WO2017170077A1 - アルコキシマグネシウム、アルコキシマグネシウムの製造方法、オレフィン類重合用固体触媒成分、オレフィン類重合用触媒およびオレフィン類重合体の製造方法 - Google Patents
アルコキシマグネシウム、アルコキシマグネシウムの製造方法、オレフィン類重合用固体触媒成分、オレフィン類重合用触媒およびオレフィン類重合体の製造方法 Download PDFInfo
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- WO2017170077A1 WO2017170077A1 PCT/JP2017/011589 JP2017011589W WO2017170077A1 WO 2017170077 A1 WO2017170077 A1 WO 2017170077A1 JP 2017011589 W JP2017011589 W JP 2017011589W WO 2017170077 A1 WO2017170077 A1 WO 2017170077A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- group
- alkoxymagnesium
- less
- catalyst component
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 134
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 130
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 105
- -1 Alkoxy magnesium Chemical compound 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 67
- 239000003054 catalyst Substances 0.000 title claims description 28
- 229920000098 polyolefin Polymers 0.000 title claims description 20
- 229910052749 magnesium Inorganic materials 0.000 title abstract description 32
- 239000011777 magnesium Substances 0.000 title abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 221
- 239000011148 porous material Substances 0.000 claims abstract description 90
- 239000000843 powder Substances 0.000 claims abstract description 78
- 239000011163 secondary particle Substances 0.000 claims abstract description 68
- 239000011164 primary particle Substances 0.000 claims abstract description 47
- 238000009826 distribution Methods 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 200
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical group [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 claims description 97
- 125000000217 alkyl group Chemical group 0.000 claims description 75
- 150000001875 compounds Chemical class 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 49
- 125000003342 alkenyl group Chemical group 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 46
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- 239000002685 polymerization catalyst Substances 0.000 claims description 33
- 239000003960 organic solvent Substances 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 29
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 4
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 4
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- 125000003545 alkoxy group Chemical group 0.000 claims description 4
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- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 3
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 claims description 3
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical group CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 3
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 claims description 3
- 229960002097 dibutylsuccinate Drugs 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- WMNULTDOANGXRT-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate Chemical compound CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC WMNULTDOANGXRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 66
- 230000037048 polymerization activity Effects 0.000 abstract description 26
- 239000000470 constituent Substances 0.000 abstract description 12
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- 238000002360 preparation method Methods 0.000 description 37
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 25
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 230000005484 gravity Effects 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 239000010419 fine particle Substances 0.000 description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 11
- 239000011976 maleic acid Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 125000003282 alkyl amino group Chemical group 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- VMSDGXIKDYLSHB-UHFFFAOYSA-N dimethyl 2,2-bis(2-methylpropyl)propanedioate Chemical compound COC(=O)C(CC(C)C)(CC(C)C)C(=O)OC VMSDGXIKDYLSHB-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
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- 238000010099 solid forming Methods 0.000 description 5
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical class CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011343 solid material Substances 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
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- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
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- 244000061456 Solanum tuberosum Species 0.000 description 1
- HGZNVFWEHHYPRF-UHFFFAOYSA-N [O-]CC.[Mg+2].[Mg+2].[O-]CC.[O-]CC.[O-]CC Chemical compound [O-]CC.[Mg+2].[Mg+2].[O-]CC.[O-]CC.[O-]CC HGZNVFWEHHYPRF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SKFSDACHJHAMAY-UHFFFAOYSA-N bis(2-ethylhexyl)-dimethoxysilane Chemical compound CCCCC(CC)C[Si](OC)(OC)CC(CC)CCCC SKFSDACHJHAMAY-UHFFFAOYSA-N 0.000 description 1
- SWBJZPDGKVYSLT-UHFFFAOYSA-N bis(2-methylpropyl) propanedioate Chemical compound CC(C)COC(=O)CC(=O)OCC(C)C SWBJZPDGKVYSLT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- FSCIRKQLFHLTOX-UHFFFAOYSA-N cyclohexyl-cyclopentyl-dimethoxysilane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCC1 FSCIRKQLFHLTOX-UHFFFAOYSA-N 0.000 description 1
- MGGAITMRMJXXMT-UHFFFAOYSA-N cyclopentyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCC1 MGGAITMRMJXXMT-UHFFFAOYSA-N 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical class OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 1
- NIXFNZVGGMZGPZ-UHFFFAOYSA-N diethyl 2,2-bis(2-methylpropyl)propanedioate Chemical compound CCOC(=O)C(CC(C)C)(CC(C)C)C(=O)OCC NIXFNZVGGMZGPZ-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- 238000011496 digital image analysis Methods 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- BZYKAVQOGYGDCD-UHFFFAOYSA-N magnesium ethanolate 6-methylheptan-1-olate Chemical compound C(C)O[Mg]OCCCCCC(C)C BZYKAVQOGYGDCD-UHFFFAOYSA-N 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WRUFJVBJAJAEPL-UHFFFAOYSA-N n-[(cyclohexylamino)-dimethoxysilyl]cyclohexanamine Chemical compound C1CCCCC1N[Si](OC)(OC)NC1CCCCC1 WRUFJVBJAJAEPL-UHFFFAOYSA-N 0.000 description 1
- NMTAMKZOXOXJQJ-UHFFFAOYSA-N n-[ethyl-(ethylamino)-methylsilyl]ethanamine Chemical compound CCN[Si](C)(CC)NCC NMTAMKZOXOXJQJ-UHFFFAOYSA-N 0.000 description 1
- QAQDIBPVZJKPJK-UHFFFAOYSA-N n-[tert-butyl-(ethylamino)-methylsilyl]ethanamine Chemical compound CCN[Si](C)(C(C)(C)C)NCC QAQDIBPVZJKPJK-UHFFFAOYSA-N 0.000 description 1
- UIKLFEQVPMEVFM-UHFFFAOYSA-N n-methyl-n-[methyl-bis(methylamino)silyl]cyclopentanamine Chemical compound CN[Si](C)(NC)N(C)C1CCCC1 UIKLFEQVPMEVFM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UTADZBVVSYSYTG-UHFFFAOYSA-N tert-butyl(methyl)silane Chemical compound C[SiH2]C(C)(C)C UTADZBVVSYSYTG-UHFFFAOYSA-N 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/28—Metal alcoholates
- C07C31/30—Alkali metal or alkaline earth metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
- C08F4/6423—Component of C08F4/64 containing at least two different metals
- C08F4/6425—Component of C08F4/64 containing at least two different metals containing magnesium
Definitions
- the present invention relates to alkoxymagnesium, a method for producing alkoxymagnesium, a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer.
- solid catalyst components for olefin polymerization containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed as constituent components of olefin polymerization catalysts, and in particular, diethoxymagnesium as a magnesium raw material.
- a solid catalyst component prepared using an alkoxymagnesium compound typified by is widely used industrially for polymerizing olefins.
- dialkoxymagnesium powder is mixed with a polycarboxylic acid halide or monocarboxylic acid in the presence of an inert organic solvent.
- a method for preparing a suspension containing a solid catalyst component precursor for olefin polymerization by treatment with an acid halide and producing a solid catalyst component for olefin polymerization using the suspension has been proposed.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2008-285573
- a dialkoxymagnesium powder composition is prepared by contacting water or a hydrate with dialkoxymagnesium powder, and the dialkoxymagnesium powder composition is prepared.
- a method for producing a solid catalyst component for olefin polymerization using a product has been proposed.
- the water or hydrate used in the preparation of the dialkoxymagnesium powder composition is used in the production of the solid catalyst component, such as a titanium halogen compound.
- the solid catalyst component such as a titanium halogen compound.
- hydrogen chloride which is a corrosive component, may be generated by reacting with the halide of the above, and even in the obtained polymer, the fine powder polymer of 45 ⁇ m or less can be reduced to a certain extent, but the titanium content in the solid catalyst component Therefore, there is a problem that the polymerization activity is lowered as compared with the conventional solid catalyst component.
- Patent Document 6 Japanese Patent Laid-Open No. 2007-297371
- the ratio of metal magnesium and alcohol used in the reaction system, the method of addition, etc. are adjusted.
- average particle diameter represented by D 50 has a spherical or ellipsoidal particle shapes ranging from 60 ⁇ 200 [mu] m, has a bulk density of 0.2 ⁇ 0.7g / ml, TEM observation inside A large number of dialkoxymagnesium particles having a large particle size distribution represented by (D 90 -D 10 ) / D 50 and having a large particle size of 0.1 to 5 ⁇ m, and the dialkoxymagnesium particles And a method for producing a solid catalyst component for olefin polymerization using the dialkoxymagnesium granules.
- the present invention provides a polymer having an excellent particle size distribution with a reduced generation rate of fine powder when olefins are polymerized as a constituent of the solid catalyst component for olefin polymerization. And to provide a method for producing the alkoxymagnesium, a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer. Is.
- alkoxymagnesium is formed by secondary particles that are aggregates of primary particles, but conventional alkoxymagnesium is exclusively secondary particles. Contains fine powder (particles having a particle diameter of 5 ⁇ m or less) that is disintegrated and exceeds 3% by mass of the total particle mass, and this fine powdery alkoxymagnesium easily forms a fine powder polymer during polymerization of olefins. I found out. Based on this finding, the present inventors have further studied, and are composed of secondary particles that are aggregates of primary particles having an average particle diameter of less than 1 ⁇ m, and the average particle diameter of the primary particles / the secondary particles.
- the ratio represented by the average particle diameter is 0.1 or less, the total pore volume is 0.5 to 1 cm 3 / g, the specific surface area is less than 50 m 2 / g, and the particle size distribution index (SPAN) is 1 or less.
- the present inventors have found that the above problems can be solved by a certain alkoxymagnesium and have completed the present invention.
- the present invention (1) It is composed of secondary particles that are aggregates of primary particles having an average particle diameter of less than 1 ⁇ m,
- the ratio represented by the average particle diameter of the primary particles / the average particle diameter of the secondary particles is 0.1 or less
- the alkoxymagnesium according to (1) or (2) above, wherein the secondary particles have an average particle size of less than 60 ⁇ m
- the carboxylic acid ester is represented by the following general formula (I); (In the formula, R 1 and R 2 are a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a straight chain having 3 to 12 carbon atoms.
- alkenyl group a branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same as or different from each other; 1 and R 2 may be bonded to each other to form a ring, and R 3 and R 4 are alkyl groups having 1 to 12 carbon atoms, which may be the same or different from each other.
- alkenyl groups branched alkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms having 3 to 12 carbon atoms, may be the same or different from each other, R 5 And R 6 , R 7 and R 8 may be bonded to each other to form a ring, and R 9 and R 10 are alkyl groups having 1 to 12 carbon atoms, and may be the same or different from each other.
- R 11 and R 12 are each a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a straight chain having 3 to 12 carbon atoms.
- alkenyl groups branched alkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms having 3 to 12 carbon atoms, may be the same or different from each other, R 11 And R 12 may be bonded to each other to form a ring, and R 13 and R 14 are alkyl groups having 1 to 12 carbon atoms, which may be the same or different.
- the carboxylic acid ester is diethyl succinate, dibutyl succinate, bis (2-ethylhexyl) succinate, diethyl maleate, dibutyl maleate, bis (2-ethylhexyl) maleate, diethyl malonate, dibutyl malonate
- a part of the solid is reacted with a carboxylic acid ester to form a reaction product, or a part of the solid is mixed in a mixture of a carboxylic acid este
- Solid catalyst component for olefin polymerization characterized (12)
- cycloalkenyl group or an aryl group having 6 to 20 carbon atoms may be R 18 and R 19 are either the same or different from each other, also may be bonded to each other to form a ring, R 18 R 19 N group
- R 20 represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, 1-20 alkoxy group, vinyloxy group, alkenyloxy group having 3-20 carbon atoms, cycloalkyl group having 3-20 carbon atoms, cycloalkyloxy group having 3-20 carbon atoms, aryl having 6-20 carbon atoms Group, an aryloxy group having 6 to 20 carbon atoms, if R 20 there are a plurality, the plurality of R 20 is optionally be the same or different .s is represented by from 1 to 3 to 3
- an olefin when polymerized as a constituent component of a solid catalyst component for olefin polymerization, a generation ratio of fine powder is reduced, and a novel polymer capable of forming a polymer having an excellent particle size distribution under a high polymerization activity.
- a method for producing the alkoxymagnesium, a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer can be provided.
- the alkoxymagnesium according to the present invention is composed of secondary particles that are aggregates of primary particles having an average particle size of less than 1 ⁇ m, and the ratio represented by the average particle size of the primary particles / the average particle size of the secondary particles is as follows.
- the total pore volume is 0.5 to 1 cm 3 / g, the specific surface area is less than 50 m 2 / g, and the particle size distribution index (SPAN) is 1 or less. .
- the alkoxymagnesium according to the present invention is composed of secondary particles that are aggregates of primary particles.
- the average particle diameter of the primary particles is less than 1 ⁇ m, preferably 0.2 ⁇ m to 0.9 ⁇ m, and more preferably 0.3 ⁇ m to 0.9 ⁇ m.
- the average particle diameter of the secondary particles is preferably less than 60 ⁇ m, more preferably 10 ⁇ m or more and less than 60 ⁇ m, and more preferably 15 ⁇ m or more and less than 60 ⁇ m.
- the alkoxymagnesium according to the present invention is composed of secondary particles that are aggregates of primary particles, so that when an olefin is polymerized as a constituent component of the solid catalyst component for olefin polymerization, a fine particle polymer Can be suitably suppressed.
- the primary particles are as large as 1 to 10 ⁇ m, and the primary particles peeled off from the surface of the secondary particles are one of the causes for forming a fine polymer.
- the alkoxymagnesium according to the present invention has a primary particle size as small as less than 1 ⁇ m, and the primary particles floating during washing in the production process of the solid catalyst component can be easily extracted into the effluent. It is considered that the amount of fine polymer particles can be reduced during the polymerization.
- the ratio represented by the average particle diameter of the primary particles constituting the alkoxymagnesium / the average particle diameter of the secondary particles constituting the alkoxymagnesium is 0.1 or less. It is preferably 001 to 0.08, and more preferably 0.005 to 0.05.
- the ratio of the average particle diameter of the primary particles / the average particle diameter of the secondary particles is 0.1 or less, so that the secondary particles are sufficiently larger than the primary particles. It is growing, and when an olefin is polymerized as a constituent component of the solid catalyst component for olefin polymerization, the formation of a fine particle polymer can be suitably suppressed.
- the average particle diameter of the primary particle of alkoxymagnesium is a statistical analysis method based on the longest diameter of 100 or more particles measured by visual observation of a negative photographed using a scanning electron microscope. Means the average particle size calculated by The average particle diameter of the alkoxymagnesium secondary particles is determined by measuring the average particle diameter D 50 (volume) when 100,000 or more measurement samples in a dry state are measured using a laser diffraction particle size distribution measuring device corresponding to dry dispersion. Means 50% of the integrated particle size in the integrated particle size distribution).
- the content of fine powder that is, particles having a particle diameter of 5 ⁇ m or less is preferably 3% by mass or less of the total particle mass, and 2% by mass or less of the total particle mass. More preferably, it is more preferably 1% by mass or less of the total particle mass.
- the fine powder is produced exclusively by the collapse of the secondary particles of alkoxymagnesium, but as long as the particle diameter satisfies the above definition, the primary particles that do not constitute the secondary particles are also included in the fine powder.
- the content of fine powder having a particle size of 5 ⁇ m or less is 3% by mass or less of the total particle mass, so that the yield of the polymer obtained during the polymerization of olefins is maintained at a high level.
- a polymer in which the amount of fine powder of a polymer having a particle size of 75 ⁇ m or less is sufficiently reduced can be easily obtained, a general-purpose polyolefin can be provided stably and at low cost.
- the alkoxymagnesium according to the present invention has a secondary particle size distribution of (D 90 -D 10 ) / D 50 (where D 90 is a cumulative particle size in the volume cumulative particle size distribution and a particle size of 90%, D 50 is 1 with 50% particle size in cumulative particle size in the volume cumulative particle size distribution (average particle size), particle size distribution index represented by D 10 is the particle diameter of 10% cumulative particle size in the volume cumulative particle size distribution.) (SPAN). What is 0 or less and 0.8 or less are preferable.
- the content rate of the fine powder which has a particle diameter of 5 micrometers or less means the value measured using the laser diffraction type particle size distribution measuring apparatus (Malvern company make, Mastersizer 3000) corresponding to dry dispersion.
- the secondary particles D 90 , D 50 and D 10 constituting the alkoxymagnesium are also the cumulative particle sizes in the volume cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer, By 90%, 50% and 10% particle size is meant.
- the shape of the secondary particles of the alkoxymagnesium according to the present invention is not particularly limited, and is in the form of granules or powder in the dry state, and the shape is usually spherical, but it is not necessarily a true sphere, It may be a body shape or a similar sphere shape such as a potato shape.
- the ratio (l / w) of the major axis diameter l to the minor axis diameter w of the secondary particles is preferably 3 or less, more preferably 1 to 2, and more preferably 1-1. More preferably, it is 5.
- the alkoxymagnesium according to the present invention has a pore diameter of 50% or more of pores having a pore diameter of 1 ⁇ m or less (more than half of pores having a pore diameter of 1 ⁇ m or less) as measured by mercury porosimetry. Is preferably 0.5 ⁇ m or less, more preferably 0.05 to 0.5 ⁇ m, and even more preferably 0.1 to 0.5 ⁇ m.
- the alkoxymagnesium according to the present invention has a total pore volume of 0.5 to 1 cm 3 / g, preferably 0.55 to 0.9 cm 3 / g, as measured by mercury porosimetry. More preferably, it is 6 to 0.8 cm 3 / g.
- the constitution of the solid catalyst component for olefin polymerization As a component, for example, when propylene and ethylene are polymerized, the rubber component made of the copolymer is retained in the pores to suppress the elution of the rubber component to the particle surface, It is possible to suppress stickiness and adhesion of the copolymer to the inside of the reaction vessel and to show good particle fluidity.
- the pore diameter distribution and pore volume of alkoxymagnesium mean values measured by the mercury intrusion method using an automatic porosimeter ⁇ ⁇ Autopore III 9400 series manufactured by Shimadzu Corporation.
- the alkoxymagnesium according to the present invention has a specific surface area of less than 50 m 2 / g, preferably 5 m 2 / g to 40 m 2 / g or less, and more preferably 10 m 2 / g to 30 m 2 / g. .
- the specific surface area of alkoxymagnesium is determined by measuring the sample in advance under vacuum at 50 ° C. for 2 hours, and then using a mixed gas of nitrogen and helium to produce an Automatic® Surface Area Analyzer HM model- By 1230, it means a value automatically measured using the BET method.
- the alkoxymagnesium according to the present invention preferably has a bulk specific gravity of 0.25 to 0.50 g / ml, more preferably 0.26 to 0.40 g / ml, and 0.28 to 0.35 g / ml. More preferably, it is ml.
- the bulk specific gravity of alkoxymagnesium means a value measured according to JIS K 6721.
- the alkoxymagnesium according to the present invention is composed of secondary particles composed of aggregates of primary particles, the specific surface area is generally larger and the pore volume is larger than that of alkoxymagnesium produced by a spray drying method or the like. Since it is large, it becomes easy to take the bulk specific gravity. Since the alkoxymagnesium according to the present invention has a large specific surface area and a large pore volume, excellent particle properties can be obtained when the solid catalyst component prepared using the alkoxymagnesium is subjected to olefin polymerization. In addition, in block copolymerization, a copolymer having excellent particle properties can be obtained in high yield even in the case where the production ratio of rubbery polymer is high. Can do.
- alkoxymagnesium examples include one or more selected from diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dipentoxymagnesium, diisooctoxymagnesium, ethoxybutoxymagnesium, ethoxyisooctoxymagnesium, and the like. Diethoxymagnesium is preferable.
- an olefin when polymerized as a constituent component of a solid catalyst component for olefin polymerization, a fine powder generation ratio is reduced, and a polymer having an excellent particle size distribution can be formed under high polymerization activity.
- a novel alkoxymagnesium can be provided.
- the alkoxymagnesium according to the present invention when used as a constituent component of a solid catalyst component for olefin polymerization, an olefin polymer powder having a better particle shape and a narrow particle size distribution can be obtained.
- the handling operability of the produced polymer powder is improved, and the occurrence of clogging or the like due to the fine powder contained in the produced polymer powder can be suitably suppressed.
- the method for producing alkoxymagnesium according to the present invention comprises a step of forming a solid by reacting metallic magnesium and an alcohol in the presence of a catalyst, and forming the solid with one or more carboxylic acid esters. And a contact step of forming a suspension by contact in a solvent.
- the magnesium metal used in the solid forming step is preferably, for example, several tens to several hundreds of mesh, more specifically about 100 mesh, and powdery reactivity. Is preferable.
- the alcohol to be reacted with the metal magnesium used in the solid formation step is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexyl alcohol, or the like.
- One or more kinds selected can be mentioned, and ethanol can be mentioned preferably.
- the alcohol is preferably one from which water has been sufficiently removed before contacting with metal magnesium and reacting.
- Examples of the catalyst used for the reaction of the metal magnesium and alcohol include alkyl halides such as methyl bromide, methyl chloride, ethyl bromide, and ethyl chloride, metal halides such as magnesium chloride and aluminum chloride, and diethoxy magnesium.
- alkyl halides such as methyl bromide, methyl chloride, ethyl bromide, and ethyl chloride
- metal halides such as magnesium chloride and aluminum chloride
- diethoxy magnesium diethoxy magnesium.
- dialkoxymagnesium, iodine, acetate ester and the like can be mentioned. Among these, at least one selected from iodine and diethoxymagnesium is particularly preferable.
- the catalyst is preferably added to the reaction system at the beginning of the solid forming step.
- Metal magnesium and alcohol are preferably brought into contact so that the mass ratio represented by metal magnesium / alcohol is 1/2 to 1/30, and preferably 1/5 to 1/20. Is more preferable, and it is further preferable to make contact so that the ratio is 1/9 to 1/15.
- the metal magnesium and alcohol can be reacted by a known method.
- the magnesium-alcohol and the alcohol are continuously or intermittently added to the reaction system containing the catalyst so as to finally reach the above mass ratio, contacted and reacted, and then kept under reflux of the alcohol.
- a method of performing an aging reaction preferably 5 to 80 minutes, and the aging time is preferably 1 to 30 hours.
- the solid obtained as described above may be used in the next step as a suspension using the alcohol used in the above reaction as a solvent, or may be used in the next step after removing the alcohol and drying. Good.
- the solid material obtained in the solid content forming step and one or more carboxylic acid esters are contacted in an organic solvent to form a suspension. Apply.
- aliphatic carboxylic acid ester is preferable, and the following general formula (I);
- R 1 and R 2 are a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a straight chain having 3 to 12 carbon atoms.
- alkenyl group a branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same as or different from each other; 1 and R 2 may be bonded to each other to form a ring, and R 3 and R 4 are alkyl groups having 1 to 12 carbon atoms, which may be the same or different from each other.
- alkenyl groups branched alkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms having 3 to 12 carbon atoms, may be the same or different from each other, R 5 And R 6 , R 7 and R 8 may be bonded to each other to form a ring, and R 9 and R 10 are alkyl groups having 1 to 12 carbon atoms, and may be the same or different from each other.
- R 11 and R 12 are each a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a straight chain having 3 to 12 carbon atoms.
- alkenyl groups branched alkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having a cycloalkyl group or having 6 to 20 carbon atoms having 3 to 12 carbon atoms, may be the same or different from each other, R 11 And R 12 may be bonded to each other to form a ring, and R 13 and R 14 are alkyl groups having 1 to 12 carbon atoms, which may be the same or different. More preferably, it is one or more selected from compounds.
- R 1 and R 2 are each a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or 3 to 3 carbon atoms. 12 linear alkenyl groups, branched alkenyl groups having 3 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, or aromatic hydrocarbon groups having 6 to 20 carbon atoms, which are the same or different from each other.
- R 1 and R 2 may be bonded to each other to form a ring.
- R 3 and R 4 are alkyl groups having 1 to 12 carbon atoms and may be the same or different from each other. As R 3 and R 4 , an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 7 to 12 carbon atoms is more preferable.
- carboxylic acid ester represented by the general formula (I) include maleic acid diesters in which R 1 and R 2 are hydrogen atoms, R 1 is a hydrogen atom, and R 2 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a linear alkenyl group having 3 to 12 carbon atoms.
- An alkylmaleic acid diester which is a branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 1 and R 2 are each Independently, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 12 carbon atoms, a branched alkenyl group having 3 to 12 carbon atoms
- a dialkylmaleic acid diester which is a group selected from a cycloalkyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, Among R 1 and R 2 , at least one selected from cycloalkyl maleic acid diesters in which at least one is a cycloalkyl group having 3 to 12 carbon atoms can be mentioned, and among the carb
- the carboxylic acid ester is represented by the following general formula (II);
- R 5 to R 8 are each a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or 3 to 3 carbon atoms.
- R 9 and R 10 are alkyl groups having 1 to 12 carbon atoms and may be the same or different from each other.
- R 9 and R 10 are preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 7 to 12 carbon atoms.
- carboxylic acid ester represented by the general formula (II) include succinic acid diesters in which R 5 to R 8 are hydrogen atoms, R 5 to R 7 are hydrogen atoms, and R 8 is a carbon number.
- R 11 and R 12 are each a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or 3 to 3 carbon atoms.
- R 13 and R 14 are alkyl groups having 1 to 12 carbon atoms and may be the same or different. As R 13 and R 14 , an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 7 to 12 carbon atoms is more preferable.
- carboxylic acid ester represented by the general formula (III) include malonic acid diesters in which R 11 and R 12 are hydrogen atoms, R 11 is a hydrogen atom, and R 12 has 1 to 12 carbon atoms.
- An alkyl malonic acid diester which is a cycloalkyl group having 12 cycloalkyl or an aromatic hydrocarbon group having 6 to 20 carbon atoms, or R 11 and R 12 are each independently a linear alkyl group having 1 to 12 carbon atoms, A branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 12 carbon atoms, a branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon number of 6 ⁇ 20 aromatic hydrocarbons
- the above carboxylic acid esters may be used alone or in combination of two or more.
- the solid and the carboxylic acid ester are contacted in an organic solvent to form a suspension.
- the organic solvent it is suitable that the carboxylic acid ester is dissolved and the solid (magnesium compound) is not dissolved.
- Aliphatic hydrocarbon compounds such as benzene, toluene, xylene and ethylbenzene, halogenated hydrocarbon compounds such as methylene chloride and 1,2-dichlorobenzene, alcohols such as methanol, ethanol and isooctyl alcohol And at least one selected from ethers such as diethyl ether.
- one or more selected from hydrocarbon compounds such as heptane, toluene, and xylene are preferable.
- the amount of contact between the solid and the carboxylic acid ester is 0. It is preferably 1 mmol or more, more preferably 0.3 to 60 mmol of carboxylic acid ester, further preferably 0.5 to 50 mmol of carboxylic acid ester, and 0.5 to 30 mmol of carboxylic acid ester. It is particularly preferred that In the contacting step of the alkoxymagnesium production method according to the present invention, the amount of the organic solvent used is preferably 0.1 to 50 ml, more preferably 1 to 30 ml, with respect to 1 g of the solid. Preferably, it is 2 to 10 ml.
- the contact temperature of the solid and the carboxylic acid ester in the organic solvent is preferably ⁇ 20 to 150 ° C., more preferably 10 to 130 ° C., and further preferably 50 to 110 ° C. preferable.
- the contact time of the solid and the carboxylic acid ester in the organic solvent is preferably 1 minute to 50 hours, more preferably 5 minutes to 30 hours, and even more preferably 10 minutes to 10 hours.
- the solid obtained in the solid forming step and one or more carboxylic acid esters are contacted in an organic solvent to form a suspension.
- a part of the solid is reacted with a carboxylic acid ester to form a reaction product, or a part of the solid is a carboxylic acid. It is believed that it dissolves in the mixture of ester and organic solvent or that some of the solid is liberated in the mixture of carboxylic acid ester and organic solvent.
- the method for producing alkoxymagnesium according to the present invention by contacting the solid obtained in the solid-forming step with a carboxylic acid ester in the contacting step, (1) an alkoxy group constituting dialkoxymagnesium, for example. At least a part of the finely powdered dialkoxymagnesium adhering to the alkoxymagnesium is carbonized due to an action such as the so-called “transesterification reaction” in which the alkyl chain of the carboxylic acid diester is replaced with the alkyl chain of the carboxylic acid diester.
- the above aggregate (aggregated solid catalyst component) forms a polymer by polymerizing olefins at a plant, the aggregate particles are broken and a fine powder polymer is easily produced.
- the solid material obtained in the solid material formation step is brought into contact with the carboxylic acid ester in the contact step, thereby suitably suppressing the generation of the fine powder polymer derived from the aggregate particles. be able to.
- a removal treatment for removing the solvent from the reaction solution may be further performed after the contact step.
- the removal treatment is preferably performed by removing the solvent from the suspension by decantation, filtration, or the like.
- the removal treatment can remove the carboxylic acid ester remaining in the reaction solution obtained in the solid formation step and the alkoxymagnesium partially dissolved in the reaction solution, thereby improving the purity of the resulting alkoxymagnesium. .
- after the removal treatment it may be further treated with an organic solvent or the like, and the excess contained in the residue (reaction product) obtained after the removal treatment by treating with an organic solvent.
- the carboxylic acid ester can be washed and removed.
- an olefin when polymerized as a constituent component of a solid catalyst component for olefin polymerization, a generation ratio of fine powder is reduced, and a novel polymer capable of forming a polymer having an excellent particle size distribution under a high polymerization activity.
- a simple method for producing alkoxymagnesium can be provided.
- the solid catalyst component for olefin polymerization according to the present invention is prepared by bringing the alkoxymagnesium (a) according to the present invention, the titanium halogen compound (b), and the electron donating compound (c) into contact with each other. It is a feature.
- the alkoxymagnesium produced by the production method according to the present invention When used as the alkoxymagnesium according to the present invention, it remains as a suspension with the organic solvent used in the contact step, or is separated or dried as necessary. In the state, it is used as a constituent component of the solid catalyst component for olefin polymerization.
- the above-mentioned process is carried out in consideration of simplification of the production process of the solid catalyst component. A suspension that does not undergo separation or drying is desirable.
- the organic solvent reacts with a titanium halogen compound (b) such as alcohol or ether, the suspension is subjected to vacuum or heating. It is preferable that the organic solvent is sufficiently removed by drying.
- titanium halogen compound (b) constituting the solid catalyst component for olefin polymerization according to the present invention include one or more selected from known materials, preferably a tetravalent titanium halogen compound, and titanium tetrachloride. More preferred.
- Examples of the electron donating compound (c) constituting the solid catalyst component for olefin polymerization according to the present invention include one or more selected from known materials, and are organic compounds having an oxygen atom or a nitrogen atom. Is preferred.
- the electron donating compound (c) is preferably at least one selected from succinic acid esters, maleic acid esters, cyclohexene carboxylic acid esters, ether carboxylic acid esters, dicarbonates and ether carbonates.
- the content of titanium atom, magnesium atom, halogen atom and electron donating compound is not particularly specified.
- the content of titanium atoms is preferably 1.8 to 8.0% by mass, more preferably 2.0 to 8.0% by mass. More preferably, the content is 3.0 to 8.0% by mass.
- the magnesium atom content is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass. More preferably, the content is 15 to 25% by mass.
- the halogen atom content is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 40 to 80% by mass. More preferably, it is more preferably 45 to 75% by mass.
- the total content of the electron donating compound (c) is preferably 0.5 to 30% by mass, and preferably 1 to 25% by mass. More preferably, the content is 2 to 20% by mass.
- the titanium content is 3 to 8% by mass
- the magnesium content is 15 to 25% by mass
- the halogen atom content in order to exhibit the overall performance in a balanced manner. Is 45 to 75% by mass
- the content of the electron donating compound (c) is preferably 2 to 20% by mass.
- the above alkoxymagnesium (a), titanium halogen compound (b) and electron donating compound (c) are inertly reacted at a boiling point of 50 to 150 ° C.
- the method of making it contact in presence of an organic solvent (d) can be mentioned.
- Examples of the inert organic solvent (d) having a boiling point of 50 to 150 ° C. include one or more selected from toluene, xylene, ethylbenzene, heptane, octane, decane and the like.
- an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound are generally used. However, if the solubility of impurities during the washing after the reaction or after the reaction does not decrease, the aromatic organic compound is aromatic.
- Inert organic solvents other than group hydrocarbons and saturated hydrocarbons may be used.
- a polysiloxane may be added to the reaction system, and the polysiloxane can be appropriately selected from conventionally known ones.
- the polysiloxane can be appropriately selected from conventionally known ones.
- One or more selected from methylcyclopentasiloxane and dimethylpolysiloxane are preferred, and decamethylcyclopentasiloxane is more preferred.
- the details of the method for preparing the solid catalyst component for olefin polymerization according to the present invention are the same as those for preparing the conventionally known solid catalyst component for olefin polymerization.
- the solid catalyst component for olefin polymerization according to the present invention is obtained by bringing the alkoxymagnesium (a) according to the present invention, the titanium halogen compound (b), and the electron donating compound (c) into contact with each other.
- the solid catalyst component for olefin polymerization due to its structure and physical properties. Inevitably, it is the common technical knowledge of those skilled in the art. For this reason, in this specification, even if the solid catalyst component for olefin polymerization is specified in a so-called product-by-process format, it is clear that the contents are clear.
- a solid catalyst component for olefin polymerization which can form a polymer having a reduced particle generation ratio and an excellent particle size distribution under high polymerization activity.
- the olefin polymerization catalyst according to the present invention comprises (A) a solid catalyst component for olefin polymerization according to the present invention, (B) the following general formula (IV); R 15 p AlQ 3-p (IV) (Wherein, R 15 represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ⁇ .R 15 is a real number p ⁇ 3 there are a plurality, each R 15 may be the same or different from each other, and when a plurality of Q are present, each Q may be the same or different.) (C) External electron donation It is characterized by including an ionic compound.
- the olefin polymerization catalyst according to the present invention comprises (B) the following general formula (IV); R 15 p AlQ 3-p (IV) (Wherein, R 15 represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is the 0 ⁇ .R 15 is a real number p ⁇ 3 there are a plurality, each R 15 may be the same or different from each other, and when a plurality of Q are present, each Q may be the same or different.
- the organoaluminum compound represented by the general formula (IV) is not particularly limited, but R 15 may include one or more selected from an ethyl group and an isobutyl group, and Q may be a hydrogen atom, chlorine One or more selected from atoms and bromine atoms can be mentioned, and p is preferably 2, 2.5 or 3, and particularly preferably 3.
- organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diethylaluminum bromide, diethyl
- alkylaluminum halide such as diethylaluminum chloride and diethylaluminum bromide
- diethyl One or more selected from aluminum hydride and the like can be mentioned.
- alkyl aluminum halides such as diethylaluminum chloride or trialkylaluminum such as triethylaluminum, tri-n-butylaluminum and triisobutylaluminum.
- triethylaluminum and triisobutylaluminum Ri preferred.
- the external electron donating compound (C) is preferably a known external electron donating compound containing an oxygen atom or a nitrogen atom.
- R 16 is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, carbon an aromatic hydrocarbon group having 6 to 15 carbon atoms having an aromatic hydrocarbon group or a substituent having 6 to 15, if R 16 there are a plurality, a plurality of R 16 may be the same or different from each other R 17 is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent
- cycloalkenyl group or an aryl group having 6 to 20 carbon atoms may be R 18 and R 19 are either the same or different from each other, also may be bonded to each other to form a ring, R 18 R 19 N group
- R 20 represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, 1-20 alkoxy group, vinyloxy group, alkenyloxy group having 3-20 carbon atoms, cycloalkyl group having 3-20 carbon atoms, cycloalkyloxy group having 3-20 carbon atoms, aryl having 6-20 carbon atoms Group, an aryloxy group having 6 to 20 carbon atoms, if R 20 there are a plurality, the plurality of R 20 is optionally be the same or different .s is represented by from 1 to 3 to 3
- organosilicon compound or aminosilane compound represented by the general formula (V) or the general formula (VI) examples include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (Alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane And trialkyl (alkylamino) silane.
- organosilicon compound or aminosilane compound represented by the general formula (V) or the general formula (VI) include n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimeth
- the solid catalyst component for olefin polymerization (A) the solid catalyst component for olefin polymerization, (B) the organoaluminum compound represented by the general formula (IV) and (C) the content ratio of the external electron donating compound are:
- the general formula (B) The organoaluminum compound represented by (IV) is preferably 1 to 2000 mol, more preferably 50 to 1000 mol.
- the external electron donating compound is preferably 0.002 to 10 mol, preferably 0.01 to 2 mol per mol of the organoaluminum compound represented by the general formula (IV). More preferably, it is 0.01 to 0.5 mol.
- the method for producing the olefin polymerization catalyst according to the present invention is not particularly limited, and (A) a solid catalyst component for olefin polymerization, (B) an organoaluminum compound represented by the general formula (IV), and (C) external
- the electron donating compound can be prepared by contacting with a known method.
- the order in which the above components are brought into contact is arbitrary, but the following contact order can be exemplified.
- ⁇ means the contact order.
- (A) a solid catalyst component for olefin polymerization ⁇ (B) represented by the general formula (IV) The organoaluminum compound ⁇ (C) external electron donating compound ”is obtained by adding (B) the organoaluminum compound represented by the general formula (IV) to the solid catalyst component for polymerization of olefins (A).
- (C) means that an external electron donating compound is added and brought into contact.
- the olefin polymerization catalyst according to the present invention comprises (A) a solid catalyst component for olefin polymerization, (B) an organoaluminum compound represented by the general formula (IV), and (C) an external electron donating compound. It may be contacted in the absence, or may be contacted in the presence of olefins (in the polymerization system).
- an olefin polymerization catalyst capable of forming a polymer having a reduced particle generation ratio and excellent particle size distribution under high polymerization activity.
- the method for producing an olefin polymer according to the present invention is characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst according to the present invention.
- the polymerization of olefins may be homopolymerization or copolymerization.
- examples of the olefin include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like. Ethylene, propylene or 1-butene is preferred, and propylene is more preferred.
- a block copolymer obtained by block copolymerization is a polymer containing a segment in which two or more types of monomer compositions are continuously changed.
- Monomer type, comonomer type, comonomer composition, comonomer content, comonomer arrangement, stereoregulation It refers to a form in which two or more types of polymer chains (segments) having different primary structures of polymers are connected in one molecular chain.
- the olefins to be copolymerized are preferably ⁇ -olefins having 2 to 20 carbon atoms (excluding propylene having 3 carbon atoms), specifically, ethylene, 1-butene, 1-pentene, 4- Examples thereof include methyl-1-pentene and vinylcyclohexane. These olefins can be used in combination of one or more. In particular, ethylene and 1-butene are preferably used.
- the polymerization of olefins can be carried out in the presence or absence of an organic solvent.
- the olefins to be polymerized can be used in either a gas or liquid state.
- the polymerization of olefins can be performed, for example, in a reaction furnace such as an autoclave, in the presence of the olefin polymerization catalyst according to the present invention, and heated and pressurized.
- the polymerization temperature is usually 200 ° C. or lower, preferably 100 ° C. or lower, and more preferably 60 to 100 ° C. from the viewpoint of improving activity and stereoregularity. 70 to 90 ° C. is more preferable.
- the polymerization pressure is preferably 10 MPa or less, more preferably 5 MPa or less.
- any of a continuous polymerization method and a batch type polymerization method is possible.
- the polymerization reaction may be performed in one stage or in two or more stages.
- the constitution of the olefin polymerization catalyst according to the present invention for the olefins to be polymerized when the olefins are polymerized (hereinafter, referred to as “main polymerization” as appropriate), the constitution of the olefin polymerization catalyst according to the present invention for the olefins to be polymerized.
- Preliminary polymerization hereinafter, appropriately referred to as prepolymerization may be performed by bringing some or all of the components into contact with each other.
- the components of the olefin polymerization catalyst according to the present invention and the contact order of the olefins are arbitrary, but the organoaluminum compound is first introduced into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere. It is preferable to contact one or more olefins such as propylene after contacting the solid catalyst component for olefin polymerization according to the present invention.
- an organoaluminum compound is first charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, then contacted with an external electron donating compound, and further contacted with the solid catalyst component for olefin polymerization according to the present invention. Then, it is preferable to contact one or more olefins such as propylene.
- the same olefins as in the main polymerization or monomers such as styrene can be used, and the prepolymerization conditions are the same as the above polymerization conditions.
- the catalytic activity is improved, and the stereoregularity and particle properties of the resulting polymer can be further improved.
- the generation rate of a fine powder is reduced and the manufacturing method of the olefin polymer which can form the polymer excellent in particle size distribution under high polymerization activity can be provided.
- a polymer powder having a good particle shape and a narrow particle size distribution in which the amount of fine powder is extremely reduced can be produced in a high yield, and the resulting polymer powder is handled during the polymerization operation.
- the operability is improved, and the occurrence of clogging or the like due to the fine powder contained in the produced polymer powder can be suitably suppressed.
- the method for producing an olefin polymer according to the present invention can be applied particularly to a polyolefin production process by a gas phase method.
- titanium atom content in the solid catalyst component for olefin polymerization The titanium atom content in the solid catalyst component for olefin polymerization was measured according to the method described in JIS 8311-1997 “Method for quantifying titanium in titanium ore” (redox titration).
- Alkoxymagnesium (secondary particles) volume-based cumulative particle size of 90% particle size (D 90 ), average particle size (volume-based cumulative particle size of 50% particle size) and volume-based cumulative particle size of 10% particle size ( D 10 ) and the amount of fine powder of alkoxymagnesium of 5 ⁇ m or less were measured by the following method under a dry method using a laser diffraction method using a laser diffraction / scattering particle size distribution measuring device (manufactured by Malvern, Mastersizer 3000) corresponding to dry dispersion.
- Measurement was performed by automatically measuring the volume-based cumulative particle size distribution of the particles to be measured under the conditions.
- Measurement condition Measurement range: 0.01 ⁇ m to 3500 ⁇ m
- Dispersion form Dry Dispersion pressure: 1.5 bar (alkoxy magnesium) 0.4 bar (solid catalyst component)
- Laser scattered light intensity 0.3-5.0%
- Particle size distribution index (SPAN) (90% particle size by volume-based cumulative particle size (D 90 ) ⁇ 10% particle size by volume-based cumulative particle size (D 10 )) / average particle size (50% by volume-based cumulative particle size) Particle size)
- Particle size distribution index (SPAN) 90% particle size by volume-based cumulative particle size (D 90 ) ⁇ 10% particle size by volume-based cumulative particle size (D 10 )) / average particle size (50% by volume-based cumulative particle size) Particle size)
- the average particle size of the solid obtained before contact with the carboxylic acid ester and the amount of fine powder of 5 ⁇ m or less are also the above-described method for measuring the average particle size of alkoxymagnesium and the amount of fine powder of 5 ⁇ m or less. It measured by the same method.
- Alkoxymagnesium was photographed with a scanning electron microscope (JSM-7500F manufactured by JEOL Ltd.) at an acceleration voltage of 5 KV and an enlargement magnification of 30,000 times. After photographing, the negative image is visually analyzed, and the average particle diameter of primary particles constituting alkoxymagnesium by a statistical analysis method (50% particle diameter based on volume-based integrated particle size) is calculated from the longest diameters of 100 or more particles. Calculated.
- Example 1 Preparation of diethoxymagnesium (1) Solids formation step In a 2000 ml round bottom flask equipped with a stirrer and a reflux condenser sufficiently substituted with nitrogen gas, 5 g of metal magnesium fine powder having a particle size of 100 mesh or less, A suspension was formed by charging 125 ml of ethanol and 3 g of iodine. The suspension was then warmed with stirring to initiate the reaction under ethanol reflux. After starting the reaction, the operation of simultaneously adding 5 g of metal magnesium powder having a particle diameter of 100 mesh or less and 62 ml of ethanol into the flask was performed four times over 20 minutes.
- the average particle size of the obtained solid was 58.3 ⁇ m, and the fine powder of 5 ⁇ m or less was 5.1% by mass.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 57.8 ⁇ m, a particle size distribution index (SPAN) of 0.8, and an average particle diameter D1 of primary particles constituting the secondary particles of 0.00.
- the ratio represented by 6 ⁇ m, average particle diameter D1 of primary particles / average particle diameter D2 of secondary particles is 0.01, and 5% or less fine powder is 0% by mass, the specific surface area is 14 m 2 / g, and the bulk specific gravity is 0.00. It was 32 g / ml.
- the diethoxymagnesium was thoroughly washed with heptane, then the solid and liquid were separated, and the content of maleic acid diester in diethoxymagnesium was measured and found to be 0% by mass.
- Table 1 shows the measurement results of the pore volume of the obtained diethoxymagnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m. In the obtained diethoxymagnesium, pores having a pore diameter exceeding 1 ⁇ m were not measured. Moreover, the result of having image
- the obtained diethoxymagnesium is composed of secondary particles, which are aggregates of primary particles, and has a smooth surface and almost no fine particles. Further, the supernatant liquid removed in the removing step was further solid-liquid separated by a centrifugal separator and dried under reduced pressure. As a result, 0.3 g of diethoxymagnesium fine particles released into the supernatant liquid and 0.04 g of solubilized diethoxymagnesium were obtained. Was recovered.
- the obtained solid product was washed 4 times with 100 ml of toluene at 90 ° C., 40 ml of titanium tetrachloride and 60 ml of toluene were newly added, the temperature was raised to 100 ° C., and the mixture was reacted for 2 hours with stirring. After completion of the reaction, the product was washed 7 times with 100 ml of n-heptane at 40 ° C. to obtain the target solid catalyst component.
- the obtained solid catalyst component has a titanium content of 2.6% by mass, an internal electron donating compound content of 13.0% by mass (diisobutylmalonic acid diester 13.0% by mass, maleic acid diester 0.0% by mass).
- the average particle diameter of the solid catalyst component and the amount of fine powder of 5 ⁇ m or less are measured by the same method as the average particle diameter of alkoxymagnesium (secondary particles) and the amount of fine powder of 5 ⁇ m or less.
- Polymerization activity (kg-PP / g-cat) indicating the amount of polymer produced (F) kg per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.
- Polymerization activity (kg-PP / g-cat) product polymer (F) kg / solid catalyst component g / 1 hour
- the amount of fine powder of 75 ⁇ m or less of the obtained polymer is automatically determined by using a digital image analysis type particle size distribution measuring device (“Camsizer”, manufactured by HORIBA, Ltd.) under the following measurement conditions. Measurement was performed to obtain a measured value (% by mass) of an average particle size (50% particle size (D 50 ) by volume-based cumulative particle size) and a fine powder amount having a particle size of 75 ⁇ m or less.
- a digital image analysis type particle size distribution measuring device (“Camsizer”, manufactured by HORIBA, Ltd.) under the following measurement conditions. Measurement was performed to obtain a measured value (% by mass) of an average particle size (50% particle size (D 50 ) by volume-based cumulative particle size) and a fine powder amount having a particle size of 75 ⁇ m or less.
- BD bulk specific gravity
- Example 2 In “2. Preparation of solid catalyst component", diethoxymagnesium preparation and solid catalyst component were prepared under the same conditions as in Example 1 except that the same mole of diethyl diisobutylmalonate was used instead of dimethyl diisobutylmalonate. Preparation, polymerization catalyst formation and polymerization were performed, and the characteristics of the resulting alkoxymagnesium (diethoxymagnesium), the solid catalyst component, the catalyst (polymerization activity) and the polymer were measured in the same manner as in Example 1. did.
- the obtained solid catalyst component had a titanium content in the solid catalyst component of 3.2% by mass and an internal electron donating compound content of 14.0% by mass (14.0% by mass of diisobutylmalonic acid diester, maleic acid diester. 0.0 weight%), the average particle diameter D 50 46.3Myuemu, the following amount of fine powder 5 ⁇ m was 0.2 wt%.
- Example 3 In “2. Preparation of solid catalyst component”, the same conditions as in Example 1 except that the same mole of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was used instead of dimethyl diisobutylmalonate.
- diethoxymagnesium preparation of solid catalyst component, formation and polymerization of polymerization catalyst, characteristics of alkoxymagnesium (diethoxymagnesium) obtained, characteristics of solid catalyst component, characteristics of catalyst (polymerization activity) and polymer The characteristics were measured in the same manner as in Example 1.
- the resulting solid catalyst component, the titanium content in the solid catalyst component is 2.0 mass%, average particle diameter D 50 50.6Myuemu, the following amount of fine powder 5 ⁇ m was 0.4 wt%.
- Example 4 In “2. Preparation of solid catalyst component”, diethoxymagnesium and solid catalyst component were prepared under the same conditions as in Example 1, except that the same mole of dibutyl phthalate was used instead of dimethyl diisobutylmalonate.
- the polymerization catalyst was formed and polymerized, and the properties of the resulting alkoxymagnesium (diethoxymagnesium), the solid catalyst component, the catalyst (polymerization activity) and the polymer were measured in the same manner as in Example 1. .
- the results are shown in Tables 1 and 2.
- Example 5 Preparation of diethoxymagnesium Diethoxymagnesium was prepared in the same manner as in Example 1, “1. Preparation of diethoxymagnesium”. 2. Preparation of solid catalyst component To a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer, the above 1. 20 g of diethoxymagnesium obtained in (1) was added, and 160 ml of toluene, 10 ml of dimethyl diisobutylmalonate and 40 ml of titanium tetrachloride were added thereto to form a turbid liquid. Thereafter, the mixed solution was heated and reacted at 110 ° C. with stirring for 3 hours.
- the obtained solid product was washed 4 times with 100 ml of toluene at 90 ° C., 40 ml of titanium tetrachloride, 1 ml of diethyl maleate and 60 ml of toluene were newly added, and the temperature was raised to 100 ° C. and stirred for 2 hours. It was made to react.
- the solid catalyst component was obtained by washing 7 times with 100 ml of n-heptane at 40 ° C. The characteristics of the obtained solid catalyst component were measured in the same manner as in Example 1.
- the titanium content was 2.1% by mass and the internal electron donating compound content was 14.5% by mass (diisobutylmalonic acid diester 10.5).
- Example 6 Preparation of diethoxymagnesium and solid catalyst component under the same conditions as in Example 1 except that in “1. Preparation of diethoxymagnesium”, bis (2-ethylhexyl) maleate was changed to the same mole of diethyl maleate. Preparation of the catalyst, formation of the polymerization catalyst and polymerization, the characteristics of the resulting alkoxymagnesium (diethoxymagnesium), the characteristics of the solid catalyst component, the characteristics of the catalyst (polymerization activity) and the characteristics of the polymer are the same as in Example 1. It was measured. The obtained diethoxymagnesium was composed of secondary particles that were aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 56.8 ⁇ m, a SPAN of 0.8, an average particle diameter D1 of primary particles constituting the secondary particles of 0.7 ⁇ m, and a primary particle.
- the ratio of the average particle size of the particles to the average particle size of the secondary particles of 0.01, 5 ⁇ m or less is 1.5% by mass
- the specific surface area is 15 m 2 / g
- the bulk specific gravity is 0.31 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the solid catalyst component obtained from the above diethoxymagnesium has a titanium content of 2.3% by mass and an internal electron donating compound content of 12.6% by mass (diisobutylmalonic acid diester 12.6% by mass, malein Acid diester 0.0 mass%), the average particle diameter D 50 was 45.6 ⁇ m, and the amount of fine powder having a particle size of 5 ⁇ m or less was 0.5 mass%.
- Example 7 In the same manner as in Example 1, except that bis (2-ethylhexyl) maleate was changed to dimethyl diisobutylmalonate in “1.
- Preparation of diethoxymagnesium” in Example 1 under the same conditions as in Example 1.
- Preparation, preparation of solid catalyst component, formation of polymerization catalyst and polymerization, and characteristics of the resulting alkoxymagnesium (diethoxymagnesium), solid catalyst component, catalyst characteristics (polymerization activity) and polymer characteristics Measurement was performed in the same manner as in Example 1.
- the obtained diethoxymagnesium was composed of secondary particles that were aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 56.5 ⁇ m, SPAN of 1.0, and an average particle diameter D1 of primary particles constituting the secondary particles of 0.5 ⁇ m.
- the ratio of the average particle diameter D1 of particles and the average particle diameter of secondary particles is 0.01, the fine powder of 5 ⁇ m or less is 1.6 mass%, the specific surface area is 15 m 2 / g, and the bulk specific gravity is 0.32 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the amount of fine powder was 0.5% by mass. The results are shown in Tables 1 and 2.
- Example 8 In the same manner as in Example 1, except that the amount of bis (2-ethylhexyl) maleate added was changed from 30 mmol to 7 mmol in “1.
- Preparation of diethoxymagnesium” in Example 1 Preparation, solid catalyst component preparation, polymerization catalyst formation and polymerization, the characteristics of the resulting alkoxymagnesium (diethoxymagnesium), solid catalyst component characteristics, catalyst characteristics (polymerization activity) and polymer characteristics Measurement was performed in the same manner as in Example 1.
- the obtained diethoxymagnesium was composed of secondary particles, which are aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 56.8 ⁇ m, a SPAN of 0.8, an average particle diameter D1 of primary particles constituting the secondary particles of 0.7 ⁇ m, and a primary particle.
- the ratio of the average particle diameter D1 of the particles and the average particle diameter D2 of the secondary particles is 0.01, 5 ⁇ m or less is 1.8% by mass, the specific surface area is 19 m 2 / g, and the bulk specific gravity is 0.00. It was 31 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the supernatant liquid removed in the removing step was further solid-liquid separated with a centrifugal separator and dried under reduced pressure. 0.2 g diethoxymagnesium fine particles released into the supernatant liquid and 0.03 g solubilized diethoxymagnesium were obtained. Was recovered.
- the solid catalyst component obtained from diethoxymagnesium has a titanium content of 2.3% by mass and an internal electron donating compound content of 12.9% by mass (diisobutylmalonic acid diester content of 12.9% by mass). %, The content of maleic diester is 0.0% by mass), the average particle diameter D 50 is 45.6 ⁇ m, and the amount of fine powder of 5 ⁇ m or less was 0.8% by mass. The results are shown in Tables 1 and 2.
- Example 9 In the same manner as in Example 1 except that the amount of bis (2-ethylhexyl) maleate added was changed from 30 mmol to 14 mmol in “1.
- Preparation of diethoxymagnesium” in Example 1 Preparation, solid catalyst component preparation, polymerization catalyst formation and polymerization, the characteristics of the resulting alkoxymagnesium (diethoxymagnesium), solid catalyst component characteristics, catalyst characteristics (polymerization activity) and polymer characteristics Measurement was performed in the same manner as in Example 1.
- the obtained diethoxymagnesium was composed of secondary particles, which are aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 57.6 ⁇ m, a SPAN of 0.9, an average particle diameter D1 of primary particles constituting the secondary particles of 0.6 ⁇ m, and a primary particle.
- the ratio of the average particle diameter D1 of the particles and the average particle diameter D2 of the secondary particles is 0.01, 5 ⁇ m or less is 0.8% by mass, the specific surface area is 16 m 2 / g, and the bulk specific gravity is 0.1. It was 31 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the supernatant liquid removed in the removing step was further solid-liquid separated with a centrifugal separator and dried under reduced pressure.
- 0.4 g of diethoxymagnesium fine particles released into the supernatant liquid and 0.04 g of solubilized diethoxymagnesium were obtained. Was recovered.
- the solid catalyst component obtained from the diethoxymagnesium has a titanium content of 2.3% by mass, an internal electron donating compound content of 13.3% by mass (diisobutylmalonic acid diester 13.3% by mass, malein Acid diester 0% by mass), and the average particle size D 50 was 47.4 ⁇ m, and the amount of fine powder having a particle size of 5 ⁇ m or less was 0% by mass.
- Example 10 In the same manner as in Example 1 except that the amount of bis (2-ethylhexyl) maleate added was changed from 30 mmol to 60 mmol in “1.
- Preparation of diethoxymagnesium” in Example 1 Preparation, solid catalyst component preparation, polymerization catalyst formation and polymerization, the characteristics of the resulting alkoxymagnesium (diethoxymagnesium), solid catalyst component characteristics, catalyst characteristics (polymerization activity) and polymer characteristics Measurement was performed in the same manner as in Example 1.
- the obtained diethoxymagnesium was composed of secondary particles, which are aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 57.8 ⁇ m, SPAN of 0.8, and an average particle diameter D1 of primary particles constituting the secondary particles of 0.6 ⁇ m.
- the ratio of the average particle diameter D1 of the particles and the average particle diameter D2 of the secondary particles is 0.01 and 5 ⁇ m or less is 0% by mass, the specific surface area is 12 m 2 / g, and the bulk specific gravity is 0.33 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the solid catalyst component obtained from the above diethoxymagnesium has a titanium content of 2.3% by mass, an internal electron donating compound content of 13.1% by mass (diisobutylmalonic acid diester 13.1% by mass, malein Acid diester 0% by mass), the average particle diameter D 50 was 48.9 ⁇ m, and the amount of fine powder of 5 ⁇ m or less was 0% by mass.
- Example 11 Preparation of Diethoxymagnesium (1) Solid Forming Step In a 2000 ml round bottom flask equipped with a stirrer and a reflux condenser sufficiently substituted with nitrogen gas, 5 g of metal magnesium fine powder having a particle size of 144 mesh or less, A suspension was formed by charging 125 ml of ethanol and 3 g of iodine. The suspension was then warmed with stirring to initiate the reaction under ethanol reflux. After starting the reaction, the operation of simultaneously adding 5 g of metal magnesium powder having a particle size of 100 mesh or less and 62 ml of ethanol into the flask was performed four times for 30 minutes.
- the characteristics of the resulting alkoxymagnesium were measured in the same manner as in Example 1.
- the obtained diethoxymagnesium was composed of secondary particles, which are aggregates of primary particles, and had a smooth surface and almost no fine powder particles.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 19.3 ⁇ m, SPAN of 0.8, and an average particle diameter D1 of primary particles constituting the secondary particles of 0.6 ⁇ m.
- the ratio of the average particle diameter D1 of the particles and the average particle diameter D2 of the secondary particles of 0.03, 5 ⁇ m or less is 1.6% by mass, the specific surface area is 22 m 2 / g, and the bulk specific gravity is 0.00. It was 24 g / ml.
- the diethoxymagnesium was thoroughly washed with heptane, then the solid and liquid were separated and the maleic acid diester content in the diethoxymagnesium was measured to find that it was 0% by mass. No adduct of maleic acid diester was formed.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxymagnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m. In the obtained diethoxymagnesium, pores having a pore diameter exceeding 1 ⁇ m were not measured.
- the supernatant liquid removed in the removing step was further solid-liquid separated with a centrifugal separator and dried under reduced pressure. 0.5 g of diethoxymagnesium fine particles released into the supernatant liquid and 0.06 g of solubilized diethoxymagnesium were obtained. Was recovered.
- solid catalyst component was prepared under the same conditions as in Example 1 except that the above diethoxymagnesium was used, and the characteristics of the obtained solid catalyst component were measured in the same manner as in Example 1.
- the obtained solid catalyst component had a titanium content of 3.3% by mass, an internal electron donating compound content of 12.6% by mass (diisobutylmalonic acid diester 12.6% by mass, maleic acid diester 0% by mass), the average particle diameter D 50 of 19.2, less amount of fine powder 5 ⁇ m was 0.1 wt%.
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 52.9 ⁇ m, SPAN of 1.1, an average particle diameter D1 of primary particles constituting the secondary particles of 0.7 ⁇ m,
- the average particle diameter D1 / the ratio represented by the average particle diameter D2 of the secondary particles is 0.01, the amount of fine powder of 5 ⁇ m or less is 4.1 mass%, the specific surface area is 25 m 2 / g, and the bulk specific gravity is 0.30 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the obtained diethoxymagnesium pores having a pore diameter exceeding 1 ⁇ m were not measured. Further, the solid catalyst component obtained from the above diethoxy magnesium, titanium content of 3.2 wt%, the content of diisobutyl malonate diester 14.5 mass%, average particle diameter D 50 is an 52.9 ⁇ m The amount of fine powder of 5 ⁇ m or less was 4.1% by mass. The results are shown in Tables 1 and 2. Moreover, the result of having image
- the obtained diethoxymagnesium has an average particle diameter D2 of secondary particles of 57.6 ⁇ m, SPAN of 1.2, an average particle diameter D1 of primary particles constituting the secondary particles of 0.7 ⁇ m,
- the average particle size D1 / the ratio expressed by the average particle size D2 of the secondary particles is 0.01, the fine powder amount of 5 ⁇ m or less is 3.4 mass%, the specific surface area is 15 m 2 / g, and the bulk specific gravity is 0.33 g / ml.
- Table 1 shows the results of measuring the pore volume of the obtained diethoxygnesium having a pore diameter of 1 ⁇ m or less and the pore volume of a pore having a pore diameter of 0.1 to 0.5 ⁇ m.
- the obtained diethoxymagnesium pores having a pore diameter exceeding 1 ⁇ m were not measured.
- the obtained solid catalyst component had a titanium content of 3.0% by mass and an internal electron donating compound content of 12.8% by mass (diisobutylmalonic acid diester 12.8% by mass, 9,9-bismethoxy). methyl fluorene 0.0 weight%), an average particle diameter D 50 is 47.2Myuemu, less amount of fine powder 5 ⁇ m was 3.5 wt%.
- Examples 1 to 11 are constituted by secondary particles that are aggregates of primary particles obtained by reacting magnesium metal with alcohol and then contacting with a carboxylic acid ester. Because of the use of alkoxymagnesium having specific physical properties, when the olefins are polymerized as a constituent component of the solid catalyst component for olefin polymerization, the generation ratio of fine powder is reduced and the polymer has an excellent particle size distribution. It can be seen that can be formed under high polymerization activity.
- Comparative Example 1 and Comparative Example 2 after reacting metal magnesium and alcohol, it does not come into contact with the carboxylic acid ester (Comparative Example 1), or instead of the carboxylic acid ester. Since the alkoxymagnesium obtained by contacting with 9,9-bismethoxymethylfluorene (Comparative Example 2), each having no specific physical property, is used, an olefin is used as a component of the solid catalyst component for olefin polymerization. It can be seen that a large amount of fine powder of not more than 75 ⁇ m is generated particularly when the polymers are polymerized.
- an olefin when polymerized as a constituent component of a solid catalyst component for olefin polymerization, a generation ratio of fine powder is reduced, and a novel polymer capable of forming a polymer having an excellent particle size distribution under a high polymerization activity.
- a method for producing the alkoxymagnesium, a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer can be provided.
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Abstract
Description
本知見に基づき、本発明者等がさらに検討を行ったところ、平均粒子径1μm未満の一次粒子の集合体である二次粒子により構成され、前記一次粒子の平均粒子径/前記二次粒子の平均粒子径で表される比が0.1以下であり、全細孔容積が0.5~1cm3/gで、比表面積が50m2/g未満、粒度分布指数(SPAN)が1以下であるアルコキシマグネシウムにより上記課題を解決し得ることを見出し、本発明を完成するに至った。
(1)平均粒子径1μm未満の一次粒子の集合体である二次粒子により構成され、
前記一次粒子の平均粒子径/前記二次粒子の平均粒子径で表される比が0.1以下であり、
全細孔容積が0.5~1cm3/gで、比表面積が50m2/g未満、粒度分布指数(SPAN)が1以下である
ことを特徴とするアルコキシマグネシウム、
(2)5μm以下の粒子径を有する微粉の含有量が全粒子質量の3質量%以下であり、全細孔容積が0.5~1cm3/gで、1μm以下の細孔径を有する細孔の50%以上が0.5μm以下の細孔径を有している上記(1)に記載のアルコキシマグネシウム、
(3)前記二次粒子の平均粒子径が60μm未満である上記(1)または(2)に記載のアルコキシマグネシウム、
(4)金属マグネシウムとアルコールとを触媒の存在下で反応させて固形物を形成する固形物形成工程と、
前記固形物と一種以上のカルボン酸エステルとを有機溶媒中で接触させ懸濁液を形成する接触工程とを
順次施すことを特徴とするアルコキシマグネシウムの製造方法、
(5)前記アルコールが、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノールおよび2-エチルヘキシルアルコールから選ばれる一種以上である上記(4)に記載のアルコキシマグネシウムの製造方法、
(6)前記有機溶媒が、脂肪族炭化水素化合物および芳香族炭化水素化合物から選ばれる一種以上である上記(4)または(5)に記載のアルコキシマグネシウムの製造方法、
(7)前記カルボン酸エステルが、下記一般式(I);
(8)前記カルボン酸エステルが、コハク酸ジエチル、コハク酸ジブチル、コハク酸ビス(2-エチルヘキシル)、マレイン酸ジエチル、マレイン酸ジブチル、マレイン酸ビス(2-エチルヘキシル)、マロン酸ジエチル、マロン酸ジブチル、マロン酸ビス(2-エチルヘキシル)から選ばれる1種以上である上記(4)~(7)のいずれかに記載のアルコキシマグネシウムの製造方法、
(9)前記アルコキシマグネシウムが、ジエトキシマグネシウムである上記(4)~(8)のいずれかに記載のアルコキシマグネシウムの製造方法、
(10)前記接触工程を施すことにより、前記固形物の一部とカルボン酸エステルとを反応させて反応物を形成するか、前記固形物の一部をカルボン酸エステルと有機溶媒との混合物中に溶解させるか、または前記固形物の一部をカルボン酸エステルと有機溶媒との混合物中に遊離させる上記(4)~(9)のいずれかに記載のアルコキシマグネシウムの製造方法、
(11)上記(1)~(3)のいずれか1項に記載のアルコキシマグネシウム(a)と、チタンハロゲン化合物(b)と、電子供与性化合物(c)とを接触させて得られることを特徴とするオレフィン類重合用固体触媒成分、
(12)(A)上記(11)に記載のオレフィン類重合用固体触媒成分、(B)下記一般式(IV);
R15 pAlQ3-p (IV)
(式中、R15は炭素数1~4のアルキル基を示し、Qは水素原子あるいはハロゲン原子を示し、pは0<p≦3の実数である。R15が複数存在する場合、各R15は互いに同一であっても異なっていてもよく、Qが複数存在する場合、各Qは同一であっても異なっていてもよい。)で表される有機アルミニウム化合物および(C)外部電子供与性化合物を含むことを特徴とするオレフィン類重合用触媒、
(13)前記(C)外部電子供与性化合物が、下記一般式(V);
R16 qSi(OR17)4-q (V)
(式中、R16は、炭素数1~12のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~12のシクロアルキル基、炭素数3~12のシクロアルケニル基、炭素数6~15の芳香族炭化水素基または置換基を有する炭素数6~15の芳香族炭化水素基を示し、R16が複数存在する場合、複数のR16は互いに同一でも異なっていてもよい。R17は、炭素数1~4のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~6のシクロアルキル基、炭素数6~12の芳香族炭化水素基または置換基を有する炭素数7~12の芳香族炭化水素基を示し、R17が複数存在する場合、複数のR17は互いに同一でも異なっていてもよい。qは0≦q≦3の整数である。)で表される有機ケイ素化合物および一般式(VI);
(R18R19N)sSiR20 4-s (VI)
(式中、R18およびR19は、水素原子、炭素数1~20のアルキル基、ビニル基、炭素数3~20のアルケニル基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルケニル基または炭素数6~20のアリール基を示し、R18およびR19は互いに同一でも異なっていてもよく、また互いに結合して環を形成してもよく、R18R19N基が複数存在する場合、複数のR18R19N基は互いに同一でも異なっていてもよい。R20は炭素数1~20のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数1~20のアルコキシ基、ビニルオキシ基、炭素数3~20のアルケニルオキシ基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルキルオキシ基、炭素数6~20のアリール基、炭素数6~20のアリールオキシ基を示し、R20が複数存在する場合、複数のR20は互いに同一でも異なっていてもよい。sは1から3の整数である。)で表されるアミノシラン化合物から選択される一種以上である
上記(12)に記載のオレフィン類重合用触媒、
(14)上記(12)または(13)に記載のオレフィン重合用触媒の存在下にオレフィン類の重合を行うことを特徴とするオレフィン類重合体の製造方法、
を提供するものである。
また、従来は一次粒子が1~10μmと大きく、二次粒子表面から剥がれた一次粒子が微粒子状の重合体を生成する原因の一つであった。しかし、本発明に係るアルコキシマグネシウムは一次粒子の粒子径が1μm未満と小さく、固体触媒成分の製造工程における洗浄時に浮遊している一次粒子を排液中に容易に抜き出し得ることから、オレフィン類の重合時に微粒子状の重合体量を低減し得ると考えられる。
を基に、統計解析手法により算出した平均粒子径を意味する。
また、アルコキシマグネシウム二次粒子の平均粒子径は、乾式分散に対応したレーザー回折式粒度分布測定装置を用い、乾燥状態の測定試料を各々10万個以上測定したときの平均粒子径D50(体積積算粒度分布における積算粒度で50%の粒子径)を意味する。
上記微粉は、専らアルコキシマグネシウムの二次粒子が崩壊して生成するものであるが、粒子径が上記規定を満たす限り、二次粒子を構成していない一次粒子等も微粉に含めるものとする。
本発明に係るアルコキシマグネシウムが、比表面積が大きく、細孔容積が大きいものであることにより、当該アルコキシマグネシウムを用いて調製した固体触媒成分をオレフィン類の重合に供した場合に、優れた粒子性状を有した重合体が高収率で得られ、しかもブロック共重合においては、ゴム状重合体の生成割合が高い場合であっても、優れた粒子性状の共重合体を高収率で得ることができる。
特に本発明に係るアルコキシマグネシウムは、オレフィン類重合用固体触媒成分の構成成分として用いた際に、より良好な粒子形状と狭い粒度分布を有するオレフィン類重合体粉末を得ることができ、重合操作時の生成重合体粉末の取扱い操作性が向上し、生成重合体粉末に含まれる微粉に起因する閉塞等の発生を好適に抑制することができる。
本発明に係るアルコキシマグネシウムの製造方法は、金属マグネシウムとアルコールとを触媒の存在下で反応させて固形物を形成する固形物形成工程と、前記固形物と一種以上のカルボン酸エステルとを、有機溶媒中で接触させ懸濁液を形成する接触工程とを順次施すことを特徴とするものである。
上記アルコールは、金属マグネシウムと接触させ反応する前に、水分を充分除去したものが望ましい。
上記触媒は固形物形成工程の初期に反応系に添加しておくことが好ましい。
例えば、最終的に上記質量比となるように、触媒を含有する反応系に、金属マグネシウムとアルコールとを連続的または断続的に添加して接触、反応させ、次いで、アルコールの還流下に保持し、熟成反応を行う方法を挙げることができる。
上記金属マグネシウムとアルコールとの反応時間は5~80分間であることが好ましく、上記熟成時間は1~30時間であることが好ましい。
R3およびR4としては、炭素数4~12のアルキル基が好ましく、炭素数7~12のアルキル基がより好ましい。
R1が水素原子であり、R2が炭素数1~12の直鎖状アルキル基、炭素数3~12の分岐鎖状のアルキル基、ビニル基、炭素数3~12の直鎖状アルケニル基、炭素数3~12の分岐鎖状アルケニル基、炭素数3~12のシクロアルキル基または炭素数6~20の芳香族炭化水素基であるアルキルマレイン酸ジエステルや、R1およびR2が、各々独立に、炭素数1~12の直鎖状アルキル基、炭素数3~12の分岐アルキル基、ビニル基、炭素数3~12の直鎖状アルケニル基、炭素数3~12の分岐鎖状アルケニル基、炭素数3~12のシクロアルキル基または炭素数6~20の芳香族炭化水素基から選ばれる基であるジアルキルマレイン酸ジエステルや、
R1およびR2のうち、少なくとも一方が炭素数3~12のシクロアルキル基であるシクロアルキルマレイン酸ジエステル等から選ばれる一種以上を挙げることができ、上記カルボン酸エステルのうち、特に、マレイン酸ジエチル、マレイン酸ジブチルまたはマレイン酸ビス2-エチルヘキシルが好ましい。
R9およびR10としては、炭素数4~12のアルキル基が好ましく、炭素数7~12のアルキル基がより好ましい。
R13およびR14としては、炭素数4~12のアルキル基が好ましく、炭素数7~12のアルキル基がより好ましい。
上記有機溶媒としては、カルボン酸エステルを溶解し、かつ固形物(マグネシウム化合物)は溶解しないものであることが適当であり、具体的には、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、シクロヘキサン等の脂肪族炭化水素化合物、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素化合物、塩化メチレン、1,2-ジクロロベンゼン等のハロゲン化炭化水素化合物、メタノール、エタノール、イソオクチルアルコール等のアルコール類、ジエチルエーテル等のエーテル類等から選ばれる一種以上が挙げられる。これらの中でも、ヘプタン、トルエン、キシレン等の炭化水素化合物から選ばれる一種以上が好適である。
また、本発明に係るアルコキシマグネシウムの製造方法の接触工程において、有機溶媒の使用量は、上記固形物1gに対して、0.1~50mlであることが好ましく、1~30mlであることがより好ましく、2~10mlであることがさらに好ましい。
本発明に係るアルコキシマグネシウムの製造方法においては、上記接触工程を施すことによって、上記固形物の一部がカルボン酸エステルと反応して反応物を形成するか、上記固形物の一部がカルボン酸エステルと有機溶媒との混合物中に溶解するか、または上記固形物の一部がカルボン酸エステルと有機溶媒との混合物中に遊離すると考えられる。
すなわち、本発明に係るアルコキシマグネシウムの製造方法においては、固形物形成工程で得られた固形物を、接触工程においてカルボン酸エステルと接触させることにより、(1)例えばジアルコキシマグネシウムを構成するアルコキシ基のアルキル鎖とカルボン酸ジエステルを構成するエステル残基のアルキル鎖が入れ替わる、いわゆる「エステル交換反応」が起こる等の作用により、アルコキシマグネシウムに付着している微粉状ジアルコキシマグネシウムの少なくとも一部がカルボン酸エステルと反応して反応物を形成し、容易に除去することができるか、(2)アルコキシマグネシウムに付着している微粉の少なくとも一部をカルボン酸エステルと有機溶媒との混合物中に溶解して、容易に除去することができるか、または、(3)アルコキシマグネシウムに付着している微粉の少なくとも一部を帯電防止などの効果により遊離し易くして、洗浄処理等により容易に除去することができると考えられる。
また、固形物形成工程で得られた固形物を、接触工程においてカルボン酸エステルと接触させることにより、固形物粒子表面の平滑度が向上し、オレフィン類重合用固体触媒成分の調製に用いたときに、均一な反応が促進され、凝集体の形成を抑制することができる。
上記凝集体(凝集した固体触媒成分)はプラントでオレフィン類を重合して重合体を形成する際に、凝集体粒子が壊れて微粉重合体を生成し易いが、本発明に係るアルコキシマグネシウムの製造方法においては、上述したように、固形物形成工程で得られた固形物を、接触工程においてカルボン酸エステルと接触させることにより、上記凝集体粒子に由来する微粉重合体の生成を好適に抑制することができる。
上記除去処理は、デカンテーションやろ過等により懸濁液から溶媒を除去することにより行うことが好ましい。
本発明に係るアルコキシマグネシウムの製造方法においては、上記除去処理後に有機溶媒等によりさらに処理してもよく、有機溶媒で処理することにより除去処理後に得られる残渣(反応生成物)中に含まれる過剰のカルボン酸エステルを洗浄、除去することができる。
本発明に係るオレフィン類重合用固体触媒成分は、本発明に係るアルコキシマグネシウム(a)と、チタンハロゲン化合物(b)と、電子供与性化合物(c)とを接触させることにより調製されることを特徴とするものである。
本発明に係るオレフィン類重合用固体触媒成分を構成するアルコキシマグネシウムとして、本発明に係る製造方法で作製されたアルコキシマグネシウムを使用する場合、固体触媒成分の製造工程の簡略化を考慮すれば、上記分離、乾燥処理を行わない懸濁液状のものが望ましいが、上記有機溶媒がアルコールやエーテルなどチタンハロゲン化合物(b)と反応するものである場合には、上記懸濁液を真空下あるいは加熱下で乾燥して有機溶媒が十分に除去されたものであることが好ましい。
沸点が50~150℃の不活性有機溶媒としては、芳香族炭化水素化合物および脂肪族炭化水素化合物が一般的であるが、反応性または反応後の洗浄時に不純物の溶解度が低下しないのであれば芳香族炭化水素および飽和炭化水素以外の不活性有機溶媒を使用してもよい。
本発明に係るオレフィン類重合用触媒は、(A)本発明に係るオレフィン類重合用固体触媒成分、(B)下記一般式(IV);
R15 pAlQ3-p (IV)
(式中、R15は炭素数1~4のアルキル基を示し、Qは水素原子あるいはハロゲン原子を示し、pは0<p≦3の実数である。R15が複数存在する場合、各R15は互いに同一であっても異なっていてもよく、Qが複数存在する場合、各Qは同一であっても異なっていてもよい。)で表される有機アルミニウム化合物および(C)外部電子供与性化合物を含むことを特徴とするものである。
R15 pAlQ3-p (IV)
(式中、R15は炭素数1~4のアルキル基を示し、Qは水素原子あるいはハロゲン原子を示し、pは0<p≦3の実数である。R15が複数存在する場合、各R15は互いに同一であっても異なっていてもよく、Qが複数存在する場合、各Qは同一であっても異なっていてもよい。)で表される有機アルミニウム化合物を含む。
下記一般式(V);
R16 qSi(OR17)4-q (V)
(式中、R16は、炭素数1~12のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~12のシクロアルキル基、炭素数3~12のシクロアルケニル基、炭素数6~15の芳香族炭化水素基または置換基を有する炭素数6~15の芳香族炭化水素基を示し、R16が複数存在する場合、複数のR16は互いに同一でも異なっていてもよい。R17は、炭素数1~4のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~6のシクロアルキル基、炭素数6~12の芳香族炭化水素基または置換基を有する炭素数7~12の芳香族炭化水素基を示し、R17が複数存在する場合、複数のR17は互いに同一でも異なっていてもよい。qは0≦q≦3の整数である。)で表される有機ケイ素化合物および一般式(VI);
(R18R19N)sSiR20 4-s (VI)
(式中、R18およびR19は、水素原子、炭素数1~20のアルキル基、ビニル基、炭素数3~20のアルケニル基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルケニル基または炭素数6~20のアリール基を示し、R18およびR19は互いに同一でも異なっていてもよく、また互いに結合して環を形成してもよく、R18R19N基が複数存在する場合、複数のR18R19N基は互いに同一でも異なっていてもよい。R20は炭素数1~20のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数1~20のアルコキシ基、ビニルオキシ基、炭素数3~20のアルケニルオキシ基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルキルオキシ基、炭素数6~20のアリール基、炭素数6~20のアリールオキシ基を示し、R20が複数存在する場合、複数のR20は互いに同一でも異なっていてもよい。sは1から3の整数である。)で表されるアミノシラン化合物から選択される一種以上を挙げることができる。
フェニルトリメトキシシラン、t-ブチルメチルジメトキシシラン、t-ブチルエチルジメトキシシラン、ジイソプロピルジメトキシシラン、イソプロピルイソブチルジメトキシシラン、ジイソペンチルジメトキシシラン、ジフェニルジメトキシシラン、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、t-ブチルメチルビス(エチルアミノ)シラン、ビス(エチルアミノ)ジシクロヘキシルシラン、ジシクロペンチルビス(エチルアミノ)シラン、ビス(パーヒドロイソキノリノ)ジメトキシシラン、ジエチルアミノトリエトキシシラン等から選ばれる一種以上が好ましい。
上記各成分を接触させる順序は任意であるが、例えば、以下の接触順序を例示することができる。
(i)(A)オレフィン類重合用固体触媒成分→(C)外部電子供与性化合物→(B)一般式(IV)で表される有機アルミニウム化合物
(ii)(B)一般式(IV)で表される有機アルミニウム化合物→(C)外部電子供与性化合物→(A)本発明の製造方法で得られたオレフィン類重合用固体触媒成分
(iii)(C)外部電子供与性化合物→(A)オレフィン類重合用固体触媒成分→(B)一般式(IV)で表される有機アルミニウム化合物
(iv)(C)外部電子供与性化合物→(B)一般式(IV)で表される有機アルミニウム化合物→(A)オレフィン類重合用固体触媒成分
上記接触例(i)~(iv)において、接触例(ii)が好適である。
なお、上記接触例(i)~(iv)において、「→」は接触順序を意味し、例えば、「(A)オレフィン類重合用固体触媒成分→(B)一般式(IV)で表される有機アルミニウム化合物→(C)外部電子供与性化合物」は、(A)オレフィン類重合用固体触媒成分中に(B)一般式(IV)で表される有機アルミニウム化合物を添加して接触させた後、(C)外部電子供与性化合物を添加して接触させることを意味する。
本発明に係るオレフィン類重合体の製造方法は、本発明に係るオレフィン重合用触媒の存在下にオレフィン類の重合を行うことを特徴とするものである。
共重合されるオレフィン類としては、炭素数2~20のα-オレフィン(炭素数3のプロピレンを除く)であることが好ましく、具体的には、エチレン、1-ブテン、1-ペンテン、4-メチル-1-ペンテン、ビニルシクロヘキサン等を挙げることができ、これ等のオレフィン類は一種以上併用することができる。とりわけ、エチレンおよび1-ブテンが好適に用いられる。
また、重合対象となるオレフィン類は、気体および液体のいずれの状態でも用いることができる。
また、連続重合法、バッチ式重合法のいずれでも可能である。更に重合反応は一段で行ってもよいし、二段以上で行ってもよい。
特に、本発明によれば、微粉量が極めて低減された良好な粒子形状と狭い粒度分布とを有する重合体粉末を高収率で作製することができ、重合操作時の生成重合体粉末の取扱い操作性が向上し、生成重合体粉末に含まれる微粉に起因する閉塞等の発生を好適に抑制することができる。
本発明に係るオレフィン類重合体の製造方法は、特に気相法によるポリオレフィンの製造プロセスに適用することができる。
なお、以下に示す実施例および比較例において、オレフィン類重合用固体触媒成分中のチタン原子の含有量、アルコキシマグネシウムの平均粒子径、固体触媒成分の平均粒子径および5μm以下の微粉量は、以下の方法により測定したものである。
オレフィン類重合用固体触媒成分中のチタン原子含有量は、JIS 8311-1997「チタン鉱石中のチタン定量方法」に記載の方法(酸化還元滴定)に準じて測定した。
アルコキシマグネシウム(二次粒子)の体積基準積算粒度で90%の粒径(D90)、平均粒子径(体積基準積算粒度で50%の粒径)および体積基準積算粒度で10%の粒径(D10)と、アルコキシマグネシウムの5μm以下の微粉量は、乾式分散に対応したレーザー回折散乱式粒度分布測定装置(マルバーン社製、マスターサイザー3000)を用いて、レーザー回折法により乾式下、下記測定条件下で測定対象粒子の体積基準積算粒度分布の自動測定を行なうことで測定した。
(測定条件)
測定範囲 :0.01μm~3500μm
分散形態 :乾式
分散圧 :1.5bar(アルコキシマグネシウム)
0.4bar(固体触媒成分)
レーザー散乱光強度:0.3~5.0%
また、上記測定により得られたアルコキシマグネシウム(二次粒子)のD90、平均粒子径、D10より、以下の算出式により、粒度分布指数(SPAN)を求めた。
粒度分布指数(SPAN)=(体積基準積算粒度で90%の粒径(D90)-体積基準積算粒度で10%の粒径(D10))/平均粒子径(体積基準積算粒度で50%の粒径)
また、アルコキシマグネシウムの製造時、カルボン酸エステルとの接触前に得られる固形物の平均粒子径および5μm以下の微粉量も、上述したアルコキシマグネシウムの平均粒子径および5μm以下の微粉量の測定方法と同様の方法で測定した。
アルコキシマグネシウムを走査型電子顕微鏡(日本電子(株)製JSM-7500F)にて、加速電圧5KV、拡大倍率30,000倍で撮影した。撮影後、ネガ画像を目視により解析し、100個以上の粒子の各最長径から、統計解析手法によりアルコキシマグネシウムを構成する一次粒子の平均粒子径(体積基準積算粒度で50%の粒径)を算出した。
1.ジエトキシマグネシウムの調製
(1)固形物形成工程
窒素ガスで十分置換された攪拌器および還流冷却器を具備した容量2000mlの丸底フラスコに、粒子径100メッシュ以下の金属マグネシウム微粉末5g、室温のエタノール125mlおよびヨウ素3gを装入し懸濁液を形成した。
次いで上記懸濁液を攪拌しながら昇温して、エタノールの還流下で反応を開始させた。反応開始後、粒子径100メッシュ以下の金属マグネシウム粉末5gとエタノール62mlとを同時にフラスコ内に添加する操作を計4回、20分間に亘って行った。添加終了後、エタノールの還流下で、攪拌しながら10時間保持した(最終添加したマグネシウムは25gであり、エタノールは、373ml(約294.3g)であり、最終添加の金属マグネシウム/エタノール=1/11.8)。その後室温まで冷却した後、上澄みをデカンテーションし、真空乾燥して、約100gの固形物を得た。得られた固形物の平均粒子径は58.3μm、5μm以下の微粉は5.1質量%であった。
窒素ガスで十分に置換され、攪拌機を具備した容量500 mlの丸底フラスコに上記(1)で得られた固形物20g、常温のトルエン115ml、マレイン酸ビス(2-エチルヘキシル)30ミリモルを投入、攪拌して懸濁液を形成した。
該懸濁液を、攪拌しながら60℃まで昇温し、60℃で1時間の接触を行った。次いで、得られた懸濁液を静置して上澄み液をデカンテーションにて除去し(除去工程)、さらに60℃のトルエン80mlを投入し攪拌する洗浄工程を3回繰り返し、ジエトキシマグネシウムを得た。
得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が57.8μm、粒度分布指数(SPAN)が0.8、二次粒子を構成している一次粒子の平均粒子径D1が0.6μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉が0質量%、比表面積が14m2/g、嵩比重が0.32g/mlであるものであった。
なお、上記のジエトキシマグネシウムをヘプタンで十分に洗浄した後、固液を分離し、ジエトキシマグネシウム中のマレイン酸ジエステルの含有量を測定したところ、0質量%であった。また、上記のジエトキシマグネシウムは、マレイン酸ビス(2-エチルヘキシル)の付加物を形成していなかった。
得られたジエトキシマグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積の測定結果を表1に示す。なお、得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
また、上記のジエトキシマグネシウムを走査型電子顕微鏡(日本電子(株)製JSM-7500F)を用いて撮影した結果を図1に示す。
図1に示すように、得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成された、表面が平滑で微粉粒子が殆ど存在しないものであることが分かる。
また、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子0.3gおよび、可溶化ジエトキシマグネシウム0.04gが回収された。
窒素ガスで十分に置換され、攪拌機を具備した容量500mlの丸底フラスコに、上記1.で得られたジエトキシマグネシウム20gを投入し、これにトルエン160ml、ジイソブチルマロン酸ジメチル10mlおよび四塩化チタン40mlを加えて混濁液を形成した。
その後、上記混濁液を昇温し、110℃で3時間攪拌しながら反応させた。反応終了後、得られた固体生成物を90℃のトルエン100mlで4回洗浄し、新たに四塩化チタン40mlおよびトルエン60mlを加え、100℃に昇温し、2時間攪拌しながら反応させた。
反応終了後、40℃のn-ヘプタン100mlで7回洗浄して、目的とする固体触媒成分を得た。
得られた固体触媒成分は、チタン含有割合が2.6質量%、内部電子供与性化合物含有割合が13.0質量%(ジイソブチルマロン酸ジエステル13.0質量%、マレイン酸ジエステル0.0質量%)、平均粒子径D50が47.1μm、5μm以下の微粉量が0質量%であった。
なお、上記固体触媒成分の平均粒子径および5μm以下の微粉量は、アルコキシマグネシウム(二次粒子)の平均粒子径および5μm以下の微粉量と同様の方法で測定したものである。
窒素ガスで完全に置換された内容積2.0リットルの攪拌機付オートクレーブに、トリエチルアルミニウム1.32ミリモル、ジイソプロピルジメトキシシラン(DIPDMS)0.13ミリモルおよび上記(A)固体触媒成分をチタン原子換算で0.0026ミリモル装入して、オレフィン類重合用触媒を形成した。
その後、水素ガス1.5リットル、液化プロピレン1.4リットルを装入し、20℃で5分間予備重合を行った後に昇温し、70℃で1時間重合反応を行った。
得られた重合体について、以下の方法により、重合活性、メルトフローレート(MFR、g-PP/10分)、得られた重合体の75μm以下の微粉量、平均粒子径(D50)、粒度分布指数(SPAN)、嵩密度(BD)を測定した。結果を表2に記載する。
固体触媒成分1g当たり、重合時間1時間当たりの重合体生成量(F)kgを示す重合活性(kg-PP/g-cat)は下式により算出した。
重合活性(kg-PP/g-cat)=生成重合体(F)kg/固体触媒成分g/1時間
得られた重合体の75μm以下の微粉量は、デジタル画像解析式粒子径分布測定装置(「カムサイザー」、堀場製作所社製)を用い、以下の測定条件において重合体の体積基準積算粒度分布の自動測定を行ない、平均粒子径(体積基準積算粒度で50%の粒子径(D50))および粒子径75μm以下の微粉量の測定値(質量%)を得た。
(測定条件)
ファネル位置 :6mm
カメラのカバーエリア :ベーシックカメラ3%未満、ズームカメラ10%未満
目標カバーエリア :0.5%
フィーダ幅 :40mm
フィーダコントロールレベル:57、40秒
測定開始レベル :47
最大コントロールレベル :80
コントロールの基準 :20
画像レート :50%(1:2)
粒子径定義 :粒子1粒ごとにn回測定したマーチン径の最小値
SPHT(球形性)フィッティング:1
クラス上限値 :対数目盛32μm~4000μmの範囲で50点を選択
また、上記方法により、得られた重合体の体積基準積算粒度で90%の粒子径(D90)および体積基準積算粒度で10%の粒子径(D10)の値についても同時に測定し、以下の方法により、粒度分布指数(SPAN)を算出した。
粒度分布指数(SPAN)=(D90-D10)/D50
重合体の嵩比重(BD)は、JIS K6721に従って測定した。
「2.固体触媒成分の調製」において、ジイソブチルマロン酸ジメチルの代わりに同モルのジイソブチルマロン酸ジエチルを用いた以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られた固体触媒成分は、固体触媒成分中のチタン含有量が3.2質量%、内部電子供与性化合物含有割合が14.0質量%(ジイソブチルマロン酸ジエステル14.0質量%、マレイン酸ジエステル0.0質量%)、平均粒子径D50が46.3μm、5μm以下の微粉量が0.2質量%であった。結果を表1および表2に示す。
「2.固体触媒成分の調製」において、ジイソブチルマロン酸ジメチルの代わりに同モルの2-イソプロピル-2-イソペンチル-1,3-ジメトキシプロパンを用いた以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られた固体触媒成分は、固体触媒成分中のチタン含有量が2.0質量%、平均粒子径D50が50.6μm、5μm以下の微粉量が0.4質量%であった。結果を表1および表2に示す。
「2.固体触媒成分の調製」において、ジイソブチルマロン酸ジメチルの代わりに同モルのフタル酸ジブチルを用いた以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られた固体触媒成分は、固体触媒成分中のチタン含有量が2.8質量%、平均粒子径D50が48.5μm、5μm以下の微粉量が0.6質量%であった。結果を表1および表2に示す。
1.ジエトキシマグネシウムの調製
実施例1「1.ジエトキシマグネシウムの調製」と同様にしてジエトキシマグネシウムを調製した。
2.固体触媒成分の調製
窒素ガスで十分に置換され、攪拌機を具備した容量500mlの丸底フラスコに、上記1.で得られたジエトキシマグネシウム20gを投入し、これにトルエン160ml、ジイソブチルマロン酸ジメチル10mlおよび四塩化チタン40mlを加えて混濁液を形成した。その後、混合溶液を昇温し、110℃で3時間攪拌しながら反応させた。反応終了後、得られた固体生成物を90℃のトルエン100mlで4回洗浄し、新たに四塩化チタン40ml、マレイン酸ジエチル1ml、トルエン60mlを加え、100℃に昇温し、2時間攪拌しながら反応させた。反応終了後、40℃のn-ヘプタン100mlで7回洗浄して、固体触媒成分を得た。
得られた固体触媒成分の特性を実施例1と同様に測定したところ、チタン含有率が2.1質量%、内部電子供与性化合物含有割合が14.5質量%(ジイソブチルマロン酸ジエステル10.5質量%、マレイン酸ジエステル4.0質量%)、平均粒子径D50が49.2μm、5μm以下の微粉量が0質量%であった。
上記2.で得られた固体触媒成分を用いた以外は、実施例1と同様に重合を行い、実施例1と同様にして、得られた触媒の特性(重合活性)および重合体の特性を測定した。
結果を表1および表2に示す。
「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)を同モルのマレイン酸ジエチルに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成され、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が56.8μm、SPANが0.8、二次粒子を構成している一次粒子の平均粒子径D1が0.7μm、一次粒子の平均粒子径/二次粒子の平均粒子径で表される比が0.01、5μm以下の微粉は1.5質量%、比表面積が15m2/g、嵩比重が0.31g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。なお、得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子に由来する固体成分0.2gおよび、上澄み液中の可溶化ジエトキシマグネシウム0.03gが回収された。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が2.3質量%、内部電子供与性化合物含有割合が12.6質量%(ジイソブチルマロン酸ジエステル12.6質量%、マレイン酸ジエステル0.0質量%)、平均粒子径D50が45.6μm、5μm以下の微粉量が0.5質量%であった。結果を表1および表2に示す。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)を同モルのジイソブチルマロン酸ジメチルに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成され、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が56.5μm、SPANが1.0、二次粒子を構成している一次粒子の平均粒子径D1が0.5μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径で表される比は0.01、5μm以下の微粉は1.6質量%、比表面積が15m2/g、嵩比重が0.32g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子に由来する固体成分0.2gおよび、上澄み液中の可溶化ジエトキシマグネシウム0.02gが回収された。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が1.9質量%、ジイソブチルマロン酸ジエステル含有割合が13.5質量%、平均粒子径D50が46.1μm、5μm以下の微粉量が0.5質量%のものであった。結果を表1および表2に示す。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)の添加量を30ミリモルから7ミリモルに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成された、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が56.8μm、SPANが0.8、二次粒子を構成している一次粒子の平均粒子径D1が0.7μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉量は1.8質量%、比表面積が19m2/g、嵩比重が0.31g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子0.2gおよび、可溶化ジエトキシマグネシウム0.03gが回収された。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が2.3質量%、内部電子供与性化合物含有割合が12.9質量%(ジイソブチルマロン酸ジエステル含有量が12.9質量%、マレイン酸ジエステル含有量が0.0質量%)、平均粒子径D50は45.6μmであり、5μm以下の微粉量は0.8質量%であった。結果を表1および表2に示す。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)の添加量を30ミリモルから14ミリモルに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成された、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が57.6μm、SPANが0.9、二次粒子を構成している一次粒子の平均粒子径D1が0.6μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉量が0.8質量%、比表面積が16m2/g、嵩比重が0.31g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子0.4gおよび、可溶化ジエトキシマグネシウム0.04gが回収された。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が2.3質量%、内部電子供与性化合物含有割合が13.3質量%(ジイソブチルマロン酸ジエステル13.3質量%、マレイン酸ジエステル0質量%)、平均粒子径D50が47.4μm、5μm以下の微粉量が0質量%であった。結果を表1および表2に示す。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)の添加量を30ミリモルから60ミリモルに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成された、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が57.8μm、SPANが0.8、二次粒子を構成している一次粒子の平均粒子径D1が0.6μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉量は0質量%、比表面積が12m2/g、嵩比重が0.33g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子0.4gおよび、可溶化ジエトキシマグネシウム0.06gが回収された。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が2.3質量%、内部電子供与性化合物含有割合が13.1質量%(ジイソブチルマロン酸ジエステル13.1質量%、マレイン酸ジエステル0質量%)、平均粒子径D50が48.9μm、5μm以下の微粉量が0質量%であった。結果を表1および表2に示す。
1.ジエトキシマグネシウムの調製
(1)固形物形成工程
窒素ガスで十分置換された攪拌器および還流冷却器を具備した容量2000mlの丸底フラスコに、粒子径144メッシュ以下の金属マグネシウム微粉末5g、室温のエタノール125mlおよびヨウ素3gを装入し懸濁液を形成した。
次いで上記懸濁液を攪拌しながら昇温して、エタノールの還流下で反応を開始させた。反応開始後、粒子径100メッシュ以下の金属マグネシウム粉末5gとエタノール62mlとを同時にフラスコ内に添加する操作を計4回、30分に亘って行った。添加終了後、エタノールの還流下で、攪拌しながら10時間保持した(最終添加したマグネシウムは25gであり、エタノールは、373ml(約294.3g)であり、最終添加の金属マグネシウム/エタノール=1/11.8)。その後室温まで冷却した後、上澄みをデカンテーションし、真空乾燥して、約100gの固形物を得た。得られた固形物の平均粒子径は20.5μm、5μm以下の微粉は5.9質量%であった。
窒素ガスで十分に置換され、攪拌機を具備した容量500 mlの丸底フラスコに上記(1)で得られた固形物20g、常温のトルエン115mlを投入して攪拌し、次いでマレイン酸ビス(2-エチルヘキシル)30ミリモルを投入して攪拌した。
その後、攪拌しながら60℃で1時間接触を行い懸濁液を得た。次いで、得られた懸濁液を静置して上澄み液をデカンテーションにて除去し(除去工程)、さらに60℃のトルエン80mlを投入し攪拌する洗浄工程を3回繰り返し、ジエトキシマグネシウムを得、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、一次粒子の集合体である二次粒子により構成された、表面が平滑で微粉粒子が殆ど存在しないものであった。また、得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が19.3μm、SPANが0.8、二次粒子を構成している一次粒子の平均粒子径D1が0.6μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.03、5μm以下の微粉量は1.6質量%、比表面積が22m2/g、嵩比重が0.24g/mlであるものであった。
なお、このジエトキシマグネシウムをヘプタンで十分に洗浄した後、固液を分離して、ジエトキシマグネシウム中のマレイン酸ジエステル含有量を測定したところ、0質量%であり、得られたジエトキシマグネシウムはマレイン酸ジエステルの付加物を形成していなかった。
得られたジエトキシマグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。なお、得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
なお、除去工程で除去した上澄み液を遠心分離機にてさらに固液分離し、それぞれ減圧乾燥したところ、上澄み液中に遊離するジエトキシマグネシウム微粒子0.5gおよび、可溶化ジエトキシマグネシウム0.06gが回収された。
上記ジエトキシマグネシウムを用いた以外は、実施例1と同様の条件で固体触媒成分の調製を行い、得られた固体触媒成分の特性を実施例1と同様に測定した。
得られた固体触媒成分は、チタン含有割合が3.3質量%、内部電子供与性化合物含有割合が12.6質量%(ジイソブチルマロン酸ジエステル12.6質量%、マレイン酸ジエステル0質量%)、平均粒子径D50が19.2μm、5μm以下の微粉量が0.1質量%であった。
実施例1と同様の条件で、オレフィン類重合用触媒の形成および重合を行い、得られた触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
結果を表1および表2に示す。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)を添加しなかった以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が52.9μm、SPANが1.1、二次粒子を構成している一次粒子の平均粒子径D1が0.7μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉量が4.1質量%、比表面積が25m2/g、嵩比重が0.30g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。なお、得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
また、上記ジエトキシマグネシウムより得られた固体触媒成分は、チタン含有量が3.2質量%、ジイソブチルマロン酸ジエステルの含有量が14.5質量%、平均粒子径D50は52.9μmであり、5μm以下の微粉量は4.1質量%であった。結果を表1および表2に示す。
また、上述した方法で得られたジエトキシマグネシウムを走査型電子顕微鏡(日本電子(株)製JSM-7500F)を用いて撮影した結果を図2に示す。
得られたジエトキシマグネシウムは、多くの微粉状粒子を含み、また粒子表面に多数の凹凸が形成されてなるものであった。
実施例1の「1.ジエトキシマグネシウムの調製」において、マレイン酸ビス(2-エチルヘキシル)を同モルの9,9-ビスメトキシメチルフルオレンに変更した以外は、実施例1と同様の条件で、ジエトキシマグネシウムの調製、固体触媒成分の調製、重合触媒の形成及び重合を行い、得られたアルコキシマグネシウム(ジエトキシマグネシウム)の特性、固体触媒成分の特性、触媒の特性(重合活性)および重合体の特性を実施例1と同様に測定した。
得られたジエトキシマグネシウムは、二次粒子の平均粒子径D2が57.6μm、SPANが1.2、二次粒子を構成している一次粒子の平均粒子径D1が0.7μm、一次粒子の平均粒子径D1/二次粒子の平均粒子径D2で表される比が0.01、5μm以下の微粉量は3.4質量%、比表面積が15m2/g、嵩比重が0.33g/mlであった。得られたジエトキシグネシウムの1μm以下の細孔径を有する細孔の細孔容積と、0.1~0.5μmの細孔径を有する細孔の細孔容積を測定した結果を表1に示す。なお、得られたジエトキシマグネシウムにおいて、1μmを超える細孔径を有する細孔は測定されなかった。
また、得られた固体触媒成分は、チタン含有量が3.0質量%、内部電子供与性化合物含有割合が12.8質量%(ジイソブチルマロン酸ジエステル12.8質量%、9,9-ビスメトキシメチルフルオレン0.0質量%)、平均粒子径D50が47.2μmであり、5μm以下の微粉量は3.5質量%であった。結果を表1および表2に示す。
Claims (14)
- 平均粒子径1μm未満の一次粒子の集合体である二次粒子により構成され、
前記一次粒子の平均粒子径/前記二次粒子の平均粒子径で表される比が0.1以下であり、全細孔容積が0.5~1cm3/gで、比表面積が50m2/g未満、粒度分布指数(SPAN)が1以下であることを特徴とするアルコキシマグネシウム。 - 5μm以下の粒子径を有する微粉の含有量が全粒子質量の3質量%以下であり、全細孔容積が0.5~1cm3/gで、1μm以下の細孔径を有する細孔の50%以上が0.5μm以下の細孔径を有している請求項1に記載のアルコキシマグネシウム。
- 前記二次粒子の平均粒子径が60μm未満である請求項1または請求項2に記載のアルコキシマグネシウム。
- 金属マグネシウムとアルコールとを触媒の存在下で反応させて固形物を形成する固形物形成工程と、
前記固形物と一種以上のカルボン酸エステルとを有機溶媒中で接触させ懸濁液を形成する接触工程とを
順次施すことを特徴とするアルコキシマグネシウムの製造方法。 - 前記アルコールが、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノールおよび2-エチルヘキシルアルコールから選ばれる一種以上である請求項4に記載のアルコキシマグネシウムの製造方法。
- 前記有機溶媒が、脂肪族炭化水素化合物および芳香族炭化水素化合物から選ばれる一種以上である請求項4または請求項5に記載のアルコキシマグネシウムの製造方法。
- 前記カルボン酸エステルが、下記一般式(I);
- 前記カルボン酸エステルが、コハク酸ジエチル、コハク酸ジブチル、コハク酸ビス(2-エチルヘキシル)、マレイン酸ジエチル、マレイン酸ジブチル、マレイン酸ビス(2-エチルヘキシル)、マロン酸ジエチル、マロン酸ジブチル、マロン酸ビス(2-エチルヘキシル)から選ばれる1種以上である請求項4に記載のアルコキシマグネシウムの製造方法。
- 前記アルコキシマグネシウムが、ジエトキシマグネシウムである請求項4に記載のアルコキシマグネシウムの製造方法。
- 前記接触工程を施すことにより、
前記固形物の一部とカルボン酸エステルとを反応させて反応物を形成するか、前記固形物の一部をカルボン酸エステルと有機溶媒との混合物中に溶解させるか、または前記固形物の一部をカルボン酸エステルと有機溶媒との混合物中に遊離させる
請求項4に記載のアルコキシマグネシウムの製造方法。 - 請求項1に記載のアルコキシマグネシウム(a)と、チタンハロゲン化合物(b)と、電子供与性化合物(c)とを接触させて得られることを特徴とするオレフィン類重合用固体触媒成分。
- (A)請求項11に記載のオレフィン類重合用固体触媒成分、(B)下記一般式(IV);
R15 pAlQ3-p (IV)
(式中、R15は炭素数1~4のアルキル基を示し、Qは水素原子あるいはハロゲン原子を示し、pは0<p≦3の実数である。R15が複数存在する場合、各R15は互いに同一であっても異なっていてもよく、Qが複数存在する場合、各Qは同一であっても異なっていてもよい。)で表される有機アルミニウム化合物および(C)外部電子供与性化合物を含むことを特徴とするオレフィン類重合用触媒。 - 前記(C)外部電子供与性化合物が、下記一般式(V);
R16 qSi(OR17)4-q (V)
(式中、R16は、炭素数1~12のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~12のシクロアルキル基、炭素数3~12のシクロアルケニル基、炭素数6~15の芳香族炭化水素基または置換基を有する炭素数6~15の芳香族炭化水素基を示し、R16が複数存在する場合、複数のR16は互いに同一でも異なっていてもよい。R17は、炭素数1~4のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数3~6のシクロアルキル基、炭素数6~12の芳香族炭化水素基または置換基を有する炭素数7~12の芳香族炭化水素基を示し、R17が複数存在する場合、複数のR17は互いに同一でも異なっていてもよい。qは0≦q≦3の整数である。)で表される有機ケイ素化合物および一般式(VI);
(R18R19N)sSiR20 4-s (VI)
(式中、R18およびR19は、水素原子、炭素数1~20のアルキル基、ビニル基、炭素数3~20のアルケニル基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルケニル基または炭素数6~20のアリール基を示し、R18およびR19は互いに同一でも異なっていてもよく、また互いに結合して環を形成してもよく、R18R19N基が複数存在する場合、複数のR18R19N基は互いに同一でも異なっていてもよい。R20は炭素数1~20のアルキル基、ビニル基、炭素数3~12のアルケニル基、炭素数1~20のアルコキシ基、ビニルオキシ基、炭素数3~20のアルケニルオキシ基、炭素数3~20のシクロアルキル基、炭素数3~20のシクロアルキルオキシ基、炭素数6~20のアリール基、炭素数6~20のアリールオキシ基を示し、R20が複数存在する場合、複数のR20は互いに同一でも異なっていてもよい。sは1から3の整数である。)で表されるアミノシラン化合物から選択される一種以上である
請求項12に記載のオレフィン類重合用触媒。 - 請求項12または請求項13に記載のオレフィン重合用触媒の存在下にオレフィン類の重合を行うことを特徴とするオレフィン類重合体の製造方法。
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CN201780019056.3A CN108779056B (zh) | 2016-03-28 | 2017-03-23 | 烷氧基镁、烷氧基镁的制造方法、烯烃类聚合用固体催化剂成分、烯烃类聚合用催化剂和烯烃类聚合物的制造方法 |
US16/088,158 US11008408B2 (en) | 2016-03-28 | 2017-03-23 | Alkoxymagnesium, method for producing alkoxymagnesium, solid catalyst component for olefin polymerization, olefin polymerization catalyst, and method for producing olefin polymer |
BR112018069661-7A BR112018069661B1 (pt) | 2016-03-28 | 2017-03-23 | Alcoximagnésio, métodos para produção de um alcoximagnésio e de um polímero de olefina, componente de catalisador sólido, e, catalisador |
EP17774618.7A EP3438083B1 (en) | 2016-03-28 | 2017-03-23 | Alkoxy magnesium, method for producing alkoxy magnesium, solid catalyst component for olefin polymerization use, catalyst for olefin polymerization use, and method for producing olefin polymer |
KR1020187024044A KR102291509B1 (ko) | 2016-03-28 | 2017-03-23 | 알콕시마그네슘, 알콕시마그네슘의 제조 방법, 올레핀류 중합용 고체 촉매 성분, 올레핀류 중합용 촉매 및 올레핀류 중합체의 제조 방법 |
JP2018509148A JP6782292B2 (ja) | 2016-03-28 | 2017-03-23 | アルコキシマグネシウム、アルコキシマグネシウムの製造方法、オレフィン類重合用固体触媒成分、オレフィン類重合用触媒およびオレフィン類重合体の製造方法 |
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US11008408B2 (en) | 2021-05-18 |
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JP6782292B2 (ja) | 2020-11-11 |
KR102291509B1 (ko) | 2021-08-19 |
EP3438083A1 (en) | 2019-02-06 |
CN108779056B (zh) | 2021-12-24 |
US20200299422A1 (en) | 2020-09-24 |
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BR112018069661B1 (pt) | 2022-09-20 |
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