethyl”, “Dibutyl”, “Diphenyl”, “Dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4- “Diyl”, “s-trans- ⁇ 4-1,4-diphenyl-1,3-butadiene”, “s-trans- ⁇ 4 -3-methyl-1,3-pentadiene”, “s-trans- ⁇ ” 4 -1,4-d
- the transition metal compound having a cyclic ⁇ -binding anion ligand used in the present embodiment can be synthesized by a generally known method. In this embodiment, these transition metal compounds may be used alone or in combination.
- activator an activator that can form a complex that reacts with a transition metal compound and exhibits catalytic activity
- Examples of the activator used in the present embodiment include compounds defined by the following formula 10.
- the non-coordinating anion is not particularly limited. Specifically, for example, tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, tris (pentafluorophenyl) (phenyl) borate, tris (2, 4-dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, tris (pentafluorophenyl) (cyclohexyl) ) Borate, tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxypheny) ) Borate, tri
- Examples of other preferable non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is replaced with an NHR group.
- R is preferably a methyl group, an ethyl group or a tert-butyl group.
- the proton-providing Bronsted acid is not particularly limited, and specific examples thereof include triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium and tri (n-octyl).
- Trialkyl group-substituted ammonium cations such as ammonium; N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanily N, N-dialkylanilinium cations such as nium; dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium; triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethyl) Triaryl phosphonium cations such as phenyl) phosphonium; or dimethyl sulfonium, diethyl full sulfonium include diphenyl sulfonium and the like.
- an organometallic oxy compound having a unit represented by the following formula 11 can also be used as an activator.
- M 6 is a metal or metalloid of Groups 13 to 15 of the periodic table
- R 14 is each independently a hydrocarbon group or substituted hydrocarbon group having 1 to 12 carbon atoms
- n is a metal M is a valence of 6 and m is an integer of 2 or more.
- a preferred example of the activator used in the present embodiment is an organoaluminum oxy compound containing a unit represented by the following formula 12, for example.
- R 15 is an alkyl group having 1 to 8 carbon atoms, and m is an integer of 2 to 60.
- a more preferable example of the activator used in the present embodiment is, for example, methylalumoxane containing a unit represented by the following formula 13. (Here, m is an integer from 2 to 60.)
- the activator components may be used alone or in combination.
- these catalyst components can be supported on a solid component and used as a supported catalyst.
- a solid component is not particularly limited.
- a porous polymer material such as polyethylene, polypropylene, or a copolymer of styrenedivinylbenzene; silica, alumina, magnesia, magnesium chloride, zirconia, titania, Inorganic solid materials of Group 2, 3, 4, 13 and 14 elements of the periodic table such as boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide and thorium oxide, and mixtures thereof; And at least one inorganic solid material selected from these double oxides.
- the complex oxide of silica such as a silica magnesia, a silica alumina, etc., and a periodic table group 2 or 13 element is mentioned, for example. It is done.
- an organoaluminum compound can be used as a catalyst component as necessary.
- the organoaluminum compound that can be used in the present embodiment is a compound represented by the following formula 14, for example.
- R 16 is an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 20 carbon atoms
- X 5 is a halogen, hydrogen or alkoxyl group
- the alkyl group is linear, branched or
- n is an integer of 1 to 3.
- the organoaluminum compound may be a mixture of compounds represented by the above formula 14.
- the organoaluminum compound that can be used in this embodiment include the above formula, wherein R 16 is a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, a tolyl group, or the like.
- Examples of X 5 include a methoxy group, an ethoxy group, a butoxy group, and chloro.
- organoaluminum compound which can be used in this embodiment, Specifically, for example, trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Or the reaction products of these organoaluminums with alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, such as dimethylmethoxyaluminum, diethylethoxyaluminum, dibutylbutoxyaluminum Etc.
- alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, such as dimethylmethoxyaluminum, diethylethoxyaluminum, dibuty
- Examples of the method for polymerizing polyethylene in the method for producing the ultrahigh molecular weight polyethylene powder of the present embodiment include a method of (co) polymerizing ethylene or a monomer containing ethylene by suspension polymerization or gas phase polymerization. .
- the suspension polymerization method that can efficiently remove the heat of polymerization is preferable.
- an inert hydrocarbon medium can be used as a medium, and the olefin itself can also be used as a solvent.
- Such an inert hydrocarbon medium is not particularly limited.
- aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene
- examples include alicyclic hydrocarbons such as pentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene, and dichloromethane; or a mixture thereof. it can.
- the polymerization temperature in the method for producing the ultrahigh molecular weight polyethylene powder of the present embodiment is usually 30 ° C. or higher and 100 ° C. or lower.
- the polymerization temperature is 30 ° C. or higher, industrially more efficient production tends to be possible.
- the polymerization temperature is 100 ° C. or lower, there is a tendency that continuous and more stable operation can be performed.
- the polymerization pressure in the method for producing the ultrahigh molecular weight polyethylene powder of the present embodiment is usually from normal pressure to 2 MPa.
- the polymerization pressure is preferably 0.1 MPa or more, more preferably 0.12 MPa or more, and preferably 1.5 MPa or less, more preferably 1.0 MPa or less.
- the polymerization pressure is higher than normal pressure, industrially more efficient production tends to be possible, and when the polymerization pressure is 2 MPa or less, partial heat generation due to rapid polymerization reaction at the time of catalyst introduction is suppressed. It tends to be able to produce polyethylene stably.
- the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods, but it is preferable to carry out polymerization in a continuous manner.
- By continuously supplying ethylene gas, solvent, catalyst, etc. into the polymerization system and continuously discharging it together with the generated polyethylene it becomes possible to suppress partial high-temperature conditions due to rapid ethylene reaction.
- the system becomes more stable.
- ethylene reacts in a uniform state in the system the formation of branches, double bonds, etc. in the polymer chain is suppressed, and it is difficult for the molecular weight and crosslinking of polyethylene to occur. Melting or unmelted material remaining at the time of dissolution is reduced, coloring is suppressed, and problems such as mechanical properties are unlikely to occur. Therefore, a continuous system in which the inside of the polymerization system becomes more uniform is preferable.
- the intrinsic viscosity of the resulting polyethylene can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, as described, for example, in DE-A-3127133. You can also.
- the intrinsic viscosity can be controlled within an appropriate range.
- the molar fraction of hydrogen is preferably 0 mol% or more and 30 mol% or less, more preferably 0 mol% or more and 25 mol% or less, and 0 mol% or more and 20 mol% or less. More preferably.
- the other well-known component useful for manufacture of polyethylene other than each above components can be included.
- an antistatic agent such as Stadis450 manufactured by The Associated Octel Company (manufactured by Maruyama Co., Ltd.) is used in order to suppress polymer adhesion to the polymerization reactor. It is also possible.
- Stadis 450 can also be diluted with an inert hydrocarbon medium and added to the polymerization reactor by a pump or the like. In this case, the addition amount is preferably in the range of 0.10 ppm to 20 ppm, more preferably in the range of 0.20 ppm to 10 ppm, with respect to the polyethylene production amount per unit time.
- baffle plates are preferably provided at equal intervals in the reactor at 2 or more and 6 or less.
- the baffle plate is preferably provided from the bottom of the reactor to the top of the reactor (opening), and the length from the top of the baffle plate to the side of the reactor is 10% to 30% of the inner diameter of the reactor.
- the width is preferably adjusted to 10% or more and 30% or less of the reactor circumferential length.
- the drying temperature is changed in the first stage (first half of the total drying time) and the second stage (second half of the total drying time) (first stage: 60 ° C. or higher and lower than 70 ° C., second stage) 70 to 90 ° C.) is preferable.
- rapid drying at a high temperature it is possible to prevent the ultrahigh molecular weight polyethylene powder from cracking and increasing the amount of fine powder by using the drying step as described above.
- the ultrahigh molecular weight polyethylene powder of the present embodiment can be obtained by adjusting each polymerization condition.
- additives such as a slip agent, a neutralizing agent, an antioxidant, a light-resistant stabilizer, an antistatic agent, and a pigment can be added to the ultrahigh molecular weight polyethylene powder of the present embodiment.
- the slipping agent or neutralizing agent is not particularly limited, and examples thereof include aliphatic hydrocarbons, higher fatty acids, higher fatty acid metal salts, fatty acid esters of alcohol, waxes, higher fatty acid amides, silicone oils, and rosins.
- content of a slip agent or a neutralizing agent is not specifically limited, It is 5000 ppm or less, Preferably it is 4000 ppm or less, More preferably, it is 3000 ppm or less.
- the antioxidant is not particularly limited.
- a phenol compound or a phenol phosphate compound is preferable.
- the amount of the antioxidant is preferably 5 parts by mass or less, and more preferably, when the total of the ultra high molecular weight polyethylene powder and the liquid paraffin is 100 parts by mass. Is 4 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.
- the antioxidant is 5 parts by mass or less, the deterioration of the polyethylene is suppressed, and embrittlement, discoloration, deterioration of mechanical properties and the like are less likely to occur, and the long-term stability is improved.
- the light-resistant stabilizer is not particularly limited, and examples thereof include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro.
- Benzotriazole light stabilizers such as benzotriazole; bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4- Hindered amine light stabilizers such as piperidyl) imino ⁇ ].
- content of a light-resistant stabilizer is not specifically limited, It is 5000 ppm or less, Preferably it is 3000 ppm or less, More preferably, it is 2000 ppm or less.
- the antistatic agent is not particularly limited, and examples thereof include aluminosilicate, kaolin, clay, natural silica, synthetic silica, silicates, talc, diatomaceous earth, and glycerin fatty acid ester.
- the ultra high molecular weight polyethylene powder of this embodiment can be processed by various methods. Moreover, the molded object obtained using this polyethylene powder can be used for various uses. Although it does not limit as a molded object, For example, it is suitable as a microporous film for secondary battery separators, especially a microporous film for lithium ion secondary battery separators, a sintered compact, a high-strength fiber, etc.
- the method for producing the microporous membrane include a processing method in which a wet process using a solvent is performed by extrusion, stretching, extraction, and drying in an extruder equipped with a T die.
- molded products obtained by sintering ethylene polymers can also be used for molded products obtained by sintering ethylene polymers, taking advantage of the high-molecular weight ethylene polymer characteristics such as wear resistance, high slidability, high strength, and high impact properties.
- Examples of a method for producing high-strength fibers include a method obtained by kneading and spinning liquid paraffin and ultrahigh molecular weight polyethylene powder and then heating and stretching.
- Viscosity average molecular weight (Mv and Mv (A)) [Kneading conditions 1] The calculation of the decomposition rate in the examples and comparative examples of the present application was obtained by obtaining a kneaded gel by the following method. For a total of 100 parts by mass of liquid paraffin and ultra high molecular weight polyethylene powder, 95 parts by mass of liquid paraffin, 5 parts by mass of ultra high molecular weight polyethylene powder, and 1 part by mass of antioxidant were kneaded.
- ultra high molecular weight polyethylene powder 38.0 g of fluid paraffin (product name: Smoyl P-350P) manufactured by Matsumura Oil Research Co., Ltd., Tetrakis [methylene (manufactured by Great Lakes Chemical Japan Co., Ltd.) 3,5-di-t-butyl-4-hydroxy-hydrocinnamate)] 0.4 g of methane (product name: ANOX20) was added to a 200 ml polycup and mixed well, and then Laboplast mill manufactured by Toyo Seiki Co., Ltd.
- fluid paraffin product name: Smoyl P-350P
- methane product name: ANOX20
- a mixer main body model: 30C150, mixer type: R-60
- kneaded at 130 ° C for 30 minutes then kneaded while heating up to 240 ° C at 22 ° C / min, and further kneaded at 240 ° C for 15 minutes.
- the kneading was performed in a nitrogen atmosphere, and all rotations were performed at 50 rpm.
- liquid paraffin was extracted from the obtained kneaded gel using hexane, and vacuum-dried for 24 hours or more to obtain a kneaded product.
- the viscosity average molecular weight Mv of the ultrahigh molecular weight polyethylene powders obtained in Examples and Comparative Examples was determined by the method described below in accordance with ISO 1628-3 (2010). First, 20 mg of ultra-high molecular weight polyethylene powder was weighed into a dissolution tube, and the dissolution tube was purged with nitrogen, and then 20 mL of decahydronaphthalene (1,6-di-tert-butyl-4-methylphenol added at 1 g / L) ) And stirred at 150 ° C. for 2 hours to dissolve the ultrahigh molecular weight polyethylene powder.
- the drop time (ts) between the marked lines was measured using a Canon-Fenske viscometer (manufactured by Shibata Kagaku Kikai Kogyo Co., Ltd .: product number-100) in a thermostatic bath at 135 ° C. Similarly, the drop time (ts) between the marked lines was similarly measured for the samples in which the amount of ultrahigh molecular weight polyethylene powder was changed to 10 mg, 5 mg, and 2 mg. The dropping time (tb) of only decahydronaphthalene without ultra high molecular weight polyethylene powder as a blank was measured. The reduced viscosity ( ⁇ sp / C) of the ultrahigh molecular weight polyethylene powder was determined according to the following formula.
- ⁇ sp / C (ts / tb ⁇ 1) /0.1 (unit: dL / g) Plot the relationship between the concentration (C) (unit: g / dL) and the reduced viscosity ( ⁇ sp / C) of the ultra-high molecular weight polyethylene powder, derive an approximate linear equation by the least square method, and extrapolate to the concentration 0
- the intrinsic viscosity ([ ⁇ ]) was determined.
- the viscosity average molecular weight (Mv) was calculated from the value of the intrinsic viscosity [ ⁇ ] using the following formula A.
- the average pore volume and pore distribution of the powder were measured using Autopore IV9500 manufactured by Shimadzu Corporation as a mercury porosimeter. Based on the obtained pore distribution, the average pore diameter was calculated.
- a pretreatment 0.5 g of the powder was placed in a sample cell, and after deaeration and drying at room temperature in a low-pressure measuring unit, mercury was filled in the sample container. The pressure was gradually increased (high pressure part), and mercury was pressed into the pores of the sample.
- the pressure conditions were set as follows. ⁇ Low pressure part: measured at 69 Pa (0.01 psia) N 2 pressure ⁇ High pressure part: 21 to 228 MPa (3000 to 33,000 pisa)
- the average particle diameter of the ultrahigh molecular weight polyethylene powder is 100 g using 10 types of sieves (openings: 710 ⁇ m, 500 ⁇ m, 425 ⁇ m, 355 ⁇ m, 300 ⁇ m, 212 ⁇ m, 150 ⁇ m, 106 ⁇ m, 75 ⁇ m, 53 ⁇ m) defined in JIS Z8801.
- the particle diameter at 50% weight was defined as the average particle diameter.
- the content of particles having a particle size of 53 ⁇ m or less in the ultrahigh molecular weight polyethylene powder is 10 types of sieves defined by JIS Z8801 (openings: 710 ⁇ m, 500 ⁇ m, 425 ⁇ m, 355 ⁇ m). , 300 ⁇ m, 212 ⁇ m, 150 ⁇ m, 106 ⁇ m, 75 ⁇ m, 53 ⁇ m), after classifying 100 g of particles, the weight of particles passing through a sieve having an opening of 53 ⁇ m with respect to the weight of all particles (ultra high molecular weight polyethylene powder), As sought.
- the content rate (%) of particles having a particle diameter of 53 ⁇ m or less was calculated from the weight of particles passed through a sieve having a mesh opening of 53 ⁇ m, as determined above, using the following formula.
- Content ratio (%) of particles having a particle diameter of 53 ⁇ m or less [weight (g) of particles passed through a sieve having a mesh size of 53 ⁇ m] / [weight of all particles (ultra high molecular weight polyethylene powder) 100 (g)] ⁇ 100
- ultra-high molecular weight polyethylene powder before passing through “aperture: 425 ⁇ m sieve” described in Examples and Comparative Examples described later was used.
- Ultra high molecular weight polyethylene powder is pressure-decomposed using a microwave decomposing device (model ETHOS TC, manufactured by Milestone General) As standard, ICP-MS (Inductively Coupled Plasma Mass Spectrometer, Model X series X7, manufactured by Thermo Fisher Scientific Co., Ltd.), Mg, Ti, Al, Si, Cl as metals in ultra high molecular weight polyethylene powder The elemental concentration of was measured. In addition, it can cut out molded objects, such as a film
- ethylene and hexane used in Examples and Comparative Examples were dehydrated using MS-3A (manufactured by Showa Union), and hexane was further used after deoxygenation by performing vacuum degassing using a vacuum pump. .
- a twin screw extruder (main body model: 2D25S) for Laboplast Mill (main body model: 30C150) manufactured by Toyo Seiki Co., Ltd. was used, and kneading and spinning operations were performed.
- the temperature at which the slurry liquid was formed in the extruder was 140 ° C. or more and 320 ° C. or less, and the melt residence time in the extruder was 5 minutes or more and 30 minutes or less. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the spinneret temperature was 140 ° C. to 250 ° C.
- the discharge rate was 0.5 g / min to 2.0 g / min
- the spinneret hole diameter was 0.3 mm to 1.5 mm.
- the discharged yarn containing liquid paraffin was put into a water bath at 5 ° C. or higher and 15 ° C. or lower through an air gap of 3 to 5 cm, and wound up while rapidly cooling.
- the winding speed was 20 m / min or more and 50 m / min or less.
- the liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum-dried for 24 hours or more.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 100 ° C. or higher and 140 ° C. or lower, and was primarily stretched to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn had a temperature of 140 ° C.
- the degree of orientation of the ultrahigh molecular weight polyethylene fibers was determined by comparing the optical system microscope (main body model: BX51TRF-6 (D)) manufactured by Olympus Corporation with the Belek Compensator (main body model) manufactured by Olympus Corporation. : U-CBE), the retardation value (Re) was calculated, and the following formula was used.
- the fiber used for the measurement was 5 single yarns, and the retardation value was obtained by measuring the orientation degree (hereinafter also referred to as retardation) at three points for each single yarn and calculating the average value.
- the obtained slurry-like liquid was substituted with nitrogen, and then passed through a feeder under a nitrogen atmosphere to a twin screw extruder (main body model: 2D25S) for Laboplast Mill (main body model: 30C150) manufactured by Toyo Seiki Co., Ltd.
- the mixture was kneaded under conditions of 200 ° C., extruded from a T-die installed at the tip of the extruder, and immediately cooled and solidified with a cast roll cooled to 25 ° C. to form a gel sheet.
- the gel sheet was stretched 7 ⁇ 7 times at 120 ° C.
- the film was formed by the method described in (7) above, and the film thickness was measured at 23 ° C. using a micro thickness gauge (type KBM (registered trademark)) manufactured by Toyo Seiki. Arbitrary 10 points were selected and measured so as to be evenly distributed for every 1 m of film, and a total of 50 points of film 5 m were measured to calculate the average film thickness. The average film thickness was 5 ⁇ m or more and 20 ⁇ m or less. (Evaluation criteria) A indicates that the film was very good, and the variation was less than ⁇ 3 ⁇ m with respect to the average film thickness. ⁇ indicates that there was no problem, and the variation was ⁇ 3 ⁇ m or more and less than 5 ⁇ m with respect to the average film thickness. X represents that it was bad, and the variation was ⁇ 5 ⁇ m or more with respect to the average film thickness.
- a micro thickness gauge type KBM (registered trademark) manufactured by Toyo Seiki.
- Arbitrary 10 points were selected and measured so as to be evenly distributed for every 1
- Catalyst Synthesis method [Reference Example 1: Catalyst Synthesis Example 1: Preparation of Solid Catalyst Component [A]] 1,600 mL of hexane was added to an 8 L stainless steel autoclave purged with nitrogen. While stirring at 15 ° C., 800 mL of 1 mol / L titanium tetrachloride hexane solution and 800 mL of hexane solution of organomagnesium compound represented by 1 mol / L composition formula AlMg 5 (C 4 H 9 ) 11 (OSiH) 2 were added. Added simultaneously over time. After the addition, the temperature was raised slowly, and the reaction was continued at 15 ° C. for 1.5 hours.
- titanium-1,3-pentadiene 200 mmol of [(Nt-butylamide) (tetramethyl- ⁇ 5 -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) was added to Isopar E (exon).
- borate bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as “borate”) was added to 50 mL of toluene and dissolved, and borate Of 100 mmol / L in toluene was obtained.
- borate toluene solution 5 mL of a 1 mol / L hexane solution of ethoxydiethylaluminum was added at room temperature, and further hexane was added so that the borate concentration in the solution was 70 mmol / L. Then, it stirred at room temperature for 2 hours and obtained the reaction mixture containing a borate.
- Example 1 Polyethylene polymerization process
- Hexane, ethylene, hydrogen, and solid catalyst component [A] were continuously fed to a Bessel type polymerization reactor equipped with a stirrer to produce polyethylene (ethylene homopolymer) at a rate of 10 kg / hour.
- hydrogen 99.99 mol% or more of hydrogen purified by contact with molecular sieves was used.
- the solid catalyst component [A] was prepared by using the above-mentioned solvent hexane as a transfer liquid, hydrogen at 10 NL / hour (NL is Normal Liter (volume converted to the standard state)), and 0.15 mmol / hour so that the production rate was 10 kg / hour.
- L was added from the middle between the liquid level and the bottom of the polymerization reactor at a rate of L.
- the solid catalyst component [A] is adjusted to 98 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / hour, and triisobutylaluminum is adjusted to 22 ° C. at a rate of 5 mmol / hour. From the bottom.
- the polymerization temperature was kept at 88 ° C. by cooling the jacket.
- the humidity in the polymerization reactor was kept at 0 ppm.
- Hexane was adjusted to 20 ° C. and fed to the polymerization vessel at 60 L / hour.
- Ethylene was supplied from the bottom of the polymerization reactor to keep the polymerization pressure at 1.0 MPa.
- the polymerization slurry was continuously drawn into a flash drum having a pressure of 0.05 MPa so that the level of the polymerization reactor was kept constant, and unreacted ethylene was separated.
- the polymerization slurry was continuously sent to a centrifuge so that the level of the flash drum was kept constant, and the polymer and other solvents were separated.
- the content of the solvent or the like contained in the ultrahigh molecular weight polyethylene powder was 10% by mass with respect to the weight of the ultrahigh molecular weight polyethylene powder.
- the separated ultra high molecular weight polyethylene powder was dried at 65 ° C. for 3 hours while being blown with nitrogen, and further dried at 75 ° C. for 2 hours.
- the ultrahigh molecular weight polyethylene powder obtained in Example 1 was obtained by removing the ultrahigh molecular weight polyethylene powder that did not pass through the sieve using a sieve having an opening of 425 ⁇ m.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- baffle plates were installed at equal intervals at four locations from the bottom of the reactor to the top (opening) of the reactor. The baffle plate protrudes on the side of the reactor, the distance from the top of the protrusion to the side of the reactor is 15% of the inner diameter of the reactor, and the width of the protrusion is 15% of the circumferential length of the reactor. It was.
- Example 2 Polyethylene polymerization process
- the polymerization temperature was 85 ° C.
- the solid catalyst component [A] was charged into the reactor at 95 ° C.
- 1-butene was introduced from the gas phase at 6.3 mol% relative to ethylene.
- the ultra high molecular weight polyethylene powder of Example 2 was obtained. Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Example 2 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- Example 2 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- the evaluation results of the obtained microporous membrane are shown in Table 1.
- Example 3 Polyethylene polymerization process
- the ultrahigh molecular weight polyethylene powder of Example 3 was obtained in the same manner as in Example 1 except that the polymerization temperature was 83 ° C. and the solid catalyst component [A] was charged into the reactor at 93 ° C.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Example 4 Polyethylene polymerization step
- Hexane, ethylene, hydrogen, and supported metallocene catalyst component [B] were continuously fed to a Bessel polymerization reactor equipped with a stirrer to produce polyethylene (ethylene homopolymer) at a rate of 10 kg / hour.
- hydrogen 99.99 mol% or more of hydrogen purified by contact with molecular sieves was used.
- the supported metallocene catalyst component [B] was prepared so that the above-mentioned solvent hexane was used as a transfer liquid, and the hydrogen was added at 10 NL / hour (NL is a normal liter (volume converted to the standard state)), and the production rate was 10 kg / hour.
- the polymerization reactor was added at a rate of 15 mmol / L from the middle between the liquid level and the bottom of the polymerization reactor.
- the supported metallocene catalyst component [B] is adjusted to 95 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / hour, and triisobutylaluminum is adjusted to 22 ° C. at a rate of 5 mmol / hour.
- the polymerization temperature was kept at 85 ° C. by jacket cooling.
- the humidity in the polymerization reactor was kept at 0 ppm. Hexane was adjusted to 20 ° C. and fed from the bottom of the polymerization vessel at 60 L / hour.
- Ethylene was supplied from the bottom of the polymerization reactor to keep the polymerization pressure at 0.8 MPa.
- the polymerization slurry was continuously drawn into a flash drum having a pressure of 0.05 MPa so that the level of the polymerization reactor was kept constant, and unreacted ethylene was separated.
- the polymerization slurry was continuously sent to a centrifuge so that the level of the flash drum was kept constant, and the polymer and other solvents were separated. At that time, the content of the solvent or the like contained in the ultrahigh molecular weight polyethylene powder was 10% by mass with respect to the weight of the ultrahigh molecular weight polyethylene powder.
- the separated ultra high molecular weight polyethylene powder was dried at 65 ° C.
- the ultrahigh molecular weight polyethylene powder obtained in Example 4 was obtained by removing the ultrahigh molecular weight polyethylene powder that did not pass through the sieve using a sieve having an opening of 425 ⁇ m.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- baffle plates were installed at equal intervals at four locations from the bottom of the reactor to the top (opening) of the reactor. The baffle plate protrudes on the side of the reactor, the distance from the top of the protrusion to the side of the reactor is 15% of the inner diameter of the reactor, and the width of the protrusion is 15% of the circumferential length of the reactor. It was.
- Example 4 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- Example 4 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- the evaluation results of the obtained microporous membrane are shown in Table 1.
- Example 5 Polyethylene polymerization process
- the polymerization temperature was 84 ° C.
- the solid catalyst component [A] was charged into the reactor at 94 ° C.
- the polymerization pressure was 1.1 MPa
- the active 18000 PE g / catalyst g was blown with nitrogen.
- baffle plates are installed at two equal intervals in the reactor, and the baffle plates are provided from the bottom of the reactor to the top (opening) of the reactor.
- Example 5 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- Example 5 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- Example 6 Polyethylene polymerization process
- the polymerization temperature is 84 ° C.
- the solid catalyst component [A] is charged into the reactor at 94 ° C.
- the polymerization pressure is 0.6 MPa
- the active 16000 PE g / catalyst g and baffle plates are installed at equal intervals in the reactor at four locations.
- the baffle plate is provided from the bottom of the reactor to the top of the reactor (opening) and protrudes from the side of the reactor.
- the distance from the top of the protrusion to the side of the reactor is 25% of the inner diameter of the reactor
- the ultrahigh molecular weight polyethylene powder of Example 6 was obtained in the same manner as in Example 2 except that the part width was changed to 25% of the reactor circumferential length. Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Example 6 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- Example 6 Method for producing microporous membrane for secondary battery separator using ultrahigh molecular weight polyethylene powder
- the evaluation results of the obtained microporous membrane are shown in Table 1.
- Example 7 Polyethylene polymerization process
- the polymerization temperature was 80 ° C.
- the solid catalyst component [A] was charged into the reactor at 90 ° C.
- the polymerization pressure was 0.6 MPa
- the activity was 14,000 PE g / catalyst g. 7 ultrahigh molecular weight polyethylene powder was obtained.
- Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- the temperature at which the slurry liquid was formed in the extruder was 200 ° C., and the melt residence time in the extruder was 10 minutes. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the temperature of the spinneret was 200 ° C.
- the discharge rate was 0.5 g / min
- the hole diameter of the spinneret was 1.0 mm.
- the discharged yarn containing liquid paraffin was put into a 5 ° C. water bath through a 4 cm air gap and wound up while rapidly cooling. The winding speed was 30 m / min.
- the liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum dried for 24 hours.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 120 ° C., and was primarily drawn to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn was at 140 ° C., and was further subjected to secondary drawing, and was drawn until just before the yarn was cut to obtain a drawn yarn.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 8 Polyethylene polymerization process Except that the polymerization temperature was 78 ° C., the solid catalyst component [A] was charged into the reactor at 88 ° C., 1-butene was introduced from the gas phase of 6.3 mol% with respect to ethylene, and the active 12000PE g / catalyst g It carried out like Example 7 and obtained ultra high molecular weight polyethylene powder of Example 8. Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- a high-strength fiber of Example 8 was obtained in the same manner as in Example 7 except that the obtained ultrahigh molecular weight polyethylene powder was used.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 9 Polyethylene polymerization process
- the ultrahigh molecular weight polyethylene powder of Example 9 was carried out in the same manner as in Example 7 except that the polymerization temperature was 70 ° C. and the solid catalyst component [A] was charged into the reactor at 80 ° C. and the activity was 9000 PE g / catalyst g. Got.
- Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- the temperature at which the slurry liquid was formed in the extruder was 220 ° C., and the melt residence time in the extruder was 10 minutes. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the temperature of the spinneret was 220 ° C.
- the discharge rate was 0.5 g / min
- the hole diameter of the spinneret was 0.6 mm.
- the discharged yarn containing liquid paraffin was put into a 5 ° C. water bath through a 3 cm air gap and wound up while rapidly cooling. The winding speed was 30 m / min. The liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum dried for 24 hours.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 120 ° C., and was primarily drawn to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn was at 140 ° C., and was further subjected to secondary drawing, and was drawn until just before the yarn was cut to obtain a drawn yarn.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 10 Polyethylene polymerization process
- Polymerization pressure is 0.5 MPa
- activity is 12000 PE g / catalyst g
- baffle plates are installed in the reactor at six equal intervals, and the baffle plates are provided from the bottom of the reactor to the top of the reactor (opening), Example 7 except that the distance from the top of the protrusion to the side of the reactor was changed to 30% of the inner diameter of the reactor and the width of the protrusion was changed to 30% of the circumference of the reactor.
- the ultrahigh molecular weight polyethylene powder of Example 10 was obtained in the same manner. Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- a high-strength fiber of Example 10 was obtained in the same manner as in Example 7 except that the obtained ultrahigh molecular weight polyethylene powder was used.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 11 Polyethylene polymerization process
- the polymerization pressure is 0.5 MPa
- the activity is 8000 PE g / catalyst g
- baffle plates are installed at two equal intervals in the reactor, and the baffle plates are provided from the bottom of the reactor to the top of the reactor (opening), Example 8 except that the distance from the top of the protrusion to the side of the reactor was changed to 10% of the inner diameter of the reactor and the width of the protrusion was changed to 10% of the circumference of the reactor.
- the ultrahigh molecular weight polyethylene powder of Example 11 was obtained in the same manner as described above. Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- a high-strength fiber of Example 11 was obtained in the same manner as in Example 8 except that the obtained ultrahigh molecular weight polyethylene powder was used.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 12 Polyethylene polymerization process
- the polymerization pressure is 0.5 MPa
- baffle plates are installed at two equal intervals in the reactor, and the baffle plates are provided from the bottom of the reactor to the top of the reactor (opening), Example 9 except that the distance from the top of the protrusion to the side of the reactor was changed to 10% of the inner diameter of the reactor and the width of the protrusion was changed to 10% of the circumference of the reactor.
- the ultrahigh molecular weight polyethylene powder of Example 12 was obtained in the same manner. Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- a high-strength fiber of Example 12 was obtained in the same manner as in Example 9 except that the obtained ultrahigh molecular weight polyethylene powder was used.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- Example 13 Polyethylene polymerization process
- the polymerization temperature is 76 ° C.
- the solid catalyst component [B] is charged to the reactor at 86 ° C.
- the polymerization pressure is 0.6 MPa
- 1-butene is introduced from the gas phase at 6.3 mol% with respect to ethylene
- active 11000 PE g / catalyst g baffle plates are installed at equal intervals in four places in the reactor, and the baffle plates are provided from the bottom of the reactor to the top of the reactor (opening) and protrude from the side of the reactor.
- Example 13 The ultrahigh molecular weight of Example 13 was obtained in the same manner as in Example 4 except that the distance from the top to the reactor side was changed to 20% of the inner diameter of the reactor, and the protrusion width was changed to 20% of the circumference of the reactor. Polyethylene powder was obtained. Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Example 13 (Method for producing high-strength fiber using ultra-high molecular weight polyethylene powder) A high strength fiber of Example 13 was obtained in the same manner as in Example 8 except that the obtained ultra high molecular weight polyethylene powder was used. The evaluation results of the obtained high strength fiber are shown in Table 2.
- L was added from the middle between the liquid level and the bottom of the polymerization reactor at a rate of L.
- the solid catalyst component [A] is adjusted to 20 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / hour, and triisobutylaluminum is adjusted to 22 ° C. at a rate of 5 mmol / hour. From the bottom.
- the polymerization temperature was kept at 88 ° C. by cooling the jacket.
- the humidity in the polymerization reactor was kept at 0 ppm.
- Hexane was adjusted to 20 ° C. and fed to the polymerization vessel at 60 L / hour.
- Ethylene was supplied from the bottom of the polymerization reactor to keep the polymerization pressure at 1.0 MPa.
- the polymerization slurry was continuously drawn into a flash drum having a pressure of 0.05 MPa so that the level of the polymerization reactor was kept constant, and unreacted ethylene was separated.
- the polymerization slurry was continuously sent to a centrifuge so that the level of the flash drum was kept constant, and the polymer and other solvents were separated.
- the content of the solvent or the like contained in the ultrahigh molecular weight polyethylene powder was 10% by mass with respect to the weight of the ultrahigh molecular weight polyethylene powder.
- the separated ultra high molecular weight polyethylene powder was dried at 100 ° C. for 5 hours while blowing nitrogen. In this drying step, the catalyst and the cocatalyst were deactivated by spraying steam on the polymerized powder.
- the ultrahigh molecular weight polyethylene powder obtained in Comparative Example 1 was obtained by removing the ultrahigh molecular weight polyethylene powder that did not pass through the sieve using a sieve having an opening of 425 ⁇ m.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Comparative Example 2 Polyethylene polymerization process
- the polymerization temperature was changed to 85 ° C.
- 1-butene was introduced from the gas phase of 6.3 mol% with respect to ethylene
- the separated ultrahigh molecular weight polyethylene powder was dried at 65 ° C. for 3 hours while blowing nitrogen, then 75 ° C.
- the ultrahigh molecular weight polyethylene powder of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that it was further dried for 2 hours.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- a microporous membrane of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the obtained ultrahigh molecular weight polyethylene powder was used.
- the evaluation results of the obtained microporous membrane are shown in Table 1.
- Comparative Example 3 Polyethylene polymerization process
- An ultrahigh molecular weight polyethylene powder of Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that the polymerization temperature was changed to 90 ° C.
- Table 1 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Comparative Example 4 Polyethylene polymerization process Comparative Example 1 except that the polymerization temperature was changed to 75 ° C., the polymerization pressure was 0.8 MPa, 1-butene was introduced from the gas phase of 6.3 mol% with respect to ethylene, and the activity was 18000 PE g / catalyst g.
- the ultra high molecular weight polyethylene powder of Comparative Example 4 was obtained.
- Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- the temperature at which the slurry liquid was formed in the extruder was 200 ° C., and the melt residence time in the extruder was 10 minutes. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the temperature of the spinneret was 200 ° C.
- the discharge rate was 0.5 g / min
- the hole diameter of the spinneret was 1.0 mm.
- the discharged yarn containing liquid paraffin was put into a 5 ° C. water bath through a 4 cm air gap and wound up while rapidly cooling. The winding speed was 30 m / min.
- the liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum dried for 24 hours.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 120 ° C., and was primarily drawn to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn was at 140 ° C., and was further subjected to secondary drawing, and was drawn until just before the yarn was cut to obtain a drawn yarn.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- the temperature at which the slurry liquid was formed in the extruder was 220 ° C., and the melt residence time in the extruder was 10 minutes. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the temperature of the spinneret was 220 ° C.
- the discharge rate was 0.5 g / min
- the hole diameter of the spinneret was 0.6 mm.
- the discharged yarn containing liquid paraffin was put into a 5 ° C. water bath through a 3 cm air gap and wound up while rapidly cooling. The winding speed was 30 m / min. The liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum dried for 24 hours.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 120 ° C., and was primarily drawn to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn was at 140 ° C., and was further subjected to secondary drawing, and was drawn until just before the yarn was cut to obtain a drawn yarn.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- the polymerization reactor was added at a rate of 15 mmol / L from the middle between the liquid level and the bottom of the polymerization reactor.
- the supported metallocene catalyst component [B] is adjusted to 86 ° C. and added from the bottom of the polymerization vessel at a rate of 0.2 g / hour, and triisobutylaluminum is adjusted to 22 ° C. at a rate of 5 mmol / hour.
- the polymerization temperature was kept at 76 ° C. by jacket cooling.
- the humidity in the polymerization reactor was kept at 0 ppm. Hexane was adjusted to 20 ° C. and fed from the bottom of the polymerization vessel at 60 L / hour.
- Ethylene was supplied from the bottom of the polymerization reactor to keep the polymerization pressure at 0.6 MPa.
- the polymerization slurry was continuously drawn into a flash drum having a pressure of 0.05 MPa so that the level of the polymerization reactor was kept constant, and unreacted ethylene was separated.
- the polymerization slurry was continuously sent to a centrifuge so that the level of the flash drum was kept constant, and the polymer and other solvents were separated. At that time, the content of the solvent or the like contained in the ultrahigh molecular weight polyethylene powder was 10% by mass with respect to the weight of the ultrahigh molecular weight polyethylene powder.
- the separated ultra high molecular weight polyethylene powder was dried at 100 ° C. for 5 hours while blowing nitrogen.
- the catalyst and the cocatalyst were deactivated by spraying steam on the polymerized powder.
- the obtained ultrahigh molecular weight polyethylene powder was removed using a sieve having a mesh opening of 425 ⁇ m, and the powder that did not pass through the sieve was removed to obtain polyethylene powder of Comparative Example 6.
- Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- Comparative Example 7 Polyethylene polymerization process
- the ultrahigh molecular weight polyethylene powder of Comparative Example 7 was obtained in the same manner as Comparative Example 1 except that the polymerization temperature was 63 ° C., the polymerization pressure was changed to 0.6 MPa, and the activity was 6000 PE g / catalyst g.
- Table 2 shows the physical properties of the obtained ultrahigh molecular weight polyethylene powder.
- the temperature at which the slurry-like liquid was formed in the extruder was 260 ° C., and the melt residence time in the extruder was 10 minutes. Thereafter, the yarn was spun through a spinneret attached to the tip of the extruder.
- the temperature of the spinneret was 240 ° C.
- the discharge rate was 0.5 g / min
- the hole diameter of the spinneret was 0.6 mm.
- the discharged yarn containing liquid paraffin was put into a 5 ° C. water bath through a 3 cm air gap and wound up while rapidly cooling. The winding speed was 20 m / min. The liquid paraffin was then removed from the yarn.
- the yarn was immersed in a solvent such as hexane and extracted, and then vacuum dried for 24 hours.
- the obtained yarn was brought into contact with a metal heater so that the yarn temperature was 120 ° C., and was primarily drawn to wind the drawn yarn.
- the drawn yarn was brought into contact with a metal heater so that the drawn yarn was at 140 ° C., and was further subjected to secondary drawing, and was drawn until just before the yarn was cut to obtain a drawn yarn.
- the evaluation results of the obtained high strength fiber are shown in Table 2.
- the ultra high molecular weight polyethylene powder of the present invention it is excellent in appearance, ease of processing, and suppression of the amount of smoke during processing. Therefore, the molded object obtained using this polyethylene powder can be used for various uses. Although it does not limit as a molded object, for example, it is suitable as a microporous film for secondary battery separators, especially a microporous film for lithium ion secondary battery separators, a sintered compact, a high-strength fiber, etc.
- a manufacturing method of a microporous film the processing method which passes through extrusion, extending
- high molecular weight ethylene polymers such as wear resistance, high slidability, high strength, and high impact properties
- compacts, filters and dusts obtained by sintering ethylene polymers can also be used as a trap material.
- the method for producing high-strength fibers include a method of producing by heating and stretching after kneading and spinning liquid paraffin and ultrahigh molecular weight polyethylene powder. The various molded articles thus obtained have industrial applicability.
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Abstract
Description
そのような分野で使用されるためには、超高分子量ポリエチレンの加工性は重要であり、加工性向上の観点から、例えば、特許文献1のような方法が開示されている。具体的には、特許文献1には、高強度、耐摩耗性、潤滑性、衛生性、及び耐薬品性などの超高分子量ポリエチレンの本来の特性を活かしつつ、優れた成形加工性を有し、外観性及び機械的強度に優れる成形体を与える超高分子量ポリエチレン樹脂組成物及びその製造方法について開示されている。
また、超高分子量ポリエチレンは、汎用ポリエチレンと比較して遥かに分子量が高いので、高配向させることができれば高強度、高弾性を有する成形物が得られることが期待されている。しかしながら、超高分子量ポリエチレンを高配向とするには分子鎖の絡み合いを十分に解す必要があり、このため従来は溶媒を超高分子量ポリエチレンに十分に含浸させてから混練を行っている。近年、超高分子量ポリエチレンの生産効率の向上が求められており、加工時間の短縮のため、溶媒を超高分子量ポリエチレンに十分に含浸させていない状態で混練することが発生してしまう。そうすると、得られる超高分子量ポリエチレンは、分子鎖の絡み合いは解れていないために混練時のシェアによって分子鎖が切れ、高配向は達成されるものの、強度は低下してしまうという課題がある。
(1)
粘度平均分子量Mvが10×104以上1000×104以下である超高分子量ポリエチレンパウダーであって、下記混練条件で混練した混練物の粘度平均分子量Mv(A)と前記Mvとが下記の関係を満たし、
{Mv-Mv(A)}/Mvが0.20以下、
粒径212μm以上の超高分子量ポリエチレンパウダーを含有し、該粒径212μm以上のパウダーにおいて、平均細孔容積が0.6ml/g以上であり、かつ平均細孔径が0.3μm以上である、
超高分子量ポリエチレンパウダー。
[粘度平均分子量Mv(A)の混練物を得るための混練条件]
原料:
超高分子量ポリエチレンパウダー、及び流動パラフィンの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に、1質量部の酸化防止剤とを含む、混合物。
条件:
130℃で前記原料を30分混練した後、240℃で15分更に混練する
130℃~240℃への昇温速度は22℃/分とする
スクリュー回転数は50rpmとする
窒素雰囲気下とする
(2)
粒径53μm以下の超高分子量ポリエチレンパウダーが占める割合が超高分子量ポリエチレンパウダー100質量%としたとき、40質量%未満である、上記(1)に記載の超高分子量ポリエチレンパウダー。
(3)
前記粒径212μm以上のパウダーの嵩密度が0.20g/cm3以上0.60g/cm3以下である、上記(1)又は(2)に記載の超高分子量ポリエチレンパウダー。
(4)
マグネシウム含有量が0.1ppm以上20ppm以下である、上記(1)~(3)のいずれかに記載の超高分子量ポリエチレンパウダー。
(5)
チタン含有量が0.1ppm以上5ppm以下である、上記(1)~(4)のいずれかに記載の超高分子量ポリエチレンパウダー。
(6)
アルミニウム含有量が0.5ppm以上10ppm以下である、上記(1)~(5)のいずれかに記載の超高分子量ポリエチレンパウダー。
(7)
ケイ素含有量が0.1ppm以上100ppm以下である、上記(1)~(6)のいずれかに記載の超高分子量ポリエチレンパウダー。
(8)
塩素含有量が1ppm以上50ppm以下である、上記(1)~(7)のいずれかに記載の超高分子量ポリエチレンパウダー。
(9)
マグネシウムとチタンとの含有量比(Mg/Ti)が0.1以上10以下である、上記(1)~(8)のいずれかに記載の超高分子量ポリエチレンパウダー。
(10)
アルミニウムとチタンとの含有量比(Al/Ti)が0.1以上20以下である、上記(1)~(9)のいずれかに記載の超高分子量ポリエチレンパウダー。
(11)
上記(1)~(10)のいずれかに記載の超高分子量ポリエチレンパウダーを含有する高強度繊維。
(12)
上記(1)~(10)のいずれかに記載の超高分子量ポリエチレンパウダーを含有する二次電池セパレーター用微多孔膜。
本実施形態の超高分子量ポリエチレンパウダー(以下、単に「パウダー」ともいう。)は、粘度平均分子量が10×104以上1000×104以下である。
また、成形性と最終物性との観点から、粘度平均分子量は、好ましくは10×104以上950×104以下の範囲であり、より好ましくは20×104以上900×104以下の範囲である。なお、本実施形態における粘度平均分子量は、ポリマー溶液の比粘度から求めた極限粘度を粘度平均分子量に換算した値を指す。
本実施形態の超高分子量ポリエチレンパウダーは、エチレン単独重合体、及び/又は、エチレンと、エチレンと共重合可能なオレフィン(以下、コモノマーともいう)との共重合体からなるパウダーであることが好ましい。
上記α-オレフィンとしては、特に限定されないが、例えば、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセン、1-オクテン、1-ノネン、1-デセン、1-ウンデセン、1-ドデセン、1-トリデセン、1-テトラデセン等が挙げられる。
本実施形態に用いるエチレン重合体が、コモノマーを含む場合、エチレン重合体中のコモノマー単位の含有量は、好ましくは0.01モル%以上5モル%以下であり、より好ましくは0.01モル%以上2モル%以下であり、更に好ましくは0.01モル%以上1モル%以下である。なお、コモノマー量は分解率抑制の観点から、5モル%以下にすることが好ましい。
本実施形態の超高分子量ポリエチレンパウダーの粘度平均分子量(Mv)は、10×104以上1000×104以下であり、好ましくは10×104以上950×104以下であり、より好ましくは20×104以上900×104以下である。
本発明者は、本実施形態の超高分子量ポリエチレンパウダーを(株)東洋精機社製ラボプラストミルミキサー(本体型式:30C150、ミキサー形式:R-60)を用いて、下記混練条件で混練した際に、混練物の分解を抑制し本発明の効果に寄与することを見出した。
原料:
超高分子量ポリエチレンパウダー、及び流動パラフィンの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを含む、混合物。
条件:
130℃で前記原料を30分混練した後、240℃で15分更に混練する
130℃~240℃への昇温速度は22℃/分とする
スクリュー回転数は50rpmとする
窒素雰囲気下とする
上述した混練条件で混練した場合、混練前の超高分子量ポリエチレンパウダーの粘度平均分子量Mvと、混練後のゲルの粘度平均分子量Mv(A)とが下記関係を満たす。
{Mv-Mv(A)}/Mvが0.20以下、より好ましくは0.15以下、更に好ましくは0.10以下、最も好ましくは0.08以下である。{Mv-Mv(A)}/Mvの下限は特に限定されないが例えば0.04以上であることが好ましい。
{Mv-Mv(A)}/Mvが0.20以下であることによって、超高分子量ポリエチレンパウダーの分解物量が抑制され(分解によるオリゴマー発生を抑制)、例えば押出成形時の紡口出口近傍に蓄積するメヤニ(オリゴマー等の分解物の蓄積)量を削減することで、加工が容易となり、生産効率を向上させることができる。更に、通常は紡口出口近傍に蓄積したメヤニが熱分解し、油煙の発生頻度が高まるため、その都度、生産を一時停止して除去する必要があるが、本実施形態の超高分子量ポリエチレンパウダーの場合は、そもそもメヤニ発生量が少ないため、油煙の発生頻度も低く、安定生産を継続することができる。また、{Mv-Mv(A)}/Mvが0.04以上であることによって、加工後の成形体の物性バラつきを抑えるのに良好である。
また、本実施形態の超高分子量ポリエチレンパウダーは、粒径212μm以上の超高分子量ポリエチレンパウダーを含有し、該粒径212μm以上のパウダーにおいて、平均細孔容積が0.6ml/g以上、かつ平均細孔径が0.3μm以上である。平均細孔容積は好ましくは0.65ml/g以上、より好ましくは0.7ml/g以上であり、平均細孔径は好ましくは0.35μm以上、より好ましくは0.4μm以上である。該平均細孔容積の上限は特に限定されないが例えば3.0ml/g以下である。また、該平均細孔径の上限は特に限定されないが例えば1.0μm以下である。
なお、本実施形態の超高分子量ポリエチレンパウダーの平均粒径(D50)は、好ましくは40μm以上200μm以下であり、より好ましくは60μm以上140μm以下であり、更に好ましくは70μm以上120μm以下である。粒径の上限は特に限定されないが例えば710μm以下である。
なお、本実施形態において、{Mv-Mv(A)}/Mv、粒径212μm以上の超高分子量ポリエチレンパウダーの平均細孔容積及び平均細孔径は、具体的には実施例に記載の方法によって測定することができる。
また、本実施形態の超高分子量ポリエチレンパウダーは、粒径53μm以下のパウダーが占める割合が超高分子量ポリエチレンパウダー100質量%としたとき、好ましくは40質量%未満、より好ましくは35質量%以下、更に好ましくは30質量%以下、より更に好ましくは25質量%以下である。粒径53μm以下のパウダーが占める割合を前記範囲に調整することで、均一な混練ゲルを得ることができる。
上記粒径53μm以下のパウダーが占める割合の下限値は特に制限されず、通常0質量%以上である。
上記粒径53μm以下のパウダーが占める割合を40質量%未満とすることにより、超高分子量ポリエチレンパウダーと流動パラフィンとを混練する際、粒子径53μm以下の微粉が膨潤するよりも前に溶融し、パウダー同士が融着することによる不均一な混練物(混練ゲル)を得る可能性を一層抑制することができる傾向にある。その結果、例えば繊維にした際は糸径が均一な糸を、膜にした際は膜厚が均一な膜を得ることができる傾向にある。
粒子径53μm以下の超高分子量ポリエチレンパウダーの含有率は、具体的には実施例に記載の方法によって測定することができる。
しかし、本実施形態の超高分子量ポリエチレンパウダーを用いることで、これらの問題を解決することができる。
また、本実施形態の超高分子量ポリエチレンパウダーは、粒径212μm以上のパウダーの嵩密度が0.20g/cm3以上0.60g/cm3以下が好ましく、より好ましくは0.25g/cm3以上0.55g/cm3以下であり、更に好ましくは0.30g/cm3以上0.55g/cm3以下である。
粒径212μm以上のパウダーの嵩密度を0.20g/cm3以上にすることで、超高分子量ポリエチレンパウダーが凝集した際に、パウダー同士が接していない隙間をある程度確保することができ、その結果、超高分子量ポリエチレンパウダー中への流動パラフィンの浸透を促進させ、溶け残りによる未溶融物の発生を低減することができる傾向にある。
また、粒径212μm以上のパウダーの嵩密度を0.60g/cm3以下にすることで、超高分子量ポリエチレンパウダーを押出機ホッパー内から押出機内部へ送り出す際に、ホッパー内で詰まることなくスムーズに送り出すことができる傾向にある。
本実施形態に係る超高分子量ポリエチレンパウダーにおいて、パウダー中のマグネシウム(Mg)含有量が0.1ppm以上20ppm以下であることが好ましく、チタン(Ti)含有量が0.1ppm以上5ppm以下であることが好ましく、より好ましくは0.1ppm以上4.0ppm以下であり、更に好ましくは0.1ppm以上3.0ppm以下であり、アルミニウム(Al)含有量が0.5ppm以上10ppm以下であることが好ましく、より好ましくは0.5ppm以上7.0ppm以下であり、更に好ましくは0.5ppm以上6.0ppm以下であり、ケイ素(Si)含有量が0.1ppm以上100ppm以下であることが好ましく、塩素(Cl)含有量が1ppm以上50ppm以下であることが好ましい。超高分子量ポリエチレンパウダー中の金属量をこのように調整することで、熱安定性により優れる超高分子量ポリエチレンパウダーとなり、成形体の長期安定性がより優れるものとなる。また、加工時に加える酸化防止剤や熱安定剤との反応を抑制でき、有機金属錯体が生成されることによる成形体の着色を抑制できる傾向にある。更に、超高分子量ポリエチレンパウダー中の金属量を調整することで、繊維にした際は糸径が均一な糸を、膜にした際は膜厚が均一な膜を得ることができる。なお、一般的には、超高分子量ポリエチレンパウダー中に残存する触媒残渣由来の金属量が多いことで、成形体の厚みムラの原因になる傾向が強い。なお、超高分子量ポリエチレンパウダー中のMg、Ti、Al、Si、Clの含有量は、単位触媒あたりのエチレン系重合体の生産性により制御することが可能である。エチレン系重合体の生産性は、製造する際の反応器の重合温度や重合圧力やスラリー濃度により制御することが可能である。つまり、本実施形態に係る超高分子量ポリエチレンパウダーの生産性を高くするには、エチレン系重合体を重合する際の重合温度を高くする、重合圧力を高くする、及び/又はスラリー濃度を高くすることが挙げられる。他の方法としては、エチレン系重合体を重合する際の、助触媒成分の種類の選択や、助触媒成分の濃度を低くすることや、エチレン系重合体を酸やアルカリで洗浄することでもアルミニウム量を制御することが可能である。なお、本実施形態において、Mg、Ti、Al、Si、Cl量の測定は実施例に記載の方法により行うことができる。
また、本実施形態に係る超高分子量ポリエチレンパウダーにおいて、パウダー中のMg/Tiの含有量比は0.1以上10以下が好ましく、より好ましくは0.2以上9.5以下、更に好ましくは0.3以上9以下である。また、パウダー中のAl/Tiの含有量比は0.1以上20以下が好ましく、より好ましくは0.1以上18以下、更に好ましくは0.15以上15以下である。
Mg/Tiの含有量比を0.1以上、又はAl/Tiの含有量比を0.1以上にすることで、加工時に加える酸化防止剤や熱安定剤との反応を抑制でき、有機金属錯体が生成されることによる成形体の着色を抑制できる傾向にある。
更に、Mg/Tiの含有量比を10以下、又はAl/Tiの含有量比を20以下にすることで、メヤニ発生量を少なくすることができ、油煙の発生頻度を抑制できる。その結果、熱分解による成形物の強度低下を抑えることができる。
(触媒成分)
本実施形態に係る超高分子量ポリエチレンパウダーの製造に使用される触媒成分としては特に限定されないが、例えば、一般的なチーグラー・ナッタ触媒及びメタロセン触媒が挙げられる。
チーグラー・ナッタ触媒としては、固体触媒成分[A]及び有機金属化合物成分[B]からなる触媒であって、固体触媒成分[A]が、下記式1で表される不活性炭化水素溶媒に可溶である有機マグネシウム化合物(A-1)と、下記式2で表されるチタン化合物(A-2)とを反応させることにより製造されるオレフィン重合用触媒であるものが好ましい。
(A-1):(M1)α(Mg)β(R2)a(R3)b(Y1)c ・・・式1
(式中、M1は周期律表第12族、第13族及び第14族からなる群に属する金属原子であり、R2及びR3は炭素数2以上20以下の炭化水素基であり、Y1はアルコキシ、シロキシ、アリロキシ、アミノ、アミド、-N=C-R4、R5、-SR6(ここで、R4、R5及びR6は炭素数1以上20以下の炭化水素基を表す。cが2の場合には、Y1はそれぞれ異なっていてもよい。)、β-ケト酸残基のいずれかであり、α、β、a、b及びcは次の関係を満たす実数である。0≦α、0<β、0≦a、0≦b、0≦c、0<a+b、0≦c/(α+β)≦2、nα+2β=a+b+c(ここで、nはM1の原子価を表す。))
(式中、dは0以上4以下の実数であり、R7は炭素数1以上20以下の炭化水素基であり、X1はハロゲン原子である。)
群(2):R2とR3とが炭素原子数の互いに相異なるアルキル基であること、好ましくはR2が炭素原子数2又は3のアルキル基であり、R3が炭素原子数4以上のアルキル基であること。
群(3):R2、R3の少なくとも一方が炭素原子数6以上の炭化水素基であること、好ましくはR2、R3に含まれる炭素原子数を加算すると12以上になるアルキル基であること。
(A-2):Ti(OR7)dX1 (4-d) ・・・式2
(式中、dは0以上4以下の実数であり、R7は炭素数1以上20以下の炭化水素基であり、X1はハロゲン原子である。)
(式中、M2は周期律表第12族、第13族及び第14族からなる群に属する金属原子であり、R8、R9及びR10はそれぞれ炭素数2以上20以下の炭化水素基であり、γ、δ、e、f及びgは次の関係を満たす実数である。0≦γ、0<δ、0≦e、0≦f、0≦g、0<e+f、0≦g/(γ+δ)≦2、kγ+2δ=e+f+g(ここで、kはM2の原子価を表す。))
(式中、R11は炭素数1以上12以下の炭化水素基であり、hとiは次の関係を満たす実数である。0<h、0<i、0<h+i≦4)
(式中、M1は周期律表第12族、第13族及び第14族からなる群に属する金属原子であり、R2及びR3は炭素数2以上20以下の炭化水素基であり、Y1はアルコキシ、シロキシ、アリロキシ、アミノ、アミド、-N=C-R4,R5、-SR6(ここで、R4、R5及びR6は炭素数1以上20以下の炭化水素基を表す。cが2の場合には、Y1はそれぞれ異なっていてもよい。)、β-ケト酸残基のいずれかであり、α、β、a、b及びcは次の関係を満たす実数である。0≦α、0<β、0≦a、0≦b、0≦c、0<a+b、0≦c/(α+β)≦2、nα+2β=a+b+c(ここで、nはM1の原子価を表す。))
(式中、dは0以上4以下の実数であり、R7は炭素数1以上20以下の炭化水素基であり、X1はハロゲン原子である。)
群(2):R8とR9とが炭素数の互いに相異なるアルキル基であること、好ましくはR8が炭素数2又は3のアルキル基であり、R9が炭素数4以上のアルキル基であること。
群(3):R8、R9の少なくとも一方が炭素数6以上の炭化水素基であること、好ましくはR8、R9に含まれる炭素数の和が12以上になるアルキル基であること。
(式中、R11は炭素数1以上12以下の炭化水素基であり、hとiは次の関係を満たす実数である。0<h、0<i、0<h+i≦4)
(式中、M1は周期律表第12族、第13族及び第14族からなる群に属する金属原子であり、R2及びR3は炭素数2以上20以下の炭化水素基であり、Y1はアルコキシ、シロキシ、アリロキシ、アミノ、アミド、-N=C-R4,R5、-SR6(ここで、R4、R5及びR6は炭素数1以上20以下の炭化水素基を表す。cが2の場合には、Y1はそれぞれ異なっていてもよい。)、β-ケト酸残基のいずれかであり、α、β、a、b及びcは次の関係を満たす実数である。0≦α、0<β、0≦a、0≦b、0<a+b、0≦c/(α+β)≦2、nα+2β=a+b+c(ここで、nはM1の原子価を表す。))
(式中、dは0以上4以下の実数であり、R7は炭素数1以上20以下の炭化水素基であり、X1はハロゲン原子である。)
本実施形態においては、(C-3)に対する(C-5)の担持方法については特に限定されず、(C-3)に対して過剰な(C-5)を反応させる方法や、第三成分を使用することにより(C-5)を効率的に担持する方法を用いてもよいが、(C-5)と有機マグネシウム化合物(C-4)との反応により担持する方法が好ましい。
(式中、R12は炭素数1以上20以下の炭化水素基、Z1は水素、ハロゲン、アルコキシ、アリロキシ、シロキシ基からなる群に属する基であり、jは2以上3以下の数である。)
(式中、M2は周期律表第12族、第13族及び第14族からなる群に属する金属原子であり、R8、R9及びR10はそれぞれ炭素数2以上20以下の炭化水素基であり、γ、δ、e、f及びgは次の関係を満たす実数である。0≦γ、0<δ、0≦e、0≦f、0≦g、0<e+f、0≦g/(γ+δ)≦2、kγ+2δ=e+f+g(ここで、kはM2の原子価を表す。))
なお、固体触媒成分及び有機金属化合物成分[B]の組み合わせ比率は特に限定されないが、固体触媒成分1gに対し有機金属化合物成分[B]は1mmol以上3,000mmol以下であることが好ましい。
メタロセン触媒を用いた例としては、一般的な遷移金属化合物が用いられる。メタロセン触媒の製造方法としては、特に限定されないが、例えば、日本国特許4868853号に記載の製造方法が挙げられる。このようなメタロセン触媒は、a)環状η結合性アニオン配位子を有する遷移金属化合物及びb)該遷移金属化合物と反応して触媒活性を発現する錯体を形成可能な活性化剤の2つの触媒成分から構成される。
L1 jWkM3X2 pX3 q ・・・式8
本実施形態に用いる活性化剤として例えば、以下の式10で定義される化合物が挙げられる。
[L2-H]d+[M5 mQp]d- ・・・式10
(式中、[L2-H]d+はプロトン供与性のブレンステッド酸を表し、但し、L2は中性のルイス塩基を表し、dは1~7の整数であり;[M5 mQp]d-は両立性の非配位性アニオンを表し、ここで、M5は、周期表第5族~第15族のいずれかに属する金属又はメタロイドを表し、Qは、各々独立して、ヒドリド、ハライド、炭素数2~20のジヒドロカルビルアミド基、炭素数1~30のヒドロカルビルオキシ基、炭素数1~30の炭化水素基、及び炭素数1~40の置換された炭化水素基からなる群より選ばれ、ここで、ハライドであるQの数は1以下であり、mは1~7の整数であり、pは2~14の整数であり、dは上で定義した通りであり、p-m=dである。)
本実施形態においては、活性化剤成分を単独で使用してもよいし組み合わせて使用してもよい。
本実施形態の超高分子量ポリエチレンパウダーの製造方法における重合温度は、通常、30℃以上100℃以下である。重合温度が30℃以上であることにより、工業的により効率的な製造ができる傾向にある。一方、重合温度が100℃以下であることにより、連続的により安定した運転ができる傾向にある。
また、重合工程において反応器内に2箇所以上6箇所以下均等間隔でバッフル板を設けることが好ましい。バッフル板は、反応器底部から反応器頂部(開口部)まで設けることが好ましく、バッフル板の突起部頂部から反応器側面部までの長さを反応器内径の10%以上30%以下、突起部幅は反応器円周長の10%以上30%以下に調整することが好ましい。
更に、超高分子量ポリエチレンパウダー乾燥工程において、前段(全乾燥時間の前半1/2)と後段(全乾燥時間の後半1/2)で乾燥温度を変える(前段:60℃以上70℃未満、後段70℃以上90℃以下)ことが好ましい。高温で急激乾燥するよりも前記のような乾燥工程とすることで超高分子量ポリエチレンパウダーが割れて微粉量が増えるのを抑制することができる。
以上のように、各重合条件を調整することで、本実施形態の超高分子量ポリエチレンパウダーを得ることができる。
本実施形態の超高分子量ポリエチレンパウダーには、必要に応じて、スリップ剤、中和剤、酸化防止剤、耐光安定剤、帯電防止剤、顔料等の添加剤を添加することができる。
本実施形態の超高分子量ポリエチレンパウダーは、種々の方法により加工することができる。また、該ポリエチレンパウダーを用いて得られる成形体は種々の用途に用いることができる。成形体としては、限定されるものではないが、例えば、二次電池セパレーター用微多孔膜、中でも、リチイムイオン二次電池セパレーター用微多孔膜、焼結体、高強度繊維等として好適である。微多孔膜の製造方法としては、溶剤を用いた湿式法において、Tダイを備え付けた押出し機にて、押出し、延伸、抽出、乾燥を経る加工方法が挙げられる。
また高分子量のエチレン重合体の特性である耐摩耗性、高摺動性、高強度、高衝撃性などの優れた特徴を活かし、エチレン重合体を焼結して得られる成形体にも使用できる。
高強度繊維の製造方法としては、例えば、流動パラフィンと超高分子量ポリエチレンパウダーとを混練紡糸後、加熱延伸することで得る方法が挙げられる。
実施例及び比較例の超高分子量ポリエチレンパウダーの物性を下記の方法で測定した。
[混練条件1]
本願の実施例及び比較例における分解率の算出は、以下に示す方法によって混練ゲルを得て求めた。流動パラフィンと超高分子量ポリエチレンパウダーとの合計100質量部に対して、流動パラフィンを95質量部と超高分子量ポリエチレンパウダーとを5質量部、更に酸化防止剤を1質量部の組成で混練した。具体的には、超高分子量ポリエチレンパウダー2.0g、(株)松村石油研究所製流動性パラフィン(製品名:スモイルP-350P)38.0g、グレートレイクスケミカル日本(株)製テトラキス[メチレン(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマート)]メタン(製品名:ANOX20)0.4gを200mlポリカップに加えてよく混合してから(株)東洋精機社製ラボプラストミルミキサー(本体型式:30C150、ミキサー形式:R-60)に仕込み、130℃で30分間混練した後、引き続き22℃/分で240℃まで昇温しながら混練し、更に240℃で15分間混練した。なお、当該混練は、窒素雰囲気下で行い、回転数は全て50rpmで行った。その後、得られた混練ゲル中から流動パラフィンをヘキサンを用いて抽出し、24時間以上真空乾燥させることで、混練物を得た。
まず、溶解管に超高分子量ポリエチレンパウダー20mgを秤量し、溶解管を窒素置換した後、20mLのデカヒドロナフタレン(2,6-ジ-t-ブチル-4-メチルフェノールを1g/L加えたもの)を加え、150℃で2時間攪拌して超高分子量ポリエチレンパウダーを溶解させた。その溶液を135℃の恒温槽で、キャノン-フェンスケの粘度計(柴田科学器械工業社製:製品番号-100)を用いて、標線間の落下時間(ts)を測定した。同様に、超高分子量ポリエチレンパウダー量を10mg、5mg、2mgに変えたサンプルについても同様に標線間の落下時間(ts)を測定した。ブランクとして超高分子量ポリエチレンパウダーを入れていない、デカヒドロナフタレンのみの落下時間(tb)を測定した。以下の式に従って超高分子量ポリエチレンパウダーの還元粘度(ηsp/C)を求めた。
ηsp/C=(ts/tb-1)/0.1 (単位:dL/g)
濃度(C)(単位:g/dL)と超高分子量ポリエチレンパウダーの還元粘度(ηsp/C)との関係をそれぞれプロットして、最小二乗法により近似直線式を導き、濃度0に外挿して極限粘度([η])を求めた。次に下記数式Aを用いて、上記極限粘度[η]の値から粘度平均分子量(Mv)を算出した。
Mv=(5.34×104)×[η]1.49 (数式A)
混練条件1によって得られた混練物の粘度平均分子量Mv(A)に関しても、超高分子量ポリエチレンパウダーの粘度平均分子量Mvと同様にして算出した。
算出した粘度平均分子量Mv及びMv(A)から下記式より分解率を求めた。
分解率={Mv-Mv(A)}/Mv
超高分子量ポリエチレンパウダーを、JIS Z8801規格に準拠した目開き:710μm、500μm、425μm、355μm、300μm、212μm、150μm、106μm、75μm、53μmのスクリーンメッシュで分級した。
分級した超高分子量ポリエチレンパウダーの各分画のうち、粒径212μm以上のパウダーを分取した。必要に応じて、該パウダーを1.0mmのふるいに通した。
水銀ポロシメーターとして島津製作所社製オートポアIV9500型を用いて該パウダーの平均細孔容積及び細孔分布を測定した。得られた細孔分布を基に平均細孔径を算出した。
前処理として該パウダー0.5gを試料セルに入れ低圧測定部で常温脱気乾燥後、水銀を試料容器内に充填した。徐々に加圧して(高圧部)水銀を試料の細孔へ圧入した。
圧力条件は以下のように設定した。
・低圧部:69Pa(0.01psia)N2圧で測定
・高圧部:21~228MPa(3000~33000pisa)
超高分子量ポリエチレンパウダーの平均粒径は、JIS Z8801で規定された10種類の篩(目開き:710μm、500μm、425μm、355μm、300μm、212μm、150μm、106μm、75μm、53μm)を用いて、100gの粒子を分級した際に得られる各篩に残った粒子の重量を目開きの大きい側から積分した積分曲線において、50%の重量になる粒子径を平均粒子径とした。
超高分子量ポリエチレンパウダーの粒子径53μm以下の粒子の含有量は、JIS Z8801で規定された10種類の篩(目開き:710μm、500μm、425μm、355μm、300μm、212μm、150μm、106μm、75μm、53μm)を用いて、100gの粒子を分級した後、全粒子(超高分子量ポリエチレンパウダー)の重量に対する、目開き53μmの篩を通過した粒子の重量、として求めた。
粒子径53μm以下の粒子の含有率(%)は、上記にて求められた、目開き53μmの目開を有する篩を通過した粒子の重量から以下の式より算出した。
粒子径53μm以下の粒子の含有率(%)=[53μmの目開を有する篩を通過した粒子の重量(g)]/[全粒子(超高分子量ポリエチレンパウダー)の重量 100(g)]×100
なお、当該測定では、後述の実施例及び比較例に記載の「目開き:425μmの篩」にかける前の超高分子量ポリエチレンパウダーを用いた。
i)超高分子量ポリエチレンパウダーを、JIS Z8801規格に準拠した目開き:710μm、500μm、425μm、355μm、300μm、212μm、150μm、106μm、75μm、53μmのスクリーンメッシュで分級した。
ii)分級した超高分子量ポリエチレンパウダーの各分画のうち、粒径212μm以上のパウダーを分取した。
iii)必要に応じて、該パウダーを1.0mmのふるいに通した。
iv)JIS K 6891に則った標準寸法の校正された漏斗のオリフィスを介して、該パウダーを、100ccの円筒形容器に溢れるまで流下させた。
v)圧密やカップからの該パウダーの溢流を防ぐため、ヘラ等の刃を、容器の上面に垂直に立てて接触させた状態で滑らかに動かし、容器の上面から過剰の該パウダーを注意深くすり落とした。
vi)容器の側面からも該パウダーをすべて除去し、容器ごと該パウダーの質量を計測し、あらかじめ測定しておいた空の測定用容器の質量を差し引くことによって、該パウダーの質量(m)を0.1gまで算出した。
vii)下記式によって嵩密度(g/cc)を計算した。
嵩密度(g/cc)=該パウダーの質量(m)/円筒形容器の容積(cc)
viii)上記測定を3回行い、その平均値を記録した。
なお、当該測定では、後述の実施例及び比較例に記載の「目開き:425μmの篩」にかける前の超高分子量ポリエチレンパウダーを用いた。
超高分子量ポリエチレンパウダーをマイクロウェーブ分解装置(型式ETHOS TC、マイルストーンゼネラル社製)を用い加圧分解し、内部標準法にて、ICP-MS(誘導結合プラズマ質量分析装置、型式Xシリーズ X7、サーモフィッシャーサイエンティフィック社製)にて、超高分子量ポリエチレンパウダー中の金属としてMg、Ti、Al、Si、Clの元素濃度を測定した。なお、膜や糸等の成形体を切り出し、上記測定によって、成形体中のMg、Ti、Al、Si、Cl含有量を測定することもできる。
(6)超高分子量ポリエチレンパウダーを用いた高強度繊維の製造方法
本実施形態の超高分子量ポリエチレンパウダーを用いた高強度繊維の製造方法について以下に記載する。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィン((株)松村石油研究所製流動パラフィン(製品名:スモイルP-350P))、更に1質量部の酸化防止剤(グレートレイクスケミカル日本(株)製テトラキス[メチレン(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマート)]メタン(製品名:ANOX20))を配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃以上で1時間以上撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度を0.1%以下に設定した。
スラリー状液体が導入される押出機は、(株)東洋精機社製ラボプラストミル(本体型式:30C150)用二軸押出機(本体型式:2D25S)を使用し、混練紡糸作業を行った。
また、スラリー状液体が押出機中で形成される温度は、140℃以上320℃以下であり、押出機内での溶融滞留時間としては5分以上30分以下であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は140℃以上250℃以下、吐出量は0.5g/分以上2.0g/分以下であり、紡糸口金の孔径は0.3mm以上1.5mm以下で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間以上真空乾燥させた。
得られた糸を糸温度が100℃以上140℃以下になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃以上160℃以下になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた延伸糸(高強度繊維)の糸径の均一性評価を以下のとおり実施した。
上記(6)に記載の方法で紡糸し破断限界まで延伸した糸を10本用意し、n=10で平均糸径を算出した。平均糸径は10μm以上20μm以下であった。
(評価基準)
◎は、非常に良かったことを表し、平均糸径に対して±5μm未満のバラつきであった。
○は、問題なかったことを表し、平均糸径に対して±5μm以上10μm未満のバラつきであった。
×は、悪かったことを表し、平均糸径に対して±10μm以上のバラつきであった。
上記(6)に記載の方法で紡糸した糸を10本用意し、n=10で糸の破断強度及び配向度を算出した。糸の破断強度及び配向度の算出方法は下記の通りとした。
[糸破断強度の測定]
実施例及び比較例における超高分子量ポリエチレン繊維の強度は、破断強度であって、破断限界まで延伸した糸を室温で破断するまで引張り、その際に糸にかかった最高荷重値を繊度で割ることで算出した。なお、繊度は糸1×104m当たりの重量であり、単位はdtexで表す。
[糸配向度の測定]
実施例及び比較例における超高分子量ポリエチレン繊維の配向度は、オリンパス(株)製の光学系システム顕微鏡(本体型式:BX51TRF-6(D))にオリンパス(株)製のベレックコンペンセータ(本体型式:U-CBE)を装着し、リタデーション値(Re)を計算し、下記式を用いて算出した。なお、測定に用いた繊維は単糸5本で、単糸1本につき配向度(以下、リタデーションともいう)を場所違いで3点測定し平均値を算出することでリタデーション値を求めた。
Re = Δn0 × P × d
Re:リタデーション
Δn0:分子の固有複屈折(PE:0.066)
P:配向度
d:サンプルの厚み(繊維の場合は糸径)
(糸破断強度の評価基準)
◎(良い) …破断強度30cN/dtex以上
○(普通) …破断強度20cN/dtex以上、30cN/dtex未満
×(悪い) …破断強度20cN/dtex未満
(糸配向度の評価基準)
◎(良い) …配向度0.70以上
○(普通) …配向度0.40以上、0.70未満
×(悪い) …配向度0.40未満
上記(6)に記載した方法で1時間紡糸作業を行った際に、紡口近傍に付着するメヤニ量を目視で判断した。
(評価基準)
◎(良い) …メヤニなし
○(普通) …メヤニあり(少ない)
×(悪い) …メヤニあり(多い)
上記(6)に記載した方法で1時間紡糸作業を行った際の油煙量を目視で判断した。
(評価基準)
◎(良い) …油煙なし
○(普通) …油煙あり(少ない)
×(悪い) …油煙あり(多い)
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたときに、30~40質量部の超高分子量ポリエチレンパウダーと60~70質量部の流動パラフィン((株)松村石油研究所製流動パラフィン(製品名:スモイルP-350P))と、更に1質量部の酸化防止剤(グレートレイクスケミカル日本(株)製テトラキス[メチレン(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマート)]メタン(製品名:ANOX20))とを配合してスラリー状液体を調製した。
得られたスラリー状液体は窒素で置換を行った後に、(株)東洋精機社製ラボプラストミル(本体型式:30C150)用二軸押出機(本体型式:2D25S)へ窒素雰囲気下でフィーダーを介して投入し、200℃条件で混練した後、押出機先端に設置したTダイから押出した後、ただちに25℃に冷却したキャストロールで冷却固化させゲル状シートを成形した。
このゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した後、この延伸フィルムをメチルエチルケトン又はヘキサンに浸漬し、流動パラフィンを抽出除去後、24時間以上真空乾燥した。更に125℃、3分で熱固定し、微多孔膜を得た。
上記(7)に記載の方法で製膜し、膜厚は、東洋精機製の微小測厚器(タイプKBM(登録商標))を用いて室温23℃で測定した。膜1mごとにまんべんなく均等になるように任意の10ヶ所を選び測定し、膜5m合計50カ所を測定し平均膜厚を算出した。平均膜厚は5μm以上20μm以下であった。
(評価基準)
◎は、非常に良かったことを表し、平均膜厚に対して±3μm未満のバラつきであった。
○は、問題なかったことを表し、平均膜厚に対して±3μm以上5μm未満のバラつきであった。
×は、悪かったことを表し、平均膜厚に対して±5μm以上のバラつきであった。
上記(7)に記載の方法で得たゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した。この時、ゲル状シートは80mm×80mmの正方形であり、四隅に注射針を用いて小さな孔を開け、孔と孔の距離を延伸前後で比較して延伸後の膜の収縮率を算出した。n=10で評価し、平均値を膜収縮率として算出した。
(評価基準)
◎(良い) …膜収縮率15%未満
○(普通) …膜収縮率15%以上25%未満
×(悪い) …膜収縮率25%以上
上記(7)に記載の方法で得たゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した。延伸膜をカトーテック製品の「KES-G5ハンディー圧縮試験器」(商標)を用いて、針先端の曲率半径0.5mm、突刺速度2mm/secの条件で突刺試験を行い、最大突刺荷重(N)を測定した。測定した最大突刺荷重(N)に基づき膜突刺強度を評価した。最大突刺荷重(N)が3.5N以上であれば、強度が十分に優れていることを示す。評価基準は、以下のとおりである。
(評価基準)
◎(良い):最大突刺荷重3.5N以上
○(普通):最大突刺荷重3.0N以上3.5N未満
×(悪い):最大突刺荷重3.0N未満
上記(7)に記載した方法で1時間製膜作業を行った際に、押出機先端に付着するメヤニ量を目視で判断した。
(評価基準)
◎(良い) …メヤニなし
○(普通) …メヤニあり(少ない)
×(悪い) …メヤニあり(多い)
上記(7)に記載した方法で1時間製膜作業を行った際の油煙量を目視で判断した。
(評価基準)
◎(良い) …油煙なし
○(普通) …油煙あり(少ない)
×(悪い) …油煙あり(多い)
[参考例1:触媒合成例1:固体触媒成分[A]の調製]
窒素置換された8Lステンレス製オートクレーブにヘキサン1,600mLを添加した。15℃で攪拌しながら1mol/Lの四塩化チタンヘキサン溶液800mLと1mol/Lの組成式AlMg5(C4H9)11(OSiH)2で表される有機マグネシウム化合物のヘキサン溶液800mLとを6時間かけて同時に添加した。添加後、ゆっくりと昇温し、15℃で1.5時間反応を継続させた。反応終了後、上澄み液を1,600mL除去し、ヘキサン1,600mLで10回洗浄することにより、固体触媒成分[A]を調製した。この固体触媒成分1g中に含まれるチタン量は3.31mmolであった。
平均粒子径が15μm、表面積が700m2/g、粒子内細孔容積が1.6mL/gの球状シリカを、窒素雰囲気下、500℃で7時間焼成し、脱水した。脱水シリカの表面水酸基の量は、SiO21gあたり1.82mmol/gであった。窒素雰囲気下、容量1.8Lのオートクレーブ内で、この脱水シリカ40gをヘキサン800mL中に分散させ、スラリーを得た。得られたスラリーを攪拌下60℃に保ちながらトリエチルアルミニウムのヘキサン溶液(濃度1mol/L)を80mL加え、その後3時間攪拌し、トリエチルアルミニウムとシリカの表面水酸基とを反応させ、トリエチルアルミニウム処理されたシリカと上澄み液とを含み、該トリエチルアルミニウム処理されたシリカの表面水酸基がトリエチルアルミニウムによりキャッピングされている成分[a]を得た。その後、得られた反応混合物中の上澄み液をデカンテーションによって除去することにより、上澄み液中の未反応のトリエチルアルミニウムを除去した。その後、ヘキサンを適量加え、トリエチルアルミニウム処理されたシリカのヘキサンスラリー850mLを得た。
(ポリエチレンの重合工程)
ヘキサン、エチレン、水素、固体触媒成分[A]を連続的に攪拌装置が付いたベッセル型重合反応器に供給し、ポリエチレン(エチレン単独重合体)を10kg/時間の速度で製造した。水素としては、モレキュラーシーブスとの接触により精製された99.99モル%以上の水素を使用した。固体触媒成分[A]は、上記溶媒ヘキサンを移送液とし、水素10NL/時間(NLはNormal Liter(標準状態に換算した容積))と共に、製造速度が10kg/時間となるように0.15mmol/Lの速度で重合反応器の液面と底部の中間から添加した。また、固体触媒成分[A]は、98℃に調整して0.2g/時間の速度で重合器の底部から添加し、トリイソブチルアルミニウムは22℃に調整して5mmol/時間の速度で重合器の底部から添加した。重合温度はジャケット冷却することで88℃に保った。重合反応器内の湿度は0ppmに保った。ヘキサンは20℃に調整して60L/時間で重合器に供給した。エチレンは重合反応器の底部より供給して重合圧力を1.0MPaに保った。重合スラリーは、重合反応器のレベルが一定に保たれるように連続的に圧力0.05MPaのフラッシュドラムに抜き、未反応のエチレンを分離した。重合スラリーは、フラッシュドラムのレベルが一定に保たれるように連続的に遠心分離機に送り、ポリマーとそれ以外の溶媒等を分離した。その際、超高分子量ポリエチレンパウダーに含まれる溶媒等の含有量は、超高分子量ポリエチレンパウダーの重量に対して10質量%であった。分離された超高分子量ポリエチレンパウダーは、窒素ブローしながら、65℃で3時間乾燥後、75℃で更に2時間乾燥した。なお、この乾燥工程で、重合後のパウダーに対し、スチームを噴霧して、触媒及び助触媒の失活を実施した。得られた超高分子量ポリエチレンパウダーを目開き425μmの篩を用いて、篩を通過しなかったものを除去して実施例1の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
なお、反応器内において、反応器底部から反応器頂部(開口部)まで4箇所均等間隔でバッフル板を設置した。また、バッフル板は、反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の15%であり、突起部幅は、反応器円周長の15%であった。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたときに、40質量部の超高分子量ポリエチレンパウダーと60質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合してスラリー状液体を調製した。得られたスラリー状液体は窒素で置換を行った後に、二軸押出機へ窒素雰囲気下でフィーダーを介して投入し、200℃条件で混練した後、押出機先端に設置したTダイから押出した後、ただちに25℃に冷却したキャストロールで冷却固化させゲル状シートを成形した。このゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した後、この延伸フィルムをメチルエチルケトン又はヘキサンに浸漬し、流動パラフィンを抽出除去後、24時間真空乾燥した。更に125℃、3分で熱固定し、実施例1の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を85℃、固体触媒成分[A]を95℃で反応器へ投入、1-ブテンをエチレンに対して6.3mol%気相から導入したこと以外は、実施例1と同様に行って実施例2の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例1と同様に行って実施例2の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を83℃、固体触媒成分[A]を93℃で反応器へ投入したこと以外は、実施例1と同様に行って実施例3の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
超高分子量ポリエチレンパウダーと流動パラフィンの合計を100質量部としたときに、30質量部の超高分子量ポリエチレンパウダーと70質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合してスラリー状液体を調製した。得られたスラリー状液体は窒素で置換を行った後に、二軸押出機へ窒素雰囲気下でフィーダーを介して投入し、200℃条件で混練した後、押出機先端に設置したTダイから押出した後、ただちに25℃に冷却したキャストロールで冷却固化させゲル状シートを成形した。このゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した後、この延伸フィルムをメチルエチルケトン又はヘキサンに浸漬し、流動パラフィンを抽出除去後、24時間真空乾燥した。更に125℃、3分で熱固定し、実施例3の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
ヘキサン、エチレン、水素、担持型メタロセン触媒成分[B]を連続的に攪拌装置が付いたベッセル型重合反応器に供給し、ポリエチレン(エチレン単独重合体)を10kg/時間の速度で製造した。水素としては、モレキュラーシーブスとの接触により精製された99.99モル%以上の水素を使用した。担持型メタロセン触媒成分[B]は、上記溶媒ヘキサンを移送液とし、水素10NL/時間(NLはNormal Liter(標準状態に換算した容積))と共に、製造速度が10kg/時間となるように0.15mmol/Lの速度で重合反応器の液面と底部の中間から添加した。また、担持型メタロセン触媒成分[B]は、95℃に調整して0.2g/時間の速度で重合器の底部から添加し、トリイソブチルアルミニウムは22℃に調整して5mmol/時間の速度で重合器の中間から添加した。重合温度はジャケット冷却することで85℃に保った。重合反応器内の湿度は0ppmに保った。ヘキサンは20℃に調整して60L/時間で重合器の底部から供給した。エチレンは重合反応器の底部より供給して重合圧力を0.8MPaに保った。重合スラリーは、重合反応器のレベルが一定に保たれるように連続的に圧力0.05MPaのフラッシュドラムに抜き、未反応のエチレンを分離した。重合スラリーは、フラッシュドラムのレベルが一定に保たれるように連続的に遠心分離機に送り、ポリマーとそれ以外の溶媒等を分離した。その際、超高分子量ポリエチレンパウダーに含まれる溶媒等の含有量は、超高分子量ポリエチレンパウダーの重量に対して10質量%であった。分離された超高分子量ポリエチレンパウダーは、窒素ブローしながら、65℃で3時間乾燥後、75℃で更に2時間乾燥した。なお、この乾燥工程で、重合後のパウダーに対し、スチームを噴霧して、触媒及び助触媒の失活を実施した。得られた超高分子量ポリエチレンパウダーを目開き425μmの篩を用いて、篩を通過しなかったものを除去して実施例4の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。なお、反応器内において、反応器底部から反応器頂部(開口部)まで4箇所均等間隔でバッフル板を設置した。また、バッフル板は、反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の15%であり、突起部幅は、反応器円周長の15%であった。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例1と同様に行って実施例4の微孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を84℃、固体触媒成分[A]を94℃で反応器へ投入、重合圧力を1.1MPa、活性18000PE g/触媒 g、分離された超高分子量ポリエチレンパウダーを窒素ブローしながら、60℃で3時間乾燥後、70℃で更に2時間乾燥、反応器内に2箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の10%、突起部幅が反応器円周長の10%に変更したこと以外は、実施例2と同様に行って実施例5の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例2と同様に行って実施例5の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を84℃、固体触媒成分[A]を94℃で反応器へ投入、重合圧力を0.6MPa、活性16000PE g/触媒 g、反応器内に4箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の25%、突起部幅が反応器円周長の25%に変更したこと以外は、実施例2と同様に行って実施例6の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例2と同様に行って実施例6の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を80℃、固体触媒成分[A]を90℃で反応器へ投入、重合圧力を0.6MPa、活性14000PE g/触媒 gにしたこと以外は、実施例1と同様に行って実施例7の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃で1時間撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度は0.1%以下になるように調整した。なお、スラリー状液体が導入される押出機は、二軸押出機を使用した。
また、スラリー状液体が押出機中で形成される温度は、200℃であり、押出機内での溶融滞留時間としては10分であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は200℃、吐出量は0.5g/分であり、紡糸口金の孔径は1.0mmであった。
次に、吐出した流動パラフィンを含む糸を、4cmのエアギャップを介して5℃の水浴中に投入し、急冷しながら巻き取った。巻取速度としては、30m/分で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間真空乾燥させた。
得られた糸を糸温度が120℃になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合温度を78℃、固体触媒成分[A]を88℃で反応器へ投入、1-ブテンをエチレンに対して6.3mol%気相から導入、活性12000PE g/触媒 gにしたこと以外は、実施例7と同様に行って実施例8の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例7と同様に行って実施例8の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合温度を70℃、固体触媒成分[A]を80℃で反応器へ投入、活性9000PE g/触媒 gにしたこと以外は、実施例7と同様に行って実施例9の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃で1時間撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度は0.1%以下になるように調整した。なお、スラリー状液体が導入される押出機は、二軸押出機を使用した。
また、スラリー状液体が押出機中で形成される温度は、220℃であり、押出機内での溶融滞留時間としては10分であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は220℃、吐出量は0.5g/分であり、紡糸口金の孔径は0.6mmであった。
次に、吐出した流動パラフィンを含む糸を、3cmのエアギャップを介して5℃の水浴中に投入し、急冷しながら巻き取った。巻取速度としては、30m/分で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間真空乾燥させた。
得られた糸を糸温度が120℃になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合圧力を0.5MPa、活性12000PE g/触媒 g、反応器内に6箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の30%、突起部幅が反応器円周長の30%に変更したこと以外は、実施例7と同様に行って実施例10の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例7と同様に行って実施例10の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合圧力を0.5MPa、活性8000PE g/触媒 g、反応器内に2箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の10%、突起部幅が反応器円周長の10%に変更したこと以外は、実施例8と同様に行って実施例11の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例8と同様に行って実施例11の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合圧力を0.5MPa、活性7000PE g/触媒 g、反応器内に2箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の10%、突起部幅が反応器円周長の10%に変更したこと以外は、実施例9と同様に行って実施例12の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例9と同様に行って実施例12の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合温度を76℃、固体触媒成分[B]を86℃で反応器へ投入、重合圧力を0.6MPa、1-ブテンをエチレンに対して6.3mol%気相から導入、活性11000PE g/触媒 g、反応器内に4箇所均等間隔でバッフル板を設置しており、バッフル板は、反応器底部から反応器頂部(開口部)まで設けられ、かつ反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の20%、突起部幅が反応器円周長の20%に変更したこと以外は、実施例4と同様に行って実施例13の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は実施例8と同様に行って実施例13の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
ヘキサン、エチレン、水素、固体触媒成分[A]を連続的に攪拌装置が付いたベッセル型重合反応器に供給し、ポリエチレン(エチレン単独重合体)を10kg/時間の速度で製造した。水素としては、モレキュラーシーブスとの接触により精製された99.99モル%以上の水素を使用した。固体触媒成分[A]は、上記溶媒ヘキサンを移送液とし、水素10NL/時間(NLはNormal Liter(標準状態に換算した容積))と共に、製造速度が10kg/時間となるように0.15mmol/Lの速度で重合反応器の液面と底部の中間から添加した。また、固体触媒成分[A]は、20℃に調整して0.2g/時間の速度で重合器の底部から添加し、トリイソブチルアルミニウムは22℃に調整して5mmol/時間の速度で重合器の底部から添加した。重合温度はジャケット冷却することで88℃に保った。重合反応器内の湿度は0ppmに保った。ヘキサンは20℃に調整して60L/時間で重合器に供給した。エチレンは重合反応器の底部より供給して重合圧力を1.0MPaに保った。重合スラリーは、重合反応器のレベルが一定に保たれるように連続的に圧力0.05MPaのフラッシュドラムに抜き、未反応のエチレンを分離した。重合スラリーは、フラッシュドラムのレベルが一定に保たれるように連続的に遠心分離機に送り、ポリマーとそれ以外の溶媒等を分離した。その際、超高分子量ポリエチレンパウダーに含まれる溶媒等の含有量は、超高分子量ポリエチレンパウダーの重量に対して10質量%であった。分離された超高分子量ポリエチレンパウダーは、窒素ブローしながら、100℃で5時間乾燥した。なお、この乾燥工程で、重合後のパウダーに対し、スチームを噴霧して、触媒及び助触媒の失活を実施した。得られた超高分子量ポリエチレンパウダーを目開き425μmの篩を用いて、篩を通過しなかったものを除去して比較例1の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたときに、40質量部の超高分子量ポリエチレンパウダーと60質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合してスラリー状液体を調製した。得られたスラリー状液体は窒素で置換を行った後に、二軸押出機へ窒素雰囲気下でフィーダーを介して投入し、200℃条件で混練した後、押出機先端に設置したTダイから押出した後、ただちに25℃に冷却したキャストロールで冷却固化させゲル状シートを成形した。このゲル状シートを120℃で同時二軸延伸機を用いて7×7倍に延伸した後、この延伸フィルムをメチルエチルケトン又はヘキサンに浸漬し、流動パラフィンを抽出除去後、24時間真空乾燥した。更に125℃、3分で熱固定し、比較例1の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を85℃に変更、1-ブテンをエチレンに対して6.3mol%気相から導入、分離された超高分子量ポリエチレンパウダーを、窒素ブローしながら、65℃で3時間乾燥後、75℃で更に2時間乾燥したこと以外は、比較例1と同様に行って比較例2の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は比較例1と同様に行って比較例2の微多孔膜を得た。得られた微多孔膜の評価結果を表1に示す。
(ポリエチレンの重合工程)
重合温度を90℃に変更したこと以外は、比較例1と同様に行って比較例3の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表1に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は比較例1と同様に行って比較例3の微多孔膜を得ようとしたが、同時二軸延伸する際に延伸途中で膜が破断し、7×7倍に延伸することが出来なかった。よって、微多孔膜を得ることができなかった。
(ポリエチレンの重合工程)
重合温度を75℃に変更、重合圧力を0.8MPa、1-ブテンをエチレンに対して6.3mol%気相から導入、活性18000PE g/触媒 gにしたこと以外は、比較例1と同様に行って比較例4の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃で1時間撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度は0.1%以下になるように調整した。なお、スラリー状液体が導入される押出機は、二軸押出機を使用した。
また、スラリー状液体が押出機中で形成される温度は、200℃であり、押出機内での溶融滞留時間としては10分であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は200℃、吐出量は0.5g/分であり、紡糸口金の孔径は1.0mmであった。
次に、吐出した流動パラフィンを含む糸を、4cmのエアギャップを介して5℃の水浴中に投入し、急冷しながら巻き取った。巻取速度としては、30m/分で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間真空乾燥させた。
得られた糸を糸温度が120℃になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合温度を70℃に変更、重合圧力を0.6MPa、活性12000PE g/触媒 g、反応器内に4箇所均等間隔でバッフル板を設置(バッフル板は、反応器底部から反応器頂部(開口部)まで設け、反応器側面に突起しており、突起部頂部から反応器側面までの距離が反応器内径の15%、突起部幅は反応器円周長の15%)したこと以外は、比較例1と同様に行って比較例5の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃で1時間撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度は0.1%以下になるように調整した。なお、スラリー状液体が導入される押出機は、二軸押出機を使用した。
また、スラリー状液体が押出機中で形成される温度は、220℃であり、押出機内での溶融滞留時間としては10分であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は220℃、吐出量は0.5g/分であり、紡糸口金の孔径は0.6mmであった。
次に、吐出した流動パラフィンを含む糸を、3cmのエアギャップを介して5℃の水浴中に投入し、急冷しながら巻き取った。巻取速度としては、30m/分で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間真空乾燥させた。
得られた糸を糸温度が120℃になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
ヘキサン、エチレン、水素、担持型メタロセン触媒成分[B]を連続的に攪拌装置が付いたベッセル型重合反応器に供給し、ポリエチレン(エチレン単独重合体)を10kg/時間の速度で製造した。水素は、モレキュラーシーブスとの接触により精製された99.99モル%以上のものを使用した。担持型メタロセン触媒成分[B]は、上記溶媒ヘキサンを移送液とし、水素10NL/時間(NLはNormal Liter(標準状態に換算した容積))と共に、製造速度が10kg/時間となるように0.15mmol/Lの速度で重合反応器の液面と底部の中間から添加した。また、担持型メタロセン触媒成分[B]は、86℃に調整して0.2g/時間の速度で重合器の底部から添加し、トリイソブチルアルミニウムは22℃に調整して5mmol/時間の速度で重合器の中間から添加した。重合温度はジャケット冷却することで76℃に保った。重合反応器内の湿度は0ppmに保った。ヘキサンは20℃に調整して60L/時間で重合器の底部から供給した。エチレンは重合反応器の底部より供給して重合圧力を0.6MPaに保った。重合スラリーは、重合反応器のレベルが一定に保たれるように連続的に圧力0.05MPaのフラッシュドラムに抜き、未反応のエチレンを分離した。重合スラリーは、フラッシュドラムのレベルが一定に保たれるように連続的に遠心分離機に送り、ポリマーとそれ以外の溶媒等を分離した。その際、超高分子量ポリエチレンパウダーに含まれる溶媒等の含有量は、超高分子量ポリエチレンパウダーの重量に対して10質量%であった。分離された超高分子量ポリエチレンパウダーは、窒素ブローしながら、100℃で5時間乾燥した。なお、この乾燥工程で、重合後のパウダーに対し、スチームを噴霧して、触媒及び助触媒の失活を実施した。得られた超高分子量ポリエチレンパウダーを目開き425μmの篩を用いて、篩を通過しなかったものを除去して比較例6のポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
得られた超高分子量ポリエチレンパウダーを用いた以外は比較例4と同様に行って比較例6の高強度繊維を得た。得られた高強度繊維の評価結果を表2に示す。
(ポリエチレンの重合工程)
重合温度を63℃、重合圧力を0.6MPa、活性6000PE g/触媒 gに変更したこと以外は、比較例1と同様に行って比較例7の超高分子量ポリエチレンパウダーを得た。得られた超高分子量ポリエチレンパウダーの物性を表2に示す。
超高分子量ポリエチレンパウダーと流動パラフィンとの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に1質量部の酸化防止剤とを配合して、スラリー状液体を調製した。
次に、スラリー状液体を80℃で1時間撹拌しながら真空脱気した後に、押出機に導入した。押出機でのスラリー状液体の混練は、窒素雰囲気下で行い、酸素濃度は0.1%以下になるように調整した。なお、スラリー状液体が導入される押出機は、二軸押出機を使用した。
また、スラリー状液体が押出機中で形成される温度は、260℃であり、押出機内での溶融滞留時間としては10分であった。
その後、押出機先端に装着した紡糸口金に通して紡糸した。紡糸口金の温度は240℃、吐出量は0.5g/分であり、紡糸口金の孔径は0.6mmであった。
次に、吐出した流動パラフィンを含む糸を、3cmのエアギャップを介して5℃の水浴中に投入し、急冷しながら巻き取った。巻取速度としては、20m/分で実施した。
ついで、該糸から流動パラフィンを除去した。ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、24時間真空乾燥させた。
得られた糸を糸温度が120℃になるように金属ヒータに接触させ、一次延伸し延伸糸を巻き取った。ついで、該延伸糸を延伸糸が140℃になるように金属ヒータに接触させ更に二次延伸し、糸が切れる直前まで延伸し、延伸糸を得た。得られた高強度繊維の評価結果を表2に示す。
また高分子量のエチレン重合体の特性である耐摩耗性、高摺動性、高強度、高衝撃性などの優れた特徴を活かし、エチレン重合体を焼結して得られる成形体、フィルターや粉塵トラップ材等にも使用できる。
高強度繊維の製造方法としては、例えば、流動パラフィンと超高分子量ポリエチレンパウダーとを混練紡糸後、加熱延伸することで製造する方法が挙げられる。
このようにして得られた種々成形体は、産業上の利用可能性を有する。
Claims (12)
- 粘度平均分子量Mvが10×104以上1000×104以下である超高分子量ポリエチレンパウダーであって、下記混練条件で混練した混練物の粘度平均分子量Mv(A)と前記Mvとが下記の関係を満たし、
{Mv-Mv(A)}/Mvが0.20以下、
粒径212μm以上の超高分子量ポリエチレンパウダーを含有し、該粒径212μm以上のパウダーにおいて、平均細孔容積が0.6ml/g以上であり、かつ平均細孔径が0.3μm以上である、
超高分子量ポリエチレンパウダー。
[粘度平均分子量Mv(A)の混練物を得るための混練条件]
原料:
超高分子量ポリエチレンパウダー、及び流動パラフィンの合計を100質量部としたとき、5質量部の超高分子量ポリエチレンパウダーと95質量部の流動パラフィンと、更に、1質量部の酸化防止剤とを含む、混合物。
条件:
130℃で前記原料を30分混練した後、240℃で15分更に混練する
130℃~240℃への昇温速度は22℃/分とする
スクリュー回転数は50rpmとする
窒素雰囲気下とする - 粒径53μm以下の超高分子量ポリエチレンパウダーが占める割合が超高分子量ポリエチレンパウダー100質量%としたとき、40質量%未満である、請求項1に記載の超高分子量ポリエチレンパウダー。
- 前記粒径212μm以上のパウダーの嵩密度が0.20g/cm3以上0.60g/cm3以下である、請求項1又は2に記載の超高分子量ポリエチレンパウダー。
- マグネシウム含有量が0.1ppm以上20ppm以下である、請求項1~3のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- チタン含有量が0.1ppm以上5ppm以下である、請求項1~4のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- アルミニウム含有量が0.5ppm以上10ppm以下である、請求項1~5のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- ケイ素含有量が0.1ppm以上100ppm以下である、請求項1~6のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- 塩素含有量が1ppm以上50ppm以下である、請求項1~7のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- マグネシウムとチタンとの含有量比(Mg/Ti)が0.1以上10以下である、請求項1~8のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- アルミニウムとチタンとの含有量比(Al/Ti)が0.1以上20以下である、請求項1~9のいずれか一項に記載の超高分子量ポリエチレンパウダー。
- 請求項1~10のいずれか一項に記載の超高分子量ポリエチレンパウダーを含有する高強度繊維。
- 請求項1~10のいずれか一項に記載の超高分子量ポリエチレンパウダーを含有する二次電池セパレーター用微多孔膜。
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