JPH04258604A - Polymerization of alpha-olefin - Google Patents
Polymerization of alpha-olefinInfo
- Publication number
- JPH04258604A JPH04258604A JP2072391A JP2072391A JPH04258604A JP H04258604 A JPH04258604 A JP H04258604A JP 2072391 A JP2072391 A JP 2072391A JP 2072391 A JP2072391 A JP 2072391A JP H04258604 A JPH04258604 A JP H04258604A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- transition metal
- metal catalyst
- olefin
- catalyst component
- 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.)
- Pending
Links
- 239000004711 α-olefin Substances 0.000 title claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 title description 11
- -1 magnesium halide Chemical class 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 7
- 150000005690 diesters Chemical class 0.000 claims abstract description 6
- 150000002363 hafnium compounds Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000008282 halocarbons Chemical class 0.000 claims description 9
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 8
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 abstract description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 abstract description 2
- 229960001826 dimethylphthalate Drugs 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920013639 polyalphaolefin Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 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
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical class ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical class CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 229940093470 ethylene Drugs 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はα−オレフィンの重合方
法に関する。詳しくは、特定の方法で得た担体型の遷移
金属触媒を用いて比較的分子量分布の広い高立体規則性
のポリα−オレフィンを製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for polymerizing α-olefins. Specifically, the present invention relates to a method for producing a highly stereoregular poly-α-olefin with a relatively wide molecular weight distribution using a carrier-type transition metal catalyst obtained by a specific method.
【０００２】0002
【従来の技術】ハロゲン化マグネシウムなどの担体に遷
移金属化合物を担持した触媒成分と有機金属化合物から
成る触媒を用いてα−オレフィンを重合する方法は特公
昭３９−１２１０５で開示されて以来多くの改良が成さ
れている。改良は主として担体側に用いる電子供与性化
合物あるいは遷移金属触媒成分と有機金属化合物とを組
み合わせて用いる電子供与性化合物として何を用いるか
という方向、さらには遷移金属触媒をどのように製造す
るかという方向の２つの方向で成されている。このなか
でも、担体側に用いる電子供与性化合物として２官能性
の化合物を用い、遷移金属触媒成分と有機金属化合物と
を組み合わせて用いる電子供与性化合物としてアルコキ
シ珪素化合物あるいは立体障害性のアミン化合物を用い
る方法は、高活性でしかも極めて立体規則性の高いポリ
α−オレフィンを与える優れた触媒系である（例えば、
特開昭５８−１３８７１０ 、同５９−１１７５０９
、同５９−２０６４０７ 、同５９−２０６４１０ 等
） 。[Prior Art] A method for polymerizing α-olefins using a catalyst consisting of a catalyst component in which a transition metal compound is supported on a carrier such as magnesium halide and an organometallic compound has been widely used since it was disclosed in Japanese Patent Publication No. 12105/1983. Improvements have been made. Improvements are mainly in the direction of what to use as the electron-donating compound to be used on the support side or as the electron-donating compound to be used in combination of the transition metal catalyst component and the organometallic compound, and furthermore, how to produce the transition metal catalyst. It is made in two directions. Among these, a bifunctional compound is used as an electron donating compound used on the carrier side, and an alkoxy silicon compound or a sterically hindered amine compound is used as an electron donating compound used in combination with a transition metal catalyst component and an organometallic compound. The method used is an excellent catalyst system that provides highly active and highly stereoregular polyα-olefins (e.g.
Japanese Patent Publication No. 58-138710, No. 59-117509
, 59-206407, 59-206410, etc.).
【０００３】0003
【発明が解決しようとする課題】しかしながら、上記触
媒系は活性と得られるポリマーの立体規則性という点で
は極めて優れたものであるが、得られるポリマーの分子
量分布が狭いという問題がある。この分子量分布が狭い
という特徴は用途によっては好ましいが、成形時の流れ
性が不良であり、特にブロー成形の用途では問題となる
。However, although the above catalyst system is extremely excellent in terms of activity and stereoregularity of the resulting polymer, there is a problem in that the molecular weight distribution of the resulting polymer is narrow. Although this characteristic of having a narrow molecular weight distribution is desirable for some uses, it results in poor flowability during molding, which is particularly problematic in blow molding applications.
【０００４】0004
【課題を解決するための手段】本発明者らは上記課題を
解決して分子量分布の広いポリマーを製造する方法につ
いて鋭意検討し本発明を完成した。[Means for Solving the Problems] The present inventors have conducted intensive studies on a method for solving the above-mentioned problems and producing a polymer having a wide molecular weight distribution, and have completed the present invention.
【０００５】即ち、本発明は、ハロゲン化マグネシウム
にチタン化合物を担持した遷移金属触媒成分と有機アル
ミニウム化合物からなる触媒を用いてα−オレフィンを
重合する方法において、遷移金属触媒成分として、ハロ
ゲン化マグネシウムとフタル酸のジエステルと少なくと
も１つのハロゲンを有する四価のチタン化合物および四
価のハフニウム化合物を共粉砕し、次いで該共粉砕物を
炭化水素化合物またはハロゲン化炭化水素化合物の存在
下に加熱処理して得たものを用いることを特徴とするα
−オレフィンの重合方法である。That is, the present invention provides a method for polymerizing α-olefins using a catalyst consisting of a transition metal catalyst component in which a titanium compound is supported on magnesium halide and an organoaluminum compound, in which magnesium halide is used as the transition metal catalyst component. and a diester of phthalic acid, a tetravalent titanium compound having at least one halogen, and a tetravalent hafnium compound are co-pulverized, and then the co-pulverized product is heat-treated in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound. α, which is characterized by using the obtained
- A method for polymerizing olefins.
【０００６】本発明において、ハロゲン化マグネシウム
としては、実質的に無水のハロゲン化マグネシウムが利
用でき、数％以下の水を含有するものであっても利用で
きる。ハロゲン化マグネシウムとして具体的には塩化マ
グネシウム、臭化マグネシウム、あるいはそれらとエー
テル、モノエステルとの錯体、あるいは塩化マグネシウ
ムと臭化マグネシウムの共晶体などが利用できる。[0006] In the present invention, as the magnesium halide, substantially anhydrous magnesium halide can be used, even if it contains several percent or less of water. Specifically, magnesium halides include magnesium chloride, magnesium bromide, complexes of these with ethers and monoesters, and eutectics of magnesium chloride and magnesium bromide.
【０００７】フタル酸のジエステルとしては、フタル酸
と炭素数１〜１２のアルコールとのエステルが好ましく
利用できフタル酸ジメチル、フタル酸ジエチル、フタル
酸ジプロピル、フタル酸ジブチル、フタル酸ジオクチル
、フタル酸ジデシル、フタル酸ジフェニル、フタル酸ジ
ベンジル、フタル酸ジ−２− エチルヘキシル、などの
他に２つのエステル結合を形成するアルコールが異なる
フタル酸ブチルベンジル、フタル酸エチルヘキシルなど
のジエステルも利用できる。As diesters of phthalic acid, esters of phthalic acid and alcohols having 1 to 12 carbon atoms are preferably used, such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, and didecyl phthalate. In addition to diphenyl phthalate, dibenzyl phthalate, di-2-ethylhexyl phthalate, etc., diesters such as butylbenzyl phthalate and ethylhexyl phthalate, which have different alcohols forming two ester bonds, can also be used.
【０００８】本発明において用いる少なくとも１つのハ
ロゲンを有する四価のチタン化合物としては、ハロゲン
として好ましくは、塩素が例示でき、アルコキシクロル
チタンが好ましく用いられるが、特に好ましくは、四塩
化チタンが用いられる。ここでハロゲン化チタン化合物
は予めフタル酸のジエステルと錯体を形成して利用する
こともできる。[0008] As the tetravalent titanium compound having at least one halogen used in the present invention, chlorine is preferably used as the halogen, alkoxychlorotitanium is preferably used, and titanium tetrachloride is particularly preferably used. . Here, the halogenated titanium compound can also be used by forming a complex with a diester of phthalic acid in advance.
【０００９】本発明において四価のハフニウム化合物と
してはハロゲン化ハフニウム、特に四塩化ハフニウムが
好ましい。In the present invention, hafnium halides, particularly hafnium tetrachloride, are preferred as the tetravalent hafnium compound.
【００１０】共粉砕においてフタル酸のジエステルとハ
ロゲン化チタンの使用割合としては好ましくは０．３：
１〜１：０．３モル比であり、より好ましくは０．５：
１〜１：０．５である。この範囲を越えるとその触媒を
用いて重合したとき活性及び得られる重合体の立体規則
性が充分でない。
またハロゲン化マグネシウムに対するハロゲン化チタン
の割合としては１：０．００１〜１：０．５重量比程度
が好ましい。また四価のハフニウム化合物と四塩化チタ
ンの使用割合としては１０：１〜０．０００１：１モル
比とするのが好ましく０．０００１以下では分子量分布
を広くする効果が殆どない。[0010] In co-pulverization, the ratio of phthalic acid diester and titanium halide used is preferably 0.3:
The molar ratio is 1 to 1:0.3, more preferably 0.5:
The ratio is 1 to 1:0.5. If it exceeds this range, the activity and stereoregularity of the resulting polymer will not be sufficient when the catalyst is used for polymerization. The ratio of titanium halide to magnesium halide is preferably about 1:0.001 to 1:0.5 by weight. The molar ratio of the tetravalent hafnium compound to titanium tetrachloride is preferably 10:1 to 0.0001:1, and if it is less than 0.0001, there is little effect of widening the molecular weight distribution.
【００１１】本発明においては、共粉砕に際してハロゲ
ン化炭化水素化合物を添加することができ、ハロゲン化
炭化水素化合物としては、炭素数１〜１２の炭化水素化
合物の水素の１〜全部が塩素、臭素、沃素で置換した化
合物が例示でき、具体的には、メチルクロライド、メチ
レンクロライド、クロロホルム、四塩化炭素、エチルク
ロライド、エチレンジクロライド、トリクロロエタン、
テトラクロロエタン、ペンタクロロエタン、パークロロ
エタン等、飽和炭化水素化合物の水素が塩素で置換した
もの、あるいは塩素を臭素、沃素で置換したもの、塩化
ビニリデン、トリクロルエチレン、パークロルエチレン
等、あるいはクロロベンゼン、ジクロロベンゼン、トリ
クロロベンゼン等の不飽和炭化水素化合物の水素が塩素
で置換したもの、あるいは塩素を臭素、沃素で置換した
もの等が例示される。In the present invention, a halogenated hydrocarbon compound can be added during co-pulverization, and the halogenated hydrocarbon compound is a hydrocarbon compound having 1 to 12 carbon atoms in which one or all of the hydrogen atoms are chlorine or bromine. Examples include compounds substituted with iodine, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, ethylene dichloride, trichloroethane,
Saturated hydrocarbon compounds in which hydrogen has been replaced with chlorine, such as tetrachloroethane, pentachloroethane, perchloroethane, etc., or compounds in which chlorine has been replaced with bromine or iodine, vinylidene chloride, trichloroethylene, perchlorethylene, etc., or chlorobenzene, dichlorobenzene. Examples include unsaturated hydrocarbon compounds such as trichlorobenzene in which hydrogen is replaced with chlorine, and chlorine in which bromine or iodine is replaced.
【００１２】これらのハロゲン化炭化水素化合物のハロ
ゲン化マグネシウムに対する使用割合としては、ハロゲ
ン化マグネシウムに対し、１：０．００１〜１：０．５
重量比、好ましくは１：０．０１〜１：０．３ 重量比
である。ハロゲン化炭化水素化合物を用いることで、使
用しない場合に比較して大幅に活性が向上する。The ratio of these halogenated hydrocarbon compounds to magnesium halide is 1:0.001 to 1:0.5 to magnesium halide.
The weight ratio is preferably 1:0.01 to 1:0.3. By using a halogenated hydrocarbon compound, the activity is significantly improved compared to the case where it is not used.
【００１３】共粉砕に際し、さらに触媒系に対し不活性
な担体を更に加えることも可能であり、シリカ、アルミ
ナなどの無機物の他にポリエチレン、ポリプロピレン、
ポリスチレンなどの高分子化合物などが利用できる。[0013] During co-pulverization, it is also possible to further add an inert carrier to the catalyst system, and in addition to inorganic materials such as silica and alumina, polyethylene, polypropylene,
Polymer compounds such as polystyrene can be used.
【００１４】本発明において、上記共粉砕物は次いで加
熱処理されるが、その際に使用される炭化水素化合物と
しては炭素数６〜１２の炭化水素化合物、具体的にはヘ
キサン、ヘプタン、オクタン、デカン、シクロヘキサン
、ベンゼン、トルエン、エチルベンゼン、キシレン、ク
メン、テトラリンなどが例示でき、ハロゲン化炭化水素
化合物としては上述の共粉砕に用いるハロゲン化炭化水
素が例示される。好ましくは、芳香族炭化水素化合物、
ハロゲン化炭化水素化合物が使用される。[0014] In the present invention, the co-pulverized product is then heat-treated, and the hydrocarbon compound used at that time is a hydrocarbon compound having 6 to 12 carbon atoms, specifically hexane, heptane, octane, Examples include decane, cyclohexane, benzene, toluene, ethylbenzene, xylene, cumene, and tetralin. Examples of the halogenated hydrocarbon compound include the halogenated hydrocarbons used in the above-mentioned co-pulverization. Preferably, an aromatic hydrocarbon compound,
Halogenated hydrocarbon compounds are used.
【００１５】これらの炭化水素化合物の使用割合として
はハロゲン化チタン１重量部に対し１〜１０００部、好
ましくは１０〜５００ 部程度である。比較的多量の溶
媒を用いて、溶解したフタル酸ジエステルとかハロゲン
化チタンを静置分離、あるいは濾過によって除去するか
、さらに炭化水素溶剤で洗浄除去して使用することもで
きる。また少量の溶媒を利用することで加熱後そのまま
重合に利用するか、あるいは他の溶剤で希釈して利用す
ることもできる。余りに多い溶媒を用いてもより効果的
なわけでなく、また１重量部未満などの余りに少ないと
得られる触媒の活性及び得られる重合体の立体規則性が
充分でない。The proportion of these hydrocarbon compounds to be used is about 1 to 1000 parts, preferably about 10 to 500 parts, per 1 part by weight of titanium halide. Dissolved phthalic acid diester or titanium halide can be removed by static separation or filtration using a relatively large amount of solvent, or it can be further used by washing and removing with a hydrocarbon solvent. Further, by using a small amount of solvent, it can be used for polymerization as it is after heating, or it can be used after being diluted with another solvent. If too much solvent is used, it will not be more effective, and if it is too small, such as less than 1 part by weight, the activity of the catalyst obtained and the stereoregularity of the resulting polymer will not be sufficient.
【００１６】加熱処理の温度としては、共粉砕時の添加
物の量比などで最適な温度は異なるが、４０℃以上好ま
しくは５０〜１５０ ℃程度である。４０℃以下の加熱
では、特に使用する溶剤が芳香族炭化水素の時には活性
及び得られるポリマーの立体規則性が充分でない。また
１５０℃以上でも性能が不充分である。[0016] The optimum temperature for the heat treatment varies depending on the amount ratio of additives during co-pulverization, etc., but it is 40°C or higher, preferably about 50 to 150°C. Heating below 40° C. does not provide sufficient activity and stereoregularity of the resulting polymer, especially when the solvent used is an aromatic hydrocarbon. Furthermore, the performance is insufficient even at temperatures above 150°C.
【００１７】本発明において有機アルミニウム化合物と
しては、好ましくはトリメチルアルミニウム、トリエチ
ルアルミニウム、トリプロピルアルミニウム、トリブチ
ルアルミニウムなどのトリアルキルアルミニウム及びそ
の１〜２個の炭化水素残基が塩素または臭素で置換され
たアルキルアルミニウムハロゲンが例示される。In the present invention, the organoaluminum compound is preferably a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, or tributylaluminium, and one or two hydrocarbon residues thereof are substituted with chlorine or bromine. An example is an alkyl aluminum halogen.
【００１８】本発明においては重合に際し、アルコキシ
シラン、置換ピペリジンを立体規則性向上剤として使用
するのが好ましい。アルコキシシランとしては、１〜４
個のアルコキシ基を含有する有機シラン化合物が好まし
く用いられ、アルコキシ基としては炭素数１〜１２のア
ルキル基またはアルケニル基に酸素が結合した構造のも
のが例示でき、残りの基としては１〜１２のアルキル基
、またはアルケニル基が例示できる。また置換ピペリジ
ンとしては、１および６位の水素の一部または全部が炭
素数１〜１２個のアルキル基、またはアルケニル基で置
換された化合物が好ましく例示できる。In the present invention, it is preferable to use an alkoxysilane or substituted piperidine as a stereoregularity improver during polymerization. As the alkoxysilane, 1 to 4
An organic silane compound containing an alkoxy group is preferably used, and examples of the alkoxy group include those having a structure in which oxygen is bonded to an alkyl group or alkenyl group having 1 to 12 carbon atoms, and the remaining groups are 1 to 12 carbon atoms. Examples include an alkyl group or an alkenyl group. Preferred examples of the substituted piperidine include compounds in which part or all of the hydrogens at the 1- and 6-positions are substituted with an alkyl group having 1 to 12 carbon atoms or an alkenyl group.
【００１９】遷移金属触媒成分中のチタンに対する有機
アルミニウムおよび立体規則性向上剤の使用割合として
は １：１：１〜１：１００００：１００００ モル比
、通常は１：１：１ 〜１：１０００：１０００ モル
比である。The molar ratio of organoaluminium and stereoregularity improver to titanium in the transition metal catalyst component is 1:1:1 to 1:10000:10000, usually 1:1:1 to 1:1000: 1000 molar ratio.
【００２０】本発明においてα−オレフィンとしては、
炭素数３〜１２のα−オレフィンの一種または、二種以
上の混合物あるいは、少量のエチレンとの混合物を意味
し、α−オレフィンとしては、プロピレン、ブテン−１
、ペンテン−１、ヘキセン−１、ヘプテン−１、オクテ
ン−１、４−メチルペンテン−１等が例示できる。[0020] In the present invention, the α-olefin is
It means one type of α-olefin having 3 to 12 carbon atoms, a mixture of two or more types, or a mixture with a small amount of ethylene. α-olefins include propylene, butene-1
, pentene-1, hexene-1, heptene-1, octene-1, 4-methylpentene-1, and the like.
【００２１】本発明においてα−オレフィンの重合方法
としては特に制限は無く公知の種々の方法が採用でき、
不活性炭化水素を媒体とする溶媒重合法、液状のα−オ
レフィンを媒体とする塊状重合法、液状の媒体が実質的
に存在しない気相重合法のいずれの方法も採用可能であ
る。[0021] In the present invention, the method for polymerizing α-olefin is not particularly limited, and various known methods can be employed.
Any of the following methods can be employed: a solvent polymerization method using an inert hydrocarbon as a medium, a bulk polymerization method using a liquid α-olefin as a medium, and a gas phase polymerization method using substantially no liquid medium.
【００２２】重合に際し温度は常温〜１５０ ℃、圧力
は常圧〜１００ Ｋｇ／ｃｍ２で行うのが一般的であり
、α−オレフィンの単独重合の他に、相互のあるいはエ
チレンとのランダムあるいはブロック共重合に本重合法
は好ましく採用できる。[0022] Polymerization is generally carried out at a temperature of room temperature to 150°C and a pressure of normal pressure to 100 Kg/cm2. This polymerization method can be preferably employed for polymerization.
【００２３】[0023]
【実施例】以下に実施例を掲げ本発明についてさらに説
明する。[Examples] The present invention will be further explained below with reference to Examples.
【００２４】実施例１
直径１２ｍｍの鋼球９Ｋｇの入った内容積４リットルの
粉砕用ポットを４個装備した振動ミルを用意する。各ポ
ットに窒素雰囲気中で塩化マグネシウム３００ｇ、フタ
ル酸ジイソブチル７５ｍｌ、四塩化チタン６０ｍｌ、四
塩化ハフニウム２ｇを加え４０時間粉砕した。Example 1 A vibratory mill equipped with four grinding pots each having an internal volume of 4 liters each containing 9 kg of steel balls with a diameter of 12 mm was prepared. 300 g of magnesium chloride, 75 ml of diisobutyl phthalate, 60 ml of titanium tetrachloride, and 2 g of hafnium tetrachloride were added to each pot in a nitrogen atmosphere and pulverized for 40 hours.
【００２５】上記共粉砕物１０ｇ を ２００ｍｌのフ
ラスコに入れトルエン６０ｍｌを加え １１４℃で３０
分間撹拌処理し、次いで静置して上澄液を除去した。次
いでｎ−ヘプタン １００ｍｌで２０℃で３回、固形分
を洗浄しさらに １００ｍｌのｎ−ヘプタンに分散して
遷移金属触媒成分スラリーとした。得られた遷移金属触
媒成分はチタンを２．１ ｗｔ％ 含有しフタル酸ジイ
ソブチルを１３．８ｗｔ％ 含有していた。[0025] Put 10 g of the above co-pulverized product into a 200 ml flask, add 60 ml of toluene, and heat at 114°C for 30 minutes.
The mixture was stirred for a minute, then allowed to stand, and the supernatant liquid was removed. Next, the solid content was washed three times with 100 ml of n-heptane at 20°C and further dispersed in 100 ml of n-heptane to obtain a transition metal catalyst component slurry. The resulting transition metal catalyst component contained 2.1 wt% titanium and 13.8 wt% diisobutyl phthalate.
【００２６】内容積５リットルの充分に乾燥し窒素で置
換したオートクレーブを準備し、ヘプタン １００ｍｌ
に希釈したトリエチルアルミニウム ０．２ｍｌ、シク
ロヘキシルメチルジメトキシシラン ０．１ｍｌ、上記
遷移金属触媒１５ｍｇを加えプロピレン１．５Ｋｇ 、
水素１．７Ｎリットルを加え７０℃で２時間重合した。
重合後未反応のプロピレンをパージし８０℃で８時間乾
燥し、秤量したところ５２０ｇのポリプロピレンが得ら
れた。またポリプロピレンの １３５℃テトラリン溶液
で測定した極限粘度（以下ηと記す）は１．６０、ソッ
クスレー抽出器で測定した沸騰ｎ−ヘプタン抽出残率（
抽出残ポリマーの重量／抽出前ポリマーの重量を １０
０分率で表示、以下ＩＩと記す）は９７．８％ 、ゲル
パーミエーションクロマトグラフィーで １３５℃の１
，２，４−トリクロロベンゼンを溶媒として測定した重
量平均分子量と数平均分子量の比（ 以下ＭＷ／ＭＮ
と記す） は６．４ であった。Prepare a fully dried autoclave with an internal volume of 5 liters and purify it with nitrogen, and add 100 ml of heptane.
Add 0.2 ml of triethylaluminum diluted to
1.7N liter of hydrogen was added and polymerization was carried out at 70°C for 2 hours. After the polymerization, unreacted propylene was purged and the mixture was dried at 80° C. for 8 hours and weighed to obtain 520 g of polypropylene. In addition, the intrinsic viscosity (hereinafter referred to as η) measured with a tetralin solution of polypropylene at 135°C is 1.60, and the boiling n-heptane extraction residue (
Weight of extracted residual polymer/weight of polymer before extraction: 10
0 fraction (hereinafter referred to as II) is 97.8%, gel permeation chromatography shows 1 at 135°C.
,2,4-trichlorobenzene as a solvent (ratio of weight average molecular weight to number average molecular weight (hereinafter referred to as MW/MN)
) was 6.4.
【００２７】比較例１
四塩化ハフニウムを使用せずに触媒を合成し重合に用い
た他は実施例１と同様にしたところポリマー６７５ ｇ
を得た。このパウダーのηは１．６５、ＩＩは９８．
１、ＭＷ／ＭＮ は５．５ であった。Comparative Example 1 The same procedure as in Example 1 was carried out except that a catalyst was synthesized and used for polymerization without using hafnium tetrachloride. 675 g of polymer was obtained.
I got it. This powder has an η of 1.65 and an II of 98.
1. MW/MN was 5.5.
【００２８】実施例２
四塩化ハフニウムの使用量を１ｇとした他は実施例１と
同様にしたところポリマー６１０ ｇ を得た。このパ
ウダーのηは１．６２、ＩＩは９８．０、ＭＷ／ＭＮ
は６．０ であった。Example 2 The procedure of Example 1 was repeated except that the amount of hafnium tetrachloride used was 1 g, and 610 g of polymer was obtained. This powder's η is 1.62, II is 98.0, MW/MN
was 6.0.
【００２９】[0029]
【発明の効果】本発明の方法を実施することで分子量分
布の比較的広い高立体規則性のポリα−オレフィンを製
造することができ工業的に価値がある。Effects of the Invention By carrying out the method of the present invention, it is possible to produce a highly stereoregular poly-α-olefin with a relatively wide molecular weight distribution, which is of industrial value.
【図１】本発明の理解を助けるためのフローチャート図
である。FIG. 1 is a flowchart diagram to aid understanding of the present invention.
Claims (1)
物を担持した遷移金属触媒成分と有機アルミニウム化合
物からなる触媒を用いてα−オレフィンを重合する方法
において、遷移金属触媒成分として、ハロゲン化マグネ
シウムとフタル酸のジエステルと少なくとも１つのハロ
ゲンを有する四価のチタン化合物および四価のハフニウ
ム化合物を共粉砕し、次いで該共粉砕物を炭化水素化合
物またはハロゲン化炭化水素化合物の存在下に加熱処理
して得たものを用いることを特徴とするα−オレフィン
の重合方法。Claim 1: A method for polymerizing α-olefin using a catalyst consisting of a transition metal catalyst component in which a titanium compound is supported on magnesium halide and an organoaluminum compound, in which the transition metal catalyst components include magnesium halide and phthalic acid. A product obtained by co-pulverizing a diester, a tetravalent titanium compound having at least one halogen, and a tetravalent hafnium compound, and then heat-treating the co-pulverized product in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound. A method for polymerizing α-olefins, characterized by using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2072391A JPH04258604A (en) | 1991-02-14 | 1991-02-14 | Polymerization of alpha-olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2072391A JPH04258604A (en) | 1991-02-14 | 1991-02-14 | Polymerization of alpha-olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04258604A true JPH04258604A (en) | 1992-09-14 |
Family
ID=12035096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2072391A Pending JPH04258604A (en) | 1991-02-14 | 1991-02-14 | Polymerization of alpha-olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04258604A (en) |
-
1991
- 1991-02-14 JP JP2072391A patent/JPH04258604A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR930008452B1 (en) | Process for producing stereoregular polymers having a narrow molecular weight distribution | |
| KR0140393B1 (en) | Process for producing olefin polymer | |
| JP3046361B2 (en) | α-Olefin polymerization method | |
| US4282114A (en) | Catalyst for polymerizing α-olefins | |
| JPH0125763B2 (en) | ||
| JP2713595B2 (en) | Continuous polymerization of propylene | |
| JP2702213B2 (en) | α-Olefin polymerization method | |
| JPH04258604A (en) | Polymerization of alpha-olefin | |
| JP2927870B2 (en) | α-Olefin polymerization method | |
| JPH05186523A (en) | Method of polymerizing alpha-olefin | |
| JP2818283B2 (en) | α-Olefin polymerization method | |
| JP3048247B2 (en) | α-Olefin polymerization method | |
| JPH05255431A (en) | Method for polymerizing alpha-olefin | |
| JP2670337B2 (en) | Propylene polymerization method | |
| JPH10168119A (en) | Purification of polyolefin | |
| JP2670339B2 (en) | Propylene polymerization method | |
| JP3065107B2 (en) | α-Olefin polymerization method | |
| JP2764107B2 (en) | Propylene polymerization method | |
| JP2818264B2 (en) | Propylene polymerization method | |
| JPH1030005A (en) | Polymerization of alpha-olefin | |
| JPH05230134A (en) | Production of polyolefin with broad molecular weight distribution | |
| JPS642125B2 (en) | ||
| JPH0333104A (en) | Catalyst for polymerization of alpha-olefin | |
| JP2764092B2 (en) | Continuous brand change method for polypropylene | |
| JPH1087720A (en) | Catalyst for polymerizing alpha-olefin |