JP6882882B2 - Method for producing olefin polymer and method for improving fluidity - Google Patents
Method for producing olefin polymer and method for improving fluidity Download PDFInfo
- Publication number
- JP6882882B2 JP6882882B2 JP2016219776A JP2016219776A JP6882882B2 JP 6882882 B2 JP6882882 B2 JP 6882882B2 JP 2016219776 A JP2016219776 A JP 2016219776A JP 2016219776 A JP2016219776 A JP 2016219776A JP 6882882 B2 JP6882882 B2 JP 6882882B2
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- Prior art keywords
- component
- olefin polymer
- polymer
- fluidity
- olefin
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920000642 polymer Polymers 0.000 claims description 98
- 239000007787 solid Substances 0.000 claims description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 38
- 239000005977 Ethylene Substances 0.000 claims description 38
- -1 Organoaluminium oxy compound Chemical class 0.000 claims description 38
- 239000011949 solid catalyst Substances 0.000 claims description 31
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 239000004711 α-olefin Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000003623 transition metal compounds Chemical class 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000012685 gas phase polymerization Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 description 76
- 239000000843 powder Substances 0.000 description 58
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000003446 ligand Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000012808 vapor phase Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000005293 duran Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JJDZBQREKCLIOM-UHFFFAOYSA-L CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C Chemical compound CC1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC(C)=C1)=[Si](C)C JJDZBQREKCLIOM-UHFFFAOYSA-L 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- GOHZWUYRQHUCJN-UHFFFAOYSA-L [Cl-].[Cl-].[SiH2]=[Zr+2](C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C)C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C Chemical compound [Cl-].[Cl-].[SiH2]=[Zr+2](C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C)C1C(=CC2=C(C=CC=C12)C1=CC=CC=C1)C GOHZWUYRQHUCJN-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
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- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- IBQDNBSGSLQZAQ-UHFFFAOYSA-N C1(C=CC=C1)[Zr](CC1=CC=CC=C1)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Zr](CC1=CC=CC=C1)C1C=CC=C1 IBQDNBSGSLQZAQ-UHFFFAOYSA-N 0.000 description 1
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- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 1
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- JJQHEAPVGPSOKX-UHFFFAOYSA-L cyclopentyl(trimethyl)silane;dichlorozirconium Chemical compound Cl[Zr]Cl.C[Si](C)(C)[C]1[CH][CH][CH][CH]1.C[Si](C)(C)[C]1[CH][CH][CH][CH]1 JJQHEAPVGPSOKX-UHFFFAOYSA-L 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- RJCAGRBHNVAJDE-UHFFFAOYSA-N di(heptan-2-yl)alumane Chemical compound C(C)(CCCCC)[AlH]C(C)CCCCC RJCAGRBHNVAJDE-UHFFFAOYSA-N 0.000 description 1
- MMLCQFVTLHFPDC-UHFFFAOYSA-N di(nonan-2-yl)alumane Chemical compound C(C)(CCCCCCC)[AlH]C(C)CCCCCCC MMLCQFVTLHFPDC-UHFFFAOYSA-N 0.000 description 1
- CDHICTNQMQYRSM-UHFFFAOYSA-N di(propan-2-yl)alumane Chemical compound CC(C)[AlH]C(C)C CDHICTNQMQYRSM-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 1
- MIILMDFFARLWKZ-UHFFFAOYSA-L dichlorozirconium;1,2,3,4,5-pentamethylcyclopentane Chemical compound [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1(C)[Zr+2]C1(C)C(C)=C(C)C(C)=C1C MIILMDFFARLWKZ-UHFFFAOYSA-L 0.000 description 1
- LOKCKYUBKHNUCV-UHFFFAOYSA-L dichlorozirconium;methylcyclopentane Chemical compound Cl[Zr]Cl.C[C]1[CH][CH][CH][CH]1.C[C]1[CH][CH][CH][CH]1 LOKCKYUBKHNUCV-UHFFFAOYSA-L 0.000 description 1
- VKTXATHVMNFXEF-UHFFFAOYSA-N dicyclohexylalumane Chemical compound C1(CCCCC1)[AlH]C1CCCCC1 VKTXATHVMNFXEF-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- HIVRDDZUKVNKAO-UHFFFAOYSA-N diphenylalumane Chemical compound C1(=CC=CC=C1)[AlH]C1=CC=CC=C1 HIVRDDZUKVNKAO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- LQGGFKNSPDEGHH-UHFFFAOYSA-N methoxy-di(propan-2-yl)alumane Chemical compound CO[Al](C(C)C)C(C)C LQGGFKNSPDEGHH-UHFFFAOYSA-N 0.000 description 1
- AQYCWSHDYILNJO-UHFFFAOYSA-N methyl 6-methyl-3-oxo-4h-1,4-benzoxazine-8-carboxylate Chemical compound N1C(=O)COC2=C1C=C(C)C=C2C(=O)OC AQYCWSHDYILNJO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- MGJXBDMLVWIYOQ-UHFFFAOYSA-N methylazanide Chemical compound [NH-]C MGJXBDMLVWIYOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- ZYTJPPRBIGGXRO-UHFFFAOYSA-N propan-2-ylalumane Chemical compound C(C)(C)[AlH2] ZYTJPPRBIGGXRO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本発明は、オレフィン重合体の製造方法および流動性改良方法に関し、より詳しくはオレフィン重合体の製造工程または貯蔵工程において重合体粉体の流動性が低下して塊等を発生することなく、長期的に安定して運転することができるオレフィン重合体の製造方法および流動性改良方法に関する。 The present invention relates to a method for producing an olefin polymer and a method for improving the fluidity. More specifically, the present invention does not reduce the fluidity of the polymer powder in the production process or the storage process of the olefin polymer to generate lumps or the like for a long period of time. The present invention relates to a method for producing an olefin polymer and a method for improving fluidity, which can be operated stably.
従来、オレフィンモノマーを重合する方法としては、液相重合や気相重合等様々な方法がある。例えば、気相重合では重合体が粉体で得られ、液相重合においても取扱い易さから重合体を粉体として回収することが多い。そして重合体粉体が存在する閉塞空間、例えば気相重合では重合体粉体を製造する重合反応器や各配管、または気相重合や液相重合で得た重合体粉体を貯蔵する貯蔵庫等において流動性に優れることが求められる。 Conventionally, there are various methods for polymerizing an olefin monomer, such as liquid phase polymerization and vapor phase polymerization. For example, in vapor phase polymerization, the polymer is obtained as a powder, and in liquid phase polymerization, the polymer is often recovered as a powder because of its ease of handling. Then, in a closed space where the polymer powder exists, for example, in a vapor phase polymerization, a polymerization reactor or a pipe for producing the polymer powder, or a storage for storing the polymer powder obtained in the vapor phase polymerization or the liquid phase polymerization, etc. It is required to have excellent fluidity.
ところで、ポリエチレン、ポリプロピレン、エチレン・α−オレフィン共重合体、プロピレン・α−オレフィン共重合体等のポリオレフィンは、例えば固体状のチタン系触媒、担体担持型メタロセン系触媒等の固体触媒の存在下にオレフィンを重合させることによって製造されている。この固体触媒は流動性が低いことが多く、重合反応器への供給が困難な場合がある。 By the way, polyolefins such as polyethylene, polypropylene, ethylene / α-olefin copolymers, and propylene / α-olefin copolymers are prepared in the presence of solid catalysts such as solid titanium catalysts and carrier-supported metallocene catalysts. It is produced by polymerizing olefins. This solid catalyst often has low fluidity, and it may be difficult to supply it to the polymerization reactor.
また、固体触媒の存在下にオレフィンを気相重合すると、流動層内でポリマー塊またはシート状物等が発生したり、オレフィン重合体の流動性が低下したりして、流動層内の混合状態が不均一となり、長期的に安定して運転することができなくなる等の問題が発生することがある。 Further, when the olefin is vapor-phase polymerized in the presence of a solid catalyst, a polymer mass or a sheet-like substance is generated in the fluidized bed, or the fluidity of the olefin polymer is lowered, so that the mixed state in the fluidized bed is reached. May become non-uniform, and problems such as inability to operate stably for a long period of time may occur.
さらに、重合反応器に付属する配管、流動床反応器を用いた気相重合を多段で行う際の各段の重合器を連結している配管、その他重合体粉体等が移動する各種設備を、固体触媒または重合体粉体が移動する際に、流動性が低下したり、各種設備での流動性が低下する場所、いわゆるデッドスペース等でポリマー塊が生成したり、シート状物に付着して、重合体粉体の流動性を低下させ、最悪の場合には配管等が閉塞するという問題が生じる場合がある。また、最終的に得られた重合体粉体を回収する、もしくは重合体粉体を貯蔵する貯蔵庫等で、重合体粉体の流動性が低下したために、重合体粉体同士が結合して貯蔵庫内でブリッジが生成する等、その後の様々な処理が滞るという問題も発生する場合がある。 In addition, the piping attached to the polymerization reactor, the piping connecting the polymer in each stage when performing gas phase polymerization using the fluidized bed reactor in multiple stages, and other various equipment to which the polymer powder etc. move. , When the solid catalyst or polymer powder moves, the fluidity decreases, polymer lumps are generated in places where the fluidity decreases in various facilities, so-called dead spaces, etc., or they adhere to sheet-like materials. As a result, the fluidity of the polymer powder is lowered, and in the worst case, there may be a problem that the piping or the like is clogged. Further, in a storage or the like for recovering the finally obtained polymer powder or storing the polymer powder, the fluidity of the polymer powder is lowered, so that the polymer powders are bonded to each other and stored in the storage. There may be a problem that various subsequent processes are delayed, such as a bridge being generated inside.
以上のような問題点を低減させる方法としては、［１］重合反応器に水を導入する方法（特許文献１）、［２］重合反応器に特定の気体を導入する方法（特許文献２）、［３］重合反応器に極性基を有する低分子化合物を導入する方法（特許文献３〜５）、［４］重合反応器に極性基を有する高分子化合物を導入する方法（特許文献６〜８）、［５］重合触媒に有機酸の金属塩を混合して重合反応器に導入する方法（特許文献９）、［６］重合触媒にポリマー粒子を混合して重合反応器に導入する方法（特許文献１０）［７］重合触媒に無機化合物を混合して重合反応器に導入する方法（特許文献１１〜１３）、等が開示されている。また特許文献１４には、諸成分の反応器への供給の不安定性の課題が開示されている。 As a method for reducing the above problems, [1] a method of introducing water into the polymerization reactor (Patent Document 1) and [2] a method of introducing a specific gas into the polymerization reactor (Patent Document 2). , [3] Method of introducing a low molecular weight compound having a polar group into a polymerization reactor (Patent Documents 3 to 5), [4] Method of introducing a polymer compound having a polar group into a polymerization reactor (Patent Documents 6 to 6). 8), [5] A method in which a metal salt of an organic acid is mixed with a polymerization catalyst and introduced into a polymerization reactor (Patent Document 9), [6] A method in which polymer particles are mixed with a polymerization catalyst and introduced into a polymerization reactor. (Patent Document 10) [7] A method of mixing an inorganic compound with a polymerization catalyst and introducing it into a polymerization reactor (Patent Documents 11 to 13) and the like are disclosed. Further, Patent Document 14 discloses a problem of instability of supply of various components to a reactor.
本発明者らの検討によれば、以上の各方法のうち、水、気体または極性基を有する低分子化合物を用いる方法では、触媒活性が低下し、触媒コストが増加するという問題があり、また、高分子化合物、無機化合物等の固体状化合物を用いる方法では、触媒活性の低下は抑制されるが、比較的過酷な条件による生産工程（例えば生産速度を高めた工程や大規模な生産工程）においてはファウリングの抑制が不十分な場合があることが分かった。そしてさらに検討を進めた結果、本発明者らは、このファウリングの問題は液状高分子化合物の粘度の高さもしくは固体状化合物の粉体性状により供給の安定性または重合器内での分散性が低下することがあるためではないかと言う考えに至った。 According to the studies by the present inventors, among the above methods, the method using a low molecular weight compound having water, gas or a polar group has a problem that the catalytic activity is lowered and the catalyst cost is increased. In the method using a solid compound such as a polymer compound or an inorganic compound, a decrease in catalytic activity is suppressed, but a production process under relatively harsh conditions (for example, a process in which the production rate is increased or a large-scale production process). It was found that the suppression of fouling may be insufficient in some cases. As a result of further studies, the present inventors have found that the problem of fouling depends on the high viscosity of the liquid polymer compound or the powder properties of the solid compound, and the stability of the supply or the dispersibility in the polymerizer. I came up with the idea that it may be because of the decrease.
本発明はこのような新たな課題に鑑みてなされたものである。すなわち本発明の目的は、オレフィン重合体の製造工程または貯蔵工程において重合体粉体の流動性が低下して塊等を発生することなく、長期的に安定して運転することができるオレフィン重合体の製造方法および流動性改良方法を提供することにある。 The present invention has been made in view of such a new problem. That is, an object of the present invention is an olefin polymer capable of stable operation over a long period of time without reducing the fluidity of the polymer powder and generating lumps or the like in the manufacturing process or storage process of the olefin polymer. To provide a manufacturing method and a method for improving fluidity.
本発明は、以下の事項により特定される。 The present invention is specified by the following matters.
［１］ オレフィン重合体の貯蔵工程における該オレフィン重合体の流動環境場に、固体成分（Ａ）を供給するオレフィン重合体の流動性改良方法において、
該固体成分（Ａ）が、アルミノケイ酸塩（Ａ−１）、ハイドロタルサイト類（Ａ−２）およびアクリル系樹脂微粒子（Ａ−３）からなる群より選ばれる少なくとも１種の成分を含むことを特徴とするオレフィン重合体の流動性改良方法。
[ 1 ] In a method for improving the fluidity of an olefin polymer, which supplies the solid component (A) to the fluid environment field of the olefin polymer in the storage step of the olefin polymer.
The solid component (A) contains at least one component selected from the group consisting of aluminosilicates (A-1), hydrotalcites (A-2) and acrylic resin fine particles (A-3). A method for improving the fluidity of an olefin polymer.
［２］ 固体成分（Ａ）の平均粒径が、０．１μｍ以上５μｍ以下である［１］に記載のオレフィン重合体の流動性改良方法。
［３］ 固体成分（Ａ）の供給量が、流動環境場中におけるオレフィン重合体の質量に対して、０．５ｐｐｍ以上５００ｐｐｍ以下である［１］または［２］に記載のオレフィン重合体の流動性改良方法。
［４］ オレフィン重合体を構成するオレフィンが、エチレン単独、またはエチレンと炭素数３以上２０以下のα−オレフィンである［１］〜［３］のいずれかに記載のオレフ
ィン重合体の流動性改良方法。
［５］ オレフィン重合体が、気相重合工程を含む製造方法により得られた重合体である［１］〜［４］のいずれかに記載のオレフィン重合体の流動性改良方法。
［６］ オレフィン重合体が、下記成分（ｘ−１）、成分（ｘ−２）および成分（ｘ−３）を含んでなる固体触媒成分（Ｘ）を用いた製造方法により得られた重合体である［１］〜［５］のいずれかに記載のオレフィン重合体の流動性改良方法。
成分（ｘ−１）：シクロペンタジエニル骨格を有する周期表第４族の遷移金属化合物
成分（ｘ−２）：有機アルミニウムオキシ化合物
成分（ｘ−３）：粒子状担体
[ 2 ] The method for improving the fluidity of an olefin polymer according to [1 ], wherein the average particle size of the solid component (A) is 0.1 μm or more and 5 μm or less.
[ 3 ] The flow of the olefin polymer according to [1 ] or [ 2 ], wherein the supply amount of the solid component (A) is 0.5 ppm or more and 500 ppm or less with respect to the mass of the olefin polymer in the flow environment field. Gender improvement method.
[ 4 ] The fluidity improvement of the olefin polymer according to any one of [1 ] to [ 3 ], wherein the olefin constituting the olefin polymer is ethylene alone or an α-olefin having 3 or more and 20 or less carbon atoms with ethylene. Method.
[ 5 ] The method for improving the fluidity of an olefin polymer according to any one of [1 ] to [ 4 ], wherein the olefin polymer is a polymer obtained by a production method including a gas phase polymerization step.
[ 6 ] A polymer obtained by a production method using a solid catalyst component (X) in which the olefin polymer contains the following components (x-1), component (x-2) and component (x-3). The method for improving the fluidity of the olefin polymer according to any one of [1 ] to [ 5].
Component (x-1): Transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton Component (x-2): Organoaluminium oxy compound Component (x-3): Particle-like carrier
本発明によれば、オレフィン重合体の製造工程または貯蔵工程において重合体粉体の流動性が低下して塊等を発生することなく、長期的に安定して運転することができる。例えば、重合時にヒートスポットが発生し難く、重合体粉体が移動する配管や各種設備等でのデッドスペースにおいても優れた流動性を確保でき、重合体粉体からポリマー塊や、シート状物を生成することが無い。また、重合触媒と接触させた際の触媒活性低下が小さいため、経済的な重合体の製造も可能である。 According to the present invention, the polymer powder can be stably operated for a long period of time without reducing the fluidity of the polymer powder and generating lumps or the like in the manufacturing process or the storage process of the olefin polymer. For example, heat spots are less likely to occur during polymerization, and excellent fluidity can be ensured even in dead spaces in piping and various equipment where polymer powder moves, and polymer lumps and sheet-like materials can be separated from polymer powder. Never generate. Further, since the decrease in catalytic activity when contacted with the polymerization catalyst is small, it is possible to economically produce a polymer.
本発明においては、オレフィン重合体の製造工程または貯蔵工程におけるオレフィン重合体の流動環境場に、特定の固体成分（Ａ）を供給することによりそのオレフィン重合体の流動性を向上させる。 In the present invention, the fluidity of the olefin polymer is improved by supplying the specific solid component (A) to the flow environment field of the olefin polymer in the manufacturing step or the storage step of the olefin polymer.
［固体成分（Ａ）］
固体成分（Ａ）は、以下に説明するアルミノケイ酸塩（Ａ−１）、ハイドロタルサイト類（Ａ−２）およびアクリル系樹脂微粒子（Ａ−３）からなる群より選ばれる少なくとも１種の成分である。
[Solid component (A)]
The solid component (A) is at least one component selected from the group consisting of the aluminosilicate (A-1), hydrotalcites (A-2) and acrylic resin fine particles (A-3) described below. Is.
（アルミノケイ酸塩（Ａ−１））
アルミノケイ酸塩（Ａ−１）は、ケイ酸塩中のケイ素原子の一部がアルミニウム原子に置換された構造を有する無機化合物であり、例えば、下記一般式（Ｉ）で表される化合物である。
(Aluminosilicate (A-1))
The aluminosilicate (A-1) is an inorganic compound having a structure in which a part of silicon atoms in the silicate is replaced with an aluminum atom, and is, for example, a compound represented by the following general formula (I). ..
ＭＩＯ・Ａｌ２Ｏ３・ｎＳｉＯ２・ｍＨ２Ｏ ・・・（Ｉ）
（一般式（Ｉ）中、ＭＩはアルカリ金属２原子またはアルカリ土類金属１原子を示し、２種以上の原子が含まれていても良く、ｎはｎ≧１であり、ｍはｍ≧０である。）
M I O · Al 2 O 3 · nSiO 2 · mH 2 O ··· (I)
(In the general formula (I), M I represents an alkali metal 2 atoms or alkaline earth metal 1 atom, may contain two or more atoms, n is n ≧ 1, m is m ≧ It is 0.)
ＭＩとしては、Ｌｉ２、Ｎａ２、Ｋ２、Ｃａ、Ｍｇ等が挙げられる。 Examples of MI include Li 2 , Na 2 , K 2 , Ca, Mg and the like.
（ハイドロタルサイト類（Ａ−２））
ハイドロタルサイト類（Ａ−２）は、下記一般式（ＩＩ）で表される層状の無機化合物である。
［ＭII２＋ １−ｘＭIII３＋ ｘ（ＯＨ）２］ｘ＋［Ａｎ− ｘ／ｎ・ｍＨ２Ｏ］ｘ−・・・（ＩＩ）
（一般式（ＩＩ）中、ＭII２＋は２価の金属イオン、ＭIII３＋は３価の金属イオン、Ａｎ−は層間陰イオン、ｎはＡｎ−の価数を示し、それぞれ２種以上のイオンが含まれていても良く、ｘは０＜ｘ＜１であり、ｍは０≦ｍ＜１である。）
(Hydrotalcites (A-2))
Hydrotalcites (A-2) are layered inorganic compounds represented by the following general formula (II).
[M II2 + 1-x M III3 + x (OH) 2 ] x + [An - x / n・ mH 2 O] x -... (II)
(In the general formula (II), M II2 + is a divalent metal ion, M III3 + is a trivalent metal ion, An− is an interlayer anion, and n is an An− valence, and each of them has two or more kinds. Ions may be contained, x is 0 <x <1, and m is 0 ≦ m <1.)
ＭII２＋（２価の金属イオン）としては、Ｍｇ２＋、Ｚｎ２＋等が挙げられ、ＭIII３＋（３価の金属イオン）としては、Ａｌ３＋、Ｆｅ３＋等が挙げられ、Ａｎ−（層間陰イオン）としては、塩素イオン（Ｃｌ−）、炭酸イオン（ＣＯ３ ２−）、硝酸イオン（ＮＯ３ −）等が挙げられる。ハイドロタルサイト類の表面処理の有無は特に限定されるものではなく、高級脂肪酸、高級アルコールの硫酸エステル、チタネートカップリング剤、シランカップリング剤、アルミネートカップリング剤、多価アルコールと脂肪酸のエステル、リン酸エステルおよびアニオン系界面活性剤等の表面処理剤で処理された粒子を使用することができる。 M II2 + as (divalent metal ions), Mg 2+, Zn 2+, and examples of the M III3 + (3-valent metal ion), Al 3+, Fe 3+, and the like, A n-(interlayer negative the ion), chloride ion (Cl -), 2-carbonate ion (CO 3), nitrate ion (NO 3 -) and the like. The presence or absence of surface treatment of hydrotalcites is not particularly limited, and higher fatty acids, higher alcohol sulfate esters, titanate coupling agents, silane coupling agents, aluminate coupling agents, polyhydric alcohol and fatty acid esters. , Phosphate, and particles treated with surface treatment agents such as anionic surfactants can be used.
（アクリル系樹脂微粒子（Ａ−３））
アクリル系樹脂微粒子（Ａ−３）は、主成分がポリアクリル酸エステル、ポリメタクリル酸エステル、またはポリアクリロニトリルである微粒子である。具体例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、アクリル酸イソブチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸イソブチル、アクリロニトリル等をモノマーとした単独重合体もしくは共重合体を主成分とする微粒子が挙げられる。共重合体におけるコモノマーとして、上記モノマーに加え、アクリル酸、メタクリル酸、ブタジエン、スチレン、酢酸ビニル等を用いることもできる。アクリル系樹脂微粒子の重合度や架橋の有無は特に限定されるものではない。
(Acrylic resin fine particles (A-3))
The acrylic resin fine particles (A-3) are fine particles whose main component is a polyacrylic acid ester, a polymethacrylic acid ester, or a polyacrylonitrile. As a specific example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, acrylonitrile and the like are used as monomers alone. Examples thereof include fine particles containing a polymer or a copolymer as a main component. As the comonomer in the copolymer, acrylic acid, methacrylic acid, butadiene, styrene, vinyl acetate and the like can also be used in addition to the above-mentioned monomers. The degree of polymerization of the acrylic resin fine particles and the presence or absence of cross-linking are not particularly limited.
固体成分（Ａ）の性状は、本発明の効果が認められる限り任意であるが、その平均粒径は好ましくは０.１μｍ以上５μｍ以下、より好ましくは０.３μｍ以上４μｍ以下である。平均粒径が５μｍ以下の場合は、供給の安定性や重合体粉体への分散性が向上する傾向にあり、また重合体をフィルム成形した場合にフィッシュアイ等の外観不良が生じにくい傾向にある。平均粒径が０.１μｍ以上の場合は、固体成分（Ａ）粒子同士の凝集が生じにくい傾向にあり、供給の安定性や重合体粉体への分散性が向上する傾向にある。 The properties of the solid component (A) are arbitrary as long as the effects of the present invention are recognized, but the average particle size thereof is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.3 μm or more and 4 μm or less. When the average particle size is 5 μm or less, the stability of supply and the dispersibility in the polymer powder tend to be improved, and when the polymer is film-molded, appearance defects such as fish eyes tend to be less likely to occur. is there. When the average particle size is 0.1 μm or more, the solid component (A) particles tend to be less likely to agglomerate, and the stability of supply and the dispersibility in the polymer powder tend to be improved.
固体成分（Ａ）の粒子形状は、分散性の観点から球状であることが好ましい。 The particle shape of the solid component (A) is preferably spherical from the viewpoint of dispersibility.
固体成分（Ａ）は、流動環境場中におけるオレフィン重合体の質量に対して、好ましくは０.５ｐｐｍ以上５００ｐｐｍ以下、より好ましくは１ｐｐｍ以上３００ｐｐｍの量で存在するように流動環境場に連続的または間歇的に供給する。供給量が上記範囲内であれば、流動性の改良効果および経済性の双方の点で有利である。 The solid component (A) is continuously or continuously in the fluid environment field so as to be present in an amount of preferably 0.5 ppm or more and 500 ppm or less, more preferably 1 ppm or more and 300 ppm with respect to the mass of the olefin polymer in the fluid environment field. Supply intermittently. If the supply amount is within the above range, it is advantageous in terms of both the liquidity improvement effect and the economic efficiency.
固体成分（Ａ）は複数の流動環境場に供給しても良い。流動環境場への供給方法は限定されず、例えば、炭化水素溶媒等の懸濁液として供給しても良く、後述する固体触媒成分（Ｘ）または予備重合触媒成分（ＸＰ）と固体成分（Ａ）とを事前に混合し、その混合物を供給しても良い。また固体成分（Ａ）は使用前に加熱、窒素流通等による脱気、脱水処理を施しても良い。 The solid component (A) may be supplied to a plurality of fluid environment fields. The method of supplying to the fluid environment field is not limited, and for example, it may be supplied as a suspension of a hydrocarbon solvent or the like, and the solid catalyst component (X) or the prepolymerization catalyst component (XP) and the solid component (A) described later may be supplied. ) And may be mixed in advance and the mixture may be supplied. Further, the solid component (A) may be degassed or dehydrated by heating, nitrogen flow or the like before use.
［オレフィン重合体］
流動環境場中に存在するオレフィン重合体としては、気相重合、溶液重合、懸濁重合等の液相重合といった公知の様々な方法で得られる重合体であれば良く、特に制限はない。オレフィン重合体の形態にも特に制限はないが、特に重合体粉体に本発明は好適に適用される。例えば気相重合で得られたそのままの重合体の粉体、また液相重合の後、液相から回収された重合体の粉体等に好適に適用される。
[Olefin polymer]
The olefin polymer present in the flow environment field may be a polymer obtained by various known methods such as gas phase polymerization, solution polymerization, suspension polymerization and the like, and is not particularly limited. The form of the olefin polymer is not particularly limited, but the present invention is particularly preferably applied to polymer powder. For example, it is suitably applied to a polymer powder as it is obtained by vapor phase polymerization, or a polymer powder recovered from a liquid phase after liquid phase polymerization.
オレフィン重合体を構成するオレフィンの具体例としては、炭素原子数が２以上２０以下のα−オレフィン、例えばエチレン、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン；および炭素原子数が３以上２０以下の環状オレフィン、例えばシクロペンテン、シクロヘプテン、ノルボルネン、５−メチル−２−ノルボルネン、テトラシクロドデセン、２−メチル−１,４,５,８−ジメタノ−１,２,３,４,４ａ,５,８,８ａ−オクタヒドロナフタレンから選ばれる少なくとも１種のオレフィンが挙げられる。中でも、エチレン単独、またはエチレンと炭素数３以上２０以下のα−オレフィンを用いることが好ましく、エチレンを１００〜２０ｍｏｌ％および炭素原子数が３以上２０以下のα−オレフィンを０〜８０ｍｏｌ％の範囲で用いることがより好ましく、エチレンを１００〜２０ｍｏｌ％および炭素原子数が４以上２０以下のα−オレフィンを０〜８０ｍｏｌ％の範囲で用いることが特に好ましい。 Specific examples of the olefin constituting the olefin polymer include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; and cyclic olefins with 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5 -Methyl-2-norbornene, tetracycloheptene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-at least one selected from octahydronaphthalene. Seed olefins. Among them, it is preferable to use ethylene alone or α-olefin having 3 or more and 20 or less carbon atoms with ethylene, and the range of 100 to 20 mol% of ethylene and 0 to 80 mol% of α-olefin having 3 or more and 20 or less carbon atoms. It is more preferable to use ethylene in the range of 100 to 20 mol% and α-olefin having 4 or more and 20 or less carbon atoms in the range of 0 to 80 mol%.
オレフィン重合体を構成するモノマーとしては、必要に応じてオレフィン以外のモノマーを併用しても良い。さらに、その重合体粉末は重合反応や成形時に有用な他の成分を含んでいても良い。 As the monomer constituting the olefin polymer, a monomer other than the olefin may be used in combination, if necessary. Furthermore, the polymer powder may contain other components useful during the polymerization reaction and molding.
オレフィン重合体の重合条件は特に制限されないが、重合温度は、通常−５０℃以上２００℃以下、好ましくは０℃以上１５０℃以下であり、重合圧力は、通常常圧以上１０ＭＰａ以下、好ましくは常圧以上５ＭＰａ以下である。重合反応は、回分式、半連続式、連続式のいずれの方法においても行うことができる。さらに反応条件の異なる２種以上の条件で多段反応を行うこともできる。 The polymerization conditions of the olefin polymer are not particularly limited, but the polymerization temperature is usually −50 ° C. or higher and 200 ° C. or lower, preferably 0 ° C. or higher and 150 ° C. or lower, and the polymerization pressure is usually normal pressure or higher and 10 MPa or lower, preferably normal. The pressure is 5 MPa or less. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, the multi-step reaction can be carried out under two or more kinds of conditions having different reaction conditions.
液相重合において用いられる媒体としては、例えば、ベンゼン、トルエン、キシレン、クメン、シメン等の芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、ヘキサデカン、オクタデカン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、シクロオクタン、メチルシクロペンタン等の脂環族炭化水素、ガソリン、灯油、軽油等の石油留分あるいは上記芳香族炭化水素、脂肪族炭化水素、脂環族炭化水素のハロゲン化物、とりわけ、塩素化物、臭素化物等のハロゲン化炭化水素溶媒が挙げられる。媒体は１種単独で用いてもよく、２種以上を混合して用いても良い。また、重合反応に供給されうる液化オレフィン自身を媒体として用いる、いわゆるバルク重合法を用いることもできる。 Examples of the medium used in the liquid phase polymerization include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum distillates such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and aliphatic hydrocarbons. In particular, halogenated hydrocarbon solvents such as chlorinated compounds and brominated compounds can be mentioned. The medium may be used alone or in combination of two or more. Further, a so-called bulk polymerization method in which the liquefied olefin itself that can be supplied to the polymerization reaction is used as a medium can also be used.
［オレフィン重合体の流動環境場］
オレフィン重合体の製造工程または貯蔵工程におけるオレフィン重合体の流動環境場としては、例えば、重合反応器およびこれに付属する配管、多段重合装置の重合反応器同士を連結する配管、得られた重合体を重合反応器から抜き出す抜き出しポットおよびこれに付属する配管、重合体の貯蔵庫およびこれに付属する配管、その他の重合体輸送用配管等の重合体が存在する空間が挙げられる。中でも、気相連続重合装置の重合反応器およびこれに付属する配管において、本発明は特に好適に適用される。
[Flow environment field of olefin polymer]
Examples of the flow environment field of the olefin polymer in the production step or storage step of the olefin polymer include a polymerization reactor and its attached pipes, a pipe connecting the polymerization reactors of the multistage polymerization apparatus, and the obtained polymer. Examples thereof include a extraction pot for extracting the polymer from the polymerization reactor and a pipe attached thereto, a storage for the polymer and a pipe attached thereto, and a space in which the polymer exists such as other pipes for transporting the polymer. Above all, the present invention is particularly preferably applied to the polymerization reactor of the gas phase continuous polymerization apparatus and the piping attached thereto.
気相連続重合装置を用いてオレフィンを重合する方法としては、例えば、後述する固体触媒成分（Ｘ）等を用いて、気相流動床反応装置においてオレフィンを重合する方法がある。気相流動床反応装置を用いてオレフィンの重合を行うに際して、固体触媒成分（Ｘ）は、例えば触媒供給ラインを介して固体粉末状態で流動床反応器に供給される。ガス状のオレフィン等は、例えば供給ガスラインから連続的に供給され、循環ガスブロワーにより循環ガスラインを介して流動床反応器下方から多孔板等のガス分散板を介して吹き込まれる。これにより、流動床（反応系）は流動状態に保持される。このような固体触媒が流動状態に保持された流動床に吹き込まれたオレフィンは、ここで重合反応して重合体粉体（オレフィン重合体）が生成する。重合体粉体は、重合体排出ラインを介して流動床反応器から連続的に抜き出される。流動床を通過した未反応のガス状のオレフィン等は、流動床反応器上方に設けられた減速域で減速されて排出ガスラインから流動床反応器外に排出され、熱交換器において重合熱が除去されて循環ガスラインから再び流動床に循環される。水素のような分子量調節剤は、気相流動床反応装置の任意の場所、例えば供給ガスラインから供給することができる。 As a method of polymerizing an olefin using a gas phase continuous polymerization apparatus, for example, there is a method of polymerizing an olefin in a gas phase flow bed reaction apparatus using a solid catalyst component (X) described later. When polymerizing an olefin using a gas phase fluidized bed reactor, the solid catalyst component (X) is supplied to the fluidized bed reactor in a solid powder state, for example, via a catalyst supply line. The gaseous olefin or the like is continuously supplied from, for example, a supply gas line, and is blown by a circulating gas blower from below the fluidized bed reactor through a gas dispersion plate such as a perforated plate. As a result, the fluidized bed (reaction system) is kept in a fluidized state. The olefin blown into the fluidized bed in which such a solid catalyst is held in a fluidized state undergoes a polymerization reaction here to produce polymer powder (olefin polymer). The polymer powder is continuously withdrawn from the fluidized bed reactor via the polymer discharge line. Unreacted gaseous olefins and the like that have passed through the fluidized bed are decelerated in the deceleration range provided above the fluidized bed reactor and discharged from the exhaust gas line to the outside of the fluidized bed reactor, and the heat of polymerization is generated in the heat exchanger. It is removed and circulated from the circulating gas line back to the fluidized bed. Molecular weight modifiers such as hydrogen can be supplied from any location in the gas phase fluidized bed reactor, eg, from a supply gas line.
このような気相流動床反応装置を用いたオレフィン重合体の製造工程に本発明を適用する場合は、固体成分（Ａ）は気相流動床反応装置の任意の場所、例えば流動床反応器、供給ガスライン、循環ガスライン、排出ガスラインに供給することができる。 When the present invention is applied to the process of producing an olefin polymer using such a gas phase fluidized bed reactor, the solid component (A) is used at any place in the gas phase fluidized bed reactor, for example, a fluidized bed reactor. It can be supplied to supply gas lines, circulating gas lines, and exhaust gas lines.
以上説明した流動環境場に固体成分（Ａ）を添加することで、オレフィンの重合体の流動性が向上し、ポリマー塊を生成したり、配管等が閉塞したりすることがなくなる。しかも触媒活性の低下や、得られたオレフィン重合体の物性等への影響がほとんどない。 By adding the solid component (A) to the fluid environment field described above, the fluidity of the olefin polymer is improved, and polymer lumps are not formed or pipes or the like are not clogged. Moreover, there is almost no effect on the deterioration of the catalytic activity and the physical properties of the obtained olefin polymer.
［固体触媒成分（Ｘ）］
例えば気相連続重合装置等による重合反応で用いられる固体触媒成分（Ｘ）としては、例えば、周期表第４〜１０族から選ばれる遷移金属化合物が粒子状担体等に担持された遷移金属化合物触媒成分、チーグラーナッタ触媒等の固体状チタン触媒成分、フィリップス触媒等の固体状クロム触媒成分が挙げられる。
[Solid catalyst component (X)]
For example, as the solid catalyst component (X) used in the polymerization reaction by a vapor phase continuous polymerization apparatus or the like, for example, a transition metal compound catalyst in which a transition metal compound selected from Groups 4 to 10 of the periodic table is supported on a particulate carrier or the like. Examples include a component, a solid titanium catalyst component such as a Ziegler-Natta catalyst, and a solid chromium catalyst component such as a Phillips catalyst.
特に本発明は、下記成分（ｘ−１）、成分（ｘ−２）および成分（ｘ−３）を含んでなる固体触媒成分（Ｘ）を用いる場合に好適に適用される。
成分（ｘ−１）：シクロペンタジエニル骨格を有する周期表第４族の遷移金属化合物
成分（ｘ−２）：有機アルミニウムオキシ化合物
成分（ｘ−３）：粒子状担体
In particular, the present invention is preferably applied when a solid catalyst component (X) containing the following component (x-1), component (x-2) and component (x-3) is used.
Component (x-1): Transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton Component (x-2): Organoaluminium oxy compound Component (x-3): Particle-like carrier
（成分（ｘ−１））
成分（ｘ−１）は、シクロペンタジエニル骨格を有する周期表第４族の遷移金属化合物であり、下記一般式（III）で表される。
(Component (x-1))
The component (x-1) is a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and is represented by the following general formula (III).
ＭＬｘ ・・・（III）
（一般式（III）中、Ｍは、周期表第４族の遷移金属であり、Ｌは遷移金属に配位する中性またはアニオン性配位子であり、ｘはＬの個数を示し、遷移金属の原子価を満たす数であり、ｘが２以上のときは複数のＬは互いに同一でも異なっていてもよい。）
MLx ・ ・ ・ (III)
(In the general formula (III), M is a transition metal of Group 4 of the periodic table, L is a neutral or anionic ligand coordinating to the transition metal, x indicates the number of L, and the transition. It is a number that satisfies the valence of the metal, and when x is 2 or more, a plurality of Ls may be the same or different from each other.)
Ｍの具体例としては、ジルコニウム、チタン、ハフニウムが挙げられる。 Specific examples of M include zirconium, titanium, and hafnium.
Ｌの具体例としては、シクロペンタジエニル骨格を有する配位子、もしくは、ホウ素、炭素、窒素、酸素、リン、硫黄、ハロゲン、水素等の原子で電荷の状態が中性またはアニオンの形式で結合する配位子が挙げられる。 Specific examples of L include a ligand having a cyclopentadienyl skeleton, or an atom such as boron, carbon, nitrogen, oxygen, phosphorus, sulfur, halogen, or hydrogen, and the charge state is in the form of neutral or anion. Includes ligands that bind.
シクロペンタジエニル骨格を有する配位子としては、例えばシクロペンタジエニル基、インデニル基、４,５,６,７−テトラヒドロインデニル基、フルオレニル基が挙げられる。ホウ素で結合する配位子としては、例えばアルキルボラン、アリールボラン、アルキルボレート、アリールボレート、ボラベンゼンが挙げられる。 Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group and a fluorenyl group. Examples of the ligand bound with boron include alkylborane, arylborane, alkylborate, arylborate, and borabenzene.
炭素で結合する配位子としては、例えばメチル、エチル、プロピル、イソプロピル、ブチル、ペンチル等のアルキル基；シクロペンチル、シクロヘキシル等のシクロアルキル基；フェニル、トリル等のアリール基；ベンジル、ネオフィル等のアラルキル基；共役ジエン化合物残基；π−アリール等が挙げられる。 Examples of carbon-bonding ligands include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and pentyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl and trill; aralkyl groups such as benzyl and neofil. Group; conjugated diene compound residue; π-aryl and the like.
窒素で結合する配位子としては、例えばアミノ、アミド、スルホンアミド、イミド、イミノアミジン、イミダゾール、アミデート、イミデートが挙げられる。 Examples of the nitrogen-bonding ligand include amino, amide, sulfonamide, imide, iminoamidine, imidazole, amidate, and imidazole.
酸素で結合する配位子としては、例えばメトキシ、エトキシ、ブトキシ等のアルコキシ基；フェノキシ等のアリーロキシ基；ｐ−トルエンスルホナト、メタンスルホナト、トリフルオロメタンスルホナト等のスルホナト基；カルボニル、エステル、カルボキシル、オキシム、ケトアルコキシ等が挙げられる。 Examples of the ligand to be bonded with oxygen include an alkoxy group such as methoxy, ethoxy, butoxy; an aryloxy group such as phenoxy; a sulfonate group such as p-toluenesulfonato, methanesulfonato, and trifluoromethanesulfonate; carbonyl, ester, and the like. Examples thereof include carboxyl, oxime, and ketoalkoxy.
リンで結合する配位子としては、例えばフォスフィン、フォスファイト、フォスフェート等が挙げられる。 Examples of the phosphorus-bonding ligand include phosphine, phosphite, and phosphate.
硫黄で結合する配位子としては、例えばスルフィド、チオケトン、チオケトエステル、チオフェノキシド、チオカルボンキシル、ジチオカルバメート等が挙げられる。 Examples of the sulfur-bonding ligand include sulfide, thioketone, thioketoester, thiophenoxide, thiocarboxylicxyl, dithiocarbamate and the like.
ハロゲンとしては、例えばフッ素、塩素、臭素、ヨウ素が挙げられる。 Examples of halogens include fluorine, chlorine, bromine and iodine.
なお配位子中の水素原子は炭化水素基、ハロゲン含有基、酸素含有基、窒素含有基、ホウ素含有基、硫黄含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基等で置換されていてもよい。ｘが２以上の場合はＬ同士が炭化水素基、ハロゲン含有基、ケイ素含有基、ゲルマニウム含有基およびスズ含有基から選ばれる２価の基で架橋されていてもよい。 The hydrogen atom in the ligand is a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like. It may be replaced. When x is 2 or more, L may be crosslinked with a divalent group selected from a hydrocarbon group, a halogen-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group.
一般式（III）で表される化合物の中では、少なくとも１つのＬがシクロペンタジエニル骨格を有する配位子が好ましい。そのような成分（ｘ−１）としては、下記の化合物を例示できる。ただし成分（ｘ−１）は、例示した化合物に限定されるものではない。 Among the compounds represented by the general formula (III), a ligand in which at least one L has a cyclopentadienyl skeleton is preferable. Examples of such a component (x-1) include the following compounds. However, the component (x-1) is not limited to the exemplified compound.
ビス（シクロペンタジエニル）ジルコニウムジクロリド、ビス（シクロペンタジエニル）ジルコニウムジブロミド、ビス（シクロペンタジエニル）メチルジルコニウムモノクロリド、ビス（シクロペンタジエニル）エチルジルコニウムモノクロリド、ビス（シクロペンタジエニル）シクロヘキシルジルコニウムモノクロリド、ビス（シクロペンタジエニル）フェニルジルコニウムモノクロリド、ビス（シクロペンタジエニル）ベンジルジルコニウムモノクロリド、ビス（シクロペンタジエニル）ジルコニウムモノクロリドモノハイドライド、ビス（シクロペンタジエニル）メチルジルコニウムモノハイドライド、ビス（シクロペンタジエニル）ジメチルジルコニウム、ビス（シクロペンタジエニル）ジフェニルジルコニウム、ビス（シクロペンタジエニル）ジベンジルジルコニウム、ビス（シクロペンタジエニル）ジルコニウムメトキシクロリド、ビス（シクロペンタジエニル）ジルコニウムエトキシクロリド、ビス（シクロペンタジエニル）ジルコニウムビス（メタンスルホナト）、ビス（シクロペンタジエニル）ジルコニウムビス（ｐ−トルエンスルホナト）、ビス（シクロペンタジエニル）ジルコニウムビス（トリフルオロメタンスルホナト）、ビス（メチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（ジメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（ジメチルシクロペンタジエニル）ジルコニウムエトキシクロリド、ビス（ジメチルシクロペンタジエニル）ジルコニウムビス（トリフルオロメタンスルホナト）、ビス（エチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（１,３−エチルメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（プロピルシクロペンタジエニル）ジルコニウムジクロリド、ビス（１,３−メチルプロピルシクロペンタジエニル）ジルコニウムジクロリド、ビス（ブチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（１,３−ブチルメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（１,３−ブチルメチルシクロペンタジエニル）ジルコニウムビス（メタンスルホナト）、ビス（トリメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（テトラメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（ペンタメチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（ヘキシルシクロペンタジエニル）ジルコニウムジクロリド、ビス（トリメチルシリルシクロペンタジエニル）ジルコニウムジクロリド； Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromid, bis (cyclopentadienyl) methylzirconium monoclonal, bis (cyclopentadienyl) ethylzirconium monolide, bis (cyclopentadienyl) Enyl) cyclohexylzirconium monolide, bis (cyclopentadienyl) phenylzirconium monolide, bis (cyclopentadienyl) benzylzirconium monolide, bis (cyclopentadienyl) zirconium monohydride, bis (cyclopentadienyl) ) Methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis ( Cyclopentadienyl) zirconium ethoxychloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (Trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (dimethylcyclopentadienyl) zirconium Bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (1,3-ethylmethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (1,, 3-Methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadienyl) zirconium dichloride, bis (1,3-butylmethylcyclopentadi) Enyl) Zirconium Bis (methanesulfonato), Bis (trimethylcyclopentadienyl) Zirconium dichloride, Bis (Tetramethylcyclopentadienyl) Zirconium dichloride, Bis (Pentamethylcyclopentadienyl) Zirconium dichloride, Bis (Hexylcyclopen) Tadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride;
ジメチルシリレンビス（シクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレンビス（２-メチルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレンビス（３-メチルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレンビス（３-ｎ-ブチルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（３−エチルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（３−ｎ−プロピルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（３−ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（３−ｎ−オクチルシクロペンタジエニル）ジルコニウムジクロリド、ジブチルシリレン（シクロペンタジエニル）（３−ｎ−プロピルシクロペンタジエニル）ジルコニウムジクロリド、トリフルオロメチルブチルシリレン（シクロペンタジエニル）（３−ｎ−プロピルシクロペンタジエニル）ジルコニウムジクロリド、トリフルオロメチルブチルシリレン（シクロペンタジエニル）（３−ｎ−ブチルシクロペンタジエニル）ジルコニウムジクロリド、トリフルオロメチルブチルシリレン（シクロペンタジエニル）（３−ｎ−オクチルシクロペンタジエニル）ジルコニウムジクロリド、（ブチルアミド）（テトラメチル−η５−シクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロリド、（メチルアミド）（テトラメチル−η５−シクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロリド； Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (3-n- Butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-ethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride , Dimethylsilylene (cyclopentadienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, dibutylsilylene (cyclopenta) Dienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-propylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopenta) Dienyl) (3-n-butylcyclopentadienyl) zirconium dichloride, trifluoromethylbutylsilylene (cyclopentadienyl) (3-n-octylcyclopentadienyl) zirconium dichloride, (butylamide) (tetramethyl-η5) -Cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl zirconium dichloride;
イソプロピリデン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、イソプロピリデン（シクロペンタジエニル）（２,７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド、イソプロピリデン（シクロペンタジエニル）（３,６−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、イソプロピリデン（シクロペンタジエニル）（オクタメチルオクタヒドリドジベンズフルオレニル）ジルコニウムジクロリド、ジブチルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、ジブチルメチレン（シクロペンタジエニル）（２,７−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、ジブチルメチレン（シクロペンタジエニル）（３,６−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、ジブチルメチレン（シクロペンタジエニル）（オクタメチルオクタヒドリドジベンズフルオレニル）ジルコニウムジクロリド、シクロヘキシリデン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、シクロヘキシリデン（シクロペンタジエニル）（２,７−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、シクロヘキシリデン（シクロペンタジエニル）（３,６−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、シクロヘキシリデン（シクロペンタジエニル）（オクタメチルオクタヒドリドジベンズフルオレニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（２,７−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリド、ジメチルシリレン（シクロペンタジエニル）（３,６−ジ−ｔ−ブチルフルオレニル）ジルコニウムジクロリドおよびジメチルシリレン（シクロペンタジエニル）（オクタメチルオクタヒドリドジベンズフルオレニル）ジルコニウムジクロリド、ジーp−トリルメチレン（シクロペンタジエニル）（オクタメチルオクタヒドリドジベンズフルオレニル）ジルコニウムジクロリド； Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3) , 6-di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (octamethyloctahidlide dibenzfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride , Dibutylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, dibutylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride , Dibutylmethylene (cyclopentadienyl) (octamethyloctahydride dibenzfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2, 7-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ( Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium Dichloride, dimethylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride and dimethylsilylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, gee p-Tolylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride;
エチレンビス（インデニル）ジルコニウムジクロリド、エチレンビス（インデニル）ジメチルジルコニウム、エチレンビス（４,５,６,７−テトラヒドロ−１−インデニル）ジルコニウムジクロリド、エチレンビス（２−メチル−１−インデニル）ジルコニウムジクロリド、エチレンビス（４−メチル−１−インデニル）ジルコニウムジクロリド、エチレンビス（５−メチル−１−インデニル）ジルコニウムジクロリド、エチレンビス（２,４−ジメチル−１−インデニル）ジルコニウムジクロリド、エチレンビス（５−メトキシ−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２−メチル−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２,４−ジメチル−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２−メチル−４−シクロヘキシル−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２−メチル−４−フェニル−１−インデニル）ジルコニウムジクロリド、ジフェニルシリレンビス（２−メチル−４−フェニル−１−インデニル）ジルコニウムジクロリド、ジ（ｐ−トリル）シリレンビス（２−メチル−４−フェニル−１−インデニル）ジルコニウムジクロリド、ジ（ｐ−クロロフェニル）シリレンビス（２−メチル−４−フェニル−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２−メチル−４,５−ベンゾ−１−インデニル）ジルコニウムジクロリド、ジメチルシリレンビス（２−メチル−４,５−アセナフトシクロペンタジエニル）ジルコニウムジクロリド、ジメチルシリレン（２−メチル−４,５−ベンゾ−１−インデニル）（２,７−ジ−ｔ−ブチル−９−フルオレニル）ジルコニウムジクロリド。 Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, Ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy) -1-Indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethyl-1-indenyl) zirconium dichloride, dimethyl Sirilenbis (2-methyl-4-cyclohexyl-1-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, diphenylsilylenebis (2-methyl-4-phenyl-1) -Indenyl) zirconium dichloride, di (p-tolyl) silylenebis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, di (p-chlorophenyl) silylenebis (2-methyl-4-phenyl-1-indenyl) zirconium Dichloride, dimethylsilylenebis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5-acenaftcyclopentadienyl) zirconium dichloride, dimethylsilylene (2- Methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride.
上記例示において、シクロペンタジエニル環の二置換体は１,２−および１,３−置換体を含み、三置換体は１,２,３−および１,２,４−置換体を含み、プロピル、ブチル等のアルキル基は、ｎ−、ｉ−、ｓｅｃ−、ｔｅｒｔ−等の異性体を含む。またジルコニウムをチタンまたはハフニウムに置き換えた遷移金属化合物を用いることもできる。 In the above example, the di-substituted cyclopentadienyl ring comprises 1,2- and 1,3-substituted, and the tri-substituted contains 1,2,3- and 1,2,4-substituted. Alkyl groups such as propyl and butyl contain isomers such as n-, i-, sec- and tert-. A transition metal compound in which zirconium is replaced with titanium or hafnium can also be used.
シクロペンタジエニル骨格以外の配位子を有する成分（ｘ−１）としては、特開平１１−３１５１０９号公報、Ｃｈｅｍ. Ｒｅｖ. ２００３, １０３, ２８３−３１５等に例示されている遷移金属化合物を用いることもできる。 Examples of the component (x-1) having a ligand other than the cyclopentadienyl skeleton include transition metal compounds exemplified in JP-A-11-315109, Chem. Rev. 2003, 103, 283-315 and the like. It can also be used.
以上の各遷移金属化合物は、１種単独または２種以上を組み合わせて用いられる。 Each of the above transition metal compounds is used alone or in combination of two or more.
（成分（ｘ−２））
成分（ｘ−２）は、有機アルミニウムオキシ化合物であり、トリアルキルアルミニウムまたはトリシクロアルキルアルミニウムから調製された有機アルミニウムオキシ化合物が好ましく、トリメチルアルミニウムまたはトリイソブチルアルミニウムから調製されたアルミノキサンが特に好ましい。アルミノキサンは少量の有機金属成分を含有しても良い。
(Component (x-2))
The component (x-2) is an organoaluminum oxy compound, preferably an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum, and particularly preferably aluminoxane prepared from trimethylaluminum or triisobutylaluminum. Alminoxane may contain a small amount of an organometallic component.
これら有機アルミニウムオキシ化合物は、１種単独または２種以上を組み合わせて用いられる。 These organoaluminum oxy compounds may be used alone or in combination of two or more.
（成分（ｘ−３））
成分（ｘ−３）は、粒子状担体であり、具体的には、ＳｉＯ2、Ａｌ2Ｏ3、ＭｇＯ、ＺｒＯ2、ＴｉＯ2、Ｂ2Ｏ3、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ2等、もしくはこれらを含む混合物、例えばＳｉＯ2−ＭｇＯ、ＳｉＯ2−Ａｌ2Ｏ3、ＳｉＯ2−ＴｉＯ2、ＳｉＯ2−Ｖ2Ｏ5、ＳｉＯ2−Ｃｒ2Ｏ3、ＳｉＯ2−ＴｉＯ2−ＭｇＯ等の無機酸化物、またはポリエチレン、ポリプロピレン、ポリ１−ブテン、ポリ４−メチル−１−ペンテン、スチレン−ジビニルベンゼン共重合体等の高分子化合物を挙げることができる。
(Component (x-3))
The component (x-3) is a particulate carrier, specifically, SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO, ThO 2, etc. Alternatively, a mixture containing these, for example, SiO 2- MgO, SiO 2- Al 2 O 3 , SiO 2- TiO 2 , SiO 2- V 2 O 5 , SiO 2- Cr 2 O 3 , SiO 2- TiO 2- MgO, etc. Inorganic oxides of the above, or polymer compounds such as polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, and styrene-divinylbenzene copolymers can be mentioned.
また、特開平１１−１４０１１３号公報、特開２０００−３８４１０号公報、特開２０００−９５８１０号公報、国際公開第２０１０／５５６５２号等に記載された方法で、上記成分（ｘ−２）を不溶化させて得られる固体成分を成分（ｘ−３）として用いることもできる。この場合、成分（ｘ−２）は必須ではない。 Further, the above component (x-2) is insolubilized by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication No. 2010/55652, and the like. The solid component thus obtained can also be used as the component (x-3). In this case, the component (x-2) is not essential.
成分（ｘ−３）の性状は何ら限定されるものではないが、その平均粒径は１μｍ以上３００μｍ以下が好ましく、１０μｍ以上２００μｍ以下がより好ましい。 The properties of the component (x-3) are not limited in any way, but the average particle size thereof is preferably 1 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.
成分（ｘ−３）として無機酸化物を用いる場合、その細孔容積は０.３ｃｍ３/ｇ以上３０ｃｍ３/ｇ以下が好ましい。細孔容積が上記範囲より小さい場合は、得られる重合体をフィルム成形した場合にフィッシュアイ等の外観不良を生じる場合があり、上記範囲より大きい場合は、破砕が起きやすく固体触媒ならびに重合体の性状を悪化させる場合がある。このような無機酸化物は、必要に応じて１００〜１０００℃、好ましくは１５０〜７００℃で焼成して用いられる。 When an inorganic oxide is used as the component (x-3), its pore volume is preferably 0.3 cm 3 / g or more and 30 cm 3 / g or less. If the pore volume is smaller than the above range, poor appearance such as fish eyes may occur when the obtained polymer is film-molded, and if it is larger than the above range, crushing is likely to occur and the solid catalyst and the polymer are easily crushed. May worsen properties. Such an inorganic oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
（成分（ｘ−４））
固体触媒成分（Ｘ）は、以上説明した成分（ｘ−１）〜（ｘ−３）以外の成分、例えば以下に説明する成分（ｘ−４）を必要に応じて含んでいても良い。成分（ｘ−４）は、下記一般式（ＩＶ）で表される有機アルミニウム化合物である。
(Component (x-4))
The solid catalyst component (X) may contain a component other than the components (x-1) to (x-3) described above, for example, a component (x-4) described below, if necessary. The component (x-4) is an organoaluminum compound represented by the following general formula (IV).
ＲａmＡｌ（ＯＲｂ)nＨpＲｃq・・・（ＩＶ）
（一般式（ＩＶ）中、ＲａおよびＲｂは、それぞれ独立に、炭素原子数が１以上１５以下の炭化水素基を示し、互いに同一でも異なっていてもよく、Ｈは水素原子を示し、Ｒｃはハロゲン原子を示し、ｍは０＜ｍ≦３、ｎは０≦ｎ＜３、ｐは０≦ｐ＜３、ｑは０≦ｑ＜３の整数であり、かつｍ＋ｎ＋ｐ＋ｑ＝３である。）
RamAl (ORb) nHpRcq ... (IV)
(In the general formula (IV), Ra and Rb each independently represent a hydrocarbon group having 1 or more and 15 or less carbon atoms, which may be the same or different from each other, H represents a hydrogen atom, and Rc represents a hydrogen atom. Indicates a halogen atom, m is an integer of 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is an integer of 0 ≦ q <3, and m + n + p + q = 3).
一般式（ＩＶ）で示される有機アルミニウム化合物としては、下記の化合物を例示することができる。 Examples of the organoaluminum compound represented by the general formula (IV) include the following compounds.
トリメチルアルミニウム、トリエチルアルミニウム、トリイソプロピルアルミニウム、トリイソブチルアルミニウム、トリヘキシルアルミニウム、トリオクチルアルミニウム、トリ２-エチルヘキシルアルミニウム等のトリアルキルアルミニウム；ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジイソプロピルアルミニウムクロリド、ジイソブチルアルミニウムクロリド、ジメチルアルミニウムブロミド等のジアルキルアルミニウムハライド；メチルアルミニウムセスキクロリド、エチルアルミニウムセスキクロリド、イソプロピルアルミニウムセスキクロリド、ブチルアルミニウムセスキクロリド、エチルアルミニウムセスキブロミド等のアルキルアルミニウムセスキハライド；メチルアルミニウムジクロリド、エチルアルミニウムジクロリド、イソプロピルアルミニウムジクロリド、エチルアルミニウムジブロミド等のアルキルアルミニウムジハライド；ジメチルアルミニウムハイドライド、ジエチルアルミニウムハイドライド、ジヒドロフェニルアルミニウムハイドライド、ジイソプロピルアルミニウムハイドライド、ジ-ｎ-ブチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド、ジイソヘキシルアルミニウムハイドライド、ジフェニルアルミニウムハイドライド、ジシクロヘキシルアルミニウムハイドライド、ジ-ｓｅｃ-ヘプチルアルミニウムハイドライド、ジ-ｓｅｃ-ノニルアルミニウムハイドライド等のアルキルアルミニウムハイドライド；ジメチルアルミニウムエトキサイド、ジエチルアルミニウムエトキサイド、ジイソプロピルアルミニウムメトキサイド、ジイソブチルアルミニウムエトキサイド、等のジアルキルアルミニウムアルコキサイド等が挙げられる。 Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethyl Dialkylaluminum halides such as aluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibramide; methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride Alkylaluminum dihalide such as ethylaluminum dibromid; dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexyl aluminum hydride, diphenylaluminum hydride. Alkylaluminum hydrides such as dicyclohexylaluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonylaluminum hydride; dialkylaluminum such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, diisobutylaluminum ethoxide, etc. Alcoxide etc. can be mentioned.
このような有機アルミニウム化合物は、１種単独または２種以上を組み合わせて用いられる。 Such organoaluminum compounds may be used alone or in combination of two or more.
［固体触媒成分（Ｘ）の調製］
固体触媒成分（Ｘ）は、例えば、上記成分（ｘ−１）、成分（ｘ−２）、成分（ｘ−３）を混合接触させることにより調製することができる。各成分の接触順序は任意に選ばれるが、成分（ｘ−２）と成分（ｘ−３）を混合接触させた後に、成分（ｘ−１）と混合接触させることが好ましい。
[Preparation of solid catalyst component (X)]
The solid catalyst component (X) can be prepared, for example, by mixing and contacting the above-mentioned component (x-1), component (x-2), and component (x-3). The contact order of each component is arbitrarily selected, but it is preferable that the component (x-2) and the component (x-3) are mixed and contacted, and then the component (x-1) is mixed and contacted.
固体触媒成分（Ｘ）の調製に用いられる溶媒としては、例えば、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環族炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；エチレンクロリド、クロルベンゼン、ジクロロメタン等のハロゲン化炭化水素あるいはこれらの混合物等を挙げることができる。 Examples of the solvent used for preparing the solid catalyst component (X) include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.
固体触媒成分（Ｘ）の調製に際して、成分（ｘ−１）は、遷移金属原子換算で、成分（x−３）１ｇ当たり、通常０.００１ｍｍｏｌ以上１.０ｍｍｏｌ以下、好ましくは０.００５ｍｍｏｌ以上０.５ｍｍｏｌ以下の量で用いられ、成分（x−２）は、アルミニウム原子換算で、通常０.１ｍｍｏｌ以上１００ｍｍｏｌ以下、好ましくは０.５ｍｍｏｌ以上２０ｍｍｏｌ以下の量で用いられる。 In the preparation of the solid catalyst component (X), the component (x-1) is usually 0.001 mmol or more and 1.0 mmol or less, preferably 0.005 mmol or more and 0, per 1 g of the component (x-3) in terms of transition metal atoms. It is used in an amount of .5 mmol or less, and the component (x-2) is usually used in an amount of 0.1 mmol or more and 100 mmol or less, preferably 0.5 mmol or more and 20 mmol or less in terms of aluminum atoms.
また必要に応じて成分（ｘ−４）を、アルミニウム原子換算で、成分（ｘ−３）１ｇ当り、通常０.００１ｍｍｏｌ以上１０００ｍｍｏｌ以下、好ましくは２ｍｍｏｌ以上５００ｍｍｏｌ以下の量で用いることができる。 Further, if necessary, the component (x-4) can be used in an amount of usually 0.001 mmol or more and 1000 mmol or less, preferably 2 mmol or more and 500 mmol or less per 1 g of the component (x-3) in terms of aluminum atom.
上記各成分を混合接触させる際の温度は、通常−５０℃以上１５０℃以下、好ましくは−２０℃以上１２０℃以下であり、接触時間は１分以上１０００分以下、好ましくは５分以上６００分以下である。 The temperature at which each of the above components is mixed and contacted is usually −50 ° C. or higher and 150 ° C. or lower, preferably −20 ° C. or higher and 120 ° C. or lower, and the contact time is 1 minute or longer and 1000 minutes or lower, preferably 5 minutes or longer and 600 minutes or lower. It is as follows.
［予備重合触媒成分（ＸＰ）の調製］
本発明では、上記固体触媒成分（Ｘ）をそのまま用いても良いし、固体触媒成分（Ｘ）にオレフィンを予備重合させ、予備重合触媒成分（ＸＰ）を形成してから用いても良い。
[Preparation of prepolymerization catalyst component (XP)]
In the present invention, the solid catalyst component (X) may be used as it is, or the solid catalyst component (X) may be prepolymerized with an olefin to form a prepolymerization catalyst component (XP) before use.
予備重合に用いられるオレフィンとしては、例えば、エチレンおよび炭素原子数が３以上８以下のα−オレフィンが挙げられる。炭素原子数が３以上８以下のα−オレフィンとしては、プロピレン、１−ヘキセン、３−メチル−１−ブテン、４−メチル−１−ペンテンが好ましい。これらのオレフィンは二種以上を用いて共重合させても良く、また一種以上のオレフィンで予備重合した後に、他のオレフィンを用いてさらに予備重合しても良い。 Examples of the olefin used for the prepolymerization include ethylene and α-olefin having 3 or more and 8 or less carbon atoms. As the α-olefin having 3 or more and 8 or less carbon atoms, propylene, 1-hexene, 3-methyl-1-butene, and 4-methyl-1-pentene are preferable. These olefins may be copolymerized using two or more kinds, or may be prepolymerized with one or more kinds of olefins and then further prepolymerized with other olefins.
予備重合量は、固体触媒成分（Ｘ）１ｇ当たり０.３ｇ以上２００ｇ以下であることが好ましい。予備重合を行う際の温度は、通常−２０℃以上８０℃以下、好ましくは０℃以上６０℃以下であり、予備重合時間は、通常０.５時間以上１００時間以下、好ましくは１時間以上５０時間以下である。 The amount of prepolymerization is preferably 0.3 g or more and 200 g or less per 1 g of the solid catalyst component (X). The temperature at which the prepolymerization is carried out is usually −20 ° C. or higher and 80 ° C. or lower, preferably 0 ° C. or higher and 60 ° C. or lower, and the prepolymerization time is usually 0.5 hours or longer and 100 hours or lower, preferably 1 hour or longer and 50. It's less than an hour.
予備重合の相状態には特に制限は無いが、液相重合が好ましく採用される。液相重合時の好ましい溶媒としては、固体触媒成分（Ｘ）の調製に用いられる溶媒と同様のものが挙げられる。またα−オレフィン自身を溶媒として用いても良く、これらの混合物を用いても良い。 The phase state of the prepolymerization is not particularly limited, but liquid phase polymerization is preferably adopted. As a preferable solvent at the time of liquid phase polymerization, the same solvent as that used for preparing the solid catalyst component (X) can be mentioned. Further, the α-olefin itself may be used as a solvent, or a mixture thereof may be used.
予備重合の際には、必要に応じて成分（ｘ−４）を、アルミニウム原子換算で、固体触媒成分（Ｘ）１ｇ当たり、通常０.０１ｍｍｏｌ以上１００ｍｍｏｌ以下、好ましくは０.１ｍｍｏｌ以上５０ｍｍｏｌ以下の量で用いることができる。 At the time of prepolymerization, if necessary, the component (x-4) is usually 0.01 mmol or more and 100 mmol or less, preferably 0.1 mmol or more and 50 mmol or less per 1 g of the solid catalyst component (X) in terms of aluminum atoms. Can be used in quantity.
液相中で調製した予備重合触媒成分（ＸＰ）は、懸濁液のまま重合反応器に導入しても良いし、乾燥等により溶媒を除去した後に固体粉末状態で重合反応器に導入しても良い。 The prepolymerization catalyst component (XP) prepared in the liquid phase may be introduced into the polymerization reactor as a suspension, or may be introduced into the polymerization reactor in a solid powder state after removing the solvent by drying or the like. Is also good.
なお本発明で用いられる固体触媒成分（Ｘ）および予備重合触媒成分（ＸＰ）は、上記各成分以外にも重合反応に有用な他の成分を含むことができる。 The solid catalyst component (X) and the prepolymerization catalyst component (XP) used in the present invention may contain other components useful for the polymerization reaction in addition to the above-mentioned components.
以下の実施例により本発明をさらに具体的に説明する。なお本発明は、以下の実施例の記載に限定されるものではない。 The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the description of the following examples.
＜（１）重合体粉体の調製＞
〔調製例１〕固体触媒成分（Ｘ−１）の調製
特開２０００−３２７７０７号公報に開示された方法で合成した。具体的には、２５０℃で１０時間乾燥した平均粒径７０μｍ、細孔容積１.３ｃｍ３／ｇのシリカゲル（成分（ｘ−３）１０ｋｇを、１５４Ｌのトルエンに懸濁した後、０℃まで冷却した。その後、この懸濁液に、メチルアミノキサン（成分（ｘ−２））のトルエン溶液（Ａｌ＝１.５２ｍｏｌ／Ｌ）５０.５Ｌを１時間かけて滴下した。この際、系内の温度を０〜５℃の範囲に保った。引続き０℃で３０分間反応させ、次いで１.５時間かけて９５℃まで昇温し、その温度で４時間反応させた。その後６０℃まで降温し、上澄み液をデカンテーション法により除去した。このようにして得られた固体成分をトルエンで２回洗浄した後、トルエン１００Ｌで再懸濁し、全量を１６０Ｌとした。
<(1) Preparation of polymer powder>
[Preparation Example 1] Preparation of solid catalyst component (X-1) The solid catalyst component (X-1) was synthesized by the method disclosed in JP-A-2000-327707. Specifically, silica gel having an average particle size of 70 μm and a pore volume of 1.3 cm 3 / g dried at 250 ° C. for 10 hours (10 kg of component (x-3) was suspended in 154 L of toluene and then up to 0 ° C. After cooling, 50.5 L of a toluene solution (Al = 1.52 mol / L) of methylaminoxane (component (x-2)) was added dropwise to this suspension over 1 hour. At this time, the inside of the system was added. The temperature was kept in the range of 0 to 5 ° C., followed by reaction at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C. The supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended with 100 L of toluene to bring the total volume to 160 L.
このようにして得られた懸濁液に、ビス（１,３−ｎ−ブチルメチルシクロペンタジエニル）ジルコニウムジクロリド（成分（ｘ−１））のトルエン溶液（Ｚｒ＝２５.７ｍｍｏｌ／Ｌ）２２.０Ｌを８０℃で３０分間かけて滴下し、さらに８０℃で２時間反応させた。その後、上澄み液を除去し、ヘキサンで２回洗浄することにより固体触媒成分（Ｘ−１）を得た。 Toluene solution (Zr = 25.7 mmol / L) of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (component (x-1)) was added to the suspension thus obtained 22. .0 L was added dropwise at 80 ° C. over 30 minutes and further reacted at 80 ° C. for 2 hours. Then, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (X-1).
〔調製例２〕重合体粉体の調製
充分に窒素置換した内容積１Ｌのステンレス製オートクレーブにｎ−ヘプタン５００ｍＬを装入し、系内をエチレンで置換した後、１−へキセン２０ｍＬ、調製例２の固体触媒成分（Ｘ−１）１３０ｍｇ（固体質量）を投入し、系内の温度を８０℃に昇温した。次いで、エチレンを導入することにより重合を開始した。その後、連続的にエチレンを供給しながら圧力を０.７８ＭＰａに保ち、９０分間重合を行った。重合終了後、脱圧し、重合体をろ過し、８０℃で１０時間真空乾燥し、エチレン系重合体の重合体粉体２０３ｇを得た。得られた重合体のメルトフローレート（ＭＦＲ）は０.２０ｇ／１０ｍｉｎ、真密度は９２７ｇ／Ｌ、嵩密度は４００ｇ／Ｌであった。これら物性の測定方法は以下のとおりである。
[Preparation Example 2] Preparation of Polymer Powder After charging 500 mL of n-heptane into a fully nitrogen-substituted stainless steel autoclave with an internal volume of 1 L and replacing the inside of the system with ethylene, 20 mL of 1-hexene, Preparation Example 130 mg (solid mass) of the solid catalyst component (X-1) of No. 2 was added, and the temperature in the system was raised to 80 ° C. Then, the polymerization was started by introducing ethylene. Then, while continuously supplying ethylene, the pressure was maintained at 0.78 MPa, and polymerization was carried out for 90 minutes. After completion of the polymerization, the polymer was decompressed, the polymer was filtered, and vacuum dried at 80 ° C. for 10 hours to obtain 203 g of a polymer powder of an ethylene-based polymer. The melt flow rate (MFR) of the obtained polymer was 0.20 g / 10 min, the true density was 927 g / L, and the bulk density was 400 g / L. The methods for measuring these physical properties are as follows.
メルトフローレート（ＭＦＲ）：ＡＳＴＭ Ｄ１２３８−８９に従い、１９０℃、２.１６ｋｇ加重の条件下で測定した。 Melt flow rate (MFR): Measured according to ASTM D1238-89 under conditions of 190 ° C. and 2.16 kg weighting.
真密度：ＪＩＳ Ｋ７１１２に従い、ＭＦＲ測定時に得られるストランドを１００℃で１時間熱処理し、更に室温で１時間放置し、密度勾配配管法で測定した。 True density: According to JIS K7112, the strands obtained at the time of MFR measurement were heat-treated at 100 ° C. for 1 hour, left at room temperature for 1 hour, and measured by a density gradient piping method.
嵩密度：ＡＳＴＭ Ｄ１８９５−９６ Ａ法に従い測定した。 Bulk density: Measured according to ASTM D1895-96 A method.
＜（２）重合体粉体を用いた流動性評価＞
〔比較例１〕
充分に窒素置換した内容積２００ｍＬの攪拌機付きステンレス製反応器に、調製例２の重合体粉体１０.０ｇを装入し、８０℃のオイルバスで加熱しながら１５０ｒｐｍで重合体粉体を３０分撹拌した。その後、撹拌を止め、反応器を傾けて重合体粉体を回収し、質量を測定したところ７.７ｇであった。反応器内部の状況を確認すると、回収されなかった重合体粉体が反応器壁や撹拌羽根に静電付着していた。
<(2) Evaluation of fluidity using polymer powder>
[Comparative Example 1]
10.0 g of the polymer powder of Preparation Example 2 was charged into a stainless steel reactor with a stirrer having an internal volume of 200 mL sufficiently nitrogen-substituted, and the polymer powder was mixed at 150 rpm while heating in an oil bath at 80 ° C. Stir for minutes. After that, the stirring was stopped, the reactor was tilted to recover the polymer powder, and the mass was measured and found to be 7.7 g. When the condition inside the reactor was confirmed, the unrecovered polymer powder was electrostatically adhered to the reactor wall and the stirring blade.
〔実施例１〕
充分に窒素置換した内容積２００ｍＬの攪拌機付きステンレス製反応器に、調製例２の重合体粉体１０.０ｇを装入し、８０℃のオイルバスで加熱しながら１５０ｒｐｍで重合体粉体の撹拌を開始した。１分後に、固体成分（Ａ）として、アルミノケイ酸塩（Ａ−１）であるシルトン(登録商標)ＪＣ−５０（平均粒径＝４μｍ、水澤化学工業社製）のヘキサン懸濁液（１０ｇ／Ｌ）を０.１０ｍＬ（重合体粉体に対する固体成分（Ａ）の添加量の質量比＝１００ｐｐｍ）を添加し、さらに８０℃で３０分撹拌した。その後、撹拌を止め、反応器を傾けて重合体粉体を回収し質量を測定したところ９.９ｇであった。反応器内部の状況を確認すると、重合体粉体の反応器壁や撹拌羽根への付着はほぼ認められなかった。
[Example 1]
1.0 g of the polymer powder of Preparation Example 2 was charged into a stainless steel reactor with an internal volume of 200 mL sufficiently nitrogen-substituted, and the polymer powder was stirred at 150 rpm while heating in an oil bath at 80 ° C. Started. After 1 minute, a hexane suspension (10 g / 10 g /) of silton (registered trademark) JC-50 (average particle size = 4 μm, manufactured by Mizusawa Industrial Chemicals Co., Ltd.), which is an aluminosilicate (A-1), as a solid component (A). 0.10 mL of L) (mass ratio of the amount of the solid component (A) added to the polymer powder = 100 ppm) was added, and the mixture was further stirred at 80 ° C. for 30 minutes. After that, the stirring was stopped, the reactor was tilted to recover the polymer powder, and the mass was measured and found to be 9.9 g. When the condition inside the reactor was confirmed, almost no adhesion of the polymer powder to the reactor wall or the stirring blade was observed.
〔実施例２〜８〕
固体成分（Ａ）の種類および添加量の質量比を表１に記載のとおり変更した以外は、実施例１と同様の条件で重合体粉体を撹拌し、撹拌後に回収した重合体粉体の質量を測定した。結果を表１に示す。反応器内部の状況を確認すると、いずれも重合体粉体の反応器壁や撹拌羽根への付着はほぼ認められなかった。
[Examples 2 to 8]
The polymer powder was stirred under the same conditions as in Example 1 except that the type of the solid component (A) and the mass ratio of the added amount were changed as shown in Table 1, and the polymer powder recovered after stirring was used. The mass was measured. The results are shown in Table 1. When the condition inside the reactor was confirmed, almost no adhesion of the polymer powder to the reactor wall or the stirring blade was observed.
〔比較例２〜５〕
固体成分（Ａ）の種類および添加量の質量比を表１に記載のとおり変更した以外は、実施例１と同様の条件で重合体粉体を撹拌し、撹拌後に回収した重合体粉体の質量を測定した。結果を表１に示す。比較例２〜５では、いずれも実施例１〜８に比べ回収した重合体粉体が少なかった。反応器内部の状況を確認すると、いずれも重合体粉体が反応器壁や撹拌羽根に静電付着していることが認められた。
[Comparative Examples 2 to 5]
The polymer powder was stirred under the same conditions as in Example 1 except that the type of the solid component (A) and the mass ratio of the added amount were changed as shown in Table 1, and the polymer powder recovered after stirring was used. The mass was measured. The results are shown in Table 1. In Comparative Examples 2 to 5, the amount of polymer powder recovered was smaller than that in Examples 1 to 8. When the condition inside the reactor was confirmed, it was confirmed that the polymer powder was electrostatically adhered to the reactor wall and the stirring blade.
（Ａ−１）：アルミノケイ酸塩（シルトン(登録商標)ＪＣ−５０、平均粒径＝４μｍ、化学組成＝ｐＣａＯ・ｑＮａ２Ｏ（ｐ＋ｑ＝１）・Ａｌ２Ｏ３・３．０〜３．９ＳｉＯ２・ｍＨ２Ｏ、水澤化学工業社製）
（Ａ−２ａ）：ハイドロタルサイト類（ＤＨＴ(登録商標)−４Ａ、平均粒径＝０.５μｍ、化学組成＝［Ｍｇ２＋ ０．６８Ａｌ３＋ ０．３２（ＯＨ）２］［ＣＯ３ ２− ０．１６・ｍＨ２Ｏ］、ステアリン酸表面処理、協和化学工業社製）
（Ａ−２ｂ）：ハイドロタルサイト類（ＤＨＴ(登録商標)−４Ｃ、平均粒径＝０.４μｍ、化学組成＝［Ｍｇ２＋ ０．６８Ａｌ３＋ ０．３２（ＯＨ）２］［ＣＯ３ ２− ０．１６・ｍＨ２Ｏ］、協和化学工業社製）
（Ａ−３）：アクリルパウダー（アートパール(登録商標)Ｊ５Ｐ、平均粒径＝３μｍ、主成分＝架橋ポリメタクリル酸メチル、根上工業社製）
（Ａ−４）：シリカゲル（サイリシア(登録商標)５３０、平均粒径＝３μｍ、富士シリシア化学社製）
（Ａ−５）：疎水化処理シリカ（サイロホービック(登録商標)５０５、平均粒径＝４μｍ、富士シリシア化学社製）
(A-1): aluminosilicate (Silton (TM) JC-50, average particle diameter = 4 [mu] m, the chemical composition = pCaO · qNa 2 O (p + q = 1) · Al 2 O 3 · 3.0~3. 9SiO 2・ mH 2 O, manufactured by Mizusawa Industrial Chemicals Co., Ltd.)
(A-2a): Hydrotalcites (DHT®-4A, average particle size = 0.5 μm, chemical composition = [Mg 2 + 0.68 Al 3+ 0.32 (OH) 2 ] [CO 3 2] − 0.16・ mH 2 O], stearic acid surface treatment, manufactured by Kyowa Chemical Industry Co., Ltd.)
(A-2b): hydrotalcite (DHT (registered trademark) -4C, average particle size = 0.4 .mu.m, chemical composition = [Mg 2+ 0.68 Al 3+ 0.32 (OH) 2] [CO 3 2 − 0.16・ mH 2 O], manufactured by Kyowa Chemical Industry Co., Ltd.)
(A-3): Acrylic powder (Art Pearl (registered trademark) J5P, average particle size = 3 μm, main component = crosslinked polymethyl methacrylate, manufactured by Negami Kogyo Co., Ltd.)
(A-4): Silica gel (Syricia (registered trademark) 530, average particle size = 3 μm, manufactured by Fuji Silysia Chemical Ltd.)
(A-5): Hydrophobicized silica (Silohobic (registered trademark) 505, average particle size = 4 μm, manufactured by Fuji Silysia Chemical Ltd.)
＜（３）気相流動床重合装置を用いた重合安定性評価＞
〔調製例３〕予備重合触媒成分（ＸＰ−１）の調製
特開２０００−３２７７０７号公報に開示された方法で合成した。具体的には、充分に窒素置換した内容積３５０Ｌの反応器に、調製例１の固体触媒成分（Ｘ−１）を固体分として７.０ｋｇとヘキサンを装入し、全容積を２８５Ｌにした。系内を１０℃まで冷却した後、エチレンを８Ｎｍ３／ｈの流量で５分間ヘキサン中に吹き込んだ。この間、系内の温度は、１０〜１５℃に保持した。その後、エチレンの供給を停止し、トリイソブチルアルミニウムを２.４ｍｏｌおよび１−ヘキセンを１.２ｋｇ装入した。系内を密閉系にした後、８Ｎｍ３／ｈの流量でエチレンの供給を再度開始した。１５分後、エチレンの流量を２Ｎｍ３／ｈに下げ、系内の圧力を０.０８ＭＰａにした。この間に、系内の温度は３５℃まで上昇した。その後、系内の温度を３２〜３５℃に調節しながら、エチレンを４Ｎｍ３／ｈの流量で３.５時間供給した。この間、系内の圧力は０.０７〜０.０８ＭＰａに保持されていた。次いで、系内を窒素により置換を行った後、上澄み液を除去しヘキサンで４回洗浄した。
<(3) Evaluation of polymerization stability using a gas phase fluidized bed polymerization apparatus>
[Preparation Example 3] Preparation of Prepolymerization Catalyst Component (XP-1) Synthesis was performed by the method disclosed in JP-A-2000-327707. Specifically, 7.0 kg of the solid catalyst component (X-1) of Preparation Example 1 as a solid component and hexane were charged into a reactor having an internal volume of 350 L sufficiently substituted with nitrogen to bring the total volume to 285 L. .. After cooling the inside of the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm 3 / h for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. Then, the supply of ethylene was stopped, and 2.4 mol of triisobutylaluminum and 1.2 kg of 1-hexene were charged. After closing the system, the supply of ethylene was restarted at a flow rate of 8 Nm 3 / h. After 15 minutes, the ethylene flow rate was reduced to 2 Nm 3 / h and the pressure in the system was 0.08 MPa. During this time, the temperature in the system rose to 35 ° C. Then, while adjusting the temperature in the system to 32 to 35 ° C., ethylene was supplied at a flow rate of 4 Nm 3 / h for 3.5 hours. During this period, the pressure in the system was maintained at 0.07 to 0.08 MPa. Then, the inside of the system was replaced with nitrogen, the supernatant was removed, and the mixture was washed with hexane four times.
次に、充分に窒素置換した内容積４３Ｌの撹拌機付き蒸発乾燥機に移送し、乾燥機内を約６０分かけて−６８ｋＰａまで減圧し、−６８ｋＰａに到達したところで約４.３時間乾燥しヘキサンおよび予備重合触媒成分中の揮発分を除去した。その後、さらに−１００ｋＰａまで減圧し、−１００ｋＰａに到達したところで８時間乾燥し、固体触媒成分（Ｘ−１）１ｇ当たり３ｇのポリマーが予備重合された予備重合触媒成分（ＸＰ−１）を得た。 Next, the mixture was transferred to an evaporation dryer with a stirrer having an internal volume of 43 L sufficiently substituted with nitrogen, the inside of the dryer was depressurized to -68 kPa over about 60 minutes, and when it reached -68 kPa, it was dried for about 4.3 hours and hexane. And the volatile matter in the prepolymerization catalyst component was removed. Then, the pressure was further reduced to -100 kPa, and when it reached -100 kPa, it was dried for 8 hours to obtain a prepolymerized catalyst component (XP-1) in which 3 g of the polymer was prepolymerized per 1 g of the solid catalyst component (X-1). ..
〔調製例４〜９〕予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）の混合
充分に窒素置換した内容積５００ｍＬのデュラン瓶に、調製例３の予備重合触媒成分（ＸＰ−１）１５０ｇと表２に記載の種類と量の固体成分（Ａ）とを装入した。蓋を閉めた後、デュラン瓶を回転させることで予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）とを十分に混合し、予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）の混合物を調製した。なお固体成分（Ａ）は、デュラン瓶に装入する前に窒素流通下で１０時間以上室温にて保管した。
[Preparation Examples 4 to 9] Mixing of Prepolymerization Catalyst Component (XP-1) and Solid Component (A) The prepolymerization catalyst component (XP-1) of Preparation Example 3 was placed in a Duran bottle with an internal volume of 500 mL that was sufficiently nitrogen-substituted. 150 g and the type and amount of the solid component (A) shown in Table 2 were charged. After closing the lid, the prepolymerization catalyst component (XP-1) and the solid component (A) are sufficiently mixed by rotating the Duran bottle, and the prepolymerization catalyst component (XP-1) and the solid component (A) are sufficiently mixed. A mixture of the above was prepared. The solid component (A) was stored at room temperature for 10 hours or more under nitrogen flow before being charged into a Duran bottle.
〔比較例６〕
気相流動床重合装置を用いて、エチレンと１−ヘキセンとの共重合を行った。重合圧力を２.０ＭＰａ、重合温度を８０℃とし、調製例３の予備重合触媒成分（ＸＰ−１）を３.５ｇ／ｈｒで重合反応器内に連続的に供給した。重合反応器内の重合体の質量が２４ｋｇ、ガス組成が、エチレン分圧＝１.５ＭＰａ、水素／エチレン＝０.０００４８ｍｏｌ比、１−ヘキセン／エチレン＝０.０２４ｍｏｌ比、となるようにエチレン、水素、１−ヘキセン、窒素を連続的に供給し、５.０ｋｇ／ｈｒでエチレン系重合体の重合体粉体を重合反応器から連続的に抜出した。
[Comparative Example 6]
Copolymerization of ethylene and 1-hexene was carried out using a gas phase fluidized bed polymerization apparatus. The polymerization pressure was 2.0 MPa, the polymerization temperature was 80 ° C., and the prepolymerization catalyst component (XP-1) of Preparation Example 3 was continuously supplied into the polymerization reactor at 3.5 g / hr. Ethylene, such that the mass of the polymer in the polymerization reactor is 24 kg, the gas composition is ethylene partial pressure = 1.5 MPa, hydrogen / ethylene = 0.00408 mol ratio, 1-hexene / ethylene = 0.024 mol ratio. Hydrogen, 1-hexene, and nitrogen were continuously supplied, and the polymer powder of the ethylene-based polymer was continuously extracted from the polymerization reactor at 5.0 kg / hr.
この重合工程においては、２４時間以内に重合反応器等でヒートスポットの発生が認められ、運転が継続できなくなった。得られた重合体のメルトフローレート（ＭＦＲ）は３.８ｇ／１０ｍｉｎ、真密度は９１７ｇ／Ｌ、嵩密度は３６０ｇ／Ｌであった。 In this polymerization step, heat spots were observed in the polymerization reactor or the like within 24 hours, and the operation could not be continued. The melt flow rate (MFR) of the obtained polymer was 3.8 g / 10 min, the true density was 917 g / L, and the bulk density was 360 g / L.
〔実施例９〕
気相流動床重合装置を用いて、エチレンと１−ヘキセンとの共重合を行った。重合圧力を２.０ＭＰａ、重合温度を８０℃とし、調製例４の予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）の混合物を３.５ｇ／ｈｒで重合反応器内に連続的に供給した。重合反応器内の重合体の質量が２４ｋｇ、ガス組成が、エチレン分圧＝１.５ＭＰａ、水素／エチレン＝０.０００４８ｍｏｌ比、１−ヘキセン／エチレン＝０.０２４ｍｏｌ比、となるようにエチレン、水素、１−ヘキセン、窒素を連続的に供給し、５.０ｋｇ／ｈｒでエチレン系重合体の重合体粉体を重合反応器から連続的に抜出した。
[Example 9]
Copolymerization of ethylene and 1-hexene was carried out using a gas phase fluidized bed polymerization apparatus. The polymerization pressure was 2.0 MPa, the polymerization temperature was 80 ° C., and the mixture of the prepolymerization catalyst component (XP-1) and the solid component (A) of Preparation Example 4 was continuously mixed in the polymerization reactor at 3.5 g / hr. Supplied. Ethylene, such that the mass of the polymer in the polymerization reactor is 24 kg, the gas composition is ethylene partial pressure = 1.5 MPa, hydrogen / ethylene = 0.00408 mol ratio, 1-hexene / ethylene = 0.024 mol ratio. Hydrogen, 1-hexene, and nitrogen were continuously supplied, and the polymer powder of the ethylene-based polymer was continuously extracted from the polymerization reactor at 5.0 kg / hr.
この時の重合体粉体に対する固体成分（Ａ）の供給量の質量比（計算値）は、１４ｐｐｍである。２４時間以上運転を継続したが、重合反応器や配管等、全ての箇所にヒートスポットの発生は見られず、安定した重合が実施できた。得られた重合体のメルトフローレート（ＭＦＲ）は３.６ｇ／１０ｍｉｎ、真密度は９１６ｇ／Ｌ、嵩密度は３６０ｇ／Ｌであった。 The mass ratio (calculated value) of the supply amount of the solid component (A) to the polymer powder at this time is 14 ppm. Although the operation was continued for 24 hours or more, no heat spots were observed in all parts such as the polymerization reactor and piping, and stable polymerization could be carried out. The melt flow rate (MFR) of the obtained polymer was 3.6 g / 10 min, the true density was 916 g / L, and the bulk density was 360 g / L.
〔実施例１０〜１３〕
予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）の混合物の種類および供給量を表３に記載のとおり変更した以外は、実施例９と同様の条件でエチレン系重合体の重合体粉体を製造した。２４時間以上運転を継続したが、重合反応器や配管等、全ての箇所にヒートスポットの発生は見られず、安定した重合が実施できた。
[Examples 10 to 13]
Polymer powder of ethylene-based polymer under the same conditions as in Example 9 except that the type and supply amount of the mixture of the prepolymerization catalyst component (XP-1) and the solid component (A) were changed as shown in Table 3. Manufactured the body. Although the operation was continued for 24 hours or more, no heat spots were observed in all parts such as the polymerization reactor and piping, and stable polymerization could be carried out.
〔比較例７〕
予備重合触媒成分（ＸＰ−１）と固体成分（Ａ）の混合物の種類および供給量を表３に記載のとおり変更した以外は、実施例９と同様の条件でエチレン系重合体の重合体粉体を製造した。２４時間以内に重合反応器等でヒートスポットの発生が認められ、運転が継続できなくなった。
[Comparative Example 7]
Polymer powder of ethylene-based polymer under the same conditions as in Example 9 except that the type and supply amount of the mixture of the prepolymerization catalyst component (XP-1) and the solid component (A) were changed as shown in Table 3. Manufactured the body. Within 24 hours, heat spots were observed in the polymerization reactor and the like, and the operation could not be continued.
〔比較例８〕
気相流動床重合装置を用いて、エチレンと１−ヘキセンとの共重合を行った。重合圧力を２.０ＭＰａ、重合温度を８０℃とし、調製例３の予備重合触媒成分（ＸＰ−１）を５.０ｇ／ｈｒ、固体成分（Ａ）の代わりにヤシ油脂肪酸ジエタノールアミドであるケミスタット(登録商標)２５００（三洋化成工業社製）を０.１３ｇ／ｈｒで重合反応器内に連続的に供給した。重合反応器内の重合体の質量が２４ｋｇ、ガス組成が、エチレン分圧＝１.５ＭＰａ、水素／エチレン＝０.０００４８ｍｏｌ比、１−ヘキセン／エチレン＝０.０２４ｍｏｌ比、となるようにエチレン、水素、１−ヘキセン、窒素を連続的に供給し、５.０ｋｇ／ｈｒでエチレン系重合体の重合体粉体を重合反応器から連続的に抜出した。
[Comparative Example 8]
Copolymerization of ethylene and 1-hexene was carried out using a gas phase fluidized bed polymerization apparatus. The polymerization pressure was 2.0 MPa, the polymerization temperature was 80 ° C., the prepolymerization catalyst component (XP-1) of Preparation Example 3 was 5.0 g / hr, and the chemistat was a coconut oil fatty acid diethanolamide instead of the solid component (A). (Registered trademark) 2500 (manufactured by Sanyo Chemical Industries, Ltd.) was continuously supplied into the polymerization reactor at 0.13 g / hr. Ethylene, such that the mass of the polymer in the polymerization reactor is 24 kg, the gas composition is ethylene partial pressure = 1.5 MPa, hydrogen / ethylene = 0.00408 mol ratio, 1-hexene / ethylene = 0.024 mol ratio. Hydrogen, 1-hexene, and nitrogen were continuously supplied, and the polymer powder of the ethylene-based polymer was continuously extracted from the polymerization reactor at 5.0 kg / hr.
この時の重合体粉体に対するヤシ油脂肪酸ジエタノールアミドの供給量の質量比（計算値）は、２６ｐｐｍである。２４時間以上運転を継続したが、重合反応器や配管等、全ての箇所にヒートスポットの発生は見られず、安定した重合が実施できた。しかし、実施例９〜１３と同じ質量の重合体粉体を製造するためには、より多くの予備重合触媒成分（ＸＰ−１）を供給する必要があった。これは触媒活性が低下したためと考えられる。 The mass ratio (calculated value) of the supply amount of the coconut oil fatty acid diethanolamide to the polymer powder at this time is 26 ppm. Although the operation was continued for 24 hours or more, no heat spots were observed in all parts such as the polymerization reactor and piping, and stable polymerization could be carried out. However, in order to produce the polymer powder having the same mass as in Examples 9 to 13, it was necessary to supply a larger amount of the prepolymerization catalyst component (XP-1). It is considered that this is because the catalytic activity decreased.
得られた重合体のメルトフローレート（ＭＦＲ）は３.７ｇ／１０ｍｉｎ、真密度は９１７ｇ／Ｌ、嵩密度は３４０ｇ／Ｌであった。 The melt flow rate (MFR) of the obtained polymer was 3.7 g / 10 min, the true density was 917 g / L, and the bulk density was 340 g / L.
本発明によれば、オレフィン重合体の製造工程または貯蔵工程において優れた流動性を確保できるため、ポリマー塊やシート状物を生成することがなく、長期間の安定運転を可能にする方法として有用である。また、重合触媒と接触させた際の触媒活性低下が小さいので、経済的な重合体の製造も可能にする方法として有用である。 According to the present invention, since excellent fluidity can be ensured in the manufacturing process or storage process of the olefin polymer, it is useful as a method for enabling stable operation for a long period of time without forming polymer lumps or sheet-like substances. Is. Further, since the decrease in catalytic activity when contacted with the polymerization catalyst is small, it is useful as a method that enables economical production of the polymer.
Claims (6)
該固体成分（Ａ）が、アルミノケイ酸塩（Ａ−１）、ハイドロタルサイト類（Ａ−２）およびアクリル系樹脂微粒子（Ａ−３）からなる群より選ばれる少なくとも１種の成分を含むことを特徴とするオレフィン重合体の流動性改良方法。 In a method for improving the fluidity of an olefin polymer, which supplies the solid component (A) to the fluid environment field of the olefin polymer in the storage step of the olefin polymer.
The solid component (A) contains at least one component selected from the group consisting of aluminosilicates (A-1), hydrotalcites (A-2) and acrylic resin fine particles (A-3). A method for improving the fluidity of an olefin polymer.
成分（ｘ−１）：シクロペンタジエニル骨格を有する周期表第４族の遷移金属化合物
成分（ｘ−２）：有機アルミニウムオキシ化合物
成分（ｘ−３）：粒子状担体
Claimed that the olefin polymer is a polymer obtained by a production method using a solid catalyst component (X) containing the following component (x-1), component (x-2) and component (x-3). Item 8. The method for improving the fluidity of an olefin polymer according to any one of Items 1 to 5.
Component (x-1): Transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton Component (x-2): Organoaluminium oxy compound Component (x-3): Particle-like carrier
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