JPH01311106A - Production of titanium catalyst component for polymerization of olefin - Google Patents
Production of titanium catalyst component for polymerization of olefinInfo
- Publication number
- JPH01311106A JPH01311106A JP14201588A JP14201588A JPH01311106A JP H01311106 A JPH01311106 A JP H01311106A JP 14201588 A JP14201588 A JP 14201588A JP 14201588 A JP14201588 A JP 14201588A JP H01311106 A JPH01311106 A JP H01311106A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- polymerization
- titanium
- catalyst component
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 89
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 85
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 60
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000003054 catalyst Substances 0.000 title abstract description 106
- 238000006116 polymerization reaction Methods 0.000 title abstract description 71
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 30
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 26
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 12
- 239000012265 solid product Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 52
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- -1 aluminum compound Chemical class 0.000 abstract description 45
- 229920000098 polyolefin Polymers 0.000 abstract description 33
- 239000007787 solid Substances 0.000 abstract description 24
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000379 polymerizing effect Effects 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 36
- 239000002904 solvent Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 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 14
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 238000012685 gas phase polymerization Methods 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012456 homogeneous solution Substances 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 235000010210 aluminium Nutrition 0.000 description 7
- 238000010908 decantation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 4
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 4
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000002140 halogenating effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000005538 phosphinite group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- GXJPKIGCMGAHTL-UHFFFAOYSA-N dipropyl benzene-1,4-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C(=O)OCCC)C=C1 GXJPKIGCMGAHTL-UHFFFAOYSA-N 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- 150000002989 phenols Chemical class 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- TXLMBPWQZULYHP-UHFFFAOYSA-N tert-butyl(dimethoxy)silane Chemical compound CO[SiH](OC)C(C)(C)C TXLMBPWQZULYHP-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium 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
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- USJZIJNMRRNDPO-UHFFFAOYSA-N tris-decylalumane Chemical compound CCCCCCCCCC[Al](CCCCCCCCCC)CCCCCCCCCC USJZIJNMRRNDPO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical group 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野]
本発明は、オレフィン重合用チタン触媒成分の製法に関
する。更に詳しくは、透明性に優れた高結晶性のポリオ
レフィン製造用遷移金属化合物触媒成分として好適なオ
レフィン重合用チタン触媒成分の製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a titanium catalyst component for olefin polymerization. More specifically, the present invention relates to a method for producing a titanium catalyst component for olefin polymerization, which is suitable as a transition metal compound catalyst component for producing a highly crystalline polyolefin with excellent transparency.
結晶性ポリプロピレン等の結晶性ポリオレフィンは、周
期律表の■〜■族の遷移金属化合物と■〜■族の金属の
有機金属化合物とからなる、いわゆるチーグラー・ナツ
タ触媒によってオレフィンを重合することによって得ら
れることはよく知られており、重合性が高く、かつ高立
体規則性のポリオレフィンを得る方法が追究されてきた
。Crystalline polyolefins such as crystalline polypropylene are obtained by polymerizing olefins using a so-called Ziegler-Natsuta catalyst, which is composed of transition metal compounds of groups ■ to ■ of the periodic table and organometallic compounds of metals of groups ■ to ■. It is well known that polyolefins have high polymerizability and stereoregularity, and methods for obtaining polyolefins with high polymerizability and high stereoregularity have been pursued.
なかでも、高立体規則性を維持しつつ、著しく高い重合
活性を示すものとしてチタン、マグネシウム、ハロゲン
、および電子供与体を含むチタン含有固体触媒成分を用
い、これと有機アルミニウム化合物、および電子供与体
を組み合わせた触媒によってオレフィンを重合し、ポリ
オレフィンを製造する方法が近年、精力的に検討されて
いる(例えば特開昭58−83006号公報等。)。Among these, a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor is used as one that exhibits extremely high polymerization activity while maintaining high stereoregularity, and this is combined with an organoaluminum compound and an electron donor. In recent years, methods for producing polyolefins by polymerizing olefins using catalysts in combination with the above have been vigorously studied (for example, Japanese Patent Laid-Open No. 83006/1983).
本出願人もこの分野において既に数多くの提案を行なっ
ており、例えば特開昭(il−209207号公報、特
開昭62−104810号公報、特開昭62−1048
11号公報、特開昭62−104812号公報、時開゛
昭62−104813号公報等において、高立体規則性
を有する粒子形状が良好なポリオレフィンを著しく高い
重合活性でもって得る方法を開示している。The present applicant has already made many proposals in this field, such as Japanese Patent Application Laid-Open No. Sho (IL-209207, Japanese Patent Laid-Open No. 62-104810, Japanese Patent Laid-Open No. 62-1048).
No. 11, JP-A No. 62-104812, Jikai No. 62-104813, etc., disclose methods for obtaining polyolefins with high stereoregularity and good particle shape and extremely high polymerization activity. There is.
しかしながらこれらの改良された方法は前述のような長
所があるものの、得られたポリオレフィンは半透明なも
のであり、用途分野においては商品価値を損なう場合が
あり、透明性の向上が望まれていた。However, although these improved methods have the above-mentioned advantages, the polyolefins obtained are translucent, which may impair commercial value in the field of application, and improvements in transparency have been desired. .
一方、ポリオレフィンの透明性を改良する試みもなされ
ており、たとえば、芳香族カルボン酸のアルミニウム塩
(特公昭40−1652号公報等)や、ベンジリデンソ
ルビトール誘導体(特開昭51−22740号公報等)
等の造核剤をポリプロピレンに添加する方法があるが、
芳香族カルボン酸のアルミニウム塩を使用した場合には
、分散性が不良なうえに、透明性の改良効果が不十分で
あり、また、ベンジリデンソルビトール誘導体を使用し
た場合には、透明性においては一定の改良が見られるも
のの、加工時に臭気が強いことや、添加物のブリード現
象(浮き出し)が生じる等の問題点を有していた。On the other hand, attempts have been made to improve the transparency of polyolefins, such as aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1652, etc.) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22740, etc.).
There is a method of adding nucleating agents such as to polypropylene, but
When aluminum salts of aromatic carboxylic acids are used, the dispersibility is poor and the transparency improvement effect is insufficient, and when benzylidene sorbitol derivatives are used, the transparency remains constant. Although improvements have been seen in this method, there have been problems such as a strong odor during processing and a bleed phenomenon (embossment) of additives.
上述の造核剤添加時の問題点を改良するものとして、プ
ロピレン、炭素数4〜18のα−オレフィン、および3
−メチルブテン−1若しくは3−メチルペンテン−1を
共重合させる方法(特公昭45−32430号公報)や
、4.4−ジメチルヘキセン−1の重合とプロピレンの
重合を多段に行なう方法(特開昭62−275109号
公報)が提案されているが、本発明者等が該提案の方法
に従って、ポリプロピレンの製造を行ったところ、いず
れの方法においてもプロピレンの重合活性が低下するの
みならず、塊状のポリマーが生成するので、工業的な長
期間の連続重合法、特にオレフィンの重合を気相で行な
う気相重合法においては採用できない方法であった。更
に、得られたポリプロピレンを用いて製造したフィルム
にはボイドが多数発生しており、商品価値を損なうもの
であった。Propylene, an α-olefin having 4 to 18 carbon atoms, and 3
- A method of copolymerizing methylbutene-1 or 3-methylpentene-1 (Japanese Patent Publication No. 45-32430), a method of multistage polymerization of 4,4-dimethylhexene-1 and propylene (Japanese Patent Publication No. 45-32430); No. 62-275109) has been proposed, but when the present inventors produced polypropylene according to the proposed method, not only did the polymerization activity of propylene decrease in both methods, but also lumps were formed. Since a polymer is produced, this method cannot be used in industrial long-term continuous polymerization methods, particularly in gas phase polymerization methods in which olefin polymerization is carried out in the gas phase. Furthermore, the film produced using the obtained polypropylene had many voids, which impaired its commercial value.
前記、枝鎖オレフィンとプロピレンの多段共重合技術の
改良方法として、有機アルミニウム化合物を多段に使い
分ける方法(特開昭62−275111号公報)やプロ
ピレンの少量重合を回分式にプロピレンの本重合前に行
なう方法(特開昭63−37105号公報)が重合活性
低下の抑制および沸騰n−ヘプタン抽出残率の低下の抑
制を目的として提案されているが、いずれの改良方法に
よっても塊状ポリマーの生成およびフィルムのボイド発
生は抑制できなかった。As methods for improving the multistage copolymerization technology of branched olefins and propylene mentioned above, there is a method in which organoaluminum compounds are selectively used in multiple stages (Japanese Unexamined Patent Publication No. 62-275111), and a method in which a small amount of propylene is polymerized batchwise before the main polymerization of propylene. A method (Japanese Unexamined Patent Publication No. 63-37105) has been proposed for the purpose of suppressing a decrease in polymerization activity and a decrease in boiling n-heptane extraction residue. The generation of voids in the film could not be suppressed.
更にまた同様な技術として、プロピレン重合用遷移金属
触媒成分の製造途中で枝鎖オレフィンの重合体を添加し
て得られた該触媒成分を用いてプロピレンを重合する方
法(特開昭63−69809号公報)が提案されている
が、該提案の方法は別途枝鎖オレフィンの重合体を製造
する工程が必要である為、工業上の不利を伴うばかりで
なく、既述の先行技術と同様なフィルムのボイド発生と
いう問題点を有していた。Furthermore, as a similar technique, a method of polymerizing propylene using a catalyst component obtained by adding a branched chain olefin polymer during the production of a transition metal catalyst component for propylene polymerization (Japanese Patent Laid-Open No. 63-69809) However, since the proposed method requires a separate step to produce a polymer of branched chain olefins, it not only has industrial disadvantages, but also produces a film similar to that of the prior art described above. This had the problem of the generation of voids.
本発明者等は、透明性の改良されたポリオレフィンを製
造する際に、ビニルシクロアルカン重合体を利用した従
来技術の抱えている塊状ポリマーの生成や分散不良に起
因するフィルムのボイド発生といった問題点を解決する
方法について鋭意研究した。In producing polyolefins with improved transparency, the present inventors have discovered that conventional techniques using vinylcycloalkane polymers have problems such as the formation of bulk polymers and the formation of voids in the film due to poor dispersion. We conducted intensive research on ways to solve the problem.
その結果、特定の方法によって技鎖オレフインの重合体
を含有せしめたチタン触媒の製法を見出し、このチタン
触媒成分を有機アルミニウム化合物、および電子供与体
と組合せた触媒を用いるときは、前述した様な従来技術
のポリオレフィン製造上の問題点を解決し、かつ分散性
が良好でボイドの発生が極めて少ない、透明性および結
晶性に優れたポリオレフィンが得られるばかりでなく、
該チタン触媒成分の35°C以上での高温における保存
安定性や、該チタン触媒成分の大規模製造時における製
造装置内での耐摩砕性においても著しい効果があること
を知って本発明に至った。As a result, we found a method for producing a titanium catalyst containing a polymer of technical chain olefin by a specific method, and when using a catalyst in which this titanium catalyst component is combined with an organoaluminum compound and an electron donor, we have developed a method as described above. This method not only solves the problems of conventional polyolefin production, but also provides a polyolefin with good dispersibility, extremely few voids, and excellent transparency and crystallinity.
The present invention was developed based on the knowledge that the titanium catalyst component has a remarkable effect on the storage stability at high temperatures of 35°C or higher and on the attrition resistance within the manufacturing equipment during large-scale production of the titanium catalyst component. Ta.
本発明は、著しく高い生産性でもってボイドの発生が極
めて少ない、透明性および結晶性の著しく高いポリオレ
フィンを製造しうるオレフィン重合用チタン触媒成分の
製法を提供することを目的とするものである。An object of the present invention is to provide a method for producing a titanium catalyst component for olefin polymerization, which can produce a polyolefin with extremely high productivity, extremely low void generation, and extremely high transparency and crystallinity.
〔問題点を解決する手段と発明の作用〕本発明は以下の
構成を有する。[Means for Solving the Problems and Effects of the Invention] The present invention has the following configuration.
(1)液状化したマグネシウム化合物と析出剤、ハロゲ
ン化合物、電子供与体およびチタン化合物(T1)を接
触して得られた固体生成物(1)を、有機アルミニウム
化合物の存在下、炭素数5以上の枝鎖オレフィンで重合
処理し、固体生成物(II)を得、該固体生成物(II
)にハロゲン化チタン化合物(T2)を反応させて得ら
れることを特徴とする、炭素数6以上の枝鎖オレフィン
の重合体を0.01重量%〜99重量%含有せしめた、
チタン、マグネシウム、ハロゲン、および電子供与体を
必須成分とするオレフィン重合用チタン触媒成分の製法
。(1) A solid product (1) obtained by contacting a liquefied magnesium compound with a precipitating agent, a halogen compound, an electron donor, and a titanium compound (T1) in the presence of an organoaluminum compound having a carbon number of 5 or more is polymerized with a branched chain olefin to obtain a solid product (II).
) with a halogenated titanium compound (T2), containing 0.01% to 99% by weight of a polymer of a branched olefin having 6 or more carbon atoms,
A method for producing a titanium catalyst component for olefin polymerization, which contains titanium, magnesium, halogen, and an electron donor as essential components.
(2)有機アルミニウム化合物として、一般式がA I
R’、、R2,−X、、 、 、♂、 (式中、R1
、R2はアルキル基、シクロアルキル基、またはアリー
ル基等の炭化水素基またはアルコキシ基を、Xはハロゲ
ンを表わし、またm、m’は0 <m+m′≦3の任意
の数を表わす。)で表わされる有機アルミニウム化合物
を用いる前記第1項に記載の製法。(2) As an organoaluminum compound, the general formula is A I
R',,R2,-X,, , ,♂, (wherein, R1
, R2 represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, or an aryl group, or an alkoxy group, X represents a halogen, and m and m' represent any number in the range 0<m+m'≦3. ) The manufacturing method according to item 1 above, using an organoaluminum compound represented by:
(3)炭素数5以上の枝鎖オレフィンとして、3−メチ
ルブテン−13−メチルペンテン−1,4,4−ジメチ
ルペンテン−1、および4,4−ジメチルヘキセン−1
から選択された1種以上の枝鎖オレフィンを用いる前記
第1項に記載の製法。(3) As a branched olefin having 5 or more carbon atoms, 3-methylbutene-13-methylpentene-1,4,4-dimethylpentene-1 and 4,4-dimethylhexene-1
The method according to item 1 above, which uses one or more branched olefins selected from.
本発明のオレフィン重合用チタン触媒成分の製法は、特
定の方法によって炭素数5以上の枝鎖オレフィン(以後
、単に枝鎖オレフィンと省略して用いる)の重合体を含
有せしめたチタン触媒成分の製法であるが、以下に詳述
する。The method for producing a titanium catalyst component for olefin polymerization of the present invention is a method for producing a titanium catalyst component containing a polymer of a branched olefin having 5 or more carbon atoms (hereinafter simply referred to as "branched olefin") by a specific method. However, this will be explained in detail below.
なお、本発明でいうマグネシウム化合物の「液状化」と
は、マグネシウム化合物自体が液体となる場合の他、そ
れ自体が溶媒に可溶であって溶液を形成する場合や、他
の化合物と反応し、若しくは錯体を形成した結果、溶媒
に可溶化して溶液を形成する場合も含む。また、溶液は
完全に溶解した場合の他、コロイド状ないし半溶解状の
物質を含む状態のものであってもさしつかえない。In addition, "liquefaction" of a magnesium compound as used in the present invention refers to cases in which the magnesium compound itself becomes liquid, cases in which the magnesium compound itself becomes soluble in a solvent and forms a solution, or cases in which it reacts with other compounds. , or as a result of forming a complex, it may be solubilized in a solvent to form a solution. In addition, the solution may be completely dissolved or may contain colloidal or semi-dissolved substances.
液状化すべきマグネシウム化合物としては、前述の「液
状化」の状態となりうるちのならばどのようなものでも
良く、例えば、マグネシウムシバライド、アルコキシマ
グネシウムハライド、アリーロキシマグネシウムハライ
ド、ジアルコキシマグネシウム、ジアルコキシマグネシ
ウム、マグネシウムオキシハライド、酸化マグネシウム
、水酸化マグネシウム、マグネシウムのカルボン酸塩、
ジアルキルマグネシウム、アルキルマグネシウムハライ
ド等の他、金属マグネシウムも用いることができる。The magnesium compound to be liquefied may be any compound as long as it can be in the above-mentioned "liquefaction" state, such as magnesium cybaride, alkoxymagnesium halide, aryloxymagnesium halide, dialkoxymagnesium, and dialkoxymagnesium. , magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate,
In addition to dialkylmagnesium, alkylmagnesium halide, etc., metal magnesium can also be used.
また、これらのマグネシウム化合物若しくは金属マグネ
シウムは、電子供与体、ケイ素化合物、アルミニウム化
合物との反応物であっても良い。Moreover, these magnesium compounds or metal magnesium may be a reaction product with an electron donor, a silicon compound, or an aluminum compound.
マグネシウム化合物を液状化する方法は公知の手段が用
いられる。例えば、マグネシウム化合物をアルコール、
アルデヒド、アミン、あるいはカルボン酸で液状化する
方法(特開昭58−811号公報等)、オルトチタン酸
エステルで液状化する方法(特開昭54−40293号
公報等)、リン化合物で液状化する方法(特開昭58−
19307月公報等)等の他、これらを組み合わせた方
法等があげられる。A known method can be used to liquefy the magnesium compound. For example, if a magnesium compound is mixed with alcohol,
Liquefaction with aldehyde, amine, or carboxylic acid (JP-A-58-811, etc.); Liquefaction with orthotitanate ester (JP-A-54-40293, etc.); Liquefaction with phosphorus compounds. Method of
1930 July Publication, etc.), as well as methods that combine these methods.
また上述の方法を適用することのできない、C−Mg結
合を有する有機マグネシウム化合物については、エーテ
ル、ジオキサン、ピリジン等に可溶であるのでこれらの
溶液として用いるか、有機金属化合物と反応させて、一
般式がM p M g Q R’rR’、(Mはアルミ
ニウム、亜鉛、ホウ素、またはベリリウム原子、R3,
R4は炭化水素残基、p+ Q+ r、S >Q、
VをMの原子価とするとr+5=vp+2qの関係にあ
る。)で示される錯化合物を形成させ(特開昭50−1
39885号公報等)、炭化水素溶媒に溶解し、液状化
することができる。Furthermore, for organomagnesium compounds having a C-Mg bond to which the above method cannot be applied, since they are soluble in ether, dioxane, pyridine, etc., they can be used as a solution of these or reacted with an organometallic compound. The general formula is M p M g Q R'rR', (M is aluminum, zinc, boron, or beryllium atom, R3,
R4 is a hydrocarbon residue, p+ Q+ r, S > Q,
When V is the valence of M, there is a relationship of r+5=vp+2q. ) to form a complex compound represented by
No. 39885, etc.), it can be dissolved in a hydrocarbon solvent and liquefied.
更にまた、金属マグネシウムを用いる場合には、アルコ
ールとオルトチタン酸エステルで液状化する方法(特開
昭50−51587号公報等)や、エーテル中でハロゲ
ン化アルキルと反応させ、いわゆるグリニヤール試薬を
形成する方法で液状化することができる。Furthermore, when metallic magnesium is used, it can be liquefied with alcohol and orthotitanate (such as JP-A-50-51587), or reacted with an alkyl halide in ether to form a so-called Grignard reagent. It can be liquefied by the following method.
以上の様なマグネシウム化合物を液状化させる方法の中
で、例えば、塩化マグネシウムをチタン酸エステルおよ
びアルコールを用いて炭化水素溶媒(DI)に溶解させ
る場合について述べると、[化マグネシウム1モルに対
して、チタン酸エステルを0.1モル〜2モル、アルコ
ールを0.1モル〜5モル、溶媒(DI )を0.1
f〜51用いて、各成分を任意の添加順序で混合し、そ
の懸濁液を撹はんしながら40°C〜200°C1好ま
しくは50°C〜150 ’Cで加熱する。該反応およ
び溶解に要する時間は5分〜7時間、好ましくは10分
〜5時間である。Among the above methods for liquefying magnesium compounds, for example, when magnesium chloride is dissolved in a hydrocarbon solvent (DI) using a titanate ester and alcohol, [per mole of magnesium chloride] , 0.1 mol to 2 mol of titanate ester, 0.1 mol to 5 mol of alcohol, and 0.1 mol of solvent (DI).
The components are mixed in any order of addition using f~51 and the suspension is heated with stirring at 40°C to 200°C, preferably 50°C to 150'C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours.
チタン酸エステルとしては、T i (OR5)4で表
わされるオルトチタン酸エステル、およびR6−f−0
−Ti (OR7) (ORI′)+−TOR9で表わ
されるポリチタン酸エステルである。ここで、R5゜B
、b、R’r、Ra、およびR9は炭素数1〜20のア
ルキル基、または炭素数3〜20のシクロアルキル基で
あり、tは2〜20の数である。As the titanate ester, orthotitanate ester represented by T i (OR5)4, and R6-f-0
-Ti (OR7) (ORI')+-TOR9 is a polytitanate ester. Here, R5゜B
, b, R'r, Ra, and R9 are an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 2 to 20.
具体的には、オルトチタン酸メチル、オルトチタン酸エ
チル、オルトチタン酸n−プロピル、オルトチタン酸i
−プロピル、オルトチタン酸n−ブチル、オルトチタン
酸i−ブチル、オルトチタン酸n−アミル、オルトチタ
ン酸2−エチルヘキシル、オルトチタン酸n−オクチル
、オルトチクン酸フェニルおよびオルトチタン酸シクロ
ヘキシルなどのオルトチタン酸エステル、ポリチタン酸
メチル、ポリチタン酸エチル、ポリチタン酸n−プロビ
ル、ポリチタン酸i−プロピル、ポリチタン酸n−ブチ
ル、ポリチタン酸n−ブチル、ポリチタン酸n−アミル
、ポリチタン酸2−エチルヘキシル、ポリチタン酸n−
オクチル、ポリチタン酸フェニルおよびポリチタン酸シ
クロヘキシルなどのポリチタン酸エステルを用いること
ができる。Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, orthotitanate i
- orthotitaniums such as propyl, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotinate and cyclohexyl orthotitanate; Acid ester, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, n-butyl polytitanate, n-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-polytitanate −
Polytitanate esters such as octyl, phenyl polytitanate and cyclohexyl polytitanate can be used.
ポリチタン酸エステルの使用量はオルトチタン酸エステ
ル単位に換算して、オルトチタン酸エステル相当量を用
いればよい。The amount of the polytitanate ester to be used may be converted into orthotitanate units, and the amount equivalent to the orthotitanate ester may be used.
アルコールとしては脂肪族飽和および不飽和アルコール
を使用することができる。具体的には、メチルアルコー
ル、エチルアルコール、n−プロピルアルコール、i−
プロピルアルコール、n−ブチルアルコール、n−アミ
ルアルコール、i −アミルアルコール、n−ヘキシル
アルコール、n−オクチルアルコール、2−エチルヘキ
シルアルコールおよびアリルアルコールなどの1価アル
コールのほかに、エチレングリコール、トリメチレング
リコールおよびグリセリンなどの多価アルコールも用い
ることができる。その中でも炭素数4〜10の脂肪族飽
和アルコールが好ましい。As alcohols it is possible to use aliphatic saturated and unsaturated alcohols. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-
In addition to monohydric alcohols such as propyl alcohol, n-butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and allyl alcohol, ethylene glycol, trimethylene glycol Polyhydric alcohols such as and glycerin can also be used. Among these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferred.
不活性炭化水素溶媒(Dl)としては、ペンタン、ヘキ
サン、ヘプタン、ノナン、デカンおよびケロシンなどの
脂肪族炭化水素、ベンゼン、トルエンおよびキシレンな
どの芳香族炭化水素、四塩化炭素、1.2−ジクロルエ
タン、C1,2−トリクロルエタン、クロルベンゼンお
よび0−ジクロルベンゼンなどのハロゲン化炭素水素を
挙げることができる。その中でも脂肪族炭化水素が好ま
しい。Inert hydrocarbon solvents (Dl) include aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, carbon tetrachloride, 1,2-dichloroethane , C1,2-trichloroethane, chlorobenzene and 0-dichlorobenzene. Among them, aliphatic hydrocarbons are preferred.
固体生成物(1)は上記の液状化したマグネシウム化合
物と析出剤(X+)、ハロゲン化合物(X2)、電子供
与体(B1)およびチタン化合物(T2)を接触して得
られる。The solid product (1) is obtained by contacting the above liquefied magnesium compound with a precipitating agent (X+), a halogen compound (X2), an electron donor (B1) and a titanium compound (T2).
析出剤(X+ )としては、ハロゲン、ハロゲン化炭化
水素、ハロゲン含有ケイ素化合物、ハロゲン含有アルミ
ニウム化合物、ハロゲン含゛有チタン化合物、ハロゲン
含有ジルコニウム化合物、ハロゲン含有バナジウム化合
物の様なハロゲン化剤があげられる。また、液状化した
マグネシウム化合物が前述した有機マグネシウム化合物
の場合はに、活性水素を有する化合物、例えば、アルコ
ール、5i−H結合を有するポリシロキサン等を用いる
こともできる。これらの析出剤(Xl)の使用量はマグ
ネシウム化合物1モルに対して0.1モル〜50モル用
いる。Examples of the precipitation agent (X+) include halogenating agents such as halogens, halogenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing titanium compounds, halogen-containing zirconium compounds, and halogen-containing vanadium compounds. . Further, when the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, such as an alcohol or a polysiloxane having a 5i-H bond, can also be used. The amount of these precipitating agents (Xl) used is 0.1 mol to 50 mol per mol of the magnesium compound.
また、ハロゲン化合物(X2)としては、ハロゲンおよ
びハロゲンを含有する化合物があげられ、析出剤の例と
してあげられたハロゲン化剤と同様なものが使用可能で
あり、析出剤としてハロゲン化剤を用いた場合には、ハ
ロゲン化合物(X2)の新たな使用を必ずしも必要とし
ない。ハロゲン化合物(X2)の使用量はマグネシウム
化合物1モルに対して0.1モル〜50モル用いる。Furthermore, examples of the halogen compound (X2) include halogens and halogen-containing compounds, and the same halogenating agents mentioned as examples of precipitating agents can be used. In this case, it is not necessarily necessary to newly use the halogen compound (X2). The amount of the halogen compound (X2) to be used is 0.1 mol to 50 mol per mol of the magnesium compound.
電子供与体(B1)としては、アルコール、フェノール
、ケトン、アルデヒド、カルボン酸、有機酸または無機
酸のエステル、エーテル、酸アミド、酸無水物等の含酸
素電子供与体、アンモニア、アミン、ニトリル、イソシ
アネート等の含窒素電子供与体、ホスフィン、ホスファ
イト、ホスフィナイト等の含燐電子供与体等を用いろこ
とができる。As the electron donor (B1), oxygen-containing electron donors such as alcohol, phenol, ketone, aldehyde, carboxylic acid, ester of organic or inorganic acid, ether, acid amide, acid anhydride, ammonia, amine, nitrile, A nitrogen-containing electron donor such as isocyanate, a phosphorus-containing electron donor such as phosphine, phosphite, phosphinite, etc. can be used.
具体的には、プロノール、エタノール、n−プロノール
、i−プロパツール、n−ブタノール、ペンタノール、
ヘキサノール、オクタツール、2−エチルヘキサノール
、アリルアルコール、ベンジルアルコール、エチレング
リコール、グリセリン等のアルコール類、フェノール、
クレゾール、キシレノール、エチルフェノール等のフェ
ノール類、アセトン、メチルエチルケトン、メチルイソ
ブチルケトン、アセトフェノン、ベンゾフェノン等のケ
トン類、アセトアルデヒド、プロピオンアルデヒド、ベ
ンズアルデヒド等のアルデヒド類、ギ酸、酢酸、プロピ
オン酸、m酸、吉草酸等のカルボン酸類、ギ酸メチル、
酢酸メチル、酪酸メチル、酢酸エチル、酢酸ビニル、酢
酸n−プロピル、酢酸i−プロピル、酢酸n−ブチル、
酢酸オクチル、酢酸フェニル、プロピオン酸エチル等の
脂肪族カルボン酸エステル類、安息香酸メチル、安息香
酸エチル、トルイル酸メチル、トルイル酸エチル、アニ
ス酸メチル、アニス酸エチル、アニス酸フェニル、等の
芳香族モノカルボン酸エステル類、フタル酸モノメチル
、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジ−
n−プロピル、フタル酸ジ−n−プロピル、フタル酸モ
ノ−n−ブチル、フタル酸ジ−n−ブチル、フタル酸ジ
ーi−ブチル、フタル酸ジ−n−ヘプチル、フタル酸ジ
−2=エチルヘキシル、フタル酸ジ−n−オクチル、イ
ソフタル酸ジエチル、イソフタル酸ジプロピル、イソフ
タル酸ジプチル、イソフタル酸ジー2−エチルヘキシル
、テレフタル酸ジエチル、テレフタル酸ジプロピル、テ
レフタル酸ジプチル、ナフタレンジカルボン酸ジーi−
ブチル等の芳香族多価カルボン酸エステル類、メチルエ
ーテル、エチルエーテル、イソプロピルエーテル、ブチ
ルエーテル、アミルエーテル、テトラヒドロフラン、ア
ニソール、ジフェニルエーテル等のエーテル類、酢酸ア
ミド、安息香酸アミド、トルイル酸アミド等の酸アミド
類、無水酢酸、無水マレイン酸、無水安息香酸、無水フ
タル酸、無水テトラヒドロフタル酸等の酸無水物、エチ
ルアミン、トリブチルアミン、アニリン、ピリジン、ピ
コリン、テトラメチルエチレンジアミン等のアミン類、
アセトニトリル、ベンゾニトリル等のニトリル類、エチ
ルホスフィン、トリエチルホスフィン、トリn−ブチル
ホスフィン、トリフェニルホスフィン等のホスフィン類
、ジメチルホスファイト、トリエチルホスファイト、ト
リフェニルホスファイト、等のホスファイト類、エチル
ジエチルホスフィナイト、エチルブチルホスフィナイト
等のホスフィナイト類、テトラエトキシシラン、テトラ
ブトキシシラン等のアルコキシシラン類が用いられ、好
ましくは、芳香族モノカルボン酸エステル類、芳香族多
価カルボン酸エステル類、アルコキシシラン類、特に好
ましくは、芳香族多価カルボン酸エステル類が用いられ
る。これら電子供与体(B1)は1種類以上が用いられ
、その使用量はマグネシウム化合物1モルに対し、0,
01モル〜5モルである。Specifically, pronol, ethanol, n-pronol, i-propanol, n-butanol, pentanol,
Alcohols such as hexanol, octatool, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenol,
Phenols such as cresol, xylenol, and ethylphenol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; aldehydes such as acetaldehyde, propionaldehyde, and benzaldehyde; formic acid, acetic acid, propionic acid, m-acid, and valeric acid. carboxylic acids such as, methyl formate,
Methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate,
Aliphatic carboxylic acid esters such as octyl acetate, phenyl acetate, and ethyl propionate, aromatic compounds such as methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, and phenyl anisate. Monocarboxylic acid esters, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-phthalate
n-propyl, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate , di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, diptyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, diptyl terephthalate, di-i-naphthalene dicarboxylate
Aromatic polyvalent carboxylic acid esters such as butyl, ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc., acid amides such as acetate amide, benzoic acid amide, toluic acid amide, etc. Acid anhydrides such as acetic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride; amines such as ethylamine, tributylamine, aniline, pyridine, picoline, and tetramethylethylenediamine;
Nitriles such as acetonitrile and benzonitrile, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, triphenylphosphine, phosphites such as dimethylphosphite, triethylphosphite, triphenylphosphite, ethyldiethyl Phosphinites such as phosphinite and ethylbutylphosphinite, alkoxysilanes such as tetraethoxysilane and tetrabutoxysilane are used, and preferably aromatic monocarboxylic acid esters, aromatic polycarboxylic acid esters, Alkoxysilanes, particularly aromatic polycarboxylic acid esters, are used. One or more types of these electron donors (B1) are used, and the amount used is 0,
01 to 5 moles.
固体生成物(1)の調製に必要なチタン化合物(Tl
)は、一般式Ti (OR’°)4−、Xu C式中、
R”はアルキル基、シクロアルキル基、またはアリール
基を、Xはハロゲンを表わし、UはO≦4の任意の数で
ある。)で表わされるハロゲン化チタン化合物や、前述
のマグネシウム化合物の液状化の際にあげられたオルト
チタン酸エステルやポリチタン酸エステルが用いられる
。Titanium compound (Tl) required for the preparation of solid product (1)
) has the general formula Ti (OR'°)4-, Xu C in the formula,
Liquefaction of a halogenated titanium compound represented by R'' is an alkyl group, a cycloalkyl group, or an aryl group, X is a halogen, and U is an arbitrary number of O≦4, or the above-mentioned magnesium compound. The orthotitanates and polytitanates mentioned above are used.
ハロゲン化チタン化合物の具体例としては、四塩化チタ
ン、四臭化チタン、三塩化メトキシチタン、三塩化エト
キシチタン、三塩化プロポキシチタン、三塩化ブトキシ
チタン、三塩化フェノキシチタン、三臭化エトキシチタ
ン、三臭化ブトキシチタン、二塩化ジメトキシチタン、
二塩化ジェトキシチタン、二塩化ジプロポキシチタン、
二塩化ジブトキシチタン、二塩化ジフェノキシチタン、
三臭化ジェトキシチタン、三臭化ジブトキシチタン、塩
化トリメトキシチタン、塩化トリエトキシチタン、塩化
トリブトキシチタン、塩化トリフエノキシチタン等があ
げられる。Specific examples of halogenated titanium compounds include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, Butoxy titanium tribromide, titanium dimethoxy dichloride,
Jetoxytitanium dichloride, dipropoxytitanium dichloride,
Dibutoxytitanium dichloride, diphenoxytitanium dichloride,
Examples include jetoxytitanium tribromide, dibutoxytitanium tribromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, and triphenoxytitanium chloride.
オルトチタン酸エステルおよびポリチタン酸エステルと
しては既述のものと同様なものがあげられる。これらチ
タン化合物(T1)は1種類以上が用いられるが、チタ
ン化合物(TI)としてハロゲン化チタン化合物を用い
た場合は、ハロゲンを有しているので析出剤(X1)お
よびハロゲン化合物(X2)の使用については任意であ
る。また、マグネシウム化合物の液状化の際にチタン酸
エステルを使用した場合にも、チタン化合物(T1)の
新たな使用は任意である。チタン化合物(T1)の使用
量はマグネシウム化合物1モルに対し、0.1モル〜1
00モルである。Examples of the orthotitanate ester and polytitanate ester include those mentioned above. One or more types of these titanium compounds (T1) are used, but when a halogenated titanium compound is used as the titanium compound (TI), since it has a halogen, the precipitation agent (X1) and the halogen compound (X2) are Use is optional. Moreover, even when a titanate ester is used during liquefaction of a magnesium compound, additional use of the titanium compound (T1) is optional. The amount of titanium compound (T1) used is 0.1 mol to 1 mol per 1 mol of magnesium compound.
00 moles.
以上の液状化したマグネシウム化合物、析出剤(X1)
、ハロゲン化合物(Xz)、電子供与体(B1)および
チタン化合物(T1)を撹はん下に接触して固体生成物
(I[[)を得る。接触の際には、不活性炭化水素溶媒
(Dt)を用いても良く、また各成分をあらかじめ希釈
して用いても良い。The above liquefied magnesium compound, precipitation agent (X1)
, a halogen compound (Xz), an electron donor (B1) and a titanium compound (T1) are brought into contact with each other with stirring to obtain a solid product (I[[). At the time of contact, an inert hydrocarbon solvent (Dt) may be used, or each component may be diluted beforehand.
用いる不活性°炭化水素溶媒(B2)としては既述の(
Dl)と同様なものが例示できる。使用量はマグネシウ
ム化合物1モルに対し、O〜5,000 mである。The inert hydrocarbon solvent (B2) used is the previously mentioned (
Dl) can be exemplified. The amount used is 0 to 5,000 m per 1 mol of the magnesium compound.
接触の方法については種々の方法があるが、例えば、■
液状化したマグネシウム化合物(Xl)を添加し、固体
を析出させ、該固体に(X2)、(Bl )、(T1)
を任意の順に接触させる方法。There are various methods of contact, for example, ■
The liquefied magnesium compound (Xl) is added to precipitate a solid, and (X2), (Bl), (T1) are added to the solid.
How to contact in any order.
■液状化したマグネシウム化合物と(B1)を接触させ
た溶液に(X1)を添加し、固体を析出させ、該固体(
X2)、(T1)を任意の順に接触させる方法。■液状
化したマグネシウム化合物と(T1)を接触させた後、
(X+ )を添加し、更に(Bl )、(X2)を任意
の順に接触させる方法等がある。(X1) is added to a solution in which the liquefied magnesium compound and (B1) are brought into contact to precipitate a solid, and the solid (
A method of bringing X2) and (T1) into contact in any order. ■After bringing the liquefied magnesium compound into contact with (T1),
There is a method of adding (X+) and then contacting (Bl) and (X2) in any order.
各成分の使用量については前述の範囲であるが、これら
の成分は一時に使用してもよいし、数段階に分けて使用
しても良い。また既述したように、一つの成分が他の成
分をも特徴づける原子若しくは基を有する場合は、他の
成分の新たな使用は必ずしも必要でない。The amount of each component to be used is within the above-mentioned range, but these components may be used all at once or in several stages. Moreover, as mentioned above, if one component has atoms or groups that also characterize the other component, it is not necessarily necessary to newly use the other component.
例えば、マグネシウム化合物を液状化する際にチタン酸
エステルを使用した場合は(T1)が、析出剤(Xl)
としてハロゲン含有チタン化合物を使用した場合は(x
2)および(T1)が、析出剤(X1) としてハロゲ
ン化剤を使用した場合は(X2)がそれぞれ任意の使用
成分となる。For example, when a titanate ester is used to liquefy a magnesium compound, (T1) becomes the precipitating agent (Xl).
When a halogen-containing titanium compound is used as (x
In 2) and (T1), when a halogenating agent is used as the precipitating agent (X1), (X2) is an optional component.
各成分の接触温度は、−40°C〜+180″C1好ま
しくは一20°C〜+150°Cであり、接触時間は反
応圧力が大気圧〜10 kg/c+fl Gで1段階ご
とに5分〜8時間、好ましくは10分〜6時間である。The contact temperature of each component is -40°C to +180''C1, preferably -20°C to +150°C, and the contact time is 5 minutes per step at a reaction pressure of atmospheric pressure to 10 kg/c+fl G. 8 hours, preferably 10 minutes to 6 hours.
以上の接触反応において固体生成物(1)が得られる。A solid product (1) is obtained in the above catalytic reaction.
該固体生成物(1)は引続いて次段階の反応をさせても
よいが、既述の不活性炭化水素溶媒により洗浄すること
が好ましい。Although the solid product (1) may be subsequently subjected to the next reaction step, it is preferably washed with the above-mentioned inert hydrocarbon solvent.
次に、前述の方法で得られた固体生成物(I)を、有機
アルミニウム化合物(Al1)の存在下、枝鎖オレフィ
ンで重合処理し、固体生成物(II)を得る。Next, the solid product (I) obtained by the above method is polymerized with a branched olefin in the presence of an organoaluminum compound (Al1) to obtain a solid product (II).
枝鎖オレフィンによる重合処理は、固体生成物(1)1
00gに対し、不活性炭化水素溶媒(B3)100+z
〜5,000,4、有機アルミニウム化合物(ALI)
5g〜5,000 gを加え、反応温度0℃〜90“C
で1分〜10時間、反応圧力は大気圧〜10kg/cr
lGの条件下で、枝鎖オレフィンを0.01g〜100
kg添加し、最終のチタン触媒成分中の枝鎖オレフィ
ン重合体の含酸が0.01重量%〜99重■%となる様
に重合させる。Polymerization treatment with branched olefins produces a solid product (1) 1
00g, inert hydrocarbon solvent (B3) 100+z
~5,000,4, organoaluminum compound (ALI)
Add 5g to 5,000g and adjust the reaction temperature to 0℃ to 90"C.
for 1 minute to 10 hours, reaction pressure is atmospheric pressure to 10 kg/cr
0.01g to 100g of branched olefin under lG conditions.
kg is added and polymerized so that the acid content of the branched olefin polymer in the final titanium catalyst component is 0.01% by weight to 99% by weight.
該枝鎖オレフィン重合体の含量が0.01重量%未満で
あると得られたポリプロピレン樹脂組成物の透明性およ
び結晶性向上の効果が不十分であり、また99重量%を
超えると該向上効果が顕著でなくなり経済的に不利とな
る。If the content of the branched olefin polymer is less than 0.01% by weight, the effect of improving the transparency and crystallinity of the obtained polypropylene resin composition will be insufficient, and if it exceeds 99% by weight, the improvement effect will be insufficient. becomes less noticeable and becomes economically disadvantageous.
また、該重合処理段階において、安息香酸エチル、トル
イル酸メチルおよびアニス酸エチル等のカルボン酸エス
テルや、フェニルトリエトキシシラン、ジフェニルジメ
トキシシランおよびメチルトリエトキシシラン等のシラ
ン化合物等に代表される電子供与体(B2)を共存させ
ることも可能である。それらの使用量は、固体生成物(
1)100g当たり0〜5,000 gである。In addition, in the polymerization step, electron donating compounds such as carboxylic acid esters such as ethyl benzoate, methyl toluate, and ethyl anisate, and silane compounds such as phenyltriethoxysilane, diphenyldimethoxysilane, and methyltriethoxysilane are used. It is also possible to coexist the body (B2). Their usage depends on the solid product (
1) 0 to 5,000 g per 100 g.
重合処理に用いられる有機アルミニウム化合物(ALI
)は、−形式がAI R’、R”、、l・X3−(m*
JlC式中、R1、R2はアルキル基、シクロアルキル
基、またはアリール基等の炭化水素基またはアルコキシ
基を、Xはハロゲンを表わし、またm、m’はO<m+
m’≦3の任意の数を表わす。)で表わされるものであ
る。Organoaluminum compounds (ALI) used in polymerization
) is -format is AI R',R'',,l・X3-(m*
In the JIC formula, R1 and R2 represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, or an aryl group, or an alkoxy group, X represents a halogen, and m and m' represent O<m+
Represents an arbitrary number of m'≦3. ).
その具体例としてはトリメチルアルミニウム、トリエチ
ルアルミニウム、トリn−プロピルアルミニウム、トリ
n−ブチルアルミニウム、トリミーブチルアルミニウム
、トリn−ヘキシルアルミニウム、トリミーヘキシルア
ルミニウム、トリ2−メチルペンチルアルミニウム、ト
リn−オクチルアルミニウム、トリn−デシルアルミニ
ウム等のトリアルキルアルミニウム類、ジエチルアルミ
ニウムモノクロライド、ジロープロピルアルミニウムモ
ノクロライド、ジi−ブチルアルミニウムモノクロライ
ド、ジエチルアルミニウムモノフルオライド、ジエチル
アルミニウムモノブロマイド、ジエチルアルミニウムモ
ノアイオダイド等のジアルキルアルミニウムモノハライ
ド類、ジエチルアルミニウムハイドライド等のジアルキ
ルアルミニウムハイドライド類、メチルアルミニウムセ
スキクロライド、エチルアルミニ
ド等のアルキルアルミニウムセスキハライド類、エチル
アルミニウムジクロライド、1−ブチルアルミニウムジ
クロライド等のモノアルキルアルミニウムシバライド類
などがあげられ、他にモノエトキシジエヂルアルミニウ
ム、ジエトキシモノエヂルアルミニウム等のアルコキシ
アルキルアルミニウム類を用いることもてきる。これら
の有機アルミニウムは2種類以上を混合して用いること
もできる。Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, trimy-butylaluminum, tri-n-hexylaluminum, trimy-hexylaluminum, tri-2-methylpentylaluminium, tri-n-octyl Aluminum, trialkylaluminums such as tri-n-decylaluminum, diethylaluminium monochloride, diropropylaluminum monochloride, di-i-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminium monobromide, diethylaluminium monoiodide, etc. dialkyl aluminum monohalides, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride and ethyl aluminide, and monoalkyl aluminum cybarides such as ethyl aluminum dichloride and 1-butyl aluminum dichloride. In addition, alkoxyalkylaluminums such as monoethoxydiedylaluminum and diethoxymonodiedylaluminium can also be used. These organic aluminums can also be used in combination of two or more types.
溶媒(B3)としては、既述の(DI )および(D.
)と同様な不活性炭化水素溶媒が示される。As the solvent (B3), the above-mentioned (DI) and (D.
) and similar inert hydrocarbon solvents are shown.
重合処理に用いられる枝鎖オレフィンの具体例としては
3−メチルブテン−1、3−メチルペンテン−1,3−
エチルペンテン−14−メチルペンテン−14−エチル
ヘキセン−L4.4−ジメチルペンテン−1、4,4−
ジメチルヘキセン−1等の炭素数5以上の枝鎖オレフィ
ンがあげられるが、なかでも3−メチルブテン−13−
メチルペンテン−1、4.4−ジメチルペンテン−11
4、4−ジメチルヘキセン1が好ましく用いられる。Specific examples of branched olefins used in polymerization include 3-methylbutene-1, 3-methylpentene-1,3-
Ethylpentene-14-methylpentene-14-ethylhexene-L4.4-dimethylpentene-1,4,4-
Examples include branched olefins having 5 or more carbon atoms such as dimethylhexene-1, among which 3-methylbutene-13-
Methylpentene-1, 4,4-dimethylpentene-11
4,4-dimethylhexene 1 is preferably used.
以上の様に枝鎖オレフィンによる重合処理を行ない、既
述の不活性炭化水素溶媒で洗浄されて、固体生成物(I
I)が得られる。Polymerization using a branched olefin is carried out as described above, washed with the above-mentioned inert hydrocarbon solvent, and a solid product (I
I) is obtained.
続いて、固体生成物(II)にハロゲン化チタン化合物
(T2)を反応させて枝鎖オレフィン重合体を含有した
チタン触媒成分が得られる。ハロゲン化チタン化合物(
T2)としては、既述の固体生成物(1)の調製に必要
なチタン化合物(T,)の例としてあげられた一形式T
i ( O R 10) a−uX.(式中、R
”はアルキル基、シクロアルキル基、またはアリール基
を、Xはハロゲンを表わしUはO<u≦4の任意の数で
ある。)で表わされるハロゲン化チタン化合物が用いら
れ、具体例としても同様なものが例示できるが、四塩化
チタンが最も好ましい。Subsequently, the solid product (II) is reacted with a halogenated titanium compound (T2) to obtain a titanium catalyst component containing a branched olefin polymer. Halogenated titanium compounds (
T2) is a type of titanium compound (T,) that is necessary for the preparation of the solid product (1) described above.
i (OR 10) a-uX. (In the formula, R
” represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and U represents an arbitrary number of O<u≦4. Among them, titanium tetrachloride is most preferred.
固体生成物(I[)とハロゲン化チタン化合物(T2)
との反応は、固体生成物(II)中のマグネシウム化合
物1モルに対して、ハロゲン化チタン化合物(T2)を
1モル以上使用して、反応温度20°C〜200°C3
反応圧力は大気圧〜10kg/ cffl Gの条件下
で5分〜6時間、好ましくは10分〜5時間反応させる
。Solid product (I[) and halogenated titanium compound (T2)
In the reaction, 1 mol or more of the halogenated titanium compound (T2) is used per 1 mol of the magnesium compound in the solid product (II), and the reaction temperature is 20°C to 200°C.
The reaction is carried out under conditions of atmospheric pressure to 10 kg/cffl G for 5 minutes to 6 hours, preferably 10 minutes to 5 hours.
また、該反応時には不活性炭化水素溶媒(B4)や電子
供与体(B3)の存在下において行なうことも可能であ
り、具体的には既述の(Dl)〜(B3)や(B1)と
同様な不活性溶媒や電子供与体が用いられる。これらの
使用量は、固体生成物(II)100gに対して(B4
)は0〜5.000雁、固体生成物(II)中の”7グ
ネシウム化合物1モルに対して(B3)は0〜2モルの
範囲が望ましい。固体生成物(II)とハロゲン化チタ
ン化合物(T2)および必要に応じて更に電子供与体と
の反応後は4別またはデカンテーション法により固体を
分離後不活性炭化水素溶媒で洗浄し、未反応物あるいは
副生物などを除去する。In addition, the reaction can be carried out in the presence of an inert hydrocarbon solvent (B4) or an electron donor (B3), and specifically, the above-mentioned (Dl) to (B3) and (B1) can be used. Similar inert solvents and electron donors can be used. These usage amounts are based on 100 g of solid product (II) (B4
) is preferably in the range of 0 to 5,000, and (B3) is preferably in the range of 0 to 2 moles per 1 mole of the 7gnesium compound in the solid product (II).The solid product (II) and the titanium halide compound After (T2) and, if necessary, further reaction with an electron donor, the solid is separated by a 4-separation method or a decantation method, and then washed with an inert hydrocarbon solvent to remove unreacted substances or by-products.
かくして目的の炭素数5以上の枝鎖オレフィンの重合体
をo、oi重量%〜99重量%含有し、かつ、チタン、
マグネシウム、ハロゲン、および電子供与体を必須成分
とするオレフィン重合用チタン触媒成分が得られる。Thus, the desired polymer of branched chain olefin having 5 or more carbon atoms is contained in o, oi weight% to 99% by weight, and titanium,
A titanium catalyst component for olefin polymerization containing magnesium, halogen, and an electron donor as essential components is obtained.
以上の様に本発明の方法によって得られたチタン触媒成
分は、公知のプロピレン等のオレフィン重合用チタン触
媒成分と同様に用いることができ、有機アルミニウム化
合物(Al1)、および電子供与体(B4)と組み合せ
て触媒とするか、更にオレフィンを少量重合させて予W
J活性化した触媒としてオレフィンの重合に用いられる
。As described above, the titanium catalyst component obtained by the method of the present invention can be used in the same manner as the known titanium catalyst component for polymerizing olefins such as propylene, and can be used as an organic aluminum compound (Al1) and an electron donor (B4). It can be used as a catalyst in combination with
Used as a J-activated catalyst in the polymerization of olefins.
オレ・フィンの重合に用いる有機アルミニウム化合物(
Al1)としては前述した本発明のチタン触媒成分を得
る際に用いた(AL+)と同様な有機アルミニウム化合
物を使用することができる。Organoaluminum compounds used for polymerization of olefins (
As Al1), the same organic aluminum compound as (AL+) used in obtaining the titanium catalyst component of the present invention described above can be used.
また電子供与体(B4)は、有機酸エステル、アルコキ
シシラン化合物やアリーロキシシラン化合物等の様な5
i−0−C結合を有する有機ケイ素化合物、エーテル、
ケトン、酸無水物、アミン等が好ましく用いられる。Further, the electron donor (B4) may be a 5-carbon compound such as an organic acid ester, an alkoxysilane compound, an aryloxysilane compound, etc.
Organosilicon compound having i-0-C bond, ether,
Ketones, acid anhydrides, amines, etc. are preferably used.
具体的には前述したチタン触媒成分を製造する際に用い
る電子供与体(B1)〜(B1)として例示したものの
他、2.2,6.6−チトラメチルピペリジン、2.2
,5.5−テトラメチルピロリジン等の立体障害の大き
いアミン類や、トリメチルメトキシシラン、トリメデル
エトキシシラン、ジメチルジメトキシシラン、ジメチル
ジェトキシシラン、ジフェニルジメトキシシラン、メチ
ルフエニルジメトキシシラン、ジフェニルジェトキシシ
ラン、エチルトリエトキシシラン、メチルトリメトキシ
シラン、ビニルトリメトキシシラン
リメトキシシラン、メチルトリエトキシシラン、エチル
!・リエトキシシラン、ビニルトリエトキシシラン、ブ
チルトリエトキシシラン、フェニルトリエトキシシラン
、エチルトリミープロポキシシラン、ビニルトリアセト
キシシラン等のSi−0−C結合を有する有機ケイ素化
合物があげられる。Specifically, in addition to those exemplified as electron donors (B1) to (B1) used in producing the titanium catalyst component described above, 2.2,6.6-titramethylpiperidine, 2.2
, 5.5-Tetramethylpyrrolidine and other highly sterically hindered amines, trimethylmethoxysilane, trimedelethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyljethoxysilane , ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilanerimethoxysilane, methyltriethoxysilane, ethyl! -Organosilicon compounds having Si-0-C bonds such as ethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrimypropoxysilane, and vinyltriacetoxysilane can be mentioned.
各触媒成分の使用量は、通常のオレフィン重合の場合と
同様であるが、具体的には、チタン触媒成分1gに対し
、有機アルミニウム化合物(ALz)0、 0 5 g
〜500g、電子供与体(B.)0.01g〜200g
程度が好ましい。The amount of each catalyst component used is the same as in the case of normal olefin polymerization, but specifically, 0.05 g of organoaluminum compound (ALz) per 1 g of titanium catalyst component.
~500g, electron donor (B.) 0.01g~200g
degree is preferred.
また予備活性化に用いられるオレフィンとしては、エチ
レン、プロピレン、プデンー11ペンテン−1、ヘキセ
ン−1、ヘプテン−1等の直鎖モノオレフィン類、4−
メチル−ペンテン−1、2−メチル−ペンテン−1′:
Jの枝鎖モノオレフィン類等である。The olefins used for preactivation include linear monoolefins such as ethylene, propylene, pudene-11pentene-1, hexene-1, heptene-1, and 4-
Methyl-pentene-1, 2-methyl-pentene-1':
These include branched monoolefins of J.
これらのオレフィンは、重合対象であるオレフィンと同
じであっても異なっていても良く、又2以上のオレフィ
ンを混合して用いることもできる。These olefins may be the same as or different from the olefin to be polymerized, or a mixture of two or more olefins may be used.
上記の触媒を用いるオレフィンの重合形式は限定されず
、スラリー重合、バルク重合の様な液相重合のほか、気
相重合でも好適に実施できる。スラリー重合またはバル
ブ重量にはチタン触媒成分と有機アルミニウム化合物(
Al1)および電子供与体(B4)を組み合わせた触媒
でも充分に効果を表わすが、気相重合の場合は、オレフ
ィンを反応させて予備活性化したものが望ましい。スラ
リー重合またはバルク重合に続いて気相重合を行う場合
は、当初使用する触媒が前者であっても気相重合のとき
は既にオレフィンの反応が行われているから、後者の触
媒と同じものとなって優れた効果が得られる。The type of polymerization of olefin using the above catalyst is not limited, and in addition to liquid phase polymerization such as slurry polymerization and bulk polymerization, gas phase polymerization can also be suitably carried out. For slurry polymerization or valve weight, titanium catalyst components and organoaluminum compounds (
Although a catalyst combining Al1) and an electron donor (B4) is sufficiently effective, in the case of gas phase polymerization, a catalyst preactivated by reacting with an olefin is preferable. When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, the olefin reaction has already taken place during gas phase polymerization, so the catalyst used is the same as the latter. This results in excellent effects.
予備活性化はプロパン、ブタン、n−ペンタン、n−ヘ
キサン、n−へブタン、ベンゼン、トルエン等の炭化水
素溶媒中で行うこともでき、液化プロピレン、液化ブテ
ン−1などの液化オレフィン中でも、気体のエチレン、
プロピレン中でも行うことができ、また予備活性化の際
に水素を共存させても良い。Preactivation can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-hebutane, benzene, toluene, etc., and even in liquefied olefins such as liquefied propylene, liquefied butene-1, etc. of ethylene,
It can be carried out in propylene, and hydrogen may also be present in the preliminary activation.
予備活性化の際にあらかじめスラリー重合又はバルク重
合又は気相重合によって得られた重合体粒子を共存させ
ることもできる。その重合体は、重合対象のオレフィン
重合体と同じであっても異なったものでもよい。共存さ
せ得る重合体粒子はチタン触媒成分1gに対し、0〜5
,000 gの範囲にある。At the time of preactivation, polymer particles previously obtained by slurry polymerization, bulk polymerization, or gas phase polymerization can also be made to coexist. The polymer may be the same as or different from the olefin polymer to be polymerized. The amount of polymer particles that can be made to coexist is 0 to 5 per 1 g of titanium catalyst component.
,000 g.
予備活性化の際に用いた溶媒又はオレフィンは、予備活
性化の途中で又は予備活性化終了後に減圧溶去又は濾別
等により、除くこともでき、又固体生成物を、その1g
当り80!を′越えない量の溶媒に懸濁させるために、
溶媒を加えることもできる。The solvent or olefin used in the preactivation can be removed by elution under reduced pressure or filtration during or after the preactivation, and the solid product can be removed by 1 g of the solid product.
Hit 80! In order to suspend in an amount of solvent not exceeding ′,
A solvent can also be added.
上記のようにして、組み合わせた本発明の方法によって
得られたチタン触媒成分と有機アルミニウム化合物(A
Lz)および電子供与体(B4)からなる触媒、又は更
にオレフィンで予備活性化した触媒は、オレフィン重合
体の製造に用いられる。As described above, the titanium catalyst component obtained by the combined method of the present invention and the organoaluminum compound (A
Catalysts consisting of Lz) and electron donors (B4) or further preactivated with olefins are used for the production of olefin polymers.
オレフィンを重合させる重合形成としては、前述したよ
うに、■n−ペンタン、n−ヘキサン、n−へブタン、
n−オクタン、ベンゼン若しくは1−ルエン等の炭化水
素溶媒中で行うスラリー重合、■液化プロピレン、液化
ブテン−1などの液化オレフィンモノマー中で行うバル
ク重合、■エチレン、プロピレン等のオレフィンを気相
で重合すせる気相重合若しくは、■以上の■〜■の二基
上を段階的に組合わせる方法がある。いずれの場合も重
合温度は室温(20″C)〜200°C1重合圧力は常
圧(Okg/’crA G )から50kg/ctQで
、通常5分〜20時間態度実施される。As mentioned above, the polymerization for polymerizing olefins includes ■n-pentane, n-hexane, n-hebutane,
Slurry polymerization carried out in a hydrocarbon solvent such as n-octane, benzene or 1-toluene, ■Bulk polymerization carried out in a liquefied olefin monomer such as liquefied propylene or liquefied butene-1, and ■Olefins such as ethylene and propylene in the gas phase. There is a method of polymerizing gas phase polymerization, or a method of stepwise combining two groups (1) to (2) above. In either case, the polymerization temperature is room temperature (20''C) to 200°C, the polymerization pressure is normal pressure (Okg/'crA G ) to 50kg/ctQ, and the polymerization is generally carried out for 5 minutes to 20 hours.
重合の際、分子量制御のためのiJ量の水素を添加する
などは従来の重合方法と同じである。重合に供せられる
オレフィンは、エチレン、プロピレン、ブテン−1、ヘ
キセン−1、オクテン−1のような直鎖モノオレフィン
類、4−メチルペンテン−1,2−メチルペンテン−1
,などの枝鎖モノオレフィン類、ブタジェン、イソプレ
ン、クロロプレンなどのジオレフィン類、スチレンなど
である。During polymerization, steps such as adding iJ of hydrogen for molecular weight control are the same as in conventional polymerization methods. The olefins to be subjected to polymerization include linear monoolefins such as ethylene, propylene, butene-1, hexene-1, octene-1, and 4-methylpentene-1,2-methylpentene-1.
, etc., diolefins such as butadiene, isoprene, chloroprene, and styrene.
また、これ等の各々の単独重合のみならず、相互に他の
オレフィンと組合わせて、例えばプロピレンとエチレン
、ブテン−1とエチレン、プロピレンとブテン−1の如
く組合わせるかプロピレン、エチレン、ブテン−1のよ
うに三成分を組合わせて共重合を行うことも出来、また
、多段重合でフィードするオレフィンの種類を変えてブ
ロック共重合を行うこともできる。In addition to the homopolymerization of each of these olefins, they can also be used in combination with other olefins, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or propylene, ethylene, butene-1, etc. Copolymerization can be performed by combining three components as in 1, or block copolymerization can be performed by changing the type of olefin fed in multistage polymerization.
本発明の主要な効果は、本発明の方法によって得られた
チタン触媒成分をオレフィン重合用遷移金属化合物触媒
成分として、オレフィンの重合に使用した場合に、著し
く高い生産性でもってボイドの発生が極めて少ない、透
明性および結晶性の著しく高いポリオレフィンを製造で
きることである。The main effect of the present invention is that when the titanium catalyst component obtained by the method of the present invention is used as a transition metal compound catalyst component for olefin polymerization in olefin polymerization, the generation of voids is extremely high with extremely high productivity. It is possible to produce polyolefins with significantly high transparency and crystallinity.
本発明の効果を更に具体的に説明する。The effects of the present invention will be explained in more detail.
本発明の第一の効果は、オレフィン重合に用いた場合、
得られたポリオレフィンの透明性と結晶性が共に向上し
、かつボイドの発生数が極めて少ないことである。以下
に示す実施例で明らかな様に、本発明の方法によって得
られたチタン触媒成分を用いて重合したポリオレフィン
のプレスフィルムの内部ヘーズはビニルシクロアルカン
重合処理をせずに得たチタン触媒成分を用いて重合した
ポリオレフィンに比べ約1/7〜1/4となっており、
著しく高い透明性を有する。また、結晶化温度も、約6
°C−12°C上昇しており、著しく結晶性が向上する
と共に、曲げ弾性率も著しく高くなっている(実施例1
〜9、比較例1,5〜10参照)。The first effect of the present invention is that when used in olefin polymerization,
Both the transparency and crystallinity of the obtained polyolefin are improved, and the number of voids generated is extremely small. As is clear from the examples shown below, the internal haze of the polyolefin press film polymerized using the titanium catalyst component obtained by the method of the present invention is different from that of the titanium catalyst component obtained without vinylcycloalkane polymerization treatment. It is about 1/7 to 1/4 compared to the polyolefin polymerized using
It has extremely high transparency. Also, the crystallization temperature is about 6
°C -12 °C, the crystallinity is significantly improved, and the flexural modulus is also significantly high (Example 1
-9, Comparative Examples 1, 5-10).
更にボイドの発生数においても本発明以外の方法によっ
て枝鎖オレフィン重合体を導入したポリオレフィンに比
べて著しく少ないことが明らかである(実施例1〜9、
比較例2.3参照)。Furthermore, it is clear that the number of voids generated is significantly smaller than in polyolefins into which branched olefin polymers are introduced by methods other than the present invention (Examples 1 to 9,
(See Comparative Example 2.3).
本発明の第二の効果は、極めて高い重合性でもって、塊
状ポリマーの生成も無く粒子形状が良好で高立体規則性
のポリオレフィンが得られることである。従って、触媒
除去工程やアククチンクポリマー除去工程を省略するこ
とができ、気相重合法等のより簡略したプロセスによっ
て、ポリオレフィンの長期間の連続重合法による製造が
可能であり、工業生産上極めて有利である。The second effect of the present invention is that a polyolefin with extremely high polymerizability, good particle shape, and high stereoregularity without the formation of bulk polymers can be obtained. Therefore, it is possible to omit the catalyst removal step and the actinic polymer removal step, and it is possible to produce polyolefin by a long-term continuous polymerization method using a simpler process such as gas phase polymerization, which is extremely useful in industrial production. It's advantageous.
本発明の第三の効果は、本発明の方法によって得られた
チタン触媒成分が保存安定性および熱安定性に優れるこ
とである。長時間に亘り、外気温の高低にかかわらず安
定に保存できることは工業上極めて大切なことである。The third effect of the present invention is that the titanium catalyst component obtained by the method of the present invention has excellent storage stability and thermal stability. It is extremely important industrially to be able to store products stably for long periods of time regardless of the outside temperature.
なお、該保存は粉体状態でも不活性炭化水素溶剤に懸濁
させた状態でも行うことができる。The preservation can be carried out either in powder form or in suspended form in an inert hydrocarbon solvent.
更に本発明の第四の効果は、本発明の方法によって得ら
れたチタン触媒成分が、耐摩砕性に優れることである。Furthermore, the fourth effect of the present invention is that the titanium catalyst component obtained by the method of the present invention has excellent attrition resistance.
該チタン触媒成分は、その使用時すなわちオレフィン重
合体製造過程のみならず触媒製造過程においても摩砕を
受けにくい。このことは、微粉触媒の生成を防ぎ、ひい
ては微粉オレフィン重合体の生成を防ぐことを意味して
いる。The titanium catalyst component is not susceptible to attrition during its use, ie, during the olefin polymer production process as well as during the catalyst production process. This means that the formation of a finely divided catalyst and, in turn, the formation of a finely divided olefin polymer is prevented.
この結果、気相重合プロセスにおけるライン閉塞トラブ
ルの防止、循環ガス中への微粉オレフィン重合体の混入
に起因するコンプレッサートラブルの防止等に極めて効
果的である。As a result, it is extremely effective in preventing line blockage troubles in the gas phase polymerization process, and in preventing compressor troubles caused by the mixing of finely divided olefin polymers into circulating gas.
以下、実施例によって本発明を説明する。実施例、比較
例において用いられている用語の定義、および測定方法
は次の通りである。The present invention will be explained below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.
fl)TY:重合活性を示し、チタン1グラム原子当り
の重合体酸M(単位:kg/グラム原子)(2111:
立体規則性を示し、沸騰n−へブタン抽出残量(単位二
重量%)
(3)BD:かさ比重(単位二重量g/nu)f4)M
FR:メルトフローインデックスASTM D−123
8(L)による。(単位:g/10分)(5)内部ヘー
ズ:表面の影響を除いたフィルム内部のヘーズであり、
プレス機を用いて温度200℃、圧力200 kg/c
nlGの条件下でポリオレフィンパウダーを厚さ150
μのフィルムとし、フィルムの両面に流動パラフィンを
塗った後、JIS K 7105に準拠してヘーズを測
定した。(単位二%)
(6)結晶化温度:示差走査熱量計を用いて、10℃/
分降温速度で測定した。(単位:°C)(7)曲げ弾性
率:ポリオレフィンパウダー100重量部に対して、テ
トラキス〔メチレン−3−(3’、5’−ジ−t−ブチ
ル−4′−ヒドロキシフェニル)プロピオネートコメタ
ン0.1 ffl量部、およびステアリン酸カルシウム
0.1重量部を混合し、該混合物をスクリュー口径40
m5の押出造粒機を用いて造粒した。ついで該造粒物を
射出成形機で溶融樹脂温度230℃、金型温度50℃で
JIS形のテストピースを作製し、該テストピースにつ
いて湿度50%、室?W23°Cの室内で72時間放置
した後、JIS K 7203に準拠して曲げ弾性率を
測定した。(単位:kgf/Cボ)
(8)ボイド:前項と同様にしてポリオレフィンの造粒
を行い、得られた造粒物をT−、グイ弐製膜機を用い、
溶融樹脂温度250 ’Cで押出し、20°Cの冷却ロ
ールで厚さ1 mmのシートを作成した。fl) TY: indicates polymerization activity, polymeric acid M per gram atom of titanium (unit: kg/gram atom) (2111:
Shows stereoregularity, boiling n-hebutane extraction residual amount (unit double weight %) (3) BD: Bulk specific gravity (unit double weight g/nu) f4) M
FR: Melt flow index ASTM D-123
According to 8(L). (Unit: g/10 minutes) (5) Internal haze: Haze inside the film excluding surface effects,
Using a press machine at a temperature of 200°C and a pressure of 200 kg/c
polyolefin powder to a thickness of 150 mm under nlG conditions.
After coating both sides of the film with liquid paraffin, the haze was measured in accordance with JIS K 7105. (Unit: 2%) (6) Crystallization temperature: Using a differential scanning calorimeter, 10℃/
It was measured by the cooling rate per minute. (Unit: °C) (7) Flexural modulus: Tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate] was added to 100 parts by weight of polyolefin powder. Mix 0.1 ffl part of methane and 0.1 part by weight of calcium stearate, and pour the mixture into a screw with a diameter of 40 mm.
It was granulated using an M5 extrusion granulator. Next, a JIS type test piece was made from the granulated product using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C, and the test piece was placed in a room at a humidity of 50%. After being left in a room at 23°C for 72 hours, the flexural modulus was measured in accordance with JIS K 7203. (Unit: kgf/Cbo) (8) Void: Polyolefin was granulated in the same manner as in the previous section, and the resulting granules were processed using a T-, Gui-ni film forming machine.
The melt was extruded at a temperature of 250'C, and a sheet with a thickness of 1 mm was produced using a cooling roll at 20°C.
該シートを150°Cの熱風で70秒間加熱し、二軸延
伸機を用いて、樅横両方向に7倍づつ延伸し、厚さ20
μの二軸延伸フィルムを得た。The sheet was heated with hot air at 150°C for 70 seconds, and then stretched by a factor of 7 in both transverse directions using a biaxial stretching machine to a thickness of 20°C.
A biaxially stretched film of μ was obtained.
該フィルムを光学顕微鏡にて観察し、直径が10μ以上
のボイドの数を測定し、1cが当たり20個未満を0.
20個以上50個未満を△、50個以上を×で示した。The film was observed with an optical microscope, and the number of voids with a diameter of 10 μ or more was measured.
20 or more and less than 50 were marked △, and 50 or more were marked ×.
実施例1
(1) チタン触媒成分の製造
攪拌機付きステンレス製反応器中において、デカン3!
、無水塩化マグネシウム480g、オルトチタン酸n−
ブチル1.7 kgおよび2−エチル−1−ヘキサノー
ル1.95 kgを混合し、撹拌しなから130°Cに
1時間加熱して溶解させ、均一な溶液とした。該均一溶
液を70°Cとし、撹拌しながらフタル酸ジイソブチル
180gを加え1時間経過後四塩化ケイ素5.2 kg
を2.5時間かけて滴下し固体を析出させ、更に70°
Cに1時間加熱した。Example 1 (1) Production of titanium catalyst component In a stainless steel reactor equipped with a stirrer, decane 3!
, anhydrous magnesium chloride 480g, orthotitanic acid n-
1.7 kg of butyl and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 1 hour without stirring to dissolve and form a homogeneous solution. The homogeneous solution was heated to 70°C, and 180 g of diisobutyl phthalate was added while stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added.
was added dropwise over 2.5 hours to precipitate the solid, and then further heated at 70°
C. for 1 hour.
固体を溶液から分離し、ヘキサンで洗浄して固体生成物
(1)を得た。The solid was separated from the solution and washed with hexane to give a solid product (1).
該固体生成物(1)全量を30°Cに保持したトリエチ
ルアルミニウム450gおよびジフェニルヅメ1−キシ
シラン145gを含むヘキサン102に%、1 QIH
させた後、3−メチルブテン−1を850g添加し、攪
拌しながら同温度において2時間重合処理を行った。処
理後、上澄液を除きn−ヘキサン61を加えてデカンテ
ーションで上澄液を除く操作を4回繰り返して、重合処
理を施した固体生成物(II)を得た。The total amount of the solid product (1) was dissolved in 102%, 1 QIH in hexane containing 450 g of triethylaluminum and 145 g of diphenyldume-1-xysilane kept at 30°C.
After that, 850 g of 3-methylbutene-1 was added, and polymerization was carried out at the same temperature for 2 hours while stirring. After the treatment, the supernatant was removed, n-hexane 61 was added, and the supernatant was removed by decantation, which was repeated four times to obtain a polymerized solid product (II).
該固体生成物(II)全量を1.2−ジクロルエタン5
1に溶かした四塩化チタン51と混合し、続いて、フタ
ル酸ジイソブチル180gを加え、撹拌しなから100
°Cに2時間反応させた後、同温度においてデカンテー
ションにより液相部を除き、再び、1.2−ジクロルエ
タン51および四塩化チタン51を加え、100°Cに
2時間撹拌し、ヘキサンで洗浄し乾燥してチタン触媒成
分を得た。The total amount of the solid product (II) was dissolved in 1,2-dichloroethane 5
1 and 51 g of titanium tetrachloride dissolved in 1, followed by adding 180 g of diisobutyl phthalate.
After reacting at °C for 2 hours, remove the liquid phase by decantation at the same temperature, add 1,2-dichloroethane 51 and titanium tetrachloride 51 again, stir at 100 °C for 2 hours, and wash with hexane. The titanium catalyst component was obtained by drying.
該チタン触媒成分は、その粒子形状が球形に近く、チタ
ン1.5重量%およびポリ13−メチルブデンー1を5
0.0重量%を含有していた。The titanium catalyst component has a nearly spherical particle shape, and contains 1.5% by weight of titanium and 5% of poly-13-methylbutene-1.
It contained 0.0% by weight.
(2)予備活性化触媒の調製
内容積30fの傾斜羽根付きステンレス製反応器を窒素
ガスで置換した後、n−ヘキサン20I!、、トリエチ
ルアルミニウム1.5kg、ジフェニルジメトキシシラ
ン480g、および(1)で得たチタン触媒成分200
gを室温で加えた。反応器を30’Cに保持、同温度に
おいて、2時間かけてエチレンを22ONl供給し、反
応させた(チタン触媒成分1gあたり、エチレン1.2
5 g反応)後、未反応エチレンを除去し、予備活性化
触媒を得た。(2) Preparation of preactivated catalyst After purging a stainless steel reactor with inclined blades with an internal volume of 30 f with nitrogen gas, 20 I of n-hexane was used! , 1.5 kg of triethylaluminum, 480 g of diphenyldimethoxysilane, and 200 g of the titanium catalyst component obtained in (1)
g was added at room temperature. The reactor was maintained at 30'C, and at the same temperature, 22 ONl of ethylene was supplied over 2 hours to cause the reaction (1.2 ethylene per 1 g of titanium catalyst component).
After 5 g reaction), unreacted ethylene was removed to obtain a preactivated catalyst.
(3) オレフィンの重合
窒素置換をした内容積80fの攪拌機のついたL/D=
3の横型重合器にM F R2,0のポリプロピレンパ
ウダー20kgを投入後、上記予備活性化触媒スラリー
(チタン触媒成分の他に、トリエチルアルミニウムおよ
びジフェニルジメトキシシランを含む)をチタン原子換
算で0.285ミリグラム原子/hrで連続的に供給し
た。(3) L/D with a stirrer with an internal volume of 80 f and nitrogen substitution for olefin polymerization =
After charging 20 kg of polypropylene powder with an M F R of 2.0 into the horizontal polymerization vessel No. 3, the preactivated catalyst slurry (containing triethylaluminum and diphenyldimethoxysilane in addition to the titanium catalyst component) was converted to 0.285 in terms of titanium atoms. It was fed continuously at milligram atoms/hr.
また気相中の濃度が0.15容積%を保っ様に水素を、
全圧が23kg/c+δGを保つ様にプロピレンをそれ
ぞれ供給して、プロピレンの気相重合を70°Cにおい
て120時間連続して行った。重合期間中は、重合内の
ポリマーの保有レベルが60容積%となる様にポリマー
を重合器から連続的に10kg/hrで抜き出した。抜
き出されたポリマーは続いてプロピレンオキサイドを0
.2容積%含む窒素ガスによって、95°Cにて30分
間接触処理された後、製品パウダーとして得られた。In addition, hydrogen was added so that the concentration in the gas phase was maintained at 0.15% by volume.
Propylene was supplied to each reactor so that the total pressure was maintained at 23 kg/c+δG, and gas phase polymerization of propylene was continuously carried out at 70° C. for 120 hours. During the polymerization period, polymer was continuously withdrawn from the polymerization vessel at a rate of 10 kg/hr such that the retention level of polymer in the polymerization was 60% by volume. The extracted polymer is then treated with 0 propylene oxide.
.. After contact treatment with nitrogen gas containing 2% by volume at 95°C for 30 minutes, a product powder was obtained.
(4)熱安定性試験
上記(1)と同様にして得たチタン触媒成分を40°C
で4ケ月保存した後、(2)、 (3)と同様にしてプ
ロピレンの重合を行った。(4) Thermal stability test The titanium catalyst component obtained in the same manner as in (1) above was heated to 40°C.
After storing for 4 months, propylene was polymerized in the same manner as in (2) and (3).
(5)耐摩砕性試験
(2)で使用した反応器に循環ポンプを備えた循環配管
を接続した後、窒素雰囲気下において、n−ヘキサン2
52、および上記(1)と同様にして得たチタン触媒成
分400gを入れた。続いて循環ポンプを動かし、循環
ラインを使用して、反応器中の懸濁液を流速10ffi
/分、温度25°Cの条件下で4時間循環させた後、(
2)、 (3)と同様にしてプロピレンの重合を行った
。(5) After connecting a circulation pipe equipped with a circulation pump to the reactor used in the attrition resistance test (2), in a nitrogen atmosphere, n-hexane 2
52, and 400 g of the titanium catalyst component obtained in the same manner as in (1) above were added. Subsequently, the circulation pump is activated and the suspension in the reactor is controlled to flow at a flow rate of 10ffi using the circulation line.
/min, after circulating for 4 hours at a temperature of 25°C, (
Polymerization of propylene was carried out in the same manner as in 2) and (3).
比較例
(1)実施例1の(1)において固体生成物(1)を3
−メチルブデンーlで重合処理することなしに固体生成
物(II)相当物とすること以外は同様にしてチタン触
媒成分を得た。Comparative Example (1) In (1) of Example 1, the solid product (1) was
A titanium catalyst component was obtained in the same manner except that the solid product (II) was obtained without polymerization with methylbutene-1.
(2)実施例1の(2)においてチタン触媒成分として
上記(1)で得られたチタン触媒成分100gを用いる
以外は同様にして予備活性化触媒の調製を行った。(2) A preactivated catalyst was prepared in the same manner as in Example 1 (2) except that 100 g of the titanium catalyst component obtained in the above (1) was used as the titanium catalyst component.
(3)実施例1の(3)において予備活性化触媒として
、上記(2)で得られた予備活性化触媒を用いる以外は
同様にしてプロピレンの重合を行った。(3) Propylene was polymerized in the same manner as in (3) of Example 1 except that the preactivated catalyst obtained in (2) above was used as the preactivated catalyst.
(4)実施例1の(4)においてチタン触媒成分として
、上記(1)と同様にして得られたチタン触媒成分を用
いる以外は同様にしてプロピレンの重合を行った。(4) Propylene was polymerized in the same manner as in Example 1 (4) except that the titanium catalyst component obtained in the same manner as in (1) above was used as the titanium catalyst component.
(5)実施例1の(5)においてチタン触媒成分として
、上記(1)と同様にして得られたチタン触媒成分を用
いる以外は同様にしてプロピレンの重合を行った。(5) Propylene was polymerized in the same manner as in (5) of Example 1, except that the titanium catalyst component obtained in the same manner as in (1) above was used as the titanium catalyst component.
比較例2
(1)比較例1の(1)と同様にしてチタン触媒成分を
得た。Comparative Example 2 (1) A titanium catalyst component was obtained in the same manner as in Comparative Example 1 (1).
(2)実施例1の(2)で使用した反応器にn−ヘプタ
ン20ρ、上記(1)で得たチタン触媒成分100g1
ジエチルアルミニウムモノクロライド400g、ジフェ
ニルジメトキシシラン120g、3−メチルブテン−1
を140g加えて40″Cで2時間反応させた。(チタ
ン触媒成分1g当り、3−メチルブテン−1が1.Og
反応)次いでれ−へブタンで洗浄後、濾過し固体を得た
。(2) In the reactor used in Example 1 (2), 20 ρ of n-heptane and 100 g of the titanium catalyst component obtained in (1) above were added.
400 g of diethylaluminium monochloride, 120 g of diphenyldimethoxysilane, 3-methylbutene-1
was added and reacted for 2 hours at 40"C. (1.Og of 3-methylbutene-1 per 1g of titanium catalyst component)
Reaction) After washing with hebutane, the mixture was filtered to obtain a solid.
更にn−へブタン20nジエチルアルミニウムモノクロ
ライド400g、ジフェニルジメトキシシラン55gを
加えた後、プロピレン280gを供給し、30°Cで1
時間反応させた(チタン触媒成分1g当りプロピレン1
.8 g 反応)。Furthermore, after adding 400 g of n-hebutane 20n diethylaluminum monochloride and 55 g of diphenyldimethoxysilane, 280 g of propylene was supplied and the mixture was heated at 30°C for 1
(propylene 1 per 1 g of titanium catalyst component)
.. 8 g reaction).
(3)実施例1の(3)において、予備活性化触媒スラ
リーの代りに上記(2)で得た触媒スラリーを、更にト
リエチルアルミニウムを1.7 g /hr、およびジ
フェニルジメトキシシランを0.30 g /hrで、
それぞれ別の供給口から供給すること以外は同様にして
プロピレンの重合を行ったところ、生成した塊状ポリマ
ーが、パウダー抜き出し配管を閉塞してしまった為、重
合開始後、14時間で製造を停止しなければならなかっ
た。(3) In (3) of Example 1, the catalyst slurry obtained in (2) above was used instead of the preactivated catalyst slurry, and 1.7 g/hr of triethylaluminum and 0.30 g/hr of diphenyldimethoxysilane were added. g/hr,
When propylene was polymerized in the same manner except for supplying from separate supply ports, the produced bulk polymer blocked the powder extraction pipe, so production was stopped 14 hours after the polymerization started. I had to.
比較例3
(1) 比較例Iの(1)において無水塩化マグネシ
ウム、オルトチタン酸n−ブチル、2−エチル−1−ヘ
キサノールおよびデカンの均一溶液にフタル酸ジイソブ
チルを添加する前に、別途比較例1の(1)と同様にし
て得たチタン触媒成分long、トリエチルアルミニウ
ム35g、およびジフェニルジメトキシシラン7.5g
を触媒として用いてn −ヘキサン100!中に添加し
た3、 5 kgの3−メチルブテン−1を60°Cに
て2時間重合した後、メタノール洗浄し、乾燥させて得
られた3、 5 kgのポI73−メチルブテン−1の
うち550gを振動ミル中で5時間粉砕後、懸濁させる
こと以外は比較例1の(1)と同様にしてポリ3−メチ
ルブテン−1を60重星%含有したチタン触媒成分を得
た。Comparative Example 3 (1) In (1) of Comparative Example I, before adding diisobutyl phthalate to a homogeneous solution of anhydrous magnesium chloride, n-butyl orthotitanate, 2-ethyl-1-hexanol, and decane, a separate comparative example was prepared. 1. Long titanium catalyst component obtained in the same manner as in (1), 35 g of triethylaluminum, and 7.5 g of diphenyldimethoxysilane.
using n-hexane as a catalyst! 550 g of 3.5 kg of 3-methylbutene-1 obtained by polymerizing 3.5 kg of 3-methylbutene-1 at 60°C for 2 hours, washing with methanol, and drying. A titanium catalyst component containing 60% poly-3-methylbutene-1 was obtained in the same manner as in Comparative Example 1 (1) except that the powder was ground in a vibrating mill for 5 hours and then suspended.
(2)チタン触媒成分として上記(1)で得たチタン触
媒成分を用いる以外は実施例1の(2)と同様にして予
備活性化触媒を得た。(2) A preactivated catalyst was obtained in the same manner as in (2) of Example 1, except that the titanium catalyst component obtained in (1) above was used as the titanium catalyst component.
(3)実施例1の(3)において予6MJ ’IA性化
触媒として上記(2)で得た予備活性化触媒を、全圧が
23kg/ cA Gを保つように供給すること以外は
同様にしてプロピレンの重合を行ないポリプロピレンを
得た。(3) In (3) of Example 1, the same procedure was carried out except that the preactivated catalyst obtained in (2) above was supplied as the pre-6MJ'IA catalyst so that the total pressure was maintained at 23 kg/cA G. Polypropylene was obtained by polymerizing propylene.
比較例4および実施例2.3
実7i1例1の(1)において重合処理に用いた3−メ
チルブテン−1の使用量を変化させて、ポリ3−メチル
プテンー1含量がそれぞれ0.001重量%、4.8重
量%、33.3重量%のチタン触媒成分を得た。後は実
施例1の(2)、 (3)と同様にしてプロピレンの重
合を行った。Comparative Example 4 and Example 2.3 Example 7i1 The amount of 3-methylbutene-1 used in the polymerization treatment in (1) of Example 1 was varied, and the poly-3-methylbutene-1 content was 0.001% by weight, respectively. A titanium catalyst component of 4.8% by weight and 33.3% by weight was obtained. After that, propylene polymerization was carried out in the same manner as in Example 1 (2) and (3).
実施例4
三塩化アルミニウム(無水)1.7kgと水酸化マグネ
シウム0.6 kgを振動ミルで250°Cにて3時間
粉砕させながら反応させた所、塩化水素ガスの発生を伴
いながら反応が起こった。加熱終了後、窒素気流中で冷
却し、マグネシウム含有固体を得た。攪拌機付きステン
レス製反応器中において、デカン61、マグネシウム含
有固体1.0 kg、オルトチタン酸n−ブチル3.4
kg、2−エチル−1−ヘキサノール3.9 kgを
混合し、攪拌しながら、130°Cに2時間加熱して溶
解させ均一な溶液とした。その溶液を70゛Cとし、p
−トルイン酸エチル0.2 kgを加え1時間反応させ
た後、フタル酸ジイソブチル0.4 kgを加え更に1
時間反応させ攪拌しなから四塩化ケイ素10kgを2時
間30分かけて滴下し固体を析出させ、更に70°C1
1時間攪拌した。固体を溶液から分離し精製へキサンに
より洗浄し固体生成物(1)を得た。Example 4 When 1.7 kg of aluminum trichloride (anhydrous) and 0.6 kg of magnesium hydroxide were reacted while being ground at 250°C in a vibrating mill for 3 hours, the reaction occurred with the generation of hydrogen chloride gas. Ta. After the heating was completed, the mixture was cooled in a nitrogen stream to obtain a magnesium-containing solid. In a stainless steel reactor with stirrer, 61 decane, 1.0 kg of magnesium-containing solid, 3.4 n-butyl orthotitanate.
kg and 3.9 kg of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 2 hours while stirring to form a uniform solution. The solution was heated to 70°C and p
- Add 0.2 kg of ethyl toluate and react for 1 hour, then add 0.4 kg of diisobutyl phthalate and react for 1 hour.
After stirring for a while, 10 kg of silicon tetrachloride was added dropwise over 2 hours and 30 minutes to precipitate a solid, and then at 70°C1.
Stirred for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (1).
該固体生成物(1)全量を25°Cに保持したトリエチ
ルアルミニウム450gおよびp−トルイル酸メチル7
5gを含むヘキサンIO!!に懸濁させた後、3−メチ
ルブテン−1を0.8 kg添加し、攪拌しながら同温
度において2時間重合処理を行った。処理後、上澄液を
除きn−ヘキサン6!を加えてデカンテーションで上澄
液を除く操作を4回繰り返して、重合処理を施した固体
生成物(II)を得た。450 g of triethylaluminum and 7 methyl p-toluate with the total amount of the solid product (1) kept at 25°C.
Hexane IO containing 5g! ! Then, 0.8 kg of 3-methylbutene-1 was added, and polymerization was carried out at the same temperature for 2 hours while stirring. After treatment, remove the supernatant liquid and use n-hexane 6! The operation of adding and removing the supernatant liquid by decantation was repeated four times to obtain a polymerized solid product (II).
該固体生成物(II)全量を1.2−ジクロルエタン1
0i!、で希釈した四塩化チタン10fとともにフタル
酸ジイソブチル0.4 kgを加え、攪拌しながら10
0°Cに2時間反応させた後、同温度にてデカンティシ
ョンにより液相部を除き、再び1,2−シクロルエタン
10I!、、四塩化チタン10!を加え、攪拌しなから
100°Cに2時間反応させた後、熱濾過にて固体部を
採取して精製ヘキサンで洗浄し、乾燥してチタン触媒成
分を得た。該チタン触媒成分のチタン含量は1.84重
量%、ポリ3−メチルブテン−1含量は45.9重量%
であった。The total amount of the solid product (II) was dissolved in 1,2-dichloroethane 1
0i! Add 0.4 kg of diisobutyl phthalate along with 10 f of titanium tetrachloride diluted with
After reacting at 0°C for 2 hours, the liquid phase was removed by decantation at the same temperature, and 1,2-cycloethane 10I! ,,Titanium tetrachloride 10! was added and reacted at 100° C. for 2 hours without stirring, and then a solid portion was collected by hot filtration, washed with purified hexane, and dried to obtain a titanium catalyst component. The titanium content of the titanium catalyst component is 1.84% by weight, and the content of poly3-methylbutene-1 is 45.9% by weight.
Met.
続いて実施例1の(2)においてジフェニルジメトキシ
シランの代わりにフェニルエトキシシラン500g、ま
たチタン触媒成分として上記のチタン触媒成分を用いる
以外は同様にして予備活性化触媒を得た後、実施例1の
(3)と同様にしてプロピレンの気相重合を行った。Next, a preactivated catalyst was obtained in the same manner as in (2) of Example 1 except that 500 g of phenylethoxysilane was used instead of diphenyldimethoxysilane, and the above titanium catalyst component was used as the titanium catalyst component. Gas phase polymerization of propylene was carried out in the same manner as in (3).
比較例5
実施例4において固体生成物(1)を3−メチルブテン
−1で重合処理することなしに固体生成物(If)相当
物とすること以外は同様にしてチタン触媒成分を得て、
プロピレンの重合を行った。Comparative Example 5 A titanium catalyst component was obtained in the same manner as in Example 4 except that solid product (1) was not polymerized with 3-methylbutene-1 to obtain a solid product (If) equivalent,
Polymerization of propylene was carried out.
実施例5
攪拌機付きステンレス製反応器中で、n−へブタンBE
、無水塩化マグネシウム1.0 kg、オルトチタン酸
n−ブチル7、4 kgを混合し、攪拌しなから90゛
Cに昇温し、2時間加熱して、溶解させ均一な溶液とし
た。次に該均一溶液を40″Cに冷却し、メチル水素ポ
リシロキサン1,500aNを滴下し固体を析出させた
。Example 5 In a stainless steel reactor with a stirrer, n-hebutane BE
, 1.0 kg of anhydrous magnesium chloride, and 7.4 kg of n-butyl orthotitanate were mixed, heated to 90° C. without stirring, and heated for 2 hours to dissolve and form a homogeneous solution. Next, the homogeneous solution was cooled to 40''C, and 1,500 aN of methylhydrogen polysiloxane was added dropwise to precipitate a solid.
これをn−へブタンで洗浄して灰白色の固体を得た。該
固体500g、およびn−ヘプタン7I!を撹拌機付き
ステンレス製反応器中に入れた。次にフタル酸ジイソブ
チル100gを加え30℃で1時間経過後四塩化ケイ素
11.3 kgと四塩化チタン500gの混合液を1時
間かけて滴下した。This was washed with n-hebutane to obtain an off-white solid. 500 g of said solid, and 7I of n-heptane! was placed in a stainless steel reactor equipped with a stirrer. Next, 100 g of diisobutyl phthalate was added and after 1 hour at 30° C., a mixed solution of 11.3 kg of silicon tetrachloride and 500 g of titanium tetrachloride was added dropwise over 1 hour.
続いて30℃で30分間、更に90℃で1時間反応させ
た。固体を溶液から分離し、n−へブタンで洗浄して固
体生成物(1)を得た。Subsequently, the mixture was reacted at 30°C for 30 minutes and then at 90°C for 1 hour. The solid was separated from the solution and washed with n-hebutane to give a solid product (1).
マグネシウム原子換算で2.5モルの該固体生成物(I
)を、30℃に保持したトリエチルアルミニウム200
g、およびジフェニルジメトキシシラン60gを含む
n−へブタン51に9.?Hさせた後、4,4−ジメチ
ルペンテン−1を380g添加し、撹拌しながら同温度
において2時間重合処理を行った。処理後固体を溶液か
ら分離し、n−へブタンで洗浄して、重合処理を施した
固体生成物(II)を得た。2.5 mol of the solid product (I
) held at 30°C.
9. g, and 51 g of n-hebutane containing 60 g of diphenyldimethoxysilane. ? After heating, 380 g of 4,4-dimethylpentene-1 was added, and polymerization was carried out at the same temperature for 2 hours while stirring. After the treatment, the solid was separated from the solution and washed with n-hebutane to obtain a polymerized solid product (II).
該固体生成物(II)全量を四塩化チタン61を含むn
−へブタン溶液121と混合し、続いてフタル酸ジヘプ
チル100gを加えて50℃で2時間反応させた後、n
−へブタンで洗浄し、更に四塩化チタン150 を加
えて90℃で洗浄してチタン触媒成分を得た。該チタン
触媒成分のチタン含mはl、76重蛍%、ポリ3−メチ
ルビニルシクロヘキサン含量は41.2重量%であった
。The total amount of the solid product (II) was converted to n containing 61 titanium tetrachloride.
- mixed with hebutane solution 121, then added 100 g of diheptyl phthalate and reacted at 50°C for 2 hours, then n
- Hebutane was added, and 150 ml of titanium tetrachloride was further added and washed at 90°C to obtain a titanium catalyst component. The titanium content of the titanium catalyst component was 1, 76% by weight, and the poly3-methylvinylcyclohexane content was 41.2% by weight.
続いて、実施例1の(2)においてジフェニルジメトキ
シシランの代わりにt−ブチルジメトキシシラン150
gを、またチタン触媒成分として上記のチタン触媒成分
全量を用いること以外は同様にして予備活性化触媒を得
た後、実施例1の(3)と同様にしてプロピレンの気相
重合を行った。Subsequently, in (2) of Example 1, t-butyldimethoxysilane 150 was used instead of diphenyldimethoxysilane.
After obtaining a preactivated catalyst in the same manner as above except using g and the entire amount of the titanium catalyst component as the titanium catalyst component, gas phase polymerization of propylene was performed in the same manner as in Example 1 (3). .
比較例6
実施例5において固体生成物(1)を4.4−ジメチル
ペンテン−1で重合処理することなしに固体生成物(I
I)相当物とすること以外は同様にしてチタン触媒成分
を得て、プロピレンの気相重合を行った。Comparative Example 6 Solid product (I) was obtained without polymerizing solid product (1) with 4,4-dimethylpentene-1 in Example 5.
I) A titanium catalyst component was obtained in the same manner except that the equivalent was used, and propylene was subjected to gas phase polymerization.
実施例6
攪拌!ffl/=Jきステンレス製反応器中において、
n−デカン2.51、無水塩化マグネシウム480gお
よび2−エチル−1−ヘキサノール1.95 kgを1
30°Cで2時間加熱して溶解させ均一な溶液とした後
、この溶液中に無水フタル酸111gを添加し、130
°Cにて更に撹拌混合を行ない、無水フタル酸を該均一
溶液に溶解させた。Example 6 Stir! ffl/=J in a stainless steel reactor,
2.51 g of n-decane, 480 g of anhydrous magnesium chloride and 1.95 kg of 2-ethyl-1-hexanol
After heating at 30°C for 2 hours to dissolve and make a homogeneous solution, 111 g of phthalic anhydride was added to this solution, and 130 g of phthalic anhydride was added.
Further stirring and mixing was performed at °C to dissolve phthalic anhydride into the homogeneous solution.
この様にして得られた均一溶液を室温に冷却した後、−
20°Cに保持された四塩化チタン、102中に1時間
かけて全量を滴下した。滴下後、この混合液の温度を4
時間かけて110°Cに昇温し、110°Cに達したと
ころで同温度にて2時間攪拌下に反応させた。固体を溶
液から分離し、ヘキサン洗浄して固体生成物(1)を得
た。After cooling the homogeneous solution thus obtained to room temperature, -
The entire amount was dropped into titanium tetrachloride 102 kept at 20°C over 1 hour. After dropping, the temperature of this mixture was set to 4.
The temperature was raised to 110°C over time, and when it reached 110°C, the reaction was continued at the same temperature for 2 hours with stirring. The solid was separated from the solution and washed with hexane to obtain a solid product (1).
該固体生成物(1)全量を40゛Cに保持した、トリエ
チルアルミニウム450gおよびジフェニルジメトキシ
シラン145gを含むn−デカン101に懸濁させた後
、3−メチルブテン−1を800g添加し、攪拌しなが
ら同温度において2時間重合処理を行った。処理後、固
体を溶液から分離し、ヘキサン洗浄して重合処理を施し
た固体生成物(If)を得た。After suspending the entire amount of the solid product (1) in 101 g of n-decane containing 450 g of triethylaluminum and 145 g of diphenyldimethoxysilane maintained at 40°C, 800 g of 3-methylbutene-1 was added and the mixture was stirred. Polymerization treatment was performed at the same temperature for 2 hours. After the treatment, the solid was separated from the solution and washed with hexane to obtain a polymerized solid product (If).
該固体生成物(II)全量を10/の四塩化チタンと混
合し、続いてフタル酸ジイソブチル350gを添加し、
撹拌しながら110℃に2時間反応させた後、同温度に
おいてデカンテーションにより、液相部を除き、再び四
塩化チタン1,000m/!を加え、110℃に2時間
、加熱反応を行った。The total amount of the solid product (II) was mixed with 10% titanium tetrachloride, followed by the addition of 350 g of diisobutyl phthalate,
After reacting at 110°C for 2 hours with stirring, the liquid phase was removed by decantation at the same temperature, and titanium tetrachloride was added again at 1,000 m/! was added, and a heating reaction was carried out at 110° C. for 2 hours.
反応終了後、同温度においてデカンテーションにより、
液相部を除いた後、80°Cのn−デカンおよびn−ヘ
キサンにて固体を洗浄し、乾燥してチタン触媒成分を得
た。該チタン成分はチタン1.54重盪%、およびポリ
3−メチルブテン−1を48.7重量%有していた。After the reaction is completed, decantation is performed at the same temperature.
After removing the liquid phase, the solid was washed with n-decane and n-hexane at 80°C and dried to obtain a titanium catalyst component. The titanium component had 1.54 weight percent titanium and 48.7 weight percent poly-3-methylbutene-1.
引き続いて、内容積が200!!の2段タービン翼を備
えた撹拌機付重合器に上記チタン触媒成分をチタン原子
換算で0.389ミリグラム原子/hr、トリエチルア
ルミニウムの20mm%n−へキサン溶液をトリエチル
アルミニウムとして8.5g/h r %ジフェニルジ
メトキシシランの20重量%n−ヘキサン溶液をジフェ
ニルジメトキシシランとして、3.0 g /hr、お
よびn−ヘキサンを21kg/hrで連続的に供給した
。Next, the internal volume is 200! ! In a polymerization reactor equipped with a stirrer equipped with two-stage turbine blades, the above titanium catalyst component was added at 0.389 milligram atom/hr in terms of titanium atoms, and the 20 mm% n-hexane solution of triethylaluminum was added at 8.5 g/h in terms of triethylaluminum. A 20% by weight solution of r% diphenyldimethoxysilane in n-hexane was continuously supplied as diphenyldimethoxysilane at a rate of 3.0 g/hr, and n-hexane was continuously supplied at a rate of 21 kg/hr.
また気相中の濃度が0.25容積%を保つ様に水素を、
全圧が8 kg / cm Gを保つ様にプロピレンを
それぞれ供給してプロピレンのスラリー重合を70°C
において120時間、連続して行った。重合期間中は、
重合器内のスラリーの保有レベルが75容積%となる様
にスラリーを重合器から連続的に内容積50I2のフラ
ッシュタンクに抜き出した。In addition, hydrogen was added so that the concentration in the gas phase was maintained at 0.25% by volume.
The slurry polymerization of propylene was carried out at 70°C by supplying each propylene so as to maintain a total pressure of 8 kg/cm G.
The test was carried out continuously for 120 hours. During the polymerization period,
The slurry was continuously drawn out from the polymerization vessel into a flash tank having an internal volume of 50 I2 so that the retention level of the slurry in the polymerization vessel was 75% by volume.
フラッシュタンクにおいて落圧され、未反応プロピレン
が除去される一方、メタノールが1kg/hrで供給さ
れ70°Cにて接触処理された。続いてスラリーは遠心
分離機によって溶媒を分離された後、乾燥機によって乾
燥され、製品パウダーが10kg/hrで連続的に得ら
れた。The pressure was reduced in a flash tank to remove unreacted propylene, while methanol was supplied at a rate of 1 kg/hr and contact treatment was carried out at 70°C. Subsequently, the slurry was separated from the solvent by a centrifugal separator and then dried by a drier to continuously obtain a product powder at 10 kg/hr.
比較例7
実施例6において3−メチルブテン−1による重合処理
をせずに、固体生成物(I)を固体生成物(II)相当
物とすること以外は同様にして得られたチタン触媒成分
を用いて実施例6と同様にプロピレンのスラリー重合を
行った。Comparative Example 7 A titanium catalyst component obtained in the same manner as in Example 6 except that the polymerization treatment with 3-methylbutene-1 was not performed and the solid product (I) was made into an equivalent to the solid product (II) was used. Slurry polymerization of propylene was carried out in the same manner as in Example 6.
実施例7
実施例1の(1)において無水塩化マグネシウムの代わ
りに、マグネシウムエトキサイド580 glまた3−
メチルブテン−1の代わりに3−メチルペンテン−1を
830g用いること以外は同様にして触媒成分を得た。Example 7 In place of anhydrous magnesium chloride in (1) of Example 1, 580 g of magnesium ethoxide and 3-
A catalyst component was obtained in the same manner except that 830 g of 3-methylpentene-1 was used instead of methylbutene-1.
後は実施例1の(2)、 (3)と同様にしてプロピレ
ンの気相重合を行った。Thereafter, gas phase polymerization of propylene was carried out in the same manner as in Example 1 (2) and (3).
比較例8
実施例7において3−メチルペンテン−1による重合処
理をせずに、固体生成物(1)を固体生成物(It)相
当物とすること以外は同様にしてチタン触媒成分を得て
プロピレンの重合を行った。Comparative Example 8 A titanium catalyst component was obtained in the same manner as in Example 7, except that the solid product (1) was made equivalent to the solid product (It) without the polymerization treatment with 3-methylpentene-1. Polymerization of propylene was carried out.
実施例8
実施例1の(1)においてオルトチタン酸化n−ブチル
の代わりにポリチタン酸n−ブチル(5量体)1、2
kgを、また3−メチルブテン−1の代わりに4.4−
ジメチルヘキセン−1を1.5kg使用すること以外は
同様にしてチタン触媒成分を得た。続いて得られたチタ
ン触媒成分を用いて実施例1の(2)。Example 8 In (1) of Example 1, n-butyl polytitanate (pentamer) 1, 2 was used instead of n-butyl orthotitanium oxide.
kg, and instead of 3-methylbutene-1, 4.4-
A titanium catalyst component was obtained in the same manner except that 1.5 kg of dimethylhexene-1 was used. Subsequently, the obtained titanium catalyst component was used in Example 1 (2).
(3)と同様にしてオレフィンの重合を行った。Olefin polymerization was carried out in the same manner as in (3).
比較例9
実施例、8において4,4−ジメチルヘキセン−1によ
る重合処理をせずに、固定生成物(1)を固体生成物(
II)相当物とすること以外は同様にしてチタン触媒成
分を得て、オレフィンの重合を行った。Comparative Example 9 Fixed product (1) was converted into solid product (
II) A titanium catalyst component was obtained in the same manner except that the equivalent product was used, and olefin polymerization was carried out.
実施例9
実施例6においてチタン触媒成分を得る際に3−メチル
ブテン−1の使用量を680g、また、オレフィン重合
時に気相中の濃度が0゜2容積%を保つ様にエチレンを
更に供給すること以外は同様にしてプロピレン−エチレ
ン共重合を行った。Example 9 In Example 6, when obtaining the titanium catalyst component, the amount of 3-methylbutene-1 used was 680 g, and during olefin polymerization, ethylene was further supplied so that the concentration in the gas phase was maintained at 0.2% by volume. Propylene-ethylene copolymerization was carried out in the same manner except for the above.
比較例10
実施例9において3=ブチルブテン−1による重合処理
をせずに、固体生成物(1)を固体生成物(II)相当
物とすること以外は同様にしてチタン触媒成分を得てプ
ロピレン−エチレン共重合体を行った。Comparative Example 10 A titanium catalyst component was obtained in the same manner as in Example 9 except that the polymerization treatment with 3=butylbutene-1 was not performed and the solid product (1) was made into a solid product (II) equivalent. - Ethylene copolymer was produced.
以上の実施例1〜9、比較例1〜lOの重合結果および
評価結果を次頁の表に示す。The polymerization results and evaluation results of the above Examples 1 to 9 and Comparative Examples 1 to 1O are shown in the table on the next page.
第1図は、本発明の詳細な説明するフローシートである
。
以上FIG. 1 is a flow sheet explaining the invention in detail. that's all
Claims (3)
ン化合物、電子供与体およびチタン化合物(T_1)を
接触して得られた固体生成物( I )を、有機アルミニ
ウム化合物の存在下、炭素数5以上の枝鎖オレフィンで
重合処理し、固体生成物(II)を得、該固体生成物(I
I)にハロゲン化チタン化合物(T_2)を反応させて
得られることを特徴とする、炭素数5以上の枝鎖オレフ
ィンの重合体を0.01重量%〜99重量%含有せしめ
た、チタン、マグネシウム、ハロゲン、および電子供与
体を必須成分とするオレフィン重合用チタン触媒成分の
製法。(1) A solid product (I) obtained by contacting a liquefied magnesium compound with a precipitating agent, a halogen compound, an electron donor, and a titanium compound (T_1) in the presence of an organoaluminum compound with a carbon number of 5 or more is polymerized with a branched chain olefin to obtain a solid product (II), and the solid product (I
Titanium, magnesium containing 0.01% to 99% by weight of a polymer of branched chain olefin having 5 or more carbon atoms, characterized by being obtained by reacting I) with a halogenated titanium compound (T_2) , a halogen, and an electron donor as essential components.
^1_mR^2_m_′−X_3_−_(_m_+_m
_′_)(式中、R^1、R^2はアルキル基、シクロ
アルキル基、またはアリール基等の炭化水素基またはア
ルコキシ基を、Xはハロゲンを表わし、またm、m′は
0<m+m′≦3の任意の数を表わす。)で表わされる
有機アルミニウム化合物を用いる特許請求の範囲第1項
に記載の製法。(2) As an organoaluminum compound, the general formula is AIR
^1_mR^2_m_'-X_3_-_(_m_+_m
_'_) (wherein, R^1 and R^2 represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, or an aryl group, or an alkoxy group, X represents a halogen, and m and m' represent 0< The method according to claim 1, which uses an organoaluminum compound represented by m+m'≦3.
ルブテン−1,3−メチルペンテン−1,4,4−ジメ
チルペンテン−1、および4,4−ジメチルヘキセン−
1から選択された1種以上の枝鎖オレフィンを用いる特
許請求の範囲第1項に記載の製法。(3) As branched olefins having 5 or more carbon atoms, 3-methylbutene-1,3-methylpentene-1,4,4-dimethylpentene-1 and 4,4-dimethylhexene-
1. The production method according to claim 1, wherein one or more branched olefins selected from 1 are used.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63142015A JPH0791332B2 (en) | 1988-06-09 | 1988-06-09 | Method for producing titanium catalyst component for olefin polymerization |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63142015A JPH0791332B2 (en) | 1988-06-09 | 1988-06-09 | Method for producing titanium catalyst component for olefin polymerization |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01311106A true JPH01311106A (en) | 1989-12-15 |
JPH0791332B2 JPH0791332B2 (en) | 1995-10-04 |
Family
ID=15305392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63142015A Expired - Lifetime JPH0791332B2 (en) | 1988-06-09 | 1988-06-09 | Method for producing titanium catalyst component for olefin polymerization |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0791332B2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02191608A (en) * | 1988-09-14 | 1990-07-27 | Mitsui Petrochem Ind Ltd | Production of catalytic component for polymerization of olefin |
JPH03163115A (en) * | 1989-08-11 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Oriented polypropylene film |
JPH03163110A (en) * | 1988-09-14 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Prepolymerized catalyst component for olefin polymerization, olefin polymerization catalyst, and method of polymerization therewith |
JPH03170511A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Polypropylene film |
JPH03170512A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Injection molded article of polypropylene |
US5717013A (en) * | 1995-08-23 | 1998-02-10 | Tonen Chemical Corporation | Polypropylene resin composition |
JP2003105022A (en) * | 2001-09-28 | 2003-04-09 | Mitsui Chemicals Inc | PROCESS FOR PRODUCING alpha-OLEFIN POLYMER |
US6863177B2 (en) | 1996-05-13 | 2005-03-08 | Matsushita Electric Industrial Co., Ltd. | Electrically conductive propylene resin composition and part-housing container |
JP2006274103A (en) * | 2005-03-30 | 2006-10-12 | Toho Catalyst Co Ltd | Solid catalytic component for polymerizing olefins, catalyst for polymerizing olefins and method for producing olefin polymer or copolymer |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6389510A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for polymerizing olefin |
JPS6389509A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for producing polyolefin |
JPS6389508A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for polymerization of olefin |
-
1988
- 1988-06-09 JP JP63142015A patent/JPH0791332B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6389510A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for polymerizing olefin |
JPS6389509A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for producing polyolefin |
JPS6389508A (en) * | 1986-10-02 | 1988-04-20 | Chisso Corp | Production of solid catalyst component for polymerization of olefin |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02191608A (en) * | 1988-09-14 | 1990-07-27 | Mitsui Petrochem Ind Ltd | Production of catalytic component for polymerization of olefin |
JPH03163110A (en) * | 1988-09-14 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Prepolymerized catalyst component for olefin polymerization, olefin polymerization catalyst, and method of polymerization therewith |
JPH03163115A (en) * | 1989-08-11 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Oriented polypropylene film |
JPH03170511A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Polypropylene film |
JPH03170512A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Injection molded article of polypropylene |
US5717013A (en) * | 1995-08-23 | 1998-02-10 | Tonen Chemical Corporation | Polypropylene resin composition |
US6863177B2 (en) | 1996-05-13 | 2005-03-08 | Matsushita Electric Industrial Co., Ltd. | Electrically conductive propylene resin composition and part-housing container |
JP2003105022A (en) * | 2001-09-28 | 2003-04-09 | Mitsui Chemicals Inc | PROCESS FOR PRODUCING alpha-OLEFIN POLYMER |
JP2006274103A (en) * | 2005-03-30 | 2006-10-12 | Toho Catalyst Co Ltd | Solid catalytic component for polymerizing olefins, catalyst for polymerizing olefins and method for producing olefin polymer or copolymer |
Also Published As
Publication number | Publication date |
---|---|
JPH0791332B2 (en) | 1995-10-04 |
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