JPH0312407A - Catalyst for production of polyolefin - Google Patents
Catalyst for production of polyolefinInfo
- Publication number
- JPH0312407A JPH0312407A JP14766089A JP14766089A JPH0312407A JP H0312407 A JPH0312407 A JP H0312407A JP 14766089 A JP14766089 A JP 14766089A JP 14766089 A JP14766089 A JP 14766089A JP H0312407 A JPH0312407 A JP H0312407A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrocarbon
- catalyst
- hydrocarbon group
- hafnium
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 150000002363 hafnium compounds Chemical class 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- -1 bis-substituted cyclopentadienyl Chemical group 0.000 abstract description 25
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 4
- 229920000576 tactic polymer Polymers 0.000 abstract description 2
- 150000001721 carbon Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CPNMBRRGIVMNSY-UHFFFAOYSA-N bis(2,4-dimethylcyclopenta-2,4-dien-1-yl)-dimethylsilane Chemical compound CC1=CC(C)=CC1[Si](C)(C)C1C(C)=CC(C)=C1 CPNMBRRGIVMNSY-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000011980 kaminsky catalyst Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［ａ業上の利用分野］
本発明は高立体規則性ポリ第１ノフイン製造用触媒に関
する。さらに詳しくは、橋架は構造を持つビス置換シク
ロペンタジェニルブリッジ型２座配位子を有する新規な
ハフニウム化合物とアルミノキサンからなる該触媒に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a catalyst for producing a highly stereoregular poly-primary nophine. More specifically, the present invention relates to a catalyst comprising a novel hafnium compound and aluminoxane having a bis-substituted cyclopentadienyl bridge type bidentate ligand having the structure.
［従来の技術およびその問題点］
オレフィン重合用均一系触媒としては、いわゆるカミン
スキー系触媒がよく知られている。この触媒系は非常に
重合活性が高く２しかも例えば、プロピレン重合におい
ては、アタクチックポリプロピレン５アイソタクチツク
ポリプロピレン、及びシンジオタクチックポリプロピレ
ンのいずれもが製造できることが公知になっている。[Prior Art and its Problems] As a homogeneous catalyst for olefin polymerization, a so-called Kaminsky catalyst is well known. It is known that this catalyst system has a very high polymerization activity2 and can produce both atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene in propylene polymerization, for example.
（Ｍａｋｒｏｍｏｌ、ｆ；ｈｅｍ、、Ｒａｐｉｄ Ｃ
ｏｍｍｕｎ、４，４１７−４２１０９８３）。(Makromol,f;hem,, Rapid C
ommun, 4,417-4210983).
八ｎｇｅｗ、Ｃｈｅｍ、Ｉｎｔ、Ｅｄ、Ｅｎｇｌ、２４
．５０７−５０８（１９８５）。8ngew, Chem, Int, Ed, Engl, 24
．． 507-508 (1985).
Ｊ、Ａ＋＋＋、Ｃｈｅｍ、Ｓｏｃ、１９８７，１０９．
８５４４−８５４５． Ｊ、八ｍ、ｃｈｅｍＳｏｃ、
１９８ｆｌ、１１０．６２５５−６２５６）アイソタク
チックポリマーを製造する遷り金属化合物としては、以
下のような化合物が公知になっている。カミンスキー等
によるエチレンビスインデニル型配位子を有する遷移金
属化合物（特開昭６１−２８４，０１０、特開昭１ｉ４
−５１．４０８、特開昭６４−６ｆｔ、２１［ｉ） 、
ニーエン等によるＲ” （Ｃｓ （Ｒ’） ４） ２
ＭｅＱｐ型メタロセン化合物（特開昭６３−２５１，４
０５、特開昭６３−２９５，６０７、特開昭６４−７４
，２０２）である。J, A+++, Chem, Soc, 1987, 109.
8544-8545. J, 8m, chemSoc,
198fl, 110.6255-6256) The following compounds are known as intermediate metal compounds for producing isotactic polymers. Transition metal compounds having ethylene bisindenyl type ligands by Kaminski et al.
-51.408, JP-A-64-6ft, 21[i),
R'' (Cs (R') 4) 2 by Nien et al.
MeQp type metallocene compound (JP-A-63-251,4
05, JP-A No. 63-295, 607, JP-A No. 64-74
, 202).
また、ステレオブロック重合体を製造するメタロセン化
合物も公知である。（特開昭６３−１．４２ 、００４
、特開昭［１３−２，００５）
しかしながら、プロピレン重合において、上記の文献中
にあるいづれのハフニウム系触媒を使用しても、得られ
るポリマーの融点が低いという問題点があった。Metallocene compounds for producing stereoblock polymers are also known. (JP-A-63-1.42, 004
, JP-A-Sho [13-2,005] However, in propylene polymerization, no matter which of the hafnium-based catalysts listed in the above literature is used, there is a problem that the resulting polymer has a low melting point.
本発明者らは、上記の問題点を解決すべく研究を重ねた
結果、上述の新規なハフニウム化合物を効率良く合成す
ることに成功し、さらにこれらの化合物とアルミノキサ
ンとからなる触媒系が融点の高い立体規則性ポリ第１ノ
フインを製造することを見いだし、この知見にもとづい
て本発明に到達した。As a result of repeated research to solve the above problems, the present inventors succeeded in efficiently synthesizing the above-mentioned novel hafnium compounds, and furthermore, the catalyst system consisting of these compounds and aluminoxane has a melting point. It was discovered that highly stereoregular poly-1-nophine can be produced, and the present invention was achieved based on this finding.
［問題点を解決するための手段］
すなわち、本発明は、（Ａ）−数式［Ｉコで表さねるハ
フニウム化合物
各Ｒ２は互いに同一でも異な）ていてもよく、水素また
は炭化水素基を示す、また、Ｘは同一でも異なっていて
もよく、水素、ハロゲンまたは炭化水素基を示す、、）
及び
ＣＢ）−数式［＋１］または一般式［ＩＩ＋ ］（但し
、Ｙはケイ素、又はゲルマニウムを示す。[Means for Solving the Problems] That is, the present invention provides a hafnium compound represented by the formula (A) - [R2 may be the same or different from each other] and represents a hydrogen or hydrocarbon group. , and X may be the same or different and represent hydrogen, halogen, or a hydrocarbon group, )
and CB) - Numerical formula [+1] or general formula [II+] (However, Y represents silicon or germanium.
Ｒ’−Ｃ，Ｈ，、及びＲ’−ＣｓＨ４□は置換シクロペ
ンタジェニル基を示し、ｎ及びｑは１〜３の整数である
。各Ｒ１は互いに同一でも異なっていてもよく、水素、
シリル基または炭化水素基を示すが、Ｒ１のシクロペン
タジェニル環上の位置及び種類は、ＩＨを含む対称面が
存在しない配置をとるものとする。また、少なくとも片
方のシクロペンタジェニル環には、Ｙに結合している炭
素の隣の少なくとも片方の炭素上にはＲ１が存在するも
のとする。R'-C, H, and R'-CsH4□ represent substituted cyclopentadienyl groups, and n and q are integers of 1 to 3. Each R1 may be the same or different, hydrogen,
Although it represents a silyl group or a hydrocarbon group, the position and type of R1 on the cyclopentadienyl ring are such that no plane of symmetry including IH exists. Further, in at least one cyclopentagenyl ring, R1 is present on at least one carbon adjacent to the carbon bonded to Y.
１（”
（但し、ｍは４〜６０の数で、Ｒ３は炭化水素基を示す
）で表されるアルミノキサンを有効成分とする高立体規
則性ポリオレフィン製造用触媒に係わるものである。The present invention relates to a catalyst for producing a highly stereoregular polyolefin, which contains an aluminoxane represented by the formula 1 (where m is a number from 4 to 60 and R3 represents a hydrocarbon group) as an active ingredient.
本発明の方法において使用される触媒構成成分のハフニ
ウム化合物（八）は、橋架は構造を持つビス置換シクロ
ペンタジェニルブリッジ型２＠配位子を有する新規なハ
フニウム化合物である。Ｙはケイ素、またはゲルマニウ
ムである。２つのシクロペンタジェニル環上の置換基の
数は、１置換から３置換までのいずれでもよい。各８１
は互いに同一でも異なっていてもよく、水素、シリル基
または炭化水素基（炭素数１〜２０を有するアルキル、
アルケニル、アリール、アルキルアリール、アリールア
ルキル等である）を示すが Ｂｌのシクロペンタジェニ
ル環上の位置及び種類は、Ｈｆを含む対称面が存在しな
い配置をとるものとする。また、少なくとも片方のシク
ロペンタジェニル環には、Ｙに結合している炭素の隣の
少なくとも片方の炭素上にはＲ１が存在するものとする
。シリル基の例としては、トリメチルシリル基、トリエ
チルシリル基、トリフェニルシリル基等を挙げることが
できる。炭化水素基の例としては、メチル基、エチル基
、プロピル基、イソプロピル基、ブチル基、５ｅｃ−ブ
チル基、 ｔｅｒｔ−ブチル基、フェニル基、トリル基
、ビフェニル基、ナフチル基等を挙げることができる。The hafnium compound (8) as a catalyst component used in the method of the present invention is a novel hafnium compound having a bis-substituted cyclopentagenyl bridge type 2@ ligand with a bridge structure. Y is silicon or germanium. The number of substituents on the two cyclopentadienyl rings may range from 1 to 3 substitutions. 81 each
may be the same or different from each other, hydrogen, silyl group or hydrocarbon group (alkyl having 1 to 20 carbon atoms,
(alkenyl, aryl, alkylaryl, arylalkyl, etc.), but the position and type of Bl on the cyclopentadienyl ring shall be such that no plane of symmetry containing Hf exists. Further, in at least one cyclopentagenyl ring, R1 is present on at least one carbon adjacent to the carbon bonded to Y. Examples of the silyl group include trimethylsilyl group, triethylsilyl group, triphenylsilyl group, and the like. Examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, tert-butyl group, phenyl group, tolyl group, biphenyl group, naphthyl group, etc. .
各８２は互いに同一でも異なっていてもよく、水素また
は上述の炭化水素基である。Each 82 may be the same or different and is hydrogen or the above-mentioned hydrocarbon group.
また、Ｘは水素、弗素、塩素、臭素、沃素などのハロゲ
ン、あるいは上記の炭化水素基である。Further, X is hydrogen, halogen such as fluorine, chlorine, bromine, iodine, or the above hydrocarbon group.
本発明の化合物［Ｉコの代表的な合成経路はｎ”ｑ・２
を例にとると以下の如く略記できるが、これに限定され
るものではない。A typical synthetic route for the compound of the present invention [I is n''q・2
For example, it can be abbreviated as follows, but it is not limited to this.
２１、ｉ（Ｒ，’−Ｃ山）”Ｒ，’ＹＣｈ＝ Ｒ：Ｙ（
Ｒ，’−ＣＪｓ）ｚ”２ＬｉｃＩＲＡＹ （Ｒ；−Ｃｓ
ｌｌｓ） ２＋２ｎ−ＢｕＬｉ→Ｌ１２ ［Ｒ：Ｙ（Ｒ
，’−Ｃａｌｌａ）ｚ］ ”２Ｃ４Ｈ１゜Ｌｉ２ＣＲ：
Ｙ（Ｒ；−ＣｓＨａ）２〕＋）ＩｆＸ４＝ ［Ｒ：Ｙ
（Ｒ，’−ＣｓＨ２） ２］ ＋）ＩｆＸ２ ◆２１．
ｉＸ上記ハフニウム化合物の非限定的な例どして、ジメ
チルシリル（メチルシクロペンタジェニル）（２，４−
ジメチルシクロペンタジェニル）ハフニウムジクロリド
、ジメチルシリル（メチルシクロペンタジェニル）
（２，３，５−トリメチルシクロペンタジェニル）ハフ
ニウムジクロリド、ジメチルシリルビス（２，４−ジメ
チルシクロペンタジェニル）ハフニウムジクロリド、ジ
フェニルシリルビス（２４−ジメチルシクロペンタジェ
ニル）ハフニウムジクロリド、ジメチルシリルビス（２
，４−ジメチルシクロペンタジェニル）ハフニウムジク
ロリド、ジメチルシリルビス（２，４−ジメチルシクロ
ペンタジェニル）ハフニウムジメチル、ジメチルシリル
（２，４−ジメチルシクロペンタジェニル） （２，
３，５−トリメチルシクロペンタジェニル）ハフニウム
ジクロリド、ジメチルシリルビス（２，３，５−トリメ
チルシクロペンタジェニル）ハフニウムジクロリド、ジ
メチルゲルミル（メチルシクロペンタジェニル） （
２，４−ジメチルシクロペンタジェニル）ハフニウムジ
クロリド、ジメチルゲルミル（メチルシクロペンタジェ
ニル） （２，３，５−トリメチルシクロペンタジェ
ニル）ハフニウムジクロリド、ジメチルゲルミルビス（
２，４−ジメチルシクロペンタジェニル）ハフニウムジ
クロリド、ジメチルゲルミル（２，４−ジメチルシクロ
ペンタジェニル）（２，３，５−トリメチルシクロペン
タジェニル）ハフニウムジクロリド、ジメチルゲルミル
ビス（２，３，５−トリメチルシクロペンタジェニル）
ハフニウムジクロリドなどを挙げることができる。21, i(R,'-C mountain)"R,'YCh= R:Y(
R,'-CJs)z"2LicIRAY (R;-Cs
lls) 2+2n-BuLi→L12 [R:Y(R
,'-Calla)z] "2C4H1°Li2CR:
Y(R;-CsHa)2]+)IfX4= [R:Y
(R,'-CsH2) 2] +) IfX2 ◆21.
iX Non-limiting examples of the above hafnium compounds include dimethylsilyl (methylcyclopentagenyl) (2,4-
dimethylcyclopentagenyl) hafnium dichloride, dimethylsilyl (methylcyclopentagenyl)
(2,3,5-trimethylcyclopentagenyl) hafnium dichloride, dimethylsilylbis(2,4-dimethylcyclopentagenyl) hafnium dichloride, diphenylsilylbis(24-dimethylcyclopentagenyl) hafnium dichloride, dimethylsilyl Screw (2
,4-dimethylcyclopentagenyl) hafnium dichloride, dimethylsilylbis(2,4-dimethylcyclopentagenyl) hafnium dimethyl, dimethylsilyl(2,4-dimethylcyclopentagenyl) (2,
3,5-trimethylcyclopentagenyl) hafnium dichloride, dimethylsilylbis(2,3,5-trimethylcyclopentagenyl) hafnium dichloride, dimethylgermyl (methylcyclopentagenyl) (
(2,4-dimethylcyclopentagenyl) hafnium dichloride, dimethylgermyl (methylcyclopentagenyl) (2,3,5-trimethylcyclopentagenyl) hafnium dichloride, dimethylgermyl bis(
2,4-dimethylcyclopentagenyl) hafnium dichloride, dimethylgermyl (2,4-dimethylcyclopentagenyl) (2,3,5-trimethylcyclopentagenyl) hafnium dichloride, dimethylgermyl bis(2, 3,5-trimethylcyclopentagenyl)
Examples include hafnium dichloride.
本発明の方法において、使用されるもう１つの触媒構成
成分のアルミノキサン（Ｂ）は、−数式［工！］または
、−数式［ＩＩＩコ、
Ｒ：Ａｆｌ→〇八℃−→へ−ＯＡＩｌ Ｒ：
［ＩＩ ］３
Ｍ＋
で表わされる有機アルミニウム化合物である。In the process of the invention, the other catalyst component aluminoxane (B) used has the formula: ] or -Math [III, R: Afl→〇8℃-→to-OAIl R:
[II] It is an organoaluminum compound represented by 3 M+.
Ｒ３はメチル基、エチル基、プロピル基、ブチル基など
の炭化水素基であり、好ましくはメチル基、エチル基で
ある０ｍは４〜６０の整数であり、好ましくは６以上で
、とりわけ１０以上であるのが好ましい。この種の化合
物の製法は公知であり、例えば、吸着水を含有する化合
物、結晶水を含有する塩類（硫酸銅水和物、硫酸アルミ
ニウム永和物など）の炭化水素媒体懸濁液にトリアルキ
ルアルミニウムを添加して反応させる方法を例示するこ
とができる。R3 is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and preferably a methyl group or an ethyl group.0m is an integer from 4 to 60, preferably 6 or more, especially 10 or more. It is preferable to have one. The preparation method of this type of compound is known, for example, a trialkyl aluminum is added to a suspension of a compound containing adsorbed water or a salt containing water of crystallization (copper sulfate hydrate, aluminum sulfate permanent, etc.) in a hydrocarbon medium. For example, a method of adding and reacting can be exemplified.
本発明の方法において、重合反応に用いられるオレフィ
ンは、プロピレン、１−ブテン、４−メチル−１−ペン
テン、１−ヘキセン、１−オクテン、１−デセン、１−
ドデセン、１−テトラデセン、ｌ−へキサデセン、ｌ−
オクタデセン、ｌ−エイコセンなどのα−オレフィンで
あり、これら２１１以上の混合成分を重合に供すること
もできる。上記α−オレフィン類とエチレンとの共重合
も可能である。さらには、ブタジェン、ｌ、４−へキサ
ジエン、１．４−ペンタジェン、１．７−オクタジエン
、１．８−ノナジェン、１，９−デカジエンなどのよう
な共役及−び非共役ジエン類、またはスチレン、または
シクロプロパン、シクロブテン、シクロヘキセン、ノル
ボルネン、ジシクロペンタジェンなどのような環状オレ
フィンとの共重合にも有効である。In the method of the present invention, the olefins used in the polymerization reaction are propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, l-hexadecene, l-
These are α-olefins such as octadecene and l-eicosene, and a mixture of 211 or more of these components can also be subjected to polymerization. Copolymerization of the above α-olefins and ethylene is also possible. Additionally, conjugated and non-conjugated dienes such as butadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, etc., or styrene or copolymerization with cyclic olefins such as cyclopropane, cyclobutene, cyclohexene, norbornene, dicyclopentadiene, etc.
本発明において用いられる重合方法は、液相重合あるい
は気相重合のいずれも可能である。液相重合の重合溶媒
としては、（＾）、（ｌ］）同成分を溶解し得る炭化水
素化合物であり、ベンゼン、トルエン、０−キシレン、
ｌ−キシレン、ｐ−キシレン、エチルベンゼン、ブチル
ベンゼン、メシチレン、ナフタレンなどの芳香族系炭化
水素が用いられ、好ましくは、トルエン、キシレンであ
る。さらに、（＾）、（Ｂ）同成分を溶解し得ない溶媒
中でも、芳香族系炭化水素中でプレ重合を行えば、重合
を行うことができる。そのような溶媒として、ブタン、
イソブタン、ペンタン、ヘキサン、オクタン、デカン、
ドデカン、ヘキサデカン、オクタデカンなどの脂肪族系
炭化水素、シクロペンタン、メチルシクロペンタン、シ
クロヘキサン、シクロオクタンなどの脂環族系炭化水素
、ガソリン、灯油、軽油などの石油留分などが挙げられ
る。これらの中では、脂肪族系炭化水素が好ましい。さ
らには、液化プロピレン、液化ブテン−１等の液化オレ
フィンそれ自体を溶媒として用いることも可能である。The polymerization method used in the present invention can be either liquid phase polymerization or gas phase polymerization. The polymerization solvent for liquid phase polymerization is a hydrocarbon compound that can dissolve the same components (^), (l), such as benzene, toluene, 0-xylene,
Aromatic hydrocarbons such as l-xylene, p-xylene, ethylbenzene, butylbenzene, mesitylene, and naphthalene are used, and toluene and xylene are preferred. Furthermore, (^), even in a solvent that cannot dissolve the same component (B), polymerization can be carried out by carrying out prepolymerization in an aromatic hydrocarbon. Such solvents include butane,
isobutane, pentane, hexane, octane, decane,
Examples include aliphatic hydrocarbons such as dodecane, hexadecane, and octadecane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane, and petroleum fractions such as gasoline, kerosene, and light oil. Among these, aliphatic hydrocarbons are preferred. Furthermore, it is also possible to use liquefied olefin itself, such as liquefied propylene and liquefied butene-1, as a solvent.
触媒成分は、（八）ハフニウム化合物、（Ｂ）アルミノ
キサンの同成分を予め混合したものを反応系に供給して
もよく、また反応系に（Ａ） 、 （Ｂ）同成分をそれ
ぞれ供給してもよい。いずれの場合においても、同成分
の重合系内における濃度、モル比については特に制限は
ないが、好ましくはハフニウム濃度で１０−’ 〜１０
−１０１１１０１／Ｊ２の範囲であり、Ａｌ／ハフニウ
ム原子のモル比は、 Ｌｏｌ１以上、特に１０００以上
の範囲が好んで用いられる。反応系のオレフィン圧には
特に制限はないが、好ましくは常圧〜５０ｋｇ／ｃｒｎ
’Ｇの範囲であり、重合温度にも制限はないが通常は一
５０〜２３０℃、好ましくは一３０〜１００℃の範囲で
あるゆ重合に際しての分子量調節は公知の手段、例えば
温度の選定あるいは水素の導入により行うことができる
。As the catalyst component, a mixture of the same components (8) hafnium compound and (B) aluminoxane may be supplied to the reaction system, or the same components (A) and (B) may be supplied to the reaction system, respectively. Good too. In either case, there is no particular restriction on the concentration or molar ratio of the same component in the polymerization system, but preferably the hafnium concentration is 10-' to 10
-1011101/J2, and the molar ratio of Al/hafnium atoms is preferably Lol1 or more, particularly 1000 or more. The olefin pressure in the reaction system is not particularly limited, but is preferably normal pressure to 50 kg/crn.
There is no limit to the polymerization temperature, but it is usually in the range of -50 to 230 degrees Celsius, preferably in the range of -130 to 100 degrees Celsius.Molecular weight adjustment during polymerization can be carried out by known means, such as temperature selection or This can be done by introducing hydrogen.
［発明の効果］
アルミノキサンと組み合わせる新規なハフニウム化合物
として、橋架は構造を持つビス置換シクロペンタジェニ
ルブリッジ型２座配位子を有するハフニウム化合物を用
いる本発明の触媒を使用すれば、融点の高い立体規則性
ポリマーを製造することができる。[Effects of the Invention] If the catalyst of the present invention is used as a novel hafnium compound in combination with aluminoxane, the hafnium compound having a bis-substituted cyclopentagenyl bridge-type bidentate ligand with a bridge structure has a high melting point. Stereoregular polymers can be produced.
［実施例コ 次に、本発明を実施例によって具体的に説明する。[Example code] Next, the present invention will be specifically explained using examples.
実施例１
「ジメチルシリルビス（２，４−ジメチルシクロペンタ
ジェニル）ハフニウムジクロリド」反応はすべて不活性
ガス雰囲気下で行った。Example 1 "Dimethylsilylbis(2,4-dimethylcyclopentadienyl)hafnium dichloride" All reactions were carried out under an inert gas atmosphere.
また、反応溶媒はあらかじめ乾燥したものを使用した。Moreover, the reaction solvent used was one that had been dried in advance.
２００ｅ＋１ガラス製反応容器中で、ジメチルビス（２
，４−ジメチルシクロペンタジェニル）シラン３．７９
ｇ （１５，５ミリモル）をテトラヒドロフラン５０ｒ
ｎｆＬに溶かした後、ｎ−ブチルリチウムの １．４９
Ｍヘキサン溶液２５ｍｊ２を水冷下ゆっくりと滴下した
。室温で４時間攪拌した後、黄色懸濁液（１，ｉ２［Ｍ
ｅ２Ｓｉ （ｙａ２−ｃｓｌ（２） ２３ ）を得た。In a 200e+1 glass reaction vessel, dimethylbis(2
,4-dimethylcyclopentadienyl)silane 3.79
g (15.5 mmol) in 50 r of tetrahydrofuran
1.49 of n-butyllithium after dissolving in nfL
25 mj2 of M hexane solution was slowly added dropwise under water cooling. After stirring at room temperature for 4 hours, a yellow suspension (1,i2[M
e2Si (ya2-csl(2) 23 ) was obtained.
５００ｆｆｉβのガラス製反応容器中で、四塩化ハフニ
ウム４．９６ｇ（１５，５ミリモル） を−７８℃にン
令却し、テトラヒドロフラン２００ｍｊ２を加えた。次
に、先の黄色懸濁液を、−６５℃でゆっくりと滴下した
。室温までゆっくり戻した後、室温で２４時間攪拌した
。In a 500 ffiβ glass reaction vessel, 4.96 g (15.5 mmol) of hafnium tetrachloride was cooled to -78°C, and 200 mj2 of tetrahydrofuran was added. Next, the above yellow suspension was slowly added dropwise at -65°C. After slowly returning to room temperature, the mixture was stirred at room temperature for 24 hours.
白色の沈澱をわずかに含む黄色溶液から溶媒を留去し、
塩化メチレン３００ｍＩｌを加え、生成した白色固体を
濾過１ノ取り除いた。得られた黄色濾液を濃縮し、ペン
タンを加えて、生成した固体を濾過し黄白色固体を得た
。トルエン−ヘキサン混合溶媒で再結晶を行い、白色結
晶０．９６ｇを得た。The solvent was distilled off from the yellow solution containing a small amount of white precipitate.
300 ml of methylene chloride was added, and the white solid produced was removed by filtration. The obtained yellow filtrate was concentrated, pentane was added, and the resulting solid was filtered to obtain a yellow-white solid. Recrystallization was performed using a toluene-hexane mixed solvent to obtain 0.96 g of white crystals.
実施例２
［重合コ
充分に窒素置換した内容積１．５ＬのＳＵＳ製オートク
レーブに精製トルエン５００ｍｕ、東洋ストウファー・
ケミガル味製メチルアルミノキサン（分子３１９３０）
３．３ミリモル及びジメチルシリルビス（２，４−ジ
メチルシクロペンタジェニル）ハフニウムジクロリド
０．００５ミリモルを順次添加し、３０℃に昇温した０
次いで、これにプロピレンを全圧が３ｋｇ／ｃｒｒ？Ｇ
を維持するように連続的に導入し、２時間重合を行った
。反応後、メタノールにより触媒成分を分解し、得られ
たポリプロピレンを乾燥した。この結果アイソタクチッ
クポリプロピレン１．９ｇが得られた。触媒活性はｌ−
１ｋｇ／ｇＨｆ−ｈｒであつた。また、ポリマーの分子
量は１４７．５００であり、融点は １６０．９℃であ
った。Example 2 [Polymerization] Purified toluene 500mu, Toyo Stouffer
Chemigal Aji methylaluminoxane (molecule 31930)
3.3 mmol and dimethylsilylbis(2,4-dimethylcyclopentagenyl) hafnium dichloride
0.005 mmol was added sequentially and the temperature was raised to 30°C.
Next, add propylene to this at a total pressure of 3 kg/crr? G
was continuously introduced so as to maintain the temperature, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, 1.9 g of isotactic polypropylene was obtained. Catalytic activity is l-
It was 1 kg/gHf-hr. Further, the molecular weight of the polymer was 147.500, and the melting point was 160.9°C.
実施例３
「ジメチルシリルビス（２，３，５−トリメチルシクロ
ペンタジェニル）ハフニウムジクロリド」反応はすべて
不活性ガス霊囲気下で行った。Example 3 "Dimethylsilylbis(2,3,5-trimethylcyclopentadienyl)hafnium dichloride" All reactions were carried out under an inert gas atmosphere.
また、反応溶媒はあらかじめ乾燥したものを使用した。Moreover, the reaction solvent used was one that had been dried in advance.
２００ｍｍガラス製反応容器中で、ジメチルビス（２，
３，５−トリメチルシクロペンタジェニル）シラン２．
６４ｇ （９，７ミリモル）をテトラヒドロフラン５０
ｉＪ２に溶かした後、ｎ−ブチルリチウムの１ 、４９
１．！ヘキサン溶液１６Ｉｌ１１１を氷冷下ゆっくりと
滴下した。室温で１２時間攪拌した後、白色懸濁液（Ｌ
ｉ２［ＭｅｚＳｉ （Ｍａ３−ＣａＨ） ２］ ）を得
た。In a 200 mm glass reaction vessel, dimethylbis(2,
3,5-trimethylcyclopentadienyl)silane2.
64 g (9.7 mmol) in tetrahydrofuran 50
After dissolving in iJ2, 1,49 of n-butyllithium
1. ! A hexane solution of 16Il111 was slowly added dropwise under ice cooling. After stirring at room temperature for 12 hours, a white suspension (L
i2[MezSi (Ma3-CaH) 2]) was obtained.
５００ｍｊ２のガラス製反応容器中で、四塩化ハフニウ
ム３．１ｇ（９，７ミリモル）を−７８℃に冷却し、テ
トラヒドロフラン２００ｍ１を加えた。次に、先の白色
懸濁液を、−７８℃で滴下した。室温までゆっくり戻し
た後、Ｎ温で４８時間攪拌した。淡黄色溶液から溶媒を
留去し、塩化メチレン３００１１ｊ２を加え、生成した
白色固体を濾過し取り除いた。得られた淡黄色濾液を濃
縮し、ペンタンを加えて、生成した固体を濾過し白色固
体を得た。熱ヘキサンで抽出を行い、濃縮乾固して白色
固体を得、さらにヘキサンで再結晶を行い、白色結晶０
．１６ｇを得た。In a 500 mj2 glass reaction vessel, 3.1 g (9.7 mmol) of hafnium tetrachloride was cooled to -78 DEG C. and 200 ml of tetrahydrofuran were added. Next, the above white suspension was added dropwise at -78°C. After slowly returning to room temperature, the mixture was stirred at N temperature for 48 hours. The solvent was distilled off from the pale yellow solution, methylene chloride 30011j2 was added, and the white solid produced was filtered off. The resulting pale yellow filtrate was concentrated, pentane was added, and the resulting solid was filtered to obtain a white solid. Extract with hot hexane, concentrate to dryness to obtain a white solid, and recrystallize with hexane to obtain 0 white crystals.
．． 16g was obtained.
実施例４
［重合］
充分に窒素置換した内容積１．５ＬのＳＵＳ製オートク
レーブに精製トルエン５００ｍｕ 、東洋ストウファー
・ケミカル■製メチルアルミノキサン（分子量９３０）
３．３ミリモル及びジメチルシリルビス（２，３，５
−）−ジメチルシクロペンタジェニル）ノ１フニウムジ
クロリド Ｑ、Ｏ［１５ミリモルを順次添加し、３０℃
に昇温した０次いで、これにプロピレンを全圧が３ｋｇ
／ｃｒｎ’Ｇを維持するように連続的に導入し、２時間
重合を行った。反応後、メタノールにより触媒成分を分
解し、得られたポリプロピレンを乾燥した。この結果ア
イソタクチックポリプロピレン３．Ｏｇが得られた。触
媒活性は１．７ｋｇ／３Ｈｆｌ＋ｒであった。また、ポ
リマーの分子量は２６０，０００であり、融点は １８
２．８℃であった。Example 4 [Polymerization] In a SUS autoclave with an internal volume of 1.5 L that was sufficiently purged with nitrogen, 500 mu of purified toluene was added, and methylaluminoxane (molecular weight 930) manufactured by Toyo Stouffer Chemical ■ was added.
3.3 mmol and dimethylsilylbis(2,3,5
-)-Dimethylcyclopentadienyl)no1phnium dichloride Q, O [15 mmol were added sequentially, and the mixture was heated at 30°C.
The temperature was raised to 0. Then, propylene was added to it at a total pressure of 3 kg.
/crn'G was continuously introduced and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, isotactic polypropylene3. Og was obtained. Catalytic activity was 1.7 kg/3Hfl+r. Also, the molecular weight of the polymer is 260,000 and the melting point is 18
The temperature was 2.8°C.
比較例１
充分に窒素置換した内容積１．ＳＬのＳＵＳ製オートク
レーブに精製トルエン５００＋ｎＱ 、東洋ストウファ
ー・ケミカル■製メチルアルミノキサン（分子量９３０
） ３．３ミリモル及びエチレンビス（インデニル）ハ
フニウムジクロリド ０．００５ミリモルを順次添加し
、３０℃に昇温しな。次いで、これにプロピレンを全圧
が３ｋｇ／ｃｒｎ’Ｇを維持するように連続的に導入し
、２時間重合を行った。反応後、メタノールにより触媒
成分を分解し、得られたポリプロピレンを乾燥した。こ
の結果アイソタクチックポリプロピレン ２１１（が得
られた。触媒活性は１２ｋｇ／ｇＨｆ−ｈｒであった。Comparative Example 1 Internal volume sufficiently replaced with nitrogen 1. Purified toluene 500+nQ in an SL SUS autoclave, methylaluminoxane (molecular weight 930) manufactured by Toyo Stouffer Chemical ■
) 3.3 mmol and 0.005 mmol of ethylenebis(indenyl)hafnium dichloride were added in sequence, and the temperature was raised to 30°C. Next, propylene was continuously introduced into this so that the total pressure was maintained at 3 kg/crn'G, and polymerization was carried out for 2 hours. After the reaction, the catalyst component was decomposed with methanol, and the obtained polypropylene was dried. As a result, isotactic polypropylene 211 was obtained. The catalyst activity was 12 kg/gHf-hr.
また、ポリマーの分子量は２５６．０００であり、融点
は １３７．５℃であった。Further, the molecular weight of the polymer was 256,000, and the melting point was 137.5°C.
ｉｔ図は、本発明の触媒を使用するポリオレフィンの製
造工程図（フローシート）である。
以 上The IT diagram is a process diagram (flow sheet) for producing polyolefin using the catalyst of the present invention. that's all
Claims (1)
物▲数式、化学式、表等があります▼［ I ］ （但し、Ｙはケイ素、又はゲルマニウムを示す。 Ｒ＾１＿ｎ−Ｃ＿５Ｈ＿４＿−＿ｎ及びＲ＾１＿ｑ−Ｃ
＿５Ｈ＿４＿−＿ｑは置換シクロペンタジエニル基を示
し、ｎ及びｑは１〜３の整数である、各Ｒ＾１は互いに
同一でも異なっていてもよく、水素、シリル基または炭
化水素基を示すが、Ｒ＾１のシクロペンタジエニル環上
の位置及び種類は、Ｈｆを含む対称面が存在しない配置
をとるものとする、また、少なくとも片方のシクロペン
タジエニル環には、Ｙに結合している炭素の隣の少なく
とも片方の炭素上にはＲ＾１が存在するものとする。 各Ｒ＾２は互いに同一でも異なっていてもよく、水素ま
たは炭化水素基を示す。また、Ｘは同一でも異なってい
てもよく、水素、ハロゲンまたは炭化水素基を示す。）
及び （Ｂ）一般式［II］または一般式［III］ ▲数式、化学式、表等があります▼［II］ ▲数式、化学式、表等があります▼［III］ （但し、ｍは４〜６０の数で、Ｒ＾３は炭化水素基を示
す）で表されるアルミノキサンを有効成分とする高立体
規則性ポリオレフィン製造用触媒。(1) (A) Hafnium compound represented by the general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (However, Y represents silicon or germanium. R^1_n-C_5H_4_-_n and R^1_q-C
_5H_4_-_q represents a substituted cyclopentadienyl group, n and q are integers of 1 to 3, each R^1 may be the same or different from each other, and represents hydrogen, a silyl group, or a hydrocarbon group; The position and type of R^1 on the cyclopentadienyl ring shall be such that there is no plane of symmetry containing Hf, and at least one of the cyclopentadienyl rings is bonded to Y. It is assumed that R^1 exists on at least one of the carbons next to the carbon. Each R^2 may be the same or different and represents hydrogen or a hydrocarbon group. Further, X may be the same or different, and represents hydrogen, halogen, or a hydrocarbon group. )
and (B) General formula [II] or general formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (However, m is 4 to 60 A catalyst for producing highly stereoregular polyolefins containing aluminoxane represented by the following number (R^3 represents a hydrocarbon group) as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1147660A JP2668733B2 (en) | 1989-06-09 | 1989-06-09 | Catalyst for polyolefin production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1147660A JP2668733B2 (en) | 1989-06-09 | 1989-06-09 | Catalyst for polyolefin production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0312407A true JPH0312407A (en) | 1991-01-21 |
| JP2668733B2 JP2668733B2 (en) | 1997-10-27 |
Family
ID=15435388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1147660A Expired - Fee Related JP2668733B2 (en) | 1989-06-09 | 1989-06-09 | Catalyst for polyolefin production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668733B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748824A1 (en) * | 1995-06-02 | 1996-12-18 | Chisso Corporation | High stereoregular polypropylenes |
| US6153710A (en) * | 1997-02-18 | 2000-11-28 | Chisso Corporation | Preactivated catalyst for olefin (CO)polymer, catalyst for olefin (CO)polymerization, olefin (CO)polymer composition, and process for producing the same |
| US6156845A (en) * | 1995-10-18 | 2000-12-05 | Chisso Corporation | Polyolefin composition and method of making |
| US6156856A (en) * | 1997-01-10 | 2000-12-05 | Chisso Corporation | Propylene-ethylene copolymers processes for the production thereof and molded articles made therefrom |
| US6231804B1 (en) | 1997-04-02 | 2001-05-15 | Chisso Corporation | Modified olefin (co)polymer composition, process for preparing the same, and modified olefin (co)polymer composition molding |
| US6235845B1 (en) | 1997-08-07 | 2001-05-22 | Chisso Corporation | Olefin (co)polymer composition |
| US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
| US6441111B1 (en) | 1997-08-15 | 2002-08-27 | Chisso Corporation | Polydisperse propylene polymer and process for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301704A (en) * | 1987-11-09 | 1989-12-05 | Chisso Corp | Catalyst for production of stereoregular polyolefin |
| JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
-
1989
- 1989-06-09 JP JP1147660A patent/JP2668733B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01301704A (en) * | 1987-11-09 | 1989-12-05 | Chisso Corp | Catalyst for production of stereoregular polyolefin |
| JPH0241303A (en) * | 1988-07-15 | 1990-02-09 | Fina Technol Inc | Method and catalyst for manufacture of syndiotactic polyolefin |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0748824A1 (en) * | 1995-06-02 | 1996-12-18 | Chisso Corporation | High stereoregular polypropylenes |
| US6096843A (en) * | 1995-06-02 | 2000-08-01 | Chisso Corporation | Process for making high stereoregular polypropylenes |
| US6156845A (en) * | 1995-10-18 | 2000-12-05 | Chisso Corporation | Polyolefin composition and method of making |
| US6313225B2 (en) | 1995-10-18 | 2001-11-06 | Chisso Corporation | Catalyst for olefin (co-)polymerization and method for producing the same |
| US6156856A (en) * | 1997-01-10 | 2000-12-05 | Chisso Corporation | Propylene-ethylene copolymers processes for the production thereof and molded articles made therefrom |
| US6153710A (en) * | 1997-02-18 | 2000-11-28 | Chisso Corporation | Preactivated catalyst for olefin (CO)polymer, catalyst for olefin (CO)polymerization, olefin (CO)polymer composition, and process for producing the same |
| US6231804B1 (en) | 1997-04-02 | 2001-05-15 | Chisso Corporation | Modified olefin (co)polymer composition, process for preparing the same, and modified olefin (co)polymer composition molding |
| US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
| US6235845B1 (en) | 1997-08-07 | 2001-05-22 | Chisso Corporation | Olefin (co)polymer composition |
| US6441111B1 (en) | 1997-08-15 | 2002-08-27 | Chisso Corporation | Polydisperse propylene polymer and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2668733B2 (en) | 1997-10-27 |
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