WO2022250034A1 - 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、オレフィン類重合体の製造方法、オレフィン類重合体、プロピレン系ブロック共重合体の製造方法及びプロピレン系ブロック共重合体 - Google Patents
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、オレフィン類重合体の製造方法、オレフィン類重合体、プロピレン系ブロック共重合体の製造方法及びプロピレン系ブロック共重合体 Download PDFInfo
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- WO2022250034A1 WO2022250034A1 PCT/JP2022/021191 JP2022021191W WO2022250034A1 WO 2022250034 A1 WO2022250034 A1 WO 2022250034A1 JP 2022021191 W JP2022021191 W JP 2022021191W WO 2022250034 A1 WO2022250034 A1 WO 2022250034A1
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- WIPO (PCT)
- Prior art keywords
- propylene
- molecular weight
- olefin polymerization
- olefin
- catalyst component
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 197
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 185
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 131
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 61
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 117
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 117
- 238000004519 manufacturing process Methods 0.000 title claims description 47
- 239000002685 polymerization catalyst Substances 0.000 title claims description 45
- 229920001400 block copolymer Polymers 0.000 title claims description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 135
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 65
- 239000010936 titanium Substances 0.000 claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000009826 distribution Methods 0.000 claims abstract description 52
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 150000002367 halogens Chemical class 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000004711 α-olefin Substances 0.000 claims description 19
- 230000000379 polymerizing effect Effects 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 99
- -1 polypropylene Polymers 0.000 description 52
- 239000000047 product Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 45
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 44
- 239000002245 particle Substances 0.000 description 36
- 238000011282 treatment Methods 0.000 description 35
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 33
- 238000005406 washing Methods 0.000 description 29
- 230000015572 biosynthetic process Effects 0.000 description 26
- 150000002681 magnesium compounds Chemical class 0.000 description 25
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 23
- 239000007788 liquid Substances 0.000 description 22
- 239000000725 suspension Substances 0.000 description 22
- 239000002002 slurry Substances 0.000 description 20
- 229920001384 propylene homopolymer Polymers 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 14
- 150000003961 organosilicon compounds Chemical class 0.000 description 14
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 13
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- KOFGHHIZTRGVAF-UHFFFAOYSA-N n-ethyl-n-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)N(CC)CC KOFGHHIZTRGVAF-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000002356 laser light scattering Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 125000003282 alkyl amino group Chemical group 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- POXXQVSKWJPZNO-UHFFFAOYSA-N 1-o-ethyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC(C)C POXXQVSKWJPZNO-UHFFFAOYSA-N 0.000 description 3
- DEPJZTNLWYQZPA-UHFFFAOYSA-N 1-o-ethyl 2-o-propan-2-yl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OC(C)C DEPJZTNLWYQZPA-UHFFFAOYSA-N 0.000 description 3
- YNOQMANFEGIPDL-UHFFFAOYSA-N 1-o-ethyl 2-o-propyl benzene-1,2-dicarboxylate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCC YNOQMANFEGIPDL-UHFFFAOYSA-N 0.000 description 3
- JEABIFHLYSDNRJ-UHFFFAOYSA-N 2-o-butyl 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC JEABIFHLYSDNRJ-UHFFFAOYSA-N 0.000 description 3
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 3
- VMODTUAZZAIDGU-UHFFFAOYSA-N diethyl 4-methylbenzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C)C=C1C(=O)OCC VMODTUAZZAIDGU-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical compound C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GAHSOBODSWGWHR-UHFFFAOYSA-N bis(2,2-dimethylpropyl) benzene-1,2-dicarboxylate Chemical compound CC(C)(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)(C)C GAHSOBODSWGWHR-UHFFFAOYSA-N 0.000 description 2
- IBQZHKUFRSQWEJ-UHFFFAOYSA-N bis(2-methylpropyl) 4-bromobenzene-1,2-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(Br)C=C1C(=O)OCC(C)C IBQZHKUFRSQWEJ-UHFFFAOYSA-N 0.000 description 2
- JANBFCARANRIKJ-UHFFFAOYSA-N bis(3-methylbutyl) benzene-1,2-dicarboxylate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1C(=O)OCCC(C)C JANBFCARANRIKJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- DORRWRARCZOGPE-UHFFFAOYSA-N dipropyl 4-methylbenzene-1,2-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C)C=C1C(=O)OCCC DORRWRARCZOGPE-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- RXVAWVPVNXHVFX-UHFFFAOYSA-N n-[dicyclopentyl(ethylamino)silyl]ethanamine Chemical compound C1CCCC1[Si](NCC)(NCC)C1CCCC1 RXVAWVPVNXHVFX-UHFFFAOYSA-N 0.000 description 2
- JGDVCUAIXUXCCK-UHFFFAOYSA-N n-[ethyl(dimethoxy)silyl]-2-methylpropan-2-amine Chemical compound CC[Si](OC)(OC)NC(C)(C)C JGDVCUAIXUXCCK-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FDYPWIDITZJTAI-UHFFFAOYSA-N n-ethyl-n-trimethoxysilylethanamine Chemical compound CCN(CC)[Si](OC)(OC)OC FDYPWIDITZJTAI-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- CVQCOFXKODWSJK-UHFFFAOYSA-N 1-o-ethyl 2-o-(3-methylbutyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCCC(C)C CVQCOFXKODWSJK-UHFFFAOYSA-N 0.000 description 1
- QCYLEFMKCDXLGX-UHFFFAOYSA-N 1-o-ethyl 2-o-hexyl benzene-1,2-dicarboxylate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCC QCYLEFMKCDXLGX-UHFFFAOYSA-N 0.000 description 1
- CWTNJOUCIAUOGI-UHFFFAOYSA-N 1-o-ethyl 2-o-pentyl benzene-1,2-dicarboxylate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCC CWTNJOUCIAUOGI-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- VLQZJOLYNOGECD-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O1 VLQZJOLYNOGECD-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 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
- LZARSADMKFKZQA-UHFFFAOYSA-N n-[cyclohexyl(dimethoxy)silyl]cyclohexanamine Chemical compound C1CCCCC1[Si](OC)(OC)NC1CCCCC1 LZARSADMKFKZQA-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-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
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- PSWKAZOCOHMXCW-UHFFFAOYSA-N tert-butyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C(C)(C)C PSWKAZOCOHMXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 1
- IVZTVZJLMIHPEY-UHFFFAOYSA-N triphenyl(triphenylsilyloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IVZTVZJLMIHPEY-UHFFFAOYSA-N 0.000 description 1
- KHQZLUVCZCAMFU-UHFFFAOYSA-N tripropyl(tripropylsilyloxy)silane Chemical compound CCC[Si](CCC)(CCC)O[Si](CCC)(CCC)CCC KHQZLUVCZCAMFU-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- 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
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing an olefin polymer, an olefin polymer, a method for producing a propylene-based block copolymer, and a propylene-based block copolymer.
- polyolefins such as polypropylene (PP) have been used for various purposes such as molded products such as automobile parts and home appliances, as well as containers and films.
- PP polypropylene
- Polypropylene resin composition is the most important plastic material because it is lightweight and has excellent moldability, as well as excellent chemical stability such as heat resistance and chemical resistance of molded products, and is also extremely cost-effective. It is used in many fields as one of For example, polypropylene, which has high stereoregularity, has been studied for application to various uses because it has excellent mechanical strength, thermal properties, and the like.
- melt flow rate MFR
- excellent moldability e.g., polypropylene with high melt flowability (melt flow rate (MFR)
- MFR melt flow rate
- high rigidity which can be used as an alternative to polystyrene and ABS resin
- Patent Document 1 US Patent Application Publication No. 2020/01405864 discloses diethoxymagnesium, titanium tetrachloride, di
- An example of producing polypropylene using a solid catalyst component obtained by reacting n-propyl phthalate with a dialkyl benzylidenemalonate or the like is disclosed.
- the flexural modulus (FM) is as high as 1800 MPa or more.
- Mz/Mw which is the ratio of the Z-average molecular weight (Mz) to the weight-average molecular weight (Mw)
- polypropylene which has a wide molecular weight distribution, tends to swell when extruding a polypropylene solution, so there has been a technical problem that it is difficult to produce various grades of textile products in the spinning process, for example.
- the present invention provides a solid catalyst component for olefin polymerization that can easily produce an olefin polymer that has excellent fluidity and high rigidity even if the molecular weight distribution is narrow, without performing complicated polymerization treatments. and to provide an olefin polymerization catalyst, a method for producing an olefin polymer, an olefin polymer, a method for producing a propylene-based block copolymer, and a propylene-based block copolymer. be.
- the present invention contains magnesium, titanium and halogen, and contains an aromatic carboxylic acid ester and a 1,3-diether compound as an internal electron donating compound.
- a solid catalyst component for olefin polymerization wherein the content of titanium is 0.5 to 2.0% by mass, and the content of aromatic carboxylic acid esters in the total content of the internal electron donating compound is The above technical problems can be solved by a solid catalyst component for olefin polymerization in which the content ratio of the 1,3-diether compound to the total content of the internal electron donating compound is 40 to 60 mol% and 40 to 60 mol%. and completed the present invention based on this finding.
- the present invention (1) A solid catalyst component for olefin polymerization containing magnesium, titanium and halogen and containing an aromatic carboxylic acid ester and a 1,3-diether compound as an internal electron donating compound,
- the titanium content is 0.5 to 2.0% by mass
- the content of the aromatic carboxylic acid ester in the total content of the internal electron donating compound is 40 to 60 mol%
- a solid catalyst component for olefin polymerization characterized in that the content of the 1,3-diether compound in the total content of the internal electron donating compound is 40 to 60 mol%;
- the titanium, the aromatic carboxylic acid esters and the 1,3-diether compound are represented by the total content of the aromatic carboxylic acid esters and the 1,3-diether compound/the content of the titanium.
- the solid catalyst component for olefin polymerization according to the above (1) which is contained so that the ratio by mass is 2.0 or more
- the titanium and the aromatic carboxylic acid ester are mixed so that the ratio represented by the content of the aromatic carboxylic acid ester/the content of the titanium is 1.5 or more in terms of mass ratio.
- the solid catalyst component for olefin polymerization according to (1) or (2) containing (4) The titanium and the 1,3-diether compound are mixed so that the ratio expressed by the content of the 1,3-diether compound/the content of the titanium is 1.5 or more by mass.
- the molecular weight distribution (Mz/Mw) is 2.0 to 7.0, An olefin polymer characterized by having a flexural modulus (FM) of 1800 MPa or more, (10) polymerizing olefins containing 95 to 100% by mass of propylene using the olefin polymerization catalyst described in (5) or (6) above; Melt flowability (MFR) of 20 g/10 minutes or more,
- Mw/Mn which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw).
- the molecular weight distribution (Mz/Mw) is 2.0 to 7.0
- a propylene-based block characterized by obtaining a propylene-based polymer having a flexural modulus (FM) of 1800 MPa or more, and then polymerizing propylene and an ⁇ -olefin other than propylene in the presence of the obtained propylene-based polymer.
- FM flexural modulus
- a method for producing a copolymer (11) polymerizing an olefin containing 95 to 100% by mass of propylene using the olefin polymerization catalyst described in (5) or (6) above; Melt flowability (MFR) of 20 g/10 minutes or more,
- MFR Melt flowability
- Mw/Mn The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw).
- the molecular weight distribution (Mz/Mw) is 2.0 to 7.0, After obtaining a propylene-based polymer having a flexural modulus (FM) of 1800 MPa or more, A propylene-based block copolymer obtained by polymerizing propylene and an ⁇ -olefin other than propylene in the presence of the obtained propylene-based polymer, It provides
- the present invention by containing predetermined amounts of titanium, aromatic carboxylic acid esters and 1,3-diether compounds in addition to magnesium and halogen, even if the molecular weight distribution is narrow, fluidity is excellent and rigidity is improved. It is possible to provide a solid catalyst component for olefin polymerization that can easily produce a high-quality olefin polymer without performing a complicated polymerization treatment.
- a polymer, a method for producing a propylene-based block copolymer, and a propylene-based block copolymer can be provided.
- the solid catalyst component for olefin polymerization according to the present invention is A solid catalyst component for olefin polymerization containing magnesium, titanium and halogen, and containing an aromatic carboxylic acid ester and a 1,3-diether compound as an internal electron donating compound,
- the titanium content is 0.5 to 2.0% by mass
- the content of the aromatic carboxylic acid ester in the total content of the internal electron donating compound is 40 to 60 mol%
- the content of the 1,3-diether compound is 40 to 60 mol % of the total content of the internal electron donating compound.
- the solid catalyst component for olefin polymerization according to the present invention contains magnesium, titanium and halogen, and also contains an aromatic carboxylic acid ester and a 1,3-diether compound as an internal electron donating compound.
- raw material components serving as sources of magnesium, titanium and halogen, and aromatic carboxylic acid esters and 1,3-diether compounds, which are internal electron donating compounds are organically combined.
- a contact reaction product obtained by contacting and reacting with each other in a solvent can be exemplified.
- a magnesium compound and a tetravalent titanium halogen compound are used as raw material components serving as magnesium, titanium and halogen supply sources. and a contact reaction product obtained by contacting these raw materials with an internal electron donating compound containing an aromatic carboxylic acid ester and a 1,3-diether compound.
- magnesium compound examples include one or more selected from dialkoxymagnesium, magnesium dihalide, alkoxymagnesium halide, and the like.
- dialkoxymagnesium and magnesium dihalide are preferred, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and magnesium dichloride.
- magnesium dibromide, magnesium diiodide and the like, and diethoxymagnesium and magnesium dichloride are particularly preferred.
- dialkoxymagnesium may be obtained by reacting metallic magnesium with alcohol in the presence of halogen or a halogen-containing metal compound.
- dialkoxymagnesium is preferably granular or powdery, and its shape may be irregular or spherical.
- spherical dialkoxymagnesium does not necessarily have to be perfectly spherical, and elliptical or potato-shaped ones can also be used.
- the average particle size (average particle size D50) of the dialkoxymagnesium is preferably 1.0 to 200.0 ⁇ m, more preferably 5.0 to 150.0 ⁇ m.
- the average particle size D50 means the particle size of 50% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction method particle size analyzer.
- the average particle diameter D50 is preferably 1.0 to 100.0 ⁇ m, more preferably 5.0 to 80.0 ⁇ m, and 10.0 to 70.0 ⁇ m. It is even more preferable to have
- dialkoxymagnesium preferably contains 20% or less, preferably 10% or less, particles having a particle diameter of 5.0 ⁇ m or less when measured using a laser light scattering diffraction particle size analyzer. is more preferred.
- the proportion of particles having a particle diameter of 100.0 ⁇ m or more is preferably 20% or less, more preferably 10% or less, as measured using a laser light scattering diffraction particle size analyzer.
- the particle size distribution is preferably 3 or less, more preferably 2 or less, in terms of ln (D90/D10).
- D90 means the particle size of 90% of the integrated particle size in the volume integrated particle size distribution when measured using a laser light scattering diffraction method particle size analyzer.
- D10 means a particle size of 10% in cumulative particle size in volume cumulative particle size distribution when measured using a laser light scattering diffraction method particle size analyzer.
- the method for producing the above-mentioned spherical dialkoxymagnesium includes, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8- This is exemplified in Japanese Patent Application Laid-Open No. 73388 and the like.
- the magnesium compound which is a raw material component serving as a supply source of magnesium, preferably has a specific surface area of 5 m 2 /g or more, preferably 5 to 50 m 2 /g. Some are more preferred, and those between 10 and 40 m 2 /g are even more preferred.
- the specific surface area of the magnesium compound means a value measured by the BET method.
- the magnesium compound is preferably in the form of a solution or a suspension during the reaction, and the solution or suspension allows the reaction to proceed favorably.
- the magnesium compound When the magnesium compound is solid, it can be dissolved in a solvent capable of solubilizing the magnesium compound to form a magnesium compound in the form of a solution, or suspended in a solvent not capable of solubilizing the magnesium compound.
- a magnesium compound suspension can be obtained by turbidity.
- the magnesium compound When the magnesium compound is liquid, it may be used as a solution magnesium compound as it is, or may be further dissolved in a solvent capable of solubilizing the magnesium compound and used as a solution magnesium compound.
- the compound capable of solubilizing the solid magnesium compound includes at least one compound selected from the group consisting of alcohols, ethers and esters, preferably alcohols such as ethanol, propanol, butanol and 2-ethylhexanol. - Ethylhexanol is particularly preferred.
- examples of the medium having no solubilizing ability for the solid magnesium compound include one or more selected from saturated hydrocarbon solvents and unsaturated hydrocarbon solvents that do not dissolve the magnesium compound.
- the tetravalent titanium halogen compound which is a raw material component serving as a supply source of titanium and halogen, is not particularly limited, but is represented by the following general formula (II): Ti(OR 2 ) rX4 -r (II) (In the formula, R 2 represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and r is an integer of 0 ⁇ r ⁇ 3. ) is preferably one or more compounds selected from the group of titanium halides or alkoxytitanium halides.
- titanium halide represented by the general formula (II) examples include one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and the like.
- alkoxytitanium halide represented by the general formula (II) examples include methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, di One or more selected from propoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride and the like.
- titanium tetravalent titanium halogen compound titanium te
- the solid catalyst component for olefin polymerization according to the present invention contains an aromatic carboxylic acid ester as an internal electron donating compound.
- aromatic carboxylic acid esters are preferably aromatic polycarboxylic acid esters.
- Aromatic polycarboxylic acid esters include aromatic dicarboxylic acid diesters.
- aromatic dicarboxylic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-phthalate Pentyl, diisopentyl phthalate, dineopentyl phthalate, di-n-hexyl phthalate, dithexyl phthalate, methyl ethyl phthalate, (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, (ethyl) n-butyl phthalate, Phthalic acid diesters such as ethyl isobutyl phthalate, (ethyl) n-pentyl phthalate, ethyl isopentyl phthalate, ethyl neopentyl phthalate, (ethyl)
- the solid catalyst component for olefin polymerization according to the present invention contains a 1,3-diether compound as an internal electron donating compound.
- the 1,3-diether compound has a structure having propane as a basic skeleton and ether groups bonded to the 1,3-positions (1,3-dialkoxypropane structure), and further desired substitution means a group of compounds which may contain a group.
- R 3OCH2CR4R5CH2OR6 III ) _ _ (wherein R 4 and R 5 are a hydrogen atom, a halogen atom, 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, or a cycloalkenyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, a substituted aromatic hydrocarbon group having 7 to 12 carbon atoms, an alkylamino group having 1 to 12 carbon atoms, or a carbon number It represents a dialkylamino group of 2 to 12.
- R 4 and R 5 may be the same or different, and R 4 and R 5 may combine with each other to form a ring.
- R 3 and R 6 are 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 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or represents a halogen-substituted aromatic hydrocarbon group or a substituted aromatic hydrocarbon group having 7 to 12 carbon atoms, wherein R 3 and R 6 may be the same or different.
- 1 or more compounds selected from the compounds described above can be exemplified.
- the solid catalyst component for olefin polymerization according to the present invention includes aromatic carboxylic acid esters and 1,3-diether compounds as internal electron-donating compounds, as well as other internal electron-donating compounds to the extent that the effects of the present invention are exhibited. (hereinafter referred to as "another internal electron donating compound").
- Other internal electron-donating compounds are not particularly limited, but organic compounds other than aromatic carboxylic acid esters and 1,3-diether compounds, which contain an oxygen atom or a nitrogen atom, are preferred.
- Other internal electron donating compounds are more preferably one or more selected from ether compounds such as monoethers, diethers and ether carbonates, and esters such as monocarboxylic acid esters and polycarboxylic acid esters. At least one selected from aliphatic polycarboxylic acid esters, alicyclic polycarboxylic acid esters, diethers and ether carbonates is more preferable.
- Other internal electron donating compounds include, inter alia, diethyl maleate, dibutyl maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate, diethyl diisobutyl maleate, diethyl succinate, diethyl methyl succinate, 2,3-diisopropyl succinate Aliphatic polycarboxylic acid esters such as diethyl, di-n-butyl malonate, diethyl malonate, dimethyl diisobutylmalonate, diethyl diisobutylmalonate, dimethyl benzylidenemalonate, diethyl benzylidenemalonate and dibutyl benzylidenemalonate; cyclohexanedicarboxylic acid Diethyl, di-n-propyl cyclohexanedicarboxylate, dibutyl cyclohexanedicarboxylate, diisobutyl cyclo
- the magnesium (magnesium atom) content is preferably 10 to 30% by mass, more preferably 15 to 25% by mass, and even more preferably 16 to 22% by mass.
- the content of titanium is 0.5 to 2.0% by mass, preferably 0.7 to 1.8% by mass, and 0.9%. ⁇ 1.8% by mass is more preferred.
- the aromatic carboxylic acid esters occupying the total content of the internal electron donating compound and the content of the 1,3-diether compound are each within a predetermined range, and when subjected to the polymerization of olefins, even if the molecular weight distribution is narrow, the olefin has excellent fluidity and high rigidity. Analog polymers can be easily produced without complicated polymerization treatments.
- the halogen (halogen atom) content is preferably 50 to 75% by mass, more preferably 55 to 70% by mass, and even more preferably 58 to 65% by mass.
- the content of magnesium in the solid catalyst component for olefin polymerization means the value measured by the EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.
- the content of titanium in the solid catalyst component for olefin polymerization means the value measured according to the method (oxidation-reduction titration) described in JIS 8311-1997 "Method for determining titanium in titanium ore". It shall be.
- the content of halogen in the solid catalyst component for olefin polymerization is determined by treating the solid catalyst component with a mixed solution of sulfuric acid and pure water to make an aqueous solution, taking a predetermined amount, and using a standard silver nitrate solution. shall mean the value measured by the silver nitrate titration method in which halogen atoms are titrated at .
- the content of aromatic carboxylic acid esters is preferably 3 to 25% by mass, more preferably 5 to 23% by mass, and more preferably 7 to 20% by mass. % by mass is more preferred.
- the content of the 1,3-diether compound is preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and 5 to 18% by mass. % by mass is more preferred.
- the content of the other internal electron donating compound in the solid catalyst component for olefin polymerization according to the present invention is 0.5. It may be 0 to 10.0% by mass.
- the content of the aromatic carboxylic acid ester in the total content of the internal electron donating compound is 40 to 60 mol%, and 42 to 58 mol%. is preferred, and 44 to 56 mol % is more preferred.
- the content of the 1,3-diether compound in the total content of the internal electron donating compound is 40 to 60 mol%, and 42 to 58 mol%. is preferred, and 44 to 56 mol % is more preferred.
- the ratio of the content of the aromatic carboxylic acid ester and the 1,3-diether to the total content of the internal electron donating compound is within the above ranges,
- the content ratio of titanium is within the above range, even if the molecular weight distribution is narrow when subjected to the polymerization of olefins, the olefins polymer having excellent fluidity and high rigidity can be obtained without complicated polymerization treatment. It can be easily manufactured without applying.
- the solid catalyst component for olefin polymerization according to the present invention contains titanium, aromatic carboxylic acid esters and 1,3-diether compounds, and the total content of aromatic carboxylic acid esters and 1,3-diether compounds /
- the ratio represented by the content of titanium is preferably 2.0 or more in mass ratio, more preferably 3.0 to 20.0 in mass ratio. It is more preferable to contain so that the ratio is 4.0 to 15.0.
- the mass ratio represented by the total content of the aromatic carboxylic acid esters and the 1,3-diether compound/the content of titanium is 2.0 or more.
- titanium and aromatic carboxylic acid esters are combined so that the ratio represented by the content of aromatic carboxylic acid esters/the content of titanium is 1.0 by mass. It is preferably contained so as to be 5 or more, more preferably contained so that the mass ratio is 3.0 to 20.0, and is contained so that the mass ratio is 4.0 to 15.0. is more preferred.
- the solid catalyst component for olefin polymerization according to the present invention contains titanium and a 1,3-diether compound, and the ratio represented by the content of the 1,3-diether compound/the content of titanium is 1.0 by mass. It is preferably contained so as to be 5 or more, more preferably contained so that the mass ratio is 3.0 to 20.0, and is contained so that the mass ratio is 4.0 to 15.0. is more preferred.
- the mass ratio represented by the content of aromatic carboxylic acid esters/the content of titanium is 1.5 or more, or the content of a 1,3-diether compound Olefin polymer having excellent fluidity and high rigidity when subjected to polymerization of olefins even if the molecular weight distribution is narrow, because the ratio represented by the amount/titanium content is 1.5 or more. can be produced more easily without complicated polymerization treatment.
- each content of aromatic carboxylic acid esters, 1,3-diether compounds and other internal electron donating compounds in the solid catalyst component for olefin polymerization is determined by gas chromatography using a standard solution. It means each value measured by a calibration curve prepared in advance. Specifically, the contents of aromatic carboxylic acid esters, 1,3-diether compounds and other internal electron donating compounds were measured using gas chromatography (GC-14B, manufactured by Shimadzu Corporation). It means a value obtained using a calibration curve measured based on a standard solution of the compound to be measured when measured under the following conditions.
- GC-14B gas chromatography
- the average particle size (average particle size D50) of the solid catalyst component for olefin polymerization according to the present invention is not particularly limited, but is preferably 5.0 to 100.0 ⁇ m, more preferably 10.0 to 80.0 ⁇ m. is more preferable, and 15.0 to 70.0 ⁇ m is even more preferable.
- the average particle size D50 means the particle size of 50% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction method particle size analyzer.
- the solid catalyst component for olefin polymerization according to the present invention includes, for example, a magnesium compound, a tetravalent titanium halogen compound, and an aromatic carboxylic acid ester and a 1,3-diether compound as an internal electron donating compound.
- the content of titanium is 0.5 to 2.0% by mass
- the content of aromatic carboxylic acid esters in the total content of the internal electron donating compound is 40 to 60 mol%
- the content of the internal electron donating compound is It can be produced by contacting and reacting with each other so that the content of the 1,3-diether compound in the total content is 40 to 60 mol %.
- the magnesium compound, the tetravalent titanium halogen compound, the aromatic carboxylic acid esters and the 1,3-diether compound are as described above.
- an internal electron donating compound together with aromatic carboxylic acid esters and 1,3-diether compounds, if necessary, other internal electrons Donor compounds may also be used. Details of other internal electron donating compounds are as described above. Moreover, it is preferable that the amount of the other internal electron donating compound to be used is appropriately blended so as to satisfy the content of the other internal electron donating compound.
- the third component poly It may also be carried out in the presence of siloxane.
- Polysiloxane is a polymer having a siloxane bond (--Si--O-- bond) in its main chain, and is also generically referred to as silicone oil. 10,000 centistokes), more preferably 0.03 to 5.00 cm 2 /s (3 to 500 centistokes), which is liquid or viscous at room temperature, meaning a linear, partially hydrogenated, cyclic or modified polysiloxane. do.
- chain polysiloxanes examples include hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, and 1 as disiloxanes.
- 3-dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, and the like, and polysiloxanes other than disiloxane include dimethylpolysiloxane, methylphenylpolysiloxane, and the like. Examples include siloxane, etc. Examples of partially hydrogenated polysiloxane include methylhydrogenpolysiloxane having a hydrogenation rate of 10 to 80%.
- cyclic polysiloxane examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, Examples include decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, etc.
- Modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group Examples include substituted dimethylsiloxane and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferred, and decamethylcyclopentasiloxane is particularly preferred.
- the treatment (contact treatment) in which the magnesium compound, the tetravalent titanium halogen compound, the aromatic carboxylic acid esters and the 1,3-diether compound are brought into contact with each other is preferably carried out in an organic solvent.
- an organic solvent an inert organic solvent is preferable.
- the inert organic solvent is preferably liquid at room temperature (20 ° C.) and has a boiling point of 50 to 150 ° C., an aromatic hydrocarbon compound that is liquid at room temperature and has a boiling point of 50 to 150 ° C. or Saturated hydrocarbon compounds are more preferred.
- the inert organic solvent examples include linear aliphatic hydrocarbon compounds such as hexane, heptane and decane; branched aliphatic hydrocarbon compounds such as methylheptane; and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene.
- aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150° C. improve the activity of the resulting solid catalyst component and improve the stereoregularity of the resulting polymer. It is preferable because it can be
- the temperature at which the above components are contacted and reacted is preferably 0 to 130°C, more preferably 40 to 130°C, even more preferably 30 to 120°C, and even more preferably 80 to 120°C.
- the reaction time is preferably 1 minute or longer, more preferably 10 minutes or longer, still more preferably 30 minutes to 6 hours, even more preferably 30 minutes to 5 hours, and even more preferably 1 to 4 hours.
- Low-temperature aging may be performed prior to the above reaction.
- the low-temperature aging means a preliminary reaction in which each component is brought into contact with each other at a temperature lower than the reaction temperature.
- the temperature during low-temperature aging is preferably -20 to 70°C, more preferably -10 to 60°C, and even more preferably -10 to 30°C.
- the low-temperature aging time is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, even more preferably 30 minutes to 3 hours.
- a magnesium compound and a tetravalent titanium halogen compound are used as raw material components serving as magnesium, titanium and halogen supply sources, and these are combined with an internal electron donating compound containing a 1,3-diether compound and an inert organic solvent.
- the amount of each component to be used may be appropriately determined according to the content ratio of each component constituting the solid catalyst component for olefin polymerization to be obtained.
- each component it is preferable to carry out the reaction while stirring in a container equipped with a stirrer in an inert gas atmosphere and under conditions where moisture and the like are removed. After completion of the reaction in the contact treatment, the obtained reaction solution is allowed to stand, and the supernatant is removed as appropriate to form a wet state (slurry state), whereby a solid catalyst component can be obtained. Further, the solid catalyst component can be obtained by drying the wet reaction liquid by hot air drying or the like.
- the reaction liquid may be subjected to a washing treatment, and the washing treatment is usually performed using a washing liquid.
- the washing liquid include those similar to the inert organic solvents described above, and linear aliphatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150° C., such as hexane, heptane, and decane; Cycloaliphatic hydrocarbon compounds, such as cyclohexane and ethylcyclohexane, which are liquid at room temperature and have a boiling point of 50 to 150° C.; One or more selected from 150° C. aromatic hydrocarbon compounds and the like are preferable.
- the solid catalyst component can be obtained by drying the reaction liquid after washing by hot air drying or the like.
- the washing treatment is preferably carried out at a temperature of 0 to 120°C, more preferably at a temperature of 0 to 110°C, even more preferably at a temperature of 30 to 110°C, and 50 to 110°C. and more preferably at a temperature of 50 to 100°C.
- the washing treatment is preferably carried out by adding a desired amount of washing liquid to the reaction liquid, stirring the mixture, and then removing the liquid phase by a filtration method or a decantation method.
- the number of times of washing may be plural times (two times or more).
- Impurities such as unreacted raw material components and reaction by-products (alkoxytitanium halide, titanium tetrachloride-carboxylic acid complex, etc.) remaining in the reaction solution after washing are removed by washing after contacting each of the above components with each other. can be removed.
- an appropriate post-treatment may be performed.
- the post-treatment for example, the reaction solution obtained after the reaction or the reaction solution after washing obtained after the washing treatment is further brought into contact with a tetravalent titanium halogen compound, or An embodiment in which washing is performed after further contact with the titanium halogen compound can be mentioned.
- the washing after the post-treatment can be performed in the same manner as the washing of the reaction solution described above.
- reaction product obtained after the post-treatment and the reaction product obtained by washing after the post-treatment are usually in the form of a suspension, and each suspension-like reaction product is allowed to stand,
- a solid catalyst component can be obtained by removing the supernatant and making it wet (slurry). Further, the solid catalyst component can be obtained by drying the wet solid catalyst component by hot air drying or the like.
- the present invention by containing predetermined amounts of titanium, aromatic carboxylic acid esters and 1,3-diether compounds in addition to magnesium and halogen, even if the molecular weight distribution is narrow, fluidity is excellent and rigidity is improved. It is possible to provide a solid catalyst component for olefin polymerization that can easily produce a high-quality olefin polymer without complicated polymerization treatments.
- the olefin polymerization catalyst according to the present invention comprises the solid catalyst component for olefin polymerization according to the present invention and the following general formula (I) R 1 p AlQ 3-p (I) (Wherein, R 1 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 ⁇ p ⁇ 3.) From the compound represented by and one or more selected organoaluminum compounds.
- the olefin polymerization catalyst according to the present invention contains the specific solid catalyst component for olefin polymerization and one or more organoaluminum compounds selected from the compounds represented by the general formula (I).
- R 1 is an alkyl group having 1 to 6 carbon atoms, specifically methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and the like.
- Q represents a hydrogen atom or a halogen atom
- examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- organoaluminum compound represented by the general formula (I) include one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride. , and triisobutylaluminum are preferred.
- the olefin polymerization catalyst according to the present invention preferably contains 1 to 2000 mol of the organoaluminum compound represented by the general formula (I) per 1 mol of the titanium atom constituting the solid catalyst component for olefin polymerization. It is more preferable to contain 50 to 1000 mol.
- the olefin polymerization catalyst according to the present invention may further contain an organosilicon compound.
- the organosilicon compound that constitutes the olefin polymerization catalyst according to the present invention functions as an external electron-donating compound, and is represented by the following general formula (IV): R 7 r Si(NR 8 R 9 ) s (OR 10 ) 4 ⁇ (t+s) (IV) (Wherein, t is 0 or an integer of 1 to 2, s is 0 or an integer of 1 to 2, t+s is 0 or an integer of 1 to 4, R 7 , R 8 or R 9 is a hydrogen atom or a carbon number of 1 to any group selected from 12 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups, phenyl groups, allyl groups and aralkyl groups, which may contain heteroatoms, may be the same or different, R 8 and R 9 may be combined to form a ring, and R 7 , R 8 and R 9 may be the same or different R 10 is any group selected from alkyl groups having 1 to 4 carbon atoms,
- R 7 is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group and Any group selected from aralkyl groups, which may contain a heteroatom.
- R 7 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched alkyl group having 1 to 8 carbon atoms. , a cycloalkyl group having 5 to 8 carbon atoms is preferred.
- R 8 or R 9 is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, Any group selected from an allyl group and an aralkyl group, which may contain a heteroatom.
- R 8 or R 9 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched chain having 1 to 8 carbon atoms. and a cycloalkyl group having 5 to 8 carbon atoms are preferred.
- R 8 and R 9 may combine to form a ring shape, and in this case, (NR 8 R 9 ) forming the ring shape is preferably a perhydroquinolino group or a perhydroisoquinolino group. .
- R7 , R8 and R9 may be the same or different.
- R 10 is any group selected from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, an allyl group and an aralkyl group, and a heteroatom may contain.
- R 10 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- compounds represented by the general formula (IV) include phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, and (alkylamino)alkoxysilanes. , alkyl(alkylamino)alkoxysilanes, alkyl(alkylamino)silanes, alkylaminosilanes and the like.
- di-n-propyldimethoxysilane diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, t -butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyld
- Compounds in which s in the general formula (IV) is 1 or 2 include di(alkylamino)dialkoxysilanes, (alkylamino)(cycloalkylamino)dialkoxysilanes, (alkylamino)(alkyl)dialkoxysilanes, di (Cycloalkylamino)dialkoxysilane, vinyl(alkylamino)dialkoxysilane, allyl(alkylamino)dialkoxysilane, (alkoxyamino)trialkoxysilane, (alkylamino)trialkoxysilane, (cycloalkylamino)trialkoxysilane
- organosilicon compounds selected from silanes and the like can be mentioned, and particularly preferably ethyl (t-butylamino)dimethoxysilane, cyclohexyl (cyclohexylamino)dimethoxysilane, ethyl (t-
- the olefin polymerization catalyst according to the present invention preferably contains 0.002 to 10 mol, and preferably 0.01 to 2 mol, of the organosilicon compound per 1 mol of the organoaluminum compound represented by the general formula (I). More preferably, it contains 0.01 to 0.5 mol.
- the olefin polymerization catalyst according to the present invention When the olefin polymerization catalyst according to the present invention is preliminarily contacted with a part of the olefins to be polymerized as described below and subjected to preliminary polymerization, the olefin polymerization catalyst according to the present invention
- the catalyst suitably contains 0.1 to 1000 parts by mass of the olefin polymer per 100 parts by mass of the solid catalyst component for olefin polymerization which constitutes the catalyst for polymerizing olefins.
- the catalyst for olefin polymerization according to the present invention comprises the solid catalyst component for olefin polymerization according to the present invention, the organoaluminum compound represented by the general formula (I), and, if necessary, an organosilicon compound. contact object.
- the catalyst for olefin polymerization according to the present invention comprises a solid catalyst component for olefin polymerization according to the present invention, an organoaluminum compound represented by general formula (I), and, if necessary, an organosilicon compound in the absence of olefins. It may be prepared by contact, or may be prepared by contact in the presence of olefins (within the polymerization system).
- the solid catalyst component for olefin polymerization and the organoaluminum compound represented by the general formula (I) are brought into contact with each other using argon, nitrogen, or the like in order to prevent deterioration of the solid catalyst component for olefin polymerization and the obtained catalyst for olefin polymerization. or an atmosphere of a monomer such as propylene.
- a dispersion medium such as an inert solvent.
- ethylbenzene and the like are used, aliphatic hydrocarbons are more preferred, and hexane, heptane and cyclohexane are more preferred.
- the temperature at which the above-mentioned solid catalyst component for olefin polymerization, the organoaluminum compound represented by the general formula (I), and, if necessary, the organosilicon compound are brought into contact is preferably less than 15°C, and preferably -15°C to 10°C. More preferably, 0°C to 10°C is even more preferable.
- the contact time for bringing the solid catalyst component for polymerization of olefins into contact with the organoaluminum compound represented by the general formula (I) and, if necessary, the organosilicon compound is preferably 30 minutes or less, and preferably 5 seconds to 20 minutes. More preferably, 30 seconds to 15 minutes is more preferable, and 1 minute to 10 minutes is even more preferable.
- an organoaluminum compound which is a co-catalyst
- a solid catalyst component for polymerization of olefins the reaction proceeds rapidly, and the aromatic carboxylic acid esters or 1,3-diether compounds constituting the solid catalyst component are eliminated.
- the solid catalyst component is activated by the organoaluminum compound as a co-catalyst, and in an inert gas atmosphere, excessive reaction tends to cause deactivation of the catalyst active sites (titanium active sites).
- the contact treatment at the above contact temperature and contact time, it is possible to effectively suppress deactivation of the catalytic active sites by suppressing excessive reaction of the organoaluminum compound to the titanium active sites in the solid catalyst component. can.
- the proportion of each component to be used may be appropriately determined according to the content of each component constituting the resulting olefin polymerization catalyst.
- the method for producing an olefin polymer according to the present invention is characterized by polymerizing olefins using the olefin polymerization catalyst according to the present invention.
- the olefin polymerization is preferably propylene homopolymerization or copolymerization of propylene and an ⁇ -olefin other than propylene.
- ⁇ -olefins other than propylene include one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like, with ethylene or 1-butene being preferred. .
- propylene may be homopolymerized, propylene and other ⁇ -olefins may be copolymerized, or propylene and other olefins may be copolymerized.
- propylene and a small amount of ⁇ -olefin monomer other than propylene are used as comonomers, and random copolymerization is performed in one stage, and olefins are polymerized in the first stage (first polymerization tank).
- a monomer containing propylene is exclusively polymerized, and propylene and other ⁇ -olefins such as ethylene are copolymerized in the second stage (second polymerization tank) or more stages (multistage polymerization tank). Polymerization is typical, and block copolymerization of propylene with other ⁇ -olefins is preferred.
- 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 gas or liquid state.
- Polymerization of olefins can be carried out, for example, in a reactor such as an autoclave by introducing olefins in the presence of the catalyst for olefin polymerization according to the present invention and heating and pressurizing.
- the olefin obtained by the production method according to the present invention is used for the olefins to be polymerized.
- Preliminary polymerization (hereinafter referred to as prepolymerization as appropriate) may be carried out by bringing some or all of the components of the analog polymerization catalyst into contact.
- the components of the catalyst for polymerization of olefins obtained by the production method according to the present invention and the order of contacting the olefins are arbitrary. It is preferred that the organoaluminum compound is first charged into the reactor, then contacted with the solid catalyst component for polymerization of olefins, and then contacted with one or more olefins such as propylene. In prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used, and the prepolymerization conditions are also the same as the above polymerization conditions.
- the catalyst activity is improved, and the stereoregularity and particle properties of the obtained polymer can be further improved.
- Examples of the polymer obtained by the method for producing an olefin polymer according to the present invention include the olefin polymer according to the present invention described below and the propylene-based block copolymer according to the present invention.
- a method for producing an olefin polymer that can easily produce an olefin polymer that has excellent fluidity and high rigidity even if it has a narrow molecular weight distribution without performing a complicated polymerization treatment. can be done.
- the olefin polymer according to the present invention is Melt flowability (MFR) of 20 g/10 minutes or more,
- MFR Melt flowability
- Mw/Mn The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw).
- Mz/Mw is 2.0 to 7.0, It is characterized by having a flexural modulus (FM) of 1800 MPa or more.
- the olefin polymer according to the present invention has a melt flowability (MFR) of 20 g/10 minutes or more, preferably 30 g/10 minutes or more, more preferably 50 g/10 minutes or more.
- MFR melt flowability
- the upper limit of the melt flowability (MFR) of the olefins polymer according to the present invention is not particularly limited, the melt flowability (MFR) of the olefins polymer according to the present invention is usually 1000 g/10 minutes or less. .
- melt flowability MFR
- excellent moldability can be easily exhibited.
- melt flowability (g/10 minutes) means a value measured according to ASTM D 1238 and JIS K 7210.
- the molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0. It is preferably 6.0, more preferably 4.0 to 5.5.
- the molecular weight distribution (Mz/Mw), which is the ratio of the Z-average molecular weight (Mz) to the weight-average molecular weight (Mw), is 2.0 to 7.0. It is preferably 6.0, more preferably 2.0 to 5.0.
- the olefin polymer according to the present invention has Mw/Mn and Mz/Mw within the above ranges and has a relatively narrow molecular weight distribution.
- fiber products of various grades can be easily produced in the spinning process.
- the number average molecular weight (Mn), weight average molecular weight (Mw) and Z average molecular weight (Mz) are measured by gel permeation chromatography (GPC) (GPCV2000 manufactured by Waters) under the following conditions. means the value obtained by Solvent: o-dichlorobenzene (ODCB) Temperature: 140°C (SEC) Column: Shodex GPC UT-806M Sample concentration: 1 g/liter-ODCB (50 mg/50 ml-ODCB) Injection volume: 0.5ml Flow rate: 1.0ml/min
- the olefin polymer according to the present invention has a flexural modulus (FM) of 1800 MPa or more, preferably 1850 MPa or more, more preferably 1900 MPa or more.
- the upper limit of the flexural modulus (FM) of the olefin polymer of the present invention is not particularly limited, the olefin polymer of the present invention generally has a flexural modulus (FM) of 2100 MPa or less.
- the olefin polymer according to the present invention has Mw/Mn and Mz/Mw within the above ranges, and has a high flexural modulus (FM) of 1800 MPa or more in spite of its relatively narrow molecular weight distribution. Therefore, excellent rigidity can be easily exhibited.
- FM flexural modulus
- the flexural modulus (FM) is measured by injection molding a test piece for physical property measurement using an olefin polymer to be measured according to JIS K 7171, and , which means the value measured using a test piece on which no liquid or powder exudation was observed on the surface after conditioning for 144 hours or more.
- the olefin polymer according to the present invention can be easily produced by the method for producing an olefin polymer according to the present invention.
- the method for producing a propylene-based block copolymer according to the present invention comprises: Polymerizing olefins containing 95 to 100% by mass of propylene using the catalyst for olefin polymerization according to the present invention, Melt flowability (MFR) of 20 g/10 minutes or more, The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw).
- the molecular weight distribution (Mz/Mw) is 2.0 to 7.0, After obtaining a propylene-based polymer having a flexural modulus (FM) of 1800 MPa or more, propylene and an ⁇ -olefin other than propylene are polymerized in the presence of the obtained propylene-based polymer. .
- FM flexural modulus
- the method for producing a propylene-based block copolymer according to the present invention corresponds to one embodiment of the above-described method for producing an olefin polymer according to the present invention.
- the content is the same as the content of the above-described method for producing an olefin polymer according to the present invention, except for the fact that it is specified.
- olefins containing 95 to 100% by mass of propylene are preferably used in the preceding step, and olefins containing 97 to 100% by mass of propylene are preferably used. It is more preferable to use olefins containing 99 to 100% by mass of.
- olefins containing 95 to 100% by mass of propylene are used in the preceding step, and the intermediate product has a melt flowability (MFR) of 20 g/10 minutes or more.
- the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is the molecular weight distribution (Mw/Mn) of 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw)
- Mz/Mw the molecular weight distribution of 2.0 to 7.0
- FM flexural modulus
- the propylene-based polymer obtained as an intermediate product is specified to consist of an olefin polymer containing 95 to 100% by mass of propylene. Except for the points, it is as described in the explanation of the olefin polymer according to the present invention.
- propylene and an ⁇ -olefin other than propylene are polymerized in the presence of the propylene-based polymer obtained as an intermediate product.
- the ⁇ -olefin other than propylene is not particularly limited as long as it is one or more selected from ⁇ -olefins other than propylene, and examples include ethylene, ethylene and 1-butene.
- an olefin monomer such as propylene can be used in either a gaseous or liquid state, and the treatments in the above-mentioned former and latter steps are carried out in the presence of an organic solvent. But it can also be done in its absence.
- a monomer is polymerized in an amount corresponding to 20 to 90% by mass of the entire propylene-based block copolymer to be obtained, and then the latter step.
- propylene and ethylene or other ⁇ -olefins are introduced, and rubber parts such as ethylene-propylene rubber (EPR), ethylene-propylene-1-butene terpolymer, etc.
- EPR ethylene-propylene rubber
- Polymerization is carried out while adjusting the reaction conditions so that the total amount of the system block copolymer is 10 to 80% by mass.
- the treatment in the latter stage is preferably carried out by a gas phase polymerization reaction in order to suppress the elution of the rubber part such as EPR from the polypropylene particles.
- the treatment in the above-mentioned first-stage process and second-stage process may be carried out by either a continuous polymerization method or a batch-type polymerization method.
- the polymerization reaction may be carried out in one stage or in multiple stages for both the former stage and the latter stage, and when each step is carried out in multiple stages, they may be carried out under the same conditions or different conditions.
- the polymerization temperature in both the former step and the latter step is preferably 200° C. or lower, more preferably 100° C. or lower.
- the polymerization pressure in the former step and the latter step is preferably 10 MPa or less, more preferably 5 MPa or less.
- the polymerization time is suitably 1 minute to 5 hours in total for each polymerization stage.
- examples of the propylene-based block copolymer obtained include the propylene-based block copolymer according to the present invention, which will be described later.
- a propylene-based block copolymer having excellent fluidity and high rigidity can be easily produced without complicated polymerization treatment even if the molecular weight distribution is narrow.
- the propylene-based block copolymer according to the present invention is Polymerizing olefins containing 95 to 100% by mass of propylene using the catalyst for olefin polymerization according to the present invention, Melt flowability (MFR) of 20 g/10 minutes or more,
- MFR Melt flowability
- Mw/Mn The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 4.0 to 7.0, and the ratio of the Z average molecular weight (Mz) to the weight average molecular weight (Mw).
- the molecular weight distribution (Mz/Mw) is 2.0 to 7.0, It is obtained by obtaining a propylene-based polymer having a flexural modulus (FM) of 1800 MPa or more, and then polymerizing propylene and an ⁇ -olefin other than propylene in the presence of the obtained propylene-based polymer. It is.
- FM flexural modulus
- the propylene-based block copolymer according to the present invention corresponds to one embodiment of the above-described olefin polymer according to the present invention. Further, the propylene-based block copolymer according to the present invention is defined by the expression relating to the production method of the block copolymer according to the present invention, and the details of the production method are as described above.
- the propylene-based block copolymer according to the present invention corresponds to one embodiment of the olefin polymer according to the present invention
- its physical properties and the like are also common to the olefin polymer according to the present invention.
- the details are as described in the explanation of the olefin polymer according to the present invention.
- Example 1 ⁇ Preparation of solid catalyst component for olefin polymerization> Di-n-butyl phthalate, which is an aromatic carboxylic acid ester, and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, which is a 1,3-diether compound, are used as internal electron-donating compounds. , a solid catalyst component for olefin polymerization was prepared by the following method.
- DCPDMS dicyclopentyldimethoxysilane
- Example 2 Using 6.0 mg of the solid catalyst component obtained in Example 1, using 0.13 mmol of dicyclopentylbis(ethylamino)silane (DCPEAS) instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), hydrogen Formation of a polymerization catalyst and propylene polymerization were carried out in the same manner as in Example 1, except that the amount of gas charged was changed to 6.0 liters, and the obtained polymer was evaluated. Table 2 shows the results.
- DCPEAS dicyclopentylbis(ethylamino)silane
- DCPDMS dicyclopentyldimethoxysilane
- DCPDMS dicyclopentyldimethoxysilane
- Example 4 Example 1 except that 6.0 milligrams of the solid catalyst component obtained in Example 3 was used and 0.13 millimoles of diethylaminotriethoxysilane (DEATES) was used in place of 0.13 millimoles of dicyclopentyldimethoxysilane (DCPDMS). Formation of a polymerization catalyst and propylene polymerization were carried out in the same manner as in 3, and evaluation of the resulting polymer was carried out. Table 2 shows the results.
- DEATES diethylaminotriethoxysilane
- DCPDMS dicyclopentyldimethoxysilane
- DCPDMS dicyclopentyldimethoxysilane
- Example 6 Using 4.0 milligrams of the solid catalyst component obtained in Example 5, replacing 0.13 millimoles of dicyclopentyldimethoxysilane (DCPDMS) with 0.13 millimoles of diethylaminotriethoxysilane (DEATES), and charging hydrogen gas. Formation of a polymerization catalyst and propylene polymerization were carried out in the same manner as in Example 5, except that the amount was changed to 6.0 liters, and the resulting polymer was evaluated. Table 2 shows the results.
- DCPDMS dicyclopentyldimethoxysilane
- DEATES diethylaminotriethoxysilane
- Example 7 Using 4.0 milligrams of the solid catalyst component obtained in Example 5, using 0.26 millimoles of dicyclopentylbis(ethylamino)silane (DCPEAS) instead of 0.13 millimoles of dicyclopentyldimethoxysilane (DCPDMS), and Formation of a polymerization catalyst and propylene polymerization were carried out in the same manner as in Example 5, except that the hydrogen gas charging amount was changed to 6.0 liters, and the obtained polymer was evaluated. Table 2 shows the results.
- DCPEAS dicyclopentylbis(ethylamino)silane
- DCPDMS dicyclopentyldimethoxysilane
- the contact product was washed twice with 125 mL of toluene at 105°C. (iv) Then add 75 mL of toluene and raise the temperature to 60° C. Add 5.0 mmol (1.4 g) of di-n-butyl phthalate and 25 mL of titanium tetrachloride, raise the temperature to 90° C., and stir for 60 minutes to react. let me (v) After extracting the supernatant, 75 mL of toluene and 25 mL of titanium tetrachloride were added, the temperature was raised to 90° C., and the mixture was stirred for 60 minutes to react.
- DEATES diethylaminotriethoxysilane
- Comparative example 2 In Comparative Example 1, formation of a polymerization catalyst and propylene polymerization were carried out in the same manner as in Comparative Example 1, except that the amount of hydrogen gas charged was changed to 4.0 liters, and the obtained polymer was evaluated. . Table 2 shows the results.
- the solid catalyst components for olefin polymerization obtained in Examples 1 to 7 contain magnesium and halogen, and also contain titanium, aromatic carboxylic acid esters and 1,3-diether compounds. It can be seen that by including each predetermined amount, an olefin polymer having excellent fluidity and high rigidity can be easily produced without complicated polymerization treatment even if the molecular weight distribution is narrow.
- a solid catalyst component for the polymerization of olefins which can easily produce an olefin polymer having excellent fluidity and high rigidity even if the molecular weight distribution is narrow, without performing a complicated polymerization treatment. It is possible to provide an olefin polymerization catalyst, a method for producing an olefin polymer, an olefin polymer, a method for producing a propylene-based block copolymer, and a propylene-based block copolymer.
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Abstract
Description
一方、分子量分布の広いポリプロピレンは、ポリプロピレン溶液を押し出す際にスウェル(Swell)を生じ易いことから、例えば紡糸工程において各種グレードの繊維製品を製造し難いという技術課題が存在していた。
(1)マグネシウム、チタン及びハロゲンを含有するとともに、内部電子供与性化合物として芳香族カルボン酸エステル類及び1,3-ジエーテル化合物を含有するオレフィン類重合用固体触媒成分であって、
前記チタンの含有割合が0.5~2.0質量%、
前記内部電子供与性化合物の全含有量中に占める芳香族カルボン酸エステル類の含有割合が40~60mol%、
前記内部電子供与性化合物の全含有量に占める1,3-ジエーテル化合物の含有割合が40~60mol%である
ことを特徴とするオレフィン類重合用固体触媒成分、
(2)前記チタンと、前記芳香族カルボン酸エステル類及び1,3-ジエーテル化合物とを、前記芳香族カルボン酸エステル類及び1,3-ジエーテル化合物の合計含有量/前記チタンの含有量で表される比が質量比で2.0以上となるように含有する上記(1)に記載のオレフィン重合用固体触媒成分、
(3)前記チタンと、前記芳香族カルボン酸エステル類とを、前記芳香族カルボン酸エステル類の含有量/前記チタンの含有量で表される比が質量比で1.5以上となるように含有する上記(1)または(2)に記載のオレフィン重合用固体触媒成分、
(4)前記チタンと、前記1,3-ジエーテル化合物とを、前記1,3-ジエーテル化合物の含有量/前記チタンの含有量で表される比が質量比で1.5以上となるように含有する上記(1)~(3)のいずれかに記載のオレフィン重合用固体触媒成分、
(5)上記(1)~(4)の何れかに記載のオレフィン類重合用固体触媒成分と、下記一般式(I)
R1 pAlQ3-p (I)
(式中、R1は、炭素数1~6のアルキル基であり、Qは、水素原子またはハロゲン原子であり、pは、0<p≦3の実数である。)で表される化合物から選ばれる一種以上の有機アルミニウム化合物とを含むことを特徴とするオレフィン類重合用触媒、
(6)さらに有機ケイ素化合物を含む上記(5)に記載のオレフィン類重合用触媒、
(7)上記(5)または(6)に記載のオレフィン類重合用触媒を用いてオレフィン類を重合することを特徴とするオレフィン類重合体の製造方法、
(8)前記オレフィン類の重合が、プロピレン単独重合であるか、プロピレン及びプロピレン以外のα-オレフィンの共重合である上記(7)に記載のオレフィン類重合体の製造方法、
(9)溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
ことを特徴とするオレフィン類重合体、
(10)プロピレンを95~100質量%含むオレフィン類を上記(5)または(6)に記載のオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させる
ことを特徴とするプロピレン系ブロック共重合体の製造方法、
(11)プロピレンを95~100質量%含むオレフィン類を上記(5)または(6)に記載のオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、
得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させて得られる
ことを特徴とするプロピレン系ブロック共重合体、
を提供するものである。
先ず、本発明に係るオレフィン類重合用固体触媒成分について説明する。
本発明に係るオレフィン類重合用固体触媒成分は、
マグネシウム、チタン及びハロゲンを含有するとともに、内部電子供与性化合物として芳香族カルボン酸エステル類及び1,3-ジエーテル化合物を含有するオレフィン類重合用固体触媒成分であって、
前記チタンの含有割合が0.5~2.0質量%、
前記内部電子供与性化合物の全含有量中に占める芳香族カルボン酸エステル類の含有割合が40~60mol%、
前記内部電子供与性化合物の全含有量に占める1,3-ジエーテル化合物の含有割合が40~60mol%である
ことを特徴とするものである。
上記マグネシウム化合物の内、ジアルコキシマグネシウムまたはマグネシウムジハライドが好ましく、具体的には、ジメトキシマグネシウム、ジエトキシマグネシウム、ジプロポキシマグネシウム、ジブトキシマグネシウム、エトキシメトキシマグネシウム、エトキシプロポキシマグネシウム、ブトキシエトキシマグネシウム、マグネシウムジクロライド、マグネシウムジブロマイド、マグネシウムジイオダイド等が挙げられ、ジエトキシマグネシウム及びマグネシウムジクロライドが特に好ましい。
ジアルコキシマグネシウムが球状である場合、上記平均粒子径D50は1.0~100.0μmであることが好ましく、5.0~80.0μmであることがより好ましく、10.0~70.0μmであることがさらに好ましい。
具体的には、ジアルコキシマグネシウムは、レーザー光散乱回折法粒度測定機を用いて測定したときに、粒子径5.0μm以下の粒子が20%以下であることが好ましく、10%以下であることがより好ましい。一方、レーザー光散乱回折法粒度測定機を用いて測定したときに、粒子径100.0μm以上の粒子が20%以下であることが好ましく、10%以下であることがより好ましい。
更にその粒度分布をln(D90/D10)で表すと3以下であることが好ましく、2以下であることがより好ましい。ここで、D90は、レーザー光散乱回折法粒度測定機を用いて測定したときの、体積積算粒度分布における積算粒度で90%の粒径を意味するものである。また、D10は、レーザー光散乱回折法粒度測定機を用いて測定したときの、体積積算粒度分布における積算粒度で10%の粒径を意味するものである。
マグネシム化合物として比表面積が上記範囲内にあるものを使用することにより、所望の比表面積を有するオレフィン類重合用固体触媒成分を容易に調製することができる。
なお、マグネシウム化合物が液体である場合には、そのまま溶液状のマグネシウム化合物として用いてもよいし、マグネシウム化合物の可溶化能を有する溶媒にさらに溶解して溶液状のマグネシウム化合物として用いてもよい。
一方、固体状のマグネシウム化合物に対して可溶化能を有さない媒体としては、マグネシウム化合物を溶解することがない、飽和炭化水素溶媒または不飽和炭化水素溶媒から選ばれる一種以上が挙げられる。
Ti(OR2)rX4-r (II)
(式中、R2は、炭素数1~4のアルキル基を示し、Xは、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を示し、rは、0≦r≦3の整数である。)で表されるチタンハライドまたはアルコキシチタンハライド群から選択される化合物の一種以上であることが好適である。
また、上記一般式(II)で表されるアルコキシチタンハライドとしては、メトキシチタントリクロライド、エトキシチタントリクロライド、プロポキシチタントリクロライド、n-ブトキシチタントリクロライド、ジメトキシチタンジクロライド、ジエトキシチタンジクロライド、ジプロポキシチタンジクロライド、ジ-n-ブトキシチタンジクロライド、トリメトキシチタンクロライド、トリエトキシチタンクロライド、トリプロポキシチタンクロライド、トリ-n-ブトキシチタンクロライド等から選ばれる一種以上が挙げられる。
四価のチタンハロゲン化合物としては、チタンテトラハライドが好ましく、チタンテトラクロライドがより好ましい。
これらのチタン化合物は単独で用いられてもよいし、2種以上併用することもできる。
芳香族ポリカルボン酸エステル類としては、芳香族ジカルボン酸ジエステルを挙げることができる。
これらの芳香族ジカルボン酸ジエステルは単独で用いられてもよいし、2種以上併用することもできる。
R3OCH2CR4R5CH2OR6 (III)
(式中、R4及びR5は、水素原子、ハロゲン原子、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もしくはシクロアルケニル基、炭素数6~12の芳香族炭化水素基もしくはハロゲン置換芳香族炭化水素基、置換基を有する炭素数7~12の芳香族炭化水素基、炭素数1~12のアルキルアミノ基または炭素数2~12のジアルキルアミノ基を示す。R4及びR5は、互いに同一であってもよいし異なっていてもよい。R4及びR5は、互いに結合して環を形成してもよい。R3及びR6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3~6のシクロアルキル基、炭素数6~12の芳香族炭化水素基もしくはハロゲン置換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す。R3及びR6は、互いに同一であってもよいし異なっていてもよい。)で表される化合物から選ばれる一種以上を挙げることができる。
から選ばれる一種以上が好ましい。
他の内部電子供与性化合物としては、特に制限されないが、芳香族カルボン酸エステル類及び1,3-ジエーテル化合物以外の有機化合物であって、酸素原子あるいは窒素原子を含有する有機化合物であることが好ましく、例えば、アルコール類、フェノール類、エーテル類、エステル類、ケトン類、酸ハライド類、アルデヒト類、アミン類、アミド類、ニトリル類、イソシアネート類、Si-O-C結合またはSi-N-C結合を含む有機ケイ素化合物等から選ばれる一種以上を挙げることができる。
本発明に係るオレフィン類重合用固体触媒成分においては、チタンの含有割合が上記範囲内にあることにより、後述するように、内部電子供与性化合物の全含有量中に占める芳香族カルボン酸エステル類の含有割合及び1,3-ジエーテル化合物の含有割合が各々所定範囲内にあることとあわせ、オレフィン類の重合に供したときに、分子量分布が狭くても、流動性に優れるとともに剛性の高いオレフィン類重合体を煩雑な重合処理を施すことなく容易に製造することができる。
本出願書類において、オレフィン類重合用固体触媒成分中のチタンの含有割合は、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)に準じて測定した値を意味するものとする。
本出願書類において、オレフィン類重合用固体触媒成分中のハロゲンの含有量は、固体触媒成分を硫酸と純水の混合溶液で処理して水溶液とした後、所定量を分取し、硝酸銀標準溶液でハロゲン原子を滴定する硝酸銀滴定法により測定した値を意味するものとする。
具体的には、芳香族カルボン酸エステル類、1,3-ジエーテル化合物及び他の内部電子供与性化合物の各含有量は、ガスクロマトグラフィー((株)島津製作所製、GC-14B)を用いて下記の条件で測定したときに、測定する化合物の標準溶液に基づいて測定した検量線を用いて求めた値を意味する。
<測定条件>
カラム:パックドカラム(φ2.6×2.1m, Silicone SE-30 10%,Chromosorb WAWDMCS 80/100、ジーエルサイエンス(株)社製)
検出器:FID(Flame IonizationDetector,水素炎イオン化型検出器)
キャリアガス:ヘリウム、流量40ml/分
測定温度:気化室280℃、カラム225℃、検出器280℃、または気化室265℃、カラム180℃、検出器265℃
ここで、平均粒子径D50は、レーザー光散乱回折法粒度測定機を用いて測定したときの、体積積算粒度分布における積算粒度で50%の粒径を意味するものである。
本発明に係るオレフィン類重合用固体触媒成分は、例えば、マグネシウム化合物と、四価のチタンハロゲン化合物と、内部電子供与性化合物として芳香族カルボン酸エステル類及び1,3-ジエーテル化合物とを、上記チタンの含有割合が0.5~2.0質量%、上記内部電子供与性化合物の全含有量中に占める芳香族カルボン酸エステル類の含有割合が40~60mol%、上記内部電子供与性化合物の全含有量に占める1,3-ジエーテル化合物の含有割合が40~60mol%となるように相互に接触して反応させることにより製造することができる。
本発明に係るオレフィン類重合用固体触媒成分を製造する方法においては、内部電子供与性化合物として、芳香族カルボン酸エステル類及び1,3-ジエーテル化合物とともに、必要に応じ、上述した他の内部電子供与性化合物を用いてもよい。
他の内部電子供与性化合物の詳細は上述したとおりである。また、他の内部電子供与性化合物の使用量も、上記他の内部電子供与性化合物の含有量を満たすように適宜配合することが好ましい。
上記不活性有機溶媒のうち、常温下において液体で、沸点が50~150℃である芳香族炭化水素化合物が、得られる固体触媒成分の活性を向上させ、得られる重合体の立体規則性を向上させることができるため、好適である。
上記接触処理における反応終了後、得られた反応液は、静置し、適宜、上澄み液を除去してウェット状(スラリー状)とすることにより固体触媒成分を得ることができる。さらに、ウェット状の反応液を、熱風乾燥等により乾燥することにより固体触媒成分を得ることもできる。
洗浄液としては、上記不活性有機溶媒と同様のものを挙げることができ、ヘキサン、ヘプタン、デカン等の常温下で液体、かつ、沸点が50~150℃の直鎖脂肪族炭化水素化合物や、メチルシクロヘキサン、エチルシクロヘキサン等の常温下で液体、かつ、沸点が50~150℃の環式脂肪族炭化水素化合物、トルエン、キシレン、エチルベンゼン、オルトジクロロベンゼン等の常温下で液体、かつ、沸点が50~150℃の芳香族炭化水素化合物等から選ばれる一種以上が好ましい。
上記洗浄液を使用することにより、反応液中から、副生成物や不純物を容易に溶解し、除去して洗浄後反応液を得ることができる。さらに、洗浄後反応液を、熱風乾燥等により乾燥することにより固体触媒成分を得ることもできる。
また、洗浄回数は複数回(2回以上)であってもよい。
上記後処理を施す場合、例えば、上記反応終了後に得られた反応液や、上記洗浄処理後に得られた洗浄後反応液に対し、四価のチタンハロゲン化合物をさらに接触させる態様や、四価のチタンハロゲン化合物をさらに接触させた後に洗浄する態様を挙げることができる。上記後処理後における洗浄は、上述した反応液の洗浄と同様に行うことができる。
次に、本発明に係るオレフィン類重合用触媒について説明する。
本発明に係るオレフィン類重合用触媒は、本発明に係るオレフィン類重合用固体触媒成分と、下記一般式(I)
R1 pAlQ3-p (I)
(式中、R1は、炭素数1~6のアルキル基であり、Qは、水素原子またはハロゲン原子であり、pは、0<p≦3の実数である。)で表される化合物から選ばれる一種以上の有機アルミニウム化合物とを含むことを特徴とするものである。
R7 rSi(NR8R9)s(OR10)4-(t+s) (IV)
(式中、tは0または1~2の整数、sは0または1~2の整数、t+sは0または1~4の整数、R7、R8又はR9は水素原子または炭素数1~12の直鎖状または分岐状アルキル基、置換又は未置換のシクロアルキル基、フェニル基、アリル基及びアラルキル基から選ばれるいずれかの基であって、ヘテロ原子を含有していてもよく、互いに同一であっても異なっていてもよい。R8とR9は結合して環形状を形成していてもよく、R7、R8及びR9は、同一であっても異なっていてもよい。また、R10は炭素数1~4のアルキル基、シクロアルキル基、フェニル基、ビニル基、アリル基及びアラルキル基から選ばれるいずれかの基であって、ヘテロ原子を含有してもよい。)で表される化合物から選ばれる一種以上が挙げられる。
R7としては、炭素数1~10の直鎖状又は分岐状のアルキル基または炭素数5~8のシクロアルキル基が好ましく、特に炭素数1~8の直鎖状または分岐鎖状のアルキル基、炭素数5~8のシクロアルキル基が好ましい。
R8またはR9としては、炭素数1~10の直鎖状または分岐鎖状のアルキル基、炭素数5~8のシクロアルキル基が好ましく、特に炭素数1~8の直鎖又は分岐鎖状のアルキル基、炭素数5~8のシクロアルキル基が好ましい。
また、R8とR9が結合して環形状を形成していてもよく、この場合、環形状を形成する(NR8R9)は、パーヒドロキノリノ基、パーヒドロイソキノリノ基が好ましい。
R10としては、炭素数1~4の直鎖状又は分岐鎖状のアルキル基が好ましい。
本発明に係るオレフィン類重合用触媒は、本発明に係るオレフィン類重合用固体触媒成分、一般式(I)で表わされる有機アルミニウム化合物及び必要に応じてさらに有機ケイ素化合物をオレフィン類不存在下で接触させることにより調製してもよいし、オレフィン類存在下で(重合系内で)接触させて調製してもよい。
また、操作の容易性を考慮すると、不活性溶媒等、分散媒の存在下において行うことも好ましく、不活性溶媒としては、ヘキサン、ヘプタン、シクロヘキサンなどの脂肪族炭化水素化合物、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素化合物等が用いられ、脂肪族炭化水素がより好ましく、中でもヘキサン、ヘプタン及びシクロヘキサンがより好ましい。
一方、上記接触温度及び接触時間で接触処理することにより、有機アルミニウム化合物による固体触媒成分中のチタン活性点への過剰な反応を抑制して触媒活性点の失活を効果的に抑制することができる。
次に、本発明に係るオレフィン類重合体の製造方法について説明する。
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類重合用触媒を用いてオレフィン類を重合することを特徴とするものである。
また、重合対象となるオレフィン類は、気体及び液体のいずれの状態でも用いることができる。
予備重合の際には、本重合と同様のオレフィン類、あるいはスチレン等のモノマーを用いることができ、予備重合条件も、上記重合条件と同様である。
本発明に係るオレフィン類重合体は、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
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体において、溶融流れ性(MFR)の上限は特に制限されないが、本発明に係るオレフィン類重合体の溶融流れ性(MFR)は、通常、1000g/10分間以下である。
溶媒 :o-ジクロロベンゼン(ODCB)
温度 :140℃(SEC)
カラム:Shodex GPC UT-806M
サンプル濃度:1g/liter-ODCB(50mg/50ml-ODCB)
注入量:0.5ml
流量 :1.0ml/min
本発明に係るオレフィン類重合体の曲げ弾性率(FM)の上限は特に制限されないが、本発明に係るオレフィン類重合体において、曲げ弾性率(FM)は、通常2100MPa以下である。
本発明に係るプロピレン系ブロック共重合体の製造方法は、
プロピレンを95~100質量%含むオレフィン類を本発明に係るオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させる
ことを特徴とするものである。
また、上記前段工程及び後段工程における処理は、連続重合法、バッチ式重合法のいずれで実施してもよい。
さらに、重合反応は、前段及び後段の処理のいずれも1段階でも多段階でもよく、各工程を多段階に実施する場合は、各々同一条件、あるいは異なる条件で実施することができる。
また、上記前段工程及び後段工程における重合圧力は、10MPa以下が好ましく、5MPa以下がより好ましい。
さらに、重合時間(反応原料の滞留時間)は、各重合段階での重合時間の合計が1分間~5時間であることが適当である。
本発明に係るプロピレン系ブロック共重合体は、
プロピレンを95~100質量%含むオレフィン類を本発明に係るオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させて得られる
ことを特徴とするものである。
また、本発明に係るプロピレン系ブロック共重合体は、本発明に係るブロック共重合体の製造方法に係る表現により規定されるものであり、係る製造方法の詳細は上述したとおりである。
<オレフィン類重合用固体触媒成分の調製>
内部電子供与性化合物として、芳香族カルボン酸エステル類であるフタル酸ジn-ブチルを採用し、1,3-ジエーテル化合物である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採用し、以下の方法によりオレフィン類重合用固体触媒成分を調製した。
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン64mL、フタル酸ジn-ブチル3.8ミリモル(1.1g)、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3.8ミリモル(0.8g)を加えてスラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン40mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル1.9ミリモル(0.5g)、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1.9ミリモル(0.4g)を加え、さらに昇温して108℃とし同温度を保持した状態で60分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて、昇温途中の80℃でフタル酸ジn-ブチル2.5ミリモル(0.7g)を加え、さらに108℃に昇温し60分間攪拌して反応させ、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
なお、表1において、芳香族カルボン酸エステル類を「(A)」で表すとともに、1,3-ジエーテル化合物を「(B)」で表している。
窒素ガスで置換された内容積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、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモル及び上記固体触媒成分を6.0ミリグラム装入して、オレフィン類重合用触媒を形成した。
その後、水素ガス9.0リットル、液化プロピレン1.4リットルを装入し、20℃で5分間予備重合を行なった後に昇温し、70℃で1時間重合反応を行って、プロピレンホモ重合体を得た。
得られたプロピレンホモ重合体の評価を行った。結果を表2に示す。
実施例1で得られた固体触媒成分6.0ミリグラムを用い、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモルの代わりにジシクロペンチルビス(エチルアミノ)シラン(DCPEAS)0.13ミリモルを用い、水素ガス装入量を6.0リットルに変更した以外は、実施例1と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム15g(131ミリモル)、トルエン64mL、フタル酸ジn-ブチル5.7ミリモル(1.6g)、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5.7ミリモル(1.2g)を加えてスラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン40mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル2.9ミリモル(0.8g)および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2.9ミリモル(0.6g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて、昇温途中の80℃でフタル酸ジn-ブチル3.8ミリモル(1.0g)を加え、さらに108℃に昇温して60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
窒素ガスで置換された内容積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、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモル及び上記固体触媒成分を6.0ミリグラム装入して、オレフィン類重合用触媒を形成した。
その後、水素ガス9.0リットル、液化プロピレン1.4リットルを装入し、20℃で5分間予備重合を行なった後に昇温し、70℃で1時間重合反応を行って、プロピレンホモ重合体を得た。
得られたプロピレンホモ重合体の評価を行った。結果を表2に示す。
実施例3で得られた固体触媒成分6.0ミリグラムを用い、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモルの代わりにジエチルアミノトリエトキシシラン(DEATES)0.13ミリモルを用いた以外は、実施例3と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、フタル酸ジn-ブチル4.6ミリモル(1.3g)、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4.6ミリモル(1.0g)を加えてスラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル2.3ミリモル(0.6g)、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2.3ミリモル(0.5g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を100℃のトルエン125mLで8回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
窒素ガスで置換された内容積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、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモル及び上記固体触媒成分を6.0ミリグラム装入して、オレフィン類重合用触媒を形成した。
その後、水素ガス9.0リットル、液化プロピレン1.4リットルを装入し、20℃で5分間予備重合を行なった後に昇温し、70℃で1時間重合反応を行って、プロピレンホモ重合体を得た。
得られたプロピレンホモ重合体の評価を行った。結果を表2に示す。
実施例5で得られた固体触媒成分4.0ミリグラムを用い、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモルの代わりにジエチルアミノトリエトキシシラン(DEATES)0.13ミリモルを用い、さらに水素ガス装入量を6.0リットルに変更した以外は、実施例5と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
実施例5で得られた固体触媒成分4.0ミリグラムを用い、ジシクロペンチルジメトキシシラン(DCPDMS)0.13ミリモルの代わりにジシクロペンチルビス(エチルアミノ)シラン(DCPEAS)0.26ミリモルを用い、さらに水素ガス装入量を6.0リットルに変更した以外は、実施例5と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、フタル酸ジn-ブチル9.0ミリモル(2.5g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル4.5ミリモル(1.3g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、トルエン76mLと、新たに四塩化チタン16mLを加えて108℃まで昇温し60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで2回洗浄した。
(iv)次いでトルエン75mLを加えて昇温し60℃でフタル酸ジn-ブチル5.0ミリモル(1.4g)、四塩化チタン25mLを加えて90℃まで昇温、60分間攪拌して反応させた。
(v)上澄液を抜き出した後、更にトルエン75mL、四塩化チタン25mLを加えて90℃まで昇温、60分間攪拌して反応させた。
(vi)次いで105℃のトルエン125mLで7回洗浄した後、60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
窒素ガスで置換された内容積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、ジエチルアミノトリエトキシシラン(DEATES)0.13ミリモル及び上記固体触媒成分を4.0ミリグラム装入して、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分間予備重合を行なった後に昇温し、70℃で1時間重合反応を行って、プロピレンホモ重合体を得た。
得られたプロピレンホモ重合体の評価を行った。結果を表2に示す。
比較例1において、水素ガス装入量を4.0リットルに変更した以外は、比較例1と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、フタル酸ジn-ブチル6.8ミリモル(1.9g)、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0.8ミリモル(0.2g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル3.4ミリモル(0.9g)、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0.4ミリモル(0.1g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
上記オレフィン類重合用固体触媒成分4.0ミリグラムを用いた以外は比較例2と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、フタル酸ジn-ブチル5.3ミリモル(1.5g)、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2.3ミリモル(0.5g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル2.6ミリモル(0.7g)、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1.1ミリモル(0.2g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
上記オレフィン類重合用固体触媒成分4.0ミリグラムを用いた以外は比較例2と同様にして、重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、フタル酸ジn-ブチル2.7ミリモル(0.8g)、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6.4ミリモル(1.4g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル1.4ミリモル(0.4g)、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3.2ミリモル(0.7g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで8回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
上記固体触媒成分を6.0ミリグラム用いた以外は、実施例1と同様の条件で重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム15g(131ミリモル)、トルエン64mL、フタル酸ジn-ブチル1.1ミリモル(0.3g)、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10.2ミリモル(2.2g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン40mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃でフタル酸ジn-ブチル0.6ミリモル(0.2g)、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5.1ミリモル(1.1g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
上記固体触媒成分4.0ミリグラムを用い、水素ガス装入量を4.0リットルに変更した以外は、実施例1と同様の条件で重合を実施、得られたプロピレンホモ重合体の評価を行った。結果を表2に示す。
<オレフィン類重合用固体触媒成分の調製>
(i)攪拌装置を備え、窒素ガスで置換された内容積500mLのフラスコに、ジエトキシマグネシウム10g(87ミリモル)、トルエン84mL、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7.6ミリモル(1.6g)を加え、スラリー懸濁液を調整し、5℃まで冷却した。このスラリー懸濁液に四塩化チタン20mLを加え第一の接触生成物を得た。
(ii)上記第一の接触生成物を昇温し、昇温途中の60℃で、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3.8ミリモル(0.8g)を加え、さらに昇温して108℃とし同温度を保持した状態で90分間反応させた。反応終了後、反応生成物である第二の接触生成物を105℃のトルエン125mLで4回洗浄した。
(iii)次に、上記洗浄後の第二の接触生成物に対し、新たに四塩化チタン48mLを加えて108℃まで昇温し、60分間攪拌して反応させた後、得られた接触生成物を105℃のトルエン125mLで7回洗浄し、次いで60℃のn-ヘプタン125mLで3回洗浄し、固液を分離してオレフィン類重合用固体触媒成分を得た。
得られたオレフィン類重合用固体触媒成分の成分分析を行った結果を表1に示す。
上記固体触媒成分6.0ミリグラム用い、水素ガス装入量を4.0リットルに変更した以外は、実施例1と同様の条件で重合用触媒の形成およびプロピレン重合を行い、得られた重合体の評価を実施した。結果を表2に示す。
Claims (11)
- マグネシウム、チタン及びハロゲンを含有するとともに、内部電子供与性化合物として芳香族カルボン酸エステル類及び1,3-ジエーテル化合物を含有するオレフィン類重合用固体触媒成分であって、
前記チタンの含有割合が0.5~2.0質量%、
前記内部電子供与性化合物の全含有量中に占める芳香族カルボン酸エステル類の含有割合が40~60mol%、
前記内部電子供与性化合物の全含有量に占める1,3-ジエーテル化合物の含有割合が40~60mol%である
ことを特徴とするオレフィン類重合用固体触媒成分。 - 前記チタンと、前記芳香族カルボン酸エステル類及び1,3-ジエーテル化合物とを、前記芳香族カルボン酸エステル類及び1,3-ジエーテル化合物の合計含有量/前記チタンの含有量で表される比が質量比で2.0以上となるように含有する請求項1に記載のオレフィン重合用固体触媒成分。
- 前記チタンと、前記芳香族カルボン酸エステル類とを、前記芳香族カルボン酸エステル類の含有量/前記チタンの含有量で表される比が質量比で1.5以上となるように含有する請求項1に記載のオレフィン重合用固体触媒成分。
- 前記チタンと、前記1,3-ジエーテル化合物とを、前記1,3-ジエーテル化合物の含有量/前記チタンの含有量で表される比が質量比で1.5以上となるように含有する請求項1に記載のオレフィン重合用固体触媒成分。
- 請求項1に記載のオレフィン類重合用固体触媒成分と、下記一般式(I)
R1 pAlQ3-p (I)
(式中、R1は、炭素数1~6のアルキル基であり、Qは、水素原子またはハロゲン原子であり、pは、0<p≦3の実数である。)で表される化合物から選ばれる一種以上の有機アルミニウム化合物とを含むことを特徴とするオレフィン類重合用触媒。 - さらに有機ケイ素化合物を含む請求項5に記載のオレフィン類重合用触媒。
- 請求項5または請求項6に記載のオレフィン類重合用触媒を用いてオレフィン類を重合することを特徴とするオレフィン類重合体の製造方法。
- 前記オレフィン類の重合が、プロピレン単独重合であるか、プロピレン及びプロピレン以外のα-オレフィンの共重合である請求項7に記載のオレフィン類重合体の製造方法。
- 溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
ことを特徴とするオレフィン類重合体。 - プロピレンを95~100質量%含むオレフィン類を請求項5~請求項7のいずれかに記載のオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させる
ことを特徴とするプロピレン系ブロック共重合体の製造方法。 - プロピレンを95~100質量%含むオレフィン類を請求項5または請求項6に記載のオレフィン類重合用触媒を用いて重合させ、
溶融流れ性(MFR)が20g/10分間以上、
数平均分子量(Mn)に対する重量平均分子量(Mw)の比である分子量分布(Mw/Mn)が4.0~7.0、重量平均分子量(Mw)に対するZ平均分子量(Mz)の比である分子量分布(Mz/Mw)が2.0~7.0であり、
曲げ弾性率(FM)が1800MPa以上である
プロピレン系重合体を得た後、
得られたプロピレン系重合体の存在下、プロピレン及びプロピレン以外のα-オレフィンを重合させて得られる
ことを特徴とするプロピレン系ブロック共重合体。
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- 2022-05-24 US US18/288,916 patent/US20240218087A1/en active Pending
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US20240218087A1 (en) | 2024-07-04 |
EP4349874A1 (en) | 2024-04-10 |
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