JPH02255811A - Polymerization of propylene - Google Patents
Polymerization of propyleneInfo
- Publication number
- JPH02255811A JPH02255811A JP8938189A JP3818989A JPH02255811A JP H02255811 A JPH02255811 A JP H02255811A JP 8938189 A JP8938189 A JP 8938189A JP 3818989 A JP3818989 A JP 3818989A JP H02255811 A JPH02255811 A JP H02255811A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- propylene
- magnesium halide
- transition metal
- metal catalyst
- 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 title description 25
- -1 magnesium halide Chemical class 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 150000005690 diesters Chemical class 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 26
- 150000008282 halocarbons Chemical class 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002370 organoaluminium group Chemical group 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 18
- 239000010936 titanium Substances 0.000 abstract description 13
- 229910052719 titanium Inorganic materials 0.000 abstract description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 3
- 229920000576 tactic polymer Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 229920000642 polymer Polymers 0.000 description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- 230000005484 gravity Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 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 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group 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
- 238000010438 heat treatment Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000000843 powder 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000001246 bromo group Chemical group Br* 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
- 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 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
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound 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
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000726103 Atta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-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
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 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
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate 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
- 230000005496 eutectics Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000000227 grinding Methods 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 Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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〕
本発明はプロピレ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る方法に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for polymerizing propylene. Specifically, the present invention relates to a method using a carrier-type transition metal catalyst obtained by a specific method.
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
担持した触媒と有機金属化合物から成る触媒を用いてプ
ロピレ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−４３性化合物或いは移金属触
媒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７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
触媒と有機金属化合物と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プロピレ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５９−２
０６４１０等）。The method of polymerizing propylene using a catalyst comprising a transition metal compound supported on a carrier such as magnesium halide and an organometallic compound has undergone many improvements since it was disclosed in Japanese Patent Publication No. 39-12105. Improvements are mainly made in the direction of what to use as the electron-donating compound used in combination of an electron-43 compound or a transfer metal catalyst and an organometallic compound to be used on the carrier side, as well as how to produce the transition metal catalyst. It is done in two directions: whether to do it or not. Among these methods, a method uses a bifunctional compound as an electron donating compound used on the carrier side, and an alkoxy silicon compound or a sterically hindered amine compound as the electron donating compound used in combination with a transition metal catalyst and an organometallic compound. is an excellent catalyst system that provides polypropylene with high activity and extremely high stereoregularity (for example, JP-A-58-138710, JP-A-58-138710, JP-A-58-13871
-117509, 59-206407, 59-2
06410 etc.).
しかしながら、上記２官能性の化合物を用いる遷移金属
触媒であっても、２官能性の化合物とハロゲン化マグネ
シウムを単に共粉砕し、ついでハＩ」ゲン化チタンを担
持する方法では性能が充分でなく、操作が繁雑で製造に
コストのかかるハロゲン化マグネシウムをアルコールな
どの電子供与性の化合物と炭化水素溶媒に可溶な反応物
とし、ついで析出させるといった方法で合成したもので
ないと性能が充分でないとか、また触媒をそのまま重合
温度付近の高温に設定された重合槽に導入すると活性及
び得られる重合体の立体規則性が充分でないという問題
があった。However, even with the transition metal catalyst using the above-mentioned bifunctional compound, the performance is not sufficient with the method of simply co-pulverizing the bifunctional compound and magnesium halide and then supporting the titanium halide. However, it is said that the performance is insufficient unless it is synthesized by a method in which magnesium halide, which is complicated to operate and expensive to manufacture, is made into a reactant soluble in an electron-donating compound such as alcohol and a hydrocarbon solvent, and then precipitated. Furthermore, there was a problem that if the catalyst was directly introduced into a polymerization tank set at a high temperature near the polymerization temperature, the activity and stereoregularity of the resulting polymer would be insufficient.
本発明者らは上記課題を解決して簡便に高性能の遷移金
属触媒を製造する方法について鋭意検討し本発明を完成
した。The present inventors have completed the present invention by intensively studying a method for easily producing a high-performance transition metal catalyst by solving the above-mentioned problems.
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と有機アルミニウム化合物から
なる触媒を用いてプロピレンを重合する方法において、
遷移金属触媒として、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
価のチタン化金物を共粉砕し、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そのまま遊離のハロゲン化チタ
ン及び／またはフタル酸のジエステルを除去することな
く、を機アルミニウムの存在下にハロゲン化マグネシウ
ム１ｇあたり０゜１〜１００ｇのプロピレンを４０℃以
下の温度で重合して得たものを用いることを特徴とする
プロピレンの重合方法である０本発明はまたハロゲン化
マグネシウムにチタン化合物を担持した遷移金属触媒と
有機アルミニウム化合物からなる触媒を用いてプロピレ
ンを重合する方法において、遷移金属触媒として、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とハロゲ
ン化炭化水素化合物を共粉砕し、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そのまま遊離のハロゲン化チ
タン及び／またはフタル酸のジエステルを除去すること
なく、有機アルミニウムの存在下にハロゲン化マグネシ
ウム１ｇあたり０．１〜１００ ｇのプロピｉ／ンを４
０℃以下の温度で重合して得たものを用いることを特徴
とするプロピレンの重合方法である。That is, the present invention provides a method for polymerizing propylene using a transition metal catalyst in which a titanium compound is supported on magnesium halide and a catalyst consisting of an organoaluminum compound.
As a transition metal catalyst, a magnesium halide, a diester of phthalic acid, and a tetravalent metal titanide having at least one halogen are co-pulverized, and then the co-pulverized product is placed in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound. The product obtained by heat treatment is heated as it is without removing free titanium halide and/or phthalic acid diester. In the presence of aluminum, 0°1 to 100 g of propylene is added per 1 g of magnesium halide to 40° C. or below. The present invention is also a method for polymerizing propylene, characterized in that propylene is polymerized at a temperature of In a method for polymerizing a halogenated hydrocarbon compound, a magnesium halide, a diester of phthalic acid, a tetravalent titanium compound having at least one halogen, and a halogenated hydrocarbon compound are co-pulverized as a transition metal catalyst, and then the co-pulverized product is converted into a hydrocarbon. The product obtained by heat treatment in the presence of a compound or a halogenated hydrocarbon compound is directly treated without removing free titanium halide and/or diester of phthalic acid, and in the presence of an organoaluminium, 0 per gram of magnesium halide is added. .1 to 100 g of propylene
This is a propylene polymerization method characterized by using propylene obtained by polymerization at a temperature of 0° C. or lower.
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。In the present invention, the magnesium halide is:
Substantially anhydrous magnesium halides can be used, even those containing a few percent or less of water. As the magnesium halide, magnesium chloride, magnesium bromide, complexes of these with ethers or monoesters, or eutectics of magnesium chloride and magnesium bromide can be used.
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１．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、
フタル酸ジー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 a diester of phthalic acid, phthalic acid and carbon number 1~
Esters with alcohols of 12 are preferably utilized and dimethyl phthalate 1. Diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, diphenyl phthalate, dibenzyl phthalate,
In addition to di-2-ethylhexyl phthalate, diesters such as butylbenzyl phthalate and ethylhexyl phthalate, which have different alcohols forming two ester bonds, can also be used.
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
。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.
本発明において用いる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、塩化ビリエタン、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。Examples of the halogenated hydrocarbon compound used in the present invention include compounds in which one or all of the hydrogen atoms of a hydrocarbon compound having 1 to 12 carbon atoms are replaced with chlorine, bromine, or iodine, and specifically, methyl chloride, methylene chloride, , chloroform, carbon tetrachloride, ethyl chloride, ethylene dichloride, trichloroethane, tetrachloroethane, pentachloroethane, perchloroethane, etc., saturated hydrocarbon compounds in which hydrogen is replaced with chlorine, or chlorine is replaced with bromine or iodine, chloride Examples include biriethane, trichlorethylene, perchlorethylene, etc., unsaturated hydrocarbon compounds such as chlorobenzene, dichlorobenzene, and trichlorobenzene in which hydrogen is replaced with chlorine, or chlorine is replaced with bromine or iodine.
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〜ｔ：Ｏ，
Ｓであり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重量此
程度が好ましい、また、ハロ、ゲン化マグネシウムに対
するハロゲン化炭化水素化合物の使用割合としては、１
：０．００１〜１：０．５好ましくは１：０．０１〜１
＋０．３重量比である。このハロゲン化炭化水素を併用
することで触媒の性能が用いない場合に比較して大幅に
向上する。In co-pulverization, the ratio of phthalic acid diester and titanium halide used is preferably 0.3:1 to 1:0.
3 molar ratio, more preferably 0.5:1 to t:O,
S, and if this range is exceeded, the activity and stereoregularity of the resulting polymer will not be sufficient when the catalyst is used for polymerization, and the ratio of titanium halide to magnesium halide is 1:0.001 to 1. :0.5 weight It is preferable to use about 1% of the halogenated hydrocarbon compound relative to the halo and magnesium genide.
:0.001-1:0.5 preferably 1:0.01-1
+0.3 weight ratio. By using this halogenated hydrocarbon in combination, the performance of the catalyst is significantly improved compared to when it is not used.
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。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, polymeric compounds such as polyethylene, polypropylene, and polystyrene can be used.
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、具体的にはへキサン、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
、先に示した共粉砕に使用する化合物が使用できる。好
ましくは、芳香族炭化水素化合物、ハロゲン化炭化水素
化合物である。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。In the present invention, the above-mentioned 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, octanedecane, cyclohexane. , benzene, toluene, ethylbenzene, xylene, cumene, tetralin, etc. As the halogenated hydrocarbon compound, the compounds used for co-pulverization mentioned above can be used. Preferred are aromatic hydrocarbon compounds and halogenated hydrocarbon compounds. The proportion of these hydrocarbon compounds to be used is 1 to 1000 parts per 1 part by weight of titanium halide;
Preferably it is about 10 to 500 parts.
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。The optimum temperature for heat treatment varies depending on the amount ratio of additives during co-pulverization, but it is 40°C or higher, preferably 50°C or higher.
The temperature is about 150°C.
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。When heated at 40°C or lower, the activity and stereoregularity of the resulting polymer are insufficient, especially when the solvent used is an aromatic hydrocarbon, and even at 150°C or higher, the performance is insufficient.
本発明においては、次いで加熱処理後の遊離のハロゲン
化チタンおよび／またはフタル酸のジエステルを含有す
る遷移金属触媒スラリーをそのまま用いて有機アルミニ
ウム化合物の存在下にプロピレンで処理される。この際
、さらに炭化水素化合物を溶媒として追加することもで
き、ここで追加する溶媒としては、上記炭化水素化合物
、あるいはハロゲン化炭化水素化合物が例示できる。希
釈の程度としてはハロゲン化マグネシウムとして０．１
ｇ／１２以上とするのが一般的である。ここで、有機ア
ルミニウムの使用量としては、その後重合に用いられる
有機アルミニウムの量より少ない限り特に制限はないが
、通常、遷移金属触媒スラリーから持ち込まれるチタン
に対しｏ、ｏｉモル倍以上、好ましくは通常０．１〜１
００モル倍程度である。In the present invention, the transition metal catalyst slurry containing free titanium halide and/or diester of phthalic acid after the heat treatment is then treated with propylene in the presence of an organoaluminum compound. At this time, a hydrocarbon compound may be further added as a solvent, and examples of the solvent added here include the above-mentioned hydrocarbon compounds or halogenated hydrocarbon compounds. The degree of dilution is 0.1 as magnesium halide.
It is common to set it to g/12 or more. Here, the amount of organoaluminum to be used is not particularly limited as long as it is less than the amount of organoaluminium that will be used in the subsequent polymerization, but it is usually at least o, oi times the mole of titanium brought in from the transition metal catalyst slurry, preferably Usually 0.1-1
It is about 00 mole times.
０．０１モル倍より少ないと、プロピレンを導入しても
重合せず好ましくなく、又、余りに多（の有機アルミニ
ウムを用いると得られた触媒スラリーの活性低下が激し
い、又、プロピレンの重合量としてはハロゲン化マグネ
シウム１ｇに対し０．１〜１００ｇ程度であるのが重合
系に導入する上で好ましく、０．１ｇ以下では得られる
重合体の嵩比重が小さく好ましくなく、また１００ｇ以
上では、重合系への触媒の導入が困難である上にプロピ
レンで処理する効果がより多くなるわけでもない。なお
この少量のプロピレンの重合は、比較的低温で行うのが
好ましく、通常４０℃以下、好ましくは一７０〜３０℃
で行われ、更に低温で行っても効果がなり、４０℃より
高い温度で行うと、触媒当たりの活性が充分でないだけ
でなく得られる重合体の立体規則性が不充分である。こ
の少量のプロピレンでの処理に際し後述の立体規則性向
上剤を併用することもできる。If it is less than 0.01 mole, propylene will not be polymerized even if it is introduced, which is not preferable, and if too much organoaluminium is used, the activity of the resulting catalyst slurry will be severely reduced, and the amount of polymerized propylene will be It is preferable to introduce it into the polymerization system in an amount of about 0.1 to 100 g per 1 g of magnesium halide; if it is less than 0.1 g, the bulk specific gravity of the obtained polymer is undesirably small, and if it is more than 100 g, the polymerization system It is difficult to introduce a catalyst into the polymer, and the effect of treatment with propylene is not increased.The polymerization of this small amount of propylene is preferably carried out at a relatively low temperature, usually below 40°C, preferably at 70~30℃
It is effective even when carried out at a lower temperature, but if carried out at a temperature higher than 40°C, not only the activity per catalyst is insufficient but also the stereoregularity of the resulting polymer is insufficient. During this treatment with a small amount of propylene, a stereoregularity improver described below can also be used in combination.
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 preferably includes trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, and tributylaluminium, and an alkylaluminum halogen in which one or two hydrocarbon residues thereof are substituted with chlorine or bromine. is exemplified.
本発明においては、こうして得られた遷移金属触媒スラ
リーは次いで、さらに有機アルミニウムを追加してより
高温で本来の重合に利用される。In the present invention, the transition metal catalyst slurry thus obtained is then used for the actual polymerization at a higher temperature with the addition of organoaluminum.
ここで追加される有機アルミニウムとしては通常、チタ
ン１モルに対し１０〜１００００モル倍の有機アルミニ
ウムが用いられる。この有機アルミニウムは重合系に上
記プロピレンで処理した触媒スラリーとは別個に導入す
ることもできる。The organic aluminum added here is usually used in an amount of 10 to 10,000 moles per mole of titanium. The organoaluminum can also be introduced into the polymerization system separately from the propylene-treated catalyst slurry.
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同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。この立体規則性向上剤は、本
来の重合のみならず、始めの少量のプロピレンの重合に
おいても添加することができ、場合によってはより高立
体規則性のポリプロピレンを与えることもできる。In the present invention, during polymerization, it is preferable to use an alkoxysilane or a substituted piperidine as a stereoregular agent.As the alkoxysilane, an organic silane compound containing 1 to 4 alkoxy groups is preferably used,
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 examples of the remaining groups include alkyl groups having 1 to 12 carbon atoms or alkenyl groups. In addition, as substituted piperidine,
Some or all of the hydrogens at the 1st and 6th positions have 1 to 12 carbon atoms.
Preferred examples include compounds substituted with alkyl groups or alkenyl groups. This stereoregularity improver can be added not only during the original polymerization but also during the initial polymerization of a small amount of propylene, and in some cases can provide polypropylene with higher stereoregularity.
有機アルミニウムと立体規則性向上網の使用割合として
は通常１：０．００１〜ｌ：１０程度である。The ratio of organoaluminum to stereoregularity improving network is usually about 1:0.001 to 1:10.
本発明において本来のプロピレンの重合の際の重合方法
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、液状のプロピ
レ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。In the present invention, the polymerization method for the original propylene polymerization is not particularly limited, and various known methods can be adopted.
Any of the following methods can be employed: a solvent polymerization method using an inert hydrocarbon as a medium, a bulk polymerization method using liquid propylene as a medium, and a gas phase polymerization method using substantially no liquid medium.
重合に際し温度は上記少量のプロピレンの処理の際の温
度より高温で〜１５０ ”Ｃ１圧力は常圧〜１００ ｋ
ｇ／ｄで行うのが一般的であり、プロピレンの単独重合
の他にエヂレン、ブテン、ペンテン、ヘキセンなどの他
のオレフィンとのランダム共重合、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。The temperature during polymerization is higher than the temperature during the above-mentioned treatment of a small amount of propylene, and the C1 pressure is from normal pressure to 100 k.
This polymerization method is generally carried out at g/d, and in addition to homopolymerization of propylene, this polymerization method can be preferably employed for random copolymerization or block copolymerization with other olefins such as ethylene, butene, pentene, and hexene.
以下に実施例を掲げ本発明についてさらに説明する。 The present invention will be further explained with reference to Examples below.
実施例１
直径１２ｍｍの鋼球９Ｋｇの入った内容積４１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１１５ａｌｊ！、四塩化チタン６０ｍを加え
４０時間粉砕した。■：記共粉砕物１０ｇを２００ｄの
フラスコに入れトルエン４０ａｄを加えｌ・ルエンの沸
騰下に加熱し３０分間撹拌処理した。このスラリーの上
澄みの一部を採取し分析したところ、四塩化チタンを３
４．２ｇ／１１、フタル酸ジイソブチルを１６．８ｇ／
ｊ！含んでいた。また一部の固型分を採取し１００℃
のトルエンで洗浄して分析したところ固型分にはチタン
が１．９ｗｔχ、フタル酸ジイソブチルが２０．５ｗｔ
χふくまれていた。この遷移金属触媒スラリーをそのま
ま使用し塩化マグネシウムとして１ｇをＩＩ！、のオー
トクレーブに入れ、トルエン２００−を追加した後０℃
とし、さらにトリエチルアルミニウム０．５ｍを加え、
０℃でプロピレンを３ｇ装入し攪拌しながら２時間重合
を行った。得られたスラリーを分析したところ塩化マグ
ネシウム当たりプロピレンを３ｇ重合していた。Example 1 A vibratory mill equipped with four grinding pots each having an internal volume of 41 and containing 9 kg of steel balls each having a diameter of 12 mm was prepared. 300 g of magnesium chloride and 115 alj of diisobutyl phthalate in each pot under nitrogen atmosphere! , 60 ml of titanium tetrachloride was added and pulverized for 40 hours. (2): 10 g of the above pulverized material was placed in a 200 d flask, 40 ad of toluene was added, and the mixture was heated to boiling of 1.toluene and stirred for 30 minutes. When a part of the supernatant of this slurry was collected and analyzed, it was found that titanium tetrachloride was
4.2g/11, diisobutyl phthalate 16.8g/11
j! It contained. In addition, some solid matter was collected and heated to 100°C.
When washed with toluene and analyzed, the solid components contained 1.9wtx of titanium and 20.5wtx of diisobutyl phthalate.
χ was included. Using this transition metal catalyst slurry as it is, 1 g of magnesium chloride is II! , put it in an autoclave, add 200℃ of toluene, and then bring it to 0℃.
and further added 0.5 m of triethyl aluminum,
3 g of propylene was charged at 0° C. and polymerization was carried out for 2 hours while stirring. Analysis of the resulting slurry revealed that 3 g of propylene was polymerized per magnesium chloride.
内容積５２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、プロピレン１．５ｋｇ、水素１．２５１！
を加え６０℃に昇温後、ヘキサン１００ｄにトリエチル
アルミニウム０．１ｄ、シクロヘキシルメチルジメトキ
シシラン０．０５ｄ、上記プロピレンで処理した遷移金
属触媒触媒スラリーを塩化マグネシウムとして１０−ｇ
を分散したスラリーを圧入して加え７０℃で２時間重合
した。A fully dried autoclave with an internal volume of 52 cm and purged with nitrogen was prepared, containing 1.5 kg of propylene and 1.251 kg of hydrogen!
was added and the temperature was raised to 60°C, and 100 d of hexane was mixed with 0.1 d of triethylaluminum, 0.05 d of cyclohexylmethyldimethoxysilane, and 10 g of the transition metal catalyst slurry treated with propylene as magnesium chloride.
A slurry in which was dispersed was added under pressure and polymerized at 70°C for 2 hours.
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６６０ｇ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と略記）は１．６３、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／抽出残ポリマーの重量を１００
分率で表示、以下ＩＩと略記）は９８．４χ、嵩比重０
．４３ｇ／ａ！であった。このプロピレンで処理した触
媒スラリーを１０℃で２４時間保存した後、同様に重合
したところパウダーを６５５ｇ得、ηは！、６１、ＩＩ
は９８．４χ、嵩比重は０．４３ ｇ ／−であった。After the polymerization, unreacted propylene was purged and the mixture was dried at 80° C. for 8 hours and weighed to obtain 660 g of polypropylene. In addition, the intrinsic viscosity (hereinafter abbreviated as η) of polypropylene measured in a tetralin solution at 135°C is 1.63, and the boiling n-heptane extraction residue (
Weight of extraction residue polymer/weight of extraction residue polymer 100
Expressed as a fraction, hereinafter abbreviated as II) is 98.4χ, bulk specific gravity 0
．． 43g/a! Met. This propylene-treated catalyst slurry was stored at 10°C for 24 hours and then similarly polymerized to obtain 655g of powder, and η was! ,61,II
was 98.4χ, and the bulk specific gravity was 0.43 g/-.
比較例１
トルエンでの処理を行わずに重合した以外は実施例１と
同様にしたところポリマーは２２０ｇ Ｌが得られず、
ポリマーのｌは１．５１、ＴＩは８３．６χにすぎなっ
かた。Comparative Example 1 The same procedure as Example 1 was carried out except that polymerization was performed without treatment with toluene, but 220 g L of polymer was not obtained.
The l of the polymer was 1.51 and the TI was only 83.6χ.
比較例２
プロピレンで処理すること無く、トルエンの沸点で加熱
したスラリーをそのもまま用いて重合を行ったところポ
リマーは６４０ｇ得られ、ηは１．６５、ＩＩは９５．
８χ、嵩比重は０．３６ ｇ ／ｄにすぎなっがた、ま
た、プロピレンでの処理をプロピレンの導入量を減少し
て塩化マグネシウム当たり０．０５ｇとしたところポリ
マーを６３０ ｇ得、ηは１．６３、ＩＩは９６．２χ
嵩比重は０．３７ｇ／ｄにすぎなっがた。Comparative Example 2 A slurry heated to the boiling point of toluene was directly used for polymerization without treatment with propylene. 640 g of polymer was obtained, η was 1.65, and II was 95.
8χ, the bulk specific gravity was only 0.36 g/d, and when the amount of propylene introduced was reduced to 0.05 g per magnesium chloride in the treatment with propylene, 630 g of polymer was obtained, and η was 1. .63, II is 96.2χ
The bulk specific gravity was only 0.37 g/d.
実施例２
共粉砕の際、フタル酸ジイソブチルに変えフタル酸ジ−
ｎ−ブチルとした他は実施例１と同様にしたところポリ
マー６２０ｇを得た。またηは１．５９、ＩＩは９８．
２！ 、嵩比重０．４２ｒ／ｘｉ ｉ？ アッタ、 ；
： （’） ７ Ｃ’ ヒレンで処理した触媒スラリー
を１０℃で２４時間保存した後、同様に重合したところ
パウダーを６１０ｇ得、ηは１．５７、ＩＩは９８．４
χ、嵩比重は０．４３８ ／ｄであった。Example 2 During co-pulverization, di-isobutyl phthalate was used instead of di-isobutyl phthalate.
The same procedure as in Example 1 was carried out except that n-butyl was used, and 620 g of polymer was obtained. Also, η is 1.59, and II is 98.
2! , bulk specific gravity 0.42r/xi i? Atta;
: (') 7 C' After storing the catalyst slurry treated with helene at 10°C for 24 hours, it was similarly polymerized to obtain 610 g of powder, η was 1.57, and II was 98.4.
The bulk specific gravity was 0.438/d.
比較例３
実施例２で得た共粉砕物１０ｇを２００ ｍのフラスコ
に入れトルエン４０ｄを加えトルエンの沸騰下に加熱し
３０分間撹拌処理した。このスラリーの上澄みを１００
℃で除去しさらにトルエン１００ｊｄを加え１００℃で
１０分間攪拌し静置し上澄みを除去する操作を５回行っ
た０次いでトルエン１００Ｊ１１を加え攪拌し静置した
時上澄みのチタン及びフタル酸ジ−ｎ−ブチルはどちら
も０．１ｇ／ｊ！以下であった。こうして得た遷移金属
触媒スラリーを実施例２と同様にプロピレンで処理した
他は実施例２と同様にしたところポリマーを５８０ｇ得
、ηは１．５７、■！は９８．４χ、嵩比重は０．４３
ｇ／−であった、またプロピレンで処理したスラリーを
実施例２と同様に１０℃で２４時間保存した後、同様に
重合したところポリマーを４９０ｇ得、ηは１．５８、
ＩＩは９８．４χ、嵩比重は０゜４３ｇ／ｄであり活性
が実施例２に比較し大幅に低下していた。Comparative Example 3 10 g of the co-pulverized material obtained in Example 2 was placed in a 200 m flask, 40 d of toluene was added thereto, heated to boiling of toluene, and stirred for 30 minutes. The supernatant of this slurry is 100%
℃, then added 100Jd of toluene, stirred at 100℃ for 10 minutes, left to stand, and removed the supernatant 5 times.Next, 100J11 of toluene was added, stirred, and left to stand to remove titanium and phthalic acid di-n in the supernatant. -Butyl is 0.1g/j for both! It was below. The transition metal catalyst slurry thus obtained was treated in the same manner as in Example 2, except that it was treated with propylene in the same manner as in Example 2. 580 g of polymer was obtained, η was 1.57, ■! is 98.4χ, bulk specific gravity is 0.43
The slurry treated with propylene was stored at 10°C for 24 hours in the same manner as in Example 2, and then polymerized in the same manner to obtain 490 g of polymer, with η of 1.58,
II had a value of 98.4χ and a bulk specific gravity of 0.43 g/d, and its activity was significantly lower than that of Example 2.
実施例３
共粉砕の際に四塩化チタン６０Ｈ１に変え四塩化チタン
３０Ｉ１１と二塩化エチレン３０ｍ１を用いた他は実施
例１と同様にした。 ８９５ｇのポリプロピレンが得ら
れた。またポリプロピレンのｌは１．５９、■■は９８
．６χ、嵩比重０．４４ｇ／−であった、このプロピレ
ンで処理した触媒スラリーを１０℃で２４時間保存した
後、同様に重合したところパウダーを８９０ｇ得、ηは
１．６０． ＩＩは９８．５χ、嵩比重は０．４４ ｇ
／ｄであった。Example 3 The same procedure as Example 1 was carried out except that titanium tetrachloride 30I11 and ethylene dichloride 30ml were used instead of titanium tetrachloride 60H1 during co-pulverization. 895 g of polypropylene was obtained. Also, l of polypropylene is 1.59, and ■■ is 98.
．． This propylene-treated catalyst slurry, which had a bulk density of 0.44 g/- and a bulk specific gravity of 0.44 g/-, was stored at 10° C. for 24 hours and then similarly polymerized to obtain 890 g of powder, with η of 1.60. II is 98.5χ, bulk specific gravity is 0.44 g
/d.
本発明の方法を実施することで効率的に高性能の遷移金
属触媒が得られ工業的に意味がある。By carrying out the method of the present invention, a high-performance transition metal catalyst can be obtained efficiently and is industrially significant.
第１図は本発明の理解を助けるためのフローチャート図
である。
特許出願人 三井東圧化学株式会社FIG. 1 is a flowchart diagram to aid understanding of the present invention. Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
遷移金属触媒と有機アルミニウム化合物からなる触媒を
用いてプロピレンを重合する方法において、遷移金属触
媒として、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
て得たものをそのまま遊離のハロゲン化チタン及び／ま
たはフタル酸のジエステルを除去することなく、有機ア
ルミニウムの存在下にハロゲン化マグネシウム１ｇあた
り０．１〜１００ｇのプロピレンを４０℃以下の温度で
重合して得たものを用いることを特徴とするプロピレン
の重合方法。 ２、ハロゲン化マグネシウムにチタン化合物を担持した
遷移金属触媒と有機アルミニウム化合物からなる触媒を
用いてプロピレンを重合する方法において、遷移金属触
媒として、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
化合物とハロゲン化炭化水素化合物を共粉砕し、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そのまま遊離
のハロゲン化チタン及び／またはフタル酸のジエステル
を除去することなく、有機アルミニウムの存在下にハロ
ゲン化マグネシウム１ｇあたり０．１〜１００ｇのプロ
ピレンを４０℃以下の温度で重合して得たものを用いる
ことを特徴とするプロピレンの重合方法。[Scope of Claims] 1. A method for polymerizing propylene using a catalyst consisting of a transition metal catalyst in which a titanium compound is supported on magnesium halide and an organoaluminum compound, wherein the transition metal catalyst is a diester of magnesium halide and phthalic acid. and a tetravalent titanium compound having at least one halogen, and then heat-treating the co-pulverized product in the presence of a hydrocarbon compound or a halogenated hydrocarbon compound to obtain free halogenated titanium as it is. and/or without removing the diester of phthalic acid, using a product obtained by polymerizing 0.1 to 100 g of propylene per 1 g of magnesium halide at a temperature of 40 ° C. or lower in the presence of organoaluminium. A method for polymerizing propylene. 2. In a method of polymerizing propylene using a catalyst consisting of a transition metal catalyst in which a titanium compound is supported on magnesium halide and an organoaluminium compound, magnesium halide, a diester of phthalic acid, and at least one halogen are used as the transition metal catalyst. A tetravalent titanium compound and a halogenated hydrocarbon 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 to obtain free halogenated titanium as it is. and/or without removing the diester of phthalic acid, using a product obtained by polymerizing 0.1 to 100 g of propylene per 1 g of magnesium halide at a temperature of 40 ° C. or lower in the presence of organoaluminium. A method for polymerizing propylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038189A JP2764107B2 (en) | 1988-12-21 | 1989-02-20 | Propylene polymerization method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32059088 | 1988-12-21 | ||
| JP63-320590 | 1988-12-21 | ||
| JP1038189A JP2764107B2 (en) | 1988-12-21 | 1989-02-20 | Propylene polymerization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255811A true JPH02255811A (en) | 1990-10-16 |
| JP2764107B2 JP2764107B2 (en) | 1998-06-11 |
Family
ID=18123119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1038189A Expired - Fee Related JP2764107B2 (en) | 1988-12-21 | 1989-02-20 | Propylene polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2764107B2 (en) |
-
1989
- 1989-02-20 JP JP1038189A patent/JP2764107B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2764107B2 (en) | 1998-06-11 |
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