TW528758B - Metallocene compounds having bis(naphthylcyclo pentadienyl) ligand and process for producing the same - Google Patents

Abstract

A racemic metallocene compound having a bis(4-naphthylcyclopentadienyl) ligand consisting of a compound of formula (1) and its enantiometric isomer, in which M represents titanium, zirconium or hafnium, Y is carbon, silicon, germanium or tin, X1 and X2 independently represent a halogen atom or a hydrocarbon group of 1-20 carbons, R1, R2, R3, R4, R5, R6, R7, R8 and R9 independently represent hydrogen, a halogen atom an alkyl group of 1-20 carbons, an aralkyl group of 7-20 carbons, an aryl group of 6-20 carbons, a substituted silyl group having a hydrocarbon group of 1-20 carbons, an alkoxy group of 1-20 carbons, an aralkyloxy group of 7-20 carbons or an aryloxy group of 6-20 carbons, each of the above groups may be further substituted with a halogen atom.

Description

528758 A7 ____B7_ V. Description of the invention (1) The present invention relates to a metal duplex compound which is very suitable as a catalyst for the polymerization of olefins, and more specifically to a compound having bis (4-naphthylcyclopentadiene). Group) a racemic metal duplex compound of a ligand and a method for producing the same. It is known that a metal duplex compound can be used as a catalyst component for the polymerization of olefins. It is possible to manufacture polyolefins that were not obtained during the previous polymerization of the Ziegler-Natta catalyst, and it is also possible to choose a metal duplex The ligands of the Nine compounds are used to polymerize olefins, especially polymerized propylene, and can produce heteropolypropylene, stereotype polypropylene, and syndiotactic polypropylene (for example, see Makromol. Chem., Rapid. Commun. 1 983, 4, 417-421; Angew. Chem., Int. Engl. 1 985, 24, 507-508; J. Am. Chem. Soc. 1 988, 1 1 0, 6255-6256). Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Metallic double-coated catalysts that can be polymerized with stereotypes have C 2 symmetry. For example, cross-linked bis-indenyl compounds are well-known, and there are also ethyl bis (indenyl) compounds or derivatives thereof, rac-ethylene dichloride bis (indenyl) chromium, and rac-ethylene dichloride. Bis (tetrahydroindenyl) chromium and the like are disclosed in Japanese Patent Application Laid-Open No. Sho 6 1-1 3 0 3 1 4 and Japanese Patent Application Laid-Open No. Sho 6-295607. In addition, Japanese Patent Laid-Open No. 2-131488 also discloses a silicon-crosslinked bisindenyl compound. In addition, in order to improve the stereoregularity, molecular weight, etc. of the obtained polymer, crosslinked indenyl compounds having various substitutions on the indenyl ring have also been developed. Such compounds include, for example, Japanese Patent Application Laid-Open No. 4 2 6 8 3 0 7 Disclosed in Japanese Patent Publication No. 4-268308, Japanese Patent Publication No. 4-300887, and Japanese Patent Publication No. 5-3 0 6 3 0 4. As mentioned above, 'Choose the type of substituent of cross-linked indenyl compound, the position can make it highly active. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 528758 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation 5. Description of the invention (2), using it can obtain a high molecular weight olefin polymer. However, the structure of the compound becomes complicated, and the synthetic steps are many and complicated. As a result, the cost of producing a crosslinked indenyl compound also increases. On the other hand, a crosslinked cyclopentadienyl system having a relatively simple structure, in which a substituent such as a methyl group is arranged on the cyclopentadienyl ring, has C 2 symmetry, and a styling polypropylene can be produced. Japanese Unexamined Patent Publication No. 1-30 0 1 7 04, Japanese Unexamined Patent Publication No. 1-319489, Japanese Unexamined Patent Publication No. 2-7.6 887, Japanese Unexamined Patent Publication No. 3 — 1 2 4 0 6 and Japanese Unexamined Patent Publication No. 4-2 1 1 6 Publication No. 9 discloses, for example, racemic dichlorodimethylsilylbis (2,3,5-trimethylcyclopentadiene) chromium, or racemic dimethylsilyldichloride. (3-Third-butyl-5-methylcyclopentadiene) chromium, etc., not only the mesomers as described above, but also mesomers or mixtures of mesomers and mesomers are described. Also effective as a catalyst ingredient. The present invention aims to provide a novel metal duplex compound, which is particularly useful as a polymerization catalyst for polyolefins having a high molecular weight, and has a high polymerization activity, and a method for producing the metal duplex compound. According to the present invention, a racemic metal duplex compound having a bis (4-naphthylcyclopentadienyl) ligand formed from a compound represented by the following formula (1) and a specular isomer thereof can be provided, (please (Please read the notes on the back first and write this page)-The size of the binding and binding paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-5-528758 A7 B7 Five 'invention description (3) R7

(Please read the precautions on the back before filling in this page) • Equipment · (where) V [represents titanium, pin or give 'γ represents carbon, silicon, germanium or tin, χ1 and X2 are independently halogen atoms or Ci -C2. Hydrocarbyl 'only 1,112, 1 ^ 3, 114, 115, 116, feet 7, 118 and 119 respectively independently represent hydrogen, halogen atom, Ci-Cz. Alkyl, C7 ~ C20 aralkyl, c6 ~ C2Q Aryl, with Ci-Cs. Substituted silicon radicals for hydrocarbon radicals, Cl ~ C2Q radicals, C7 ~ C2Q aromatic radicals or C6 ~ C 2. Aryloxy radicals, each radical can also be replaced by halogen atoms) . In the racemic-metallic dual-metal compound of formula (1), M is selected from titanium, a pin and a group of transition metals, preferably chromium or a group. The halogen atom system of X 1 and X 2 may be, for example, fluorine, chlorine, bromine and iodine, Cl to C2. The hydrocarbon-based system contains, for example, Cl to C2. Fluorenyl, C7 ~ C20 arylfluorenyl, C6 ~ C2Q aryl, substituted alkane with Cl ~ C2Q hydrocarbon group. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ g Order the Central Standards Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative 528758 A7 B7 V. Invention Description (4) Base, Ci-Cs. Alkoxy ·, C7 ~ C2. Aralkyloxy and c6 ~ C2Q aryloxy. The aforementioned group may be substituted with a halogen atom. The χ1 & χ2 system is preferably a halogen atom, and more preferably chlorine. Samarium is selected from the group consisting of carbon, silicon, germanium and tin, preferably silicon or germanium. Each is independently selected from the group consisting of hydrogen, a halogen atom, and Ci-C2. Alkyl, C7 ~ C2Q aromatic radical, Ce ~ C2Q aromatic radical, substituted with Ci ~ C2Q hydrocarbon radical, sand radical, Cl ~ C2Q radical, C7 ~ C2. A group of aryloxy groups or C 6 ~ C2 aryloxy groups. These groups can also be replaced by halogen atoms. Cl ~ C 20 groups defined as substituents can be methyl, ethyl, n Propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, isopentyl, second pentyl, third pentyl, hexyl, heptyl, octyl , Nonyl, decyl, etc., and halogenated alkyl groups in which these alkyl groups are replaced with halogen atoms such as fluorine, chlorine, bromine, and iodine. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back to write this page) C7 ~ C 2. Aryl groups include, for example, benzyl, 2-methylbenzyl, 3-methylbenzyl, 2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5 —Dimethylbenzyl, 2,6-dimethylbenzyl, 2,3,4-trimethylbenzyl, 2,3,5-trimethylbenzyl, 2,3,6 —Trimethylbenzyl, ethylbenzyl, propylbenzyl, butylbenzyl, naphthylbenzyl, anthracenylmethyl, and halogenated aralkyl groups substituted with a halogen atom . C6 ~ C2Q's aryl system contains, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4. This paper is applicable to Chinese National Standards (CNS) A4 specifications (210X297 public director) 528758 A7 B7 V. Description of the invention (5) Tolyl, 2,5-dimethylbenzyl, 2,6-xylyl, 3,4-xylyl, 3,5-di Tolyl, 2,4,6-trimethylphenyl, naphthyl, anthracenyl, etc., and halogenated aryl groups substituted with these groups by halogen atoms. Substituted silane groups include compounds having C i ~ C 2 (D alkyl , Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, etc. CC 1 () alkane Aryl groups such as phenyl, phenyl, and the like, and silyl groups having a halogenated hydrocarbon group substituted with a halogen atom. Such substituted silyl groups may be, for example, trimethylsilyl, triethylsilyl, and tri-n-propylsilyl. , Triisopropylsilyl, tri-n-butylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, triphenylsilyl and the like.

Ci-Cso alkoxy contains, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, third butoxy, n-pentoxy, n-hexyloxy Radicals, n-octyloxy, n-decyloxy and halogenated alkoxy radicals in which these radicals are substituted by halogen atoms. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) C7 ~ C2Q aralkyloxy includes, for example, benzoyloxy, 2-methylbenzyloxy, 3-methyl Benzyloxy, 2,3-dimethylbenzyloxy, 2,4-dimethylbenzyloxy, 2,5-dimethylbenzyloxy, 2,6-dimethylbenzyl Oxy, 2,3,4-trimethylbenzyloxy, 2,3,5-trimethylbenzyloxy, 2,3,6-trimethylbenzyloxy, ethylbenzyloxy Groups, propylbenzyloxy, butylbenzyloxy, naphthylmethoxy, anthrylmethoxy, and the like, and halogenated aralkoxy groups in which these groups are further substituted with a halogen atom. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ~ Τβί 528758 A7 B7 V. Description of the invention (6) C 6 ~ C 2 Q aryloxy_ series includes phenoxy, 2-methylbenzene Oxygen, (Please read the precautions on the back ^^ Write this page first) 3-methylphenoxy, 4-monomethylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethyl Methylphenoxy, 2,5-dimethylphenoxy, 2'6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2 , 4,6-trimethylphenoxy, naphthyloxy, anthracenyloxy, and the like, and halogenated aryloxy groups in which these groups are substituted with halogen atoms. R1 is a halogen atom, Ci-Ce linear or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl A group such as phenyl or the like is preferred. R2 may be hydrogen, except for Ci-Ce linear or branched alkyl groups as described above, especially Cx-Cd alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second butyl, and third butyl are preferred. In addition, all of R3 to R9 are hydrogen, or any of them is a halogen atom, preferably fluorine, methoxy, Ci ~ C6 straight or branched alkyl, such as methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, second butyl, third butyl and the like. In the formula (1) printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, M is chromium, and X1 and X2 are chlorine racemic metal duplexes. Specific examples of the compounds are shown below. Υ is silicon, Ri is methyl, R3, R4, r5, r6, R7, R8 and R9 are hydrogen. Examples may be dimethylsilyl dichloride di (4-naphthylcyclopentadienyl) chromium , Dimethylsilyl dichloride di (2-methyl-1,4-naphthylcyclopentadienyl) chromium, Dimethylsilyl dichloride di (2-ethyl-4, naphthylnaphthalene ring) Pentadienyl) zirconium, dimethylsilyl dichloride (2-n-propyl-4, naphthylcyclopentadienyl) chromium, dichlorinated. This paper applies Chinese National Standard (CNS) A4. Zug (210X297 mm) -9-528758 A 7 B7 V. Description of the invention (7) Dimethylsilylbis (2'-isopropyl-4 4-naphthylcyclopentadienyl) chromium, dichloride Dimethylsilylbis (2-n-butyl-4naphthylcyclopentadienyl) chromium, dimethylsilylbis (2-isobutyl-4naphthylcyclopentadienyl) dichloride Dienyl) zirconium, dimethylsilyl dichloride (2-2nd butyl-4-octylcyclopentyl-phenyl) pin, monomethylsilyl chloride (2 -Tert-butyl-4 naphthylcyclopentadienyl) pin and so on. Y is silicon, Ri is ethyl, R3, R4., R5, r6, R7, R8, and R9 are hydrogen. Examples include diethylsilyl dichloride (4-naphthylcyclopentadienyl) dichloride. Chromium, diethylsilyl dichloride di (2-methyl-1,4-naphthylcyclopentadienyl) chromium, diethylsilyl dichloride di (2-ethyl-4, naphthylnaphthyl) Cyclopentadienyl) zirconium, diethylsilyl dichloride di (2-n-propyl-4-naphthylcyclopentadienyl) zirconium, diethylsilyl dichloride di (2- Isopropyl-4-naphthylcyclopentadienyl) chromium, diethylsilyl dichloride di (2-n-butyl-4 naphthylcyclopentadienyl) zirconium, diethyl dichloride Silylbis (2-isobutyl-4naphthylcyclopentadienyl) chromium, diethylsilyl dichloride (2nd-2butylbutyl-4naphthylcyclopentadiene) Group) zirconium, diethylsilyl dichloride, bis (2-third-butyl-4, naphthylcyclopentadienyl) zirconium and the like. Y is silicon, R1 is n-propyl, R3, R4, R5, R6, R7, R8 and R9 are hydrogen. Examples may be di-n-propylsilylidene dichloride (4-naphthylcyclopentadienyl dichloride). ) 鍩, di-n-propylsilyl dichloride di (2-methyl-1, 4-naphthylcyclopentadienyl) pin, di-n-propyl disilyl dichloride (2-ethyl-4) Mononaphthylcyclopentadienyl) pin, di-n-propyl silylidene dichloride (2-n-propyl-4 mononaphthylcyclopentadienyl) The paper size applies to Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) -1 〇- (Please read the notes on the back to write this page) Γ Printed by the Employees 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 _B7__ 5 Description of the invention (8) Chromium, di-n-propyl di'alkylene dichloride di (2-isopropyl-4-naphthylcyclopentadienyl) zirconium, di-n-propyl dialkylene dichloride (2-n-butyl-4naphthylcyclopentadienyl) zirconium, di-n-propylsilyl dichloride di (2-isobutyl-4naphthylcyclopentadienyl) zirconium, two Di-n-propyl chloride Silylbis (2-second-butyl-4naphthylcyclopentadienyl) chromium, di-n-propyldialkylene dichloride (2-third-butyl-4naphthylcyclopentadienyl) Alkenyl) chromium and the like. Y is silicon, Ri is phenyl, R3, R4, r5, r6, R7, R8, and R9 are hydrogen. Examples may be diphenylsilyl dichloride (4-naphthylcyclopentadienyl) dichloride. , Diphenylsilyl dichloride (2-methyl-4 mononaphthylcyclopentadienyl) fluorene, diphenylsilyl dichloride di (2-ethyl-4 4-naphthyl ring) Pentadienyl) chromium, diphenyldiphenylsilyl dichloride (2-n-propyl-4-naphthylcyclopentadienyl) zirconium, diphenylsilyl dichloride di (2-isopropyl Propyl-4naphthylcyclopentadienyl) zirconium, diphenyldiphenylsilyl dichloride (2-n-butyl-4naphthylcyclopentadienyl) zirconium, diphenyl dichloride Silylbis (2-isobutyl-4naphthylcyclopentadienyl) zirconium, diphenyldiphenylsilyl dichloride (2-2ndbutyl-4naphthylcyclopentadienyl) ) Zirconium, diphenylsilyl dichloride, bis (2-third-butyl-4-naphthylcyclopentadienyl) chromium, etc. Y is germanium, R1 is methyl, R3, R4, r5, r6, R7, R8 and R9 are hydrogen. Examples may be dimethyl germanium dichloride dichloride (4-naphthylcyclopentadienyl) Chromium, dimethyl germanium dichloride di (2-methyl-1, 4-naphthylcyclopentadienyl) zirconium, dimethyl germanium dichloride di (2-ethyl-1, 4-one) Naphthylcyclopentadienyl) chromium, dimethylgermanium dichloride This paper is in accordance with Chinese National Standard (CNS) 8 4 Zhuge (210X297 mm) _-(Please read the precautions on the back first ^% write (This page)

1A 528758 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7_V. Description of the Invention (9) Alkylbis (2-n-propyl-1_naphthylcyclopentadienyl) zirconium, dichloride Methylgermanium bis (2-isopropyl-4naphthylcyclopentadienyl) cone, dimethylgermanyl dichloride di (2-n-butyl-4naphthylcyclopentadienyl) Dienyl) chromium, dimethyl germanium dichloride bis (2-isobutyl-4naphthylcyclopentadienyl) chromium, dimethyl germanium dichloride di (2 — Second butyl-1, 4-naphthylcyclopentadienyl) chromium 'dichloride dimethyl germanium alkylene bis (2-third butyl-4, naphthyl · cyclopentadienyl) pin, etc. Y is germanium, R1 is ethyl, R3, r4, r5, r6, R7, R8 and R9 are hydrogen. Examples may be diethylgermanyl dichloride dichloride (4-naphthylcyclopentadienyl) Zirconium, diethylgermanium dichloride di (2-methyl-1, 4-naphthylcyclopentadienyl) hafnium, diethylgermanium dichloride, di (2-ethyl-1, 4-a Naphthylcyclopentadienyl) fluorene, diethylgermanyl dichloride bis (2-n-propyl-4 4-naphthylcyclopentadienyl) chromium, diethylgermanyl dichloride Bis (2-isopropyl-4naphthylcyclopentadienyl) chromium, diethylgermanyl dichloride bis (2-n-naphthylcyclopentadienyl) zirconium, Diethylgermanium dichloride di (2-isobutyl-1,4-naphthylcyclopentadienyl) chromium diethylgermanium dichloride Mononaphthylcyclopentadienyl) zirconium, diethylgermanyl dichloride di (2-third butyl-4 naphthylcyclopentadienyl) chromium and the like. Y is germanium, R1 is n-propyl, r3, r4, r5, r6, r7, R8 and R9 are hydrogen. Examples may be di-n-propylgermanylene dichloride di (4-naphthylcyclopentadiene) ) Zirconium, di-n-propylgermanium dichloride di (2-methyl-1, 4-naphthylcyclopentadienyl) zirconium, di-n-propyl germanium dichloride (please read the note on the back first) Matters written on this page) Binding. Binding / (V double radical, ethyl chloride, chlorodichromylene, dipentylcyclonaphthalene) This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) _ 〇-Central Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Standards Bureau 528758 A7 B7_ V. Description of the invention (10) N-propyl germanium bis (2-n-propyl-1, 4-naphthylcyclopentadienyl) chromium, di-n-propyl dichloride Germanium alkylene bis (2-isopropyl-4naphthylcyclopentadienyl) zirconium, di-n-propyl germanium alkylene bis (2-n-butyl-4 naphthylcyclopentadienyl) Dienyl) zirconium, di-n-propylgermanylidenedichloride bis (2-isobutyl-4naphthylcyclopentadienyl) chromium, di-n-propylgermanylalkyldichloride di ( 2 —Second-butyl-4 Naphthylcyclopentadiene Group) Chromium, di-n-propylgermanylene dichloride di (2.-third butyl-4naphthylcyclopentadienyl) zirconium, etc. γ is germanium, ri is phenyl, R3, R4 For example, r5, r6, R7, R8 and R9 are hydrogen. Diphenyl germanium dichloride, bis (4-naphthylcyclopentadienyl) chromium, diphenyl germanium dichloride Bis (2-methyl-4naphthylcyclopentadienyl) chromium, diphenylgermanylene dichloride bis (2-ethyl-4naphthylcyclopentadienyl) zirconium, dichloro Diphenyl germanium alkylene bis (2-n-propyl-4 mononaphthylcyclopentadienyl) zirconium, diphenyl germanium alkyl bis (2-isopropyl-4 4-naphthyl) Cyclopentadienyl) pin, diphenylgermanyl dichloride dichloride (2-n-butyl-4-naphthylcyclopentanyl), diphenylene dichloride 2-isobutyl-1, 4-naphthylcyclopentadienyl) zirconium, diphenylgermanylene dichloride di (2, 2nd-butyl-4, naphthylcyclopentadienyl) zirconium, di Diphenylgermanyl chloride bis (2-third-butyl-4naphthylcyclopentadienyl) zirconium, etc. Y is silicon, R1 is methyl, R5 Fluorine, R3, R4, R6, R7, R8 and R9 are examples of hydrogen. Dimethylsilyl dichloride [4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, dichloride Dimethylsilylene bis [2-methyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium This paper size is applicable to the Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) _ j 3 β (Please read the notes on the back first and write this page)

528758 A7 B7 V. Description of the invention (11), Dichlorodimethylsilylene'ylbis [2-ethyl-4 (4- (fluorofluoronaphthyl) cyclopentadienyl]] chromium, dimethyl dichloride Silylidenebis [2-n-propyl-4 (4-fluoronaphthyl) cyclopentadienyl] chrome'dichlorodimethylsilylidenebis [2-isopropyl-4 (1 —Fluoronaphthyl) cyclopentadienyl] cone, dimethylsilyl dichloride [2-n-butyl-4 (4-fluoronaphthyl) cyclopentadienyl] zirconium, dichlorinated Dimethylsilyl bis [2-isobutyl-1, 4- (4-fluoronaphthyl.) Cyclopentadienyl] chromium, dimethylsilyl dichloride, [2-second butyl-1 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, dimethylsilyl dichloride [2- third butyl-4 (4-fluoronaphthyl) cyclopentadienyl] Chrome etc. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back ^ fill in this page) Y is silicon, R1 is ethyl, R5 is fluorine, R3, R4, R6, R7, R8 and R9 are hydrogen For example, it can be diethylsilyl dichloride [4-((4 win) Zeyl) cyclopentyl- * yl] pin '-^-chloro- * ethylsynylene bis [2-methyl One 4 (4-fluoronaphthyl) cyclopentadienyl] zirconium, diethylsilyl dichloride [2-ethyl-4 (4-fluoronaphthyl) cyclopentadienyl] pin , Diethylsilyl dichloride [2-n-propyl-4 4- (chlorochlorozetyl) cyclopentyl-methyl] pin, mono-ethyl silyl bis [2 — Isopropyl-4-mono (4-fluoronaphthyl) cyclopentadienyl] pin, diethylsilyl dichloride [2-n-butyl-1 4-mono (4-kinetenyl) cyclopentyl] ^ Anthropyl] pin 'one gasified monoethyl sulfinyl bis [2-isobutyl-4 mono (4 monofluoronaphthyl) cyclopentadienyl] zirconium, diethylsilyl dichloride [ 2-Second-butyl-4 mono (.4 monofluoronaphthyl) cyclopentadienyl] fluorene, Silicon chloride, alkyl diethyl sulfoxide bis [2 - 4_ a sec-butyl (4-chloro-Cai-yl) cyclopentyl] a pin too yl temple. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -14-528758 A7 _B7__ 5. Description of the invention (12) γ is silicon, R1 is n-propyl, R5 is fluorine, R3, R4, R6, Examples of R7, R8 and R9 being hydrogen may be di-n-propylsilyl dichloride bis [4-((4-fluoronaphthyl) cyclopentadienyl] zirconium, di-n-propyl silyl dichloride) Bis [2-methyl-4 mono (4-fluoronaphthyl) cyclopentadienyl] zirconium, di-n-propylsilyl dichloride di [2-ethyl-4 mono (4-fluoronaphthyl) Cyclopentadienyl] Chromium, Di-n-propyl dithionite dichloride Bi- [2-n-propyl-4 4 (4-one Zeolyl). Cyclopentyl-pentyl] pin Propylsilyl bis [2-isopropyl-4 4- (4-fluoronaphthyl) cyclopentadienyl] cone, di-n-propyl disilyl dichloride [2-n-butyl-4 1 (4 monofluoronaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride di [2-isobutyl-1,4-mono (4-fluoronaphthyl) cyclopentadienyl] chromium, Di-n-propylsilyl dichloride —Fluoronaphthyl) cyclopentadienyl] chromium, di-n-propylsilylidene dichloride [2-third butyl-1 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium and the like. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed Y as silicon, R1 as phenyl, R5 as fluorine, R3, R4, R6, R7, R8, and R9 as hydrogen. Examples include diphenyldiphenylsilyldichloride [4-mono (4-fluoronaphthyl) cyclopentadienyl] pin, diphenyldiphenylsilylene dichloride [2-methyl-4 (4-fluoronaphthyl) cyclopentadienyl] 鍩, Diphenylsilyl dichloride [2-ethyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] chromium, diphenyl silyl dichloride [2-phenyl-1, dichloride 4 mono (4 monofluoronaphthyl) cyclopentadienyl] zirconium, diphenylsilyl dichloride di [2-isopropyl 4- (4-fluoronaphthyl) cyclopentadienyl] chromium , Diphenyldiphenylsilyl dichloride [2-n-butyl-4] (This paper size applies to the Chinese National Standard (CNS) A4 Zhuge (210 X297 mm) _ 15 _ 528758 Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives A7 B7 V. Description of the invention (13) 4 monofluoronaphthyl) cyclopentadienyl] chromium, diphenylsilyl dichloride [2-isobutyl-1, 4-one (4-fluoro) Naphthyl) cyclopentadienyl] chromium, di Diphenylsilyl bis [2-second butyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] chromium, diphenylsilyl dichloride [2-third butyl —4 — (4 Yiqi table base) cyclopentyl. Y is germanium, R1 is methyl, R5 is fluorine, R3, R4, R6, R7, R8 and R9 are hydrogen. Examples may be dimethyl germanium dichloride dichloride [4 — (4 monofluoronaphthyl ) Cyclopentadienyl] zirconium, dimethylgermanylene dichloride bis [2-methyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium, dimethyl dichloride Germanium bis [2-ethyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride dichloride [2--n-propyl-1, 4-1 (4-1 Fluoronaphthyl) cyclopentadienyl] chromium, dimethyldigermanylene dichloride bis [2-isopropyl-4 4- (4-fluoronaphthyl) cyclopentadienyl] cone, dichloride Dimethyl germanium alkylene bis [2-n-butyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, dimethyl germanium alkylene bis [2-isobutyl-1 4 mono (4 monofluoronaphthyl) cyclopentadienyl] chromium, dimethyl germanium alkyl dichloride [2-second butyl 4- (4-fluoronaphthyl) cyclopentadienyl ] Chromium, dimethyl germanium dichloride dichloride [2-third butyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium and the like. Y is germanium, R1 is ethyl, R5 is fluorine, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be diethylgermanyl dichloride dichloride [4-(4-fluoronaphthyl) ) Cyclopentadienyl] zirconium, diethylgermanium dichloride, bis [2-methyl-1, 4-one (4-one-Czechyl) cyclopentyl-1, 2-yl] pin, diethyl dichloride Germanium alkyl bis [2-ethyl-1, 4-a (4-fluoronaphthalene (please read the precautions on the back first \? ^ Write this page) >

、 1T This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ ig 528758 A7 B7_ 5. Description of the invention (14) base) cyclopentadienyl] zirconium, 'diethylgermanium dichloride Alkyl bis [2-n-propyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium, diethylgermanium dichloride dichloride [2-isopropyl-1 4 1 (4-1 Fluoronaphthyl) cyclopentadienyl] chromium, diethylgermanyl dichloride dichloride [2-n-butyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium, dichloride Diethylgermanylalkylbis [2-isobutyl-1,4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, diethylgermanylalkyl dichloride [2-second. A 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, diethylgermanyl dichloride di [2 — third butyl — 4 — (4-fluorozeolyl) cyclopentyl Chan Ki] Waited. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed Y as germanium, R1 as n-propyl, R5 as fluorine, R3., R4, r6, R7, R8, and R9 as hydrogen. Examples can be di-n-propyl dichloride. Germanium bis [4- (4-fluoronaphthyl) cyclopentadienyl] fluorene, di-n-propylgermanylene dichloride di [2-methyl-1 4- (4-fluoronaphthyl) ring Pentadienyl] chromium, di-n-propylgermanylidene dichloride bis [2-ethyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium, di-n-propyl dichloride Germanium bis [2-n-propyl-4— (4-one-Czechyl) cyclopentyl-1]] pin, di-n-propylgermanylidene bis [2-isopropyl-4— ( 4 monofluoronaphthyl) cyclopentadienyl] fluorene, di-n-propylgermanylidene dichloride bis [2-n-butyl-1, 4-a (4-aqueenyl) cyclopenta- * yl] pin ' -►Gasification-1-n-propyl germanium alkylene bis [2-isobutyl-4-1 (4-fluoronaphthyl) cyclopentadienyl] zirconium, di-n-propyl germanium alkyl dichloride [2-Second-butyl-1, 4- (4-fluoronaphthyl) cyclopentadienyl] zirconium, di-n-propylgermanyl dichloride [2 - a 4-tert-butyl (4-fluoro-naphthyl) cyclopentadienyl] zirconium. This paper size applies to Chinese National Standard (CNS) A4 (210X297mm) -17-printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 B7 V. Description of the invention (15) Y is germanium, R1 is phenyl, R5 is fluorine, and R3, R4, R6, R7, R8 and R9 are hydrogen. Examples may be diphenylgermanylene dichloride di [4-(4-fluoronaphthyl) cyclopentadienyl] zirconium, Diphenylgermanium dichloride, bis [2-methyl-1, 4- (4-fluoronaphthyl) cyclopentyl-1, 2-yl] zirconium, diphenylgermanyl dichloride, di [2-ethyl One 4 mono (4-fluoronaphthyl) cyclopentadienyl] chromium, diphenylgermanylene dichloride bis [2-n-propyl-4-(4-monofluoronaphthyl) cyclopentadienyl ] Zirconium, diphenyl germanium alkyl dichloride [2-isopropyl-4 (4-fluoronaphthyl) cyclopentadienyl] chromium, diphenyl germanium alkyl dichloride [ 2-n-butyl-1, 4-mono (4-fluoronaphthyl) cyclopentadienyl] chromium, diphenyl germanium alkylene dichloride [2-isobutyl-1, 4-mono (4-fluoronaphthyl) Cyclopentadienyl] pin, diphenylgermanium fluorenyl dichloride bis [2-first A 4-a (4-a-naphthyl) cyclopentadienyl] zirconium, a diphenyl germanium alkyl dichloride [2-the third butyl 4- 4 (fluorofluoronaphthyl) cyclopentadiene Base] pin etc. Y is silicon, R1 is methyl, R5 is methoxy, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be dimethylsilyl dichloride [4 1 (4-methoxy Naphthyl) cyclopentadienyl] chromium, dichlorodimethylsilylene di [2-methyl-1, 4- (4-methoxynaphthyl) cyclopentadienyl] chromium, dimethyl dichloride Silylidene bis [2-ethyl-4 (4-methoxynaphthyl) cyclopentadienyl] zirconium, dimethylsilyl dichloride [2-n-propyl-1. 4 one ( 4 monomethoxynaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride bis [2-isopropyl-1, 4-mono (naphthyl) cyclopentadienyl] zirconium, Dichlorinated dimethylsilyl bis [2-n-butyl-1, 4- (4-methoxyzekiyl) cyclopentyl-1 * yl] pin, monochlorinated paper standard applicable to Chinese National Standard (CNS) A4 Specifications (210X297 mm) _ 18-(Please read the precautions on the back first \ ^ Write this page) Equipment · 528758 A7 B7__ V. Description of the invention (16) Dimethylsilylbis [2 diisobutyl-1 4 Mono (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dimethyl dichloride Silylidenebis [2-second butyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2-third butyl-4 Mono (4-monomethoxynaphthyl) cyclopentadienyl] chromium and the like. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back to write this page) Y is silicon, R1 is ethyl, R5 is methoxy, R3, R4, Re, R 7, R 8 and R Examples where 9 is hydrogen can be diethylsilyl dichloride [4-mono (4-methoxynaphthyl) cyclopentadienyl] chromium, diethyl silyl dichloride [2-methyl 4- (4-monomethoxynaphthyl) cyclopentadienyl] zirconium, diethyl dichlorite dichloride bis [2-ethyl 4- (4-methoxynaphthyl) cyclopentadienyl) Alkenyl] zirconium, diethylsilyl dichloride [2-n-propyl-4— (4-monomethoxynaphthyl) cyclopentadienyl] zirconium, diethylsilyl dichloride [2-Isopropyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride [2-n-butyl-4 (4-monomethoxynaphthalene) Group) cyclopentadienyl] chromium, diethylsilyl dichloride [2-isobutyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] zirconium, diethyl dichloride Silylidenebis [2-second butyl-4 mono (4-methoxynaphthyl) cyclopentadienyl ] Zirconium, diethylsilyl dichloride [2--third butyl-1 4- (4-methoxynaphthyl) cyclopentyl-methyl], etc. Y is silicon, R1 is n-propyl, R5 is methoxy, R3, R4, R6, R7, R8 and R9 are hydrogen Monomethoxynaphthyl) cyclopentadienyl] zirconium, di-n-propylsilylidene dichloride [2-methyl-4 (4-monomethoxynaphthyl) ring This paper applies Chinese national standards ( CNS) A4 Zhuge (210X297 mm) -19- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 B7 __ V. Description of the Invention (17) Pentadienyl] Chromium, Dichloride · Di-n-propylidene Silyl bis [2-ethyl-4— (4-monomethoxynaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride [2-n-propyl-1 4— (4— Methoxynaphthyl) cyclopentadienyl] chromium, di-n-propyl silylidene dichloride [2-isopropyl-4 4- (4-methoxynaphthyl) cyclopentadienyl] chromium, di Di-n-propyl sulfinyl chloride bis [2-n-butyl-1 4- (4-methoxynaphthyl) cyclopentyl-1] fluorene, di-n-propylsilyl dichloride · [2 -Isobutyl-1,4- (4-methoxynaphthyl) cyclopentadienyl] Chromium, di-n-propylsilyldichloride dichloride [2-second butyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, di-n-propylsilyldichloride dichloride [2-Third-butyl-4- (4-methoxynaphthyl) cyclopentadienyl] etc. Y is silicon, R1 is phenyl, R5 is methoxy, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be diphenyldiphenylsilyl dichloride [4 — (4-monomethoxy Naphthyl) cyclopentadienyl] chromium, diphenyldiphenylsilylene dichloride [2-methyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] pin, diphenyl dichloride Silylidenebis [2-ethyl-4 (4-methoxynaphthyl) cyclopentadienyl] chromium, diphenyldiphenylsilyldichloride [2-n-propyl-1 4 1 (4 Monomethoxynaphthyl) cyclopentadienyl] zirconium, diphenyldiphenylsilylene dichloride [2-isopropyl-4, 4- (methoxynaphthyl) cyclopentadienyl] zirconium, di Diphenylsilyl chloride bis [2-n-butyl-1,4-monomethoxynaphthyl) cyclopentadienyl] chromium, diphenylsilyl chloride di [2-isobutyl 4- (4-monomethoxynaphthyl) cyclopentadienyl] zirconium, diphenyldiphenylsilylene dichloride [2-second butyl-1 4-mono (4-methoxynaphthyl) cyclopentadienyl] Alkenyl] Zirconium, Diphenyl Dichloride Paper Size Applicable to Chinese National Standard (CNS) A4 Zhuge (210X297) ) ~ .20- (Please read the precautions on the back to write this page) Assembling, ordering 528758 A7 _B7_ V. Description of the invention (18) Silicon silicon base double [2 — 第 _ 三 butyl—4 one (4 Monomethoxynaphthyl) cyclopentadienyl] chromium and the like. Y is germanium, R1 is methyl, R5 is methoxy, R3, R4,, R7, R8, and R9 are hydrogen. Examples may be dimethyl germanium dichloride dichloride [4 — (4-monomethoxy Naphthyl) cyclopentadienyl] zirconium dimethyl digermanylene alkyl bis [2-methyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dichloride Methyl germanium alkyl bis [2-ethyl-4 (4-methoxynaphthyl) cyclopentadienyl] chromium, dimethyl germanium alkyl dibis [2-n-propyl-4 Mono (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dimethyl germanium alkyl dichloride bis [2-isopropyl-1, 4-mono (4-methoxynaphthyl) cyclopentadienyl ] Zirconium, dimethyl germanium dichloride dichloride [2-n-butyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride dichloride [2-isobutyl-4 mono (4-methoxynaphthyl) cyclopentadienyl] zirconium, dimethyl germanium dichloride dichloride [2-second butyl-4 4- (1-methyl Oxyzekiyl) cyclopentyl-pentyl group] pin '-* monomethylgermanyl chloride bis [2-third butyl-4 4- (4-methoxynaphthyl) ring Pentadienyl] zirconium and the like. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed Y as germanium, R1 as ethyl, R5 as methoxy, R3, R4, R6, R7, R8 and R9 as hydrogen. Examples can be diethylgermanium dichloride Alkylbis [4- (4-methoxynaphthyl) cyclopentadienyl] zirconium, diethylgermanyl dichloride di [2-methyl-4 (4-monomethoxynaphthyl) ring Pentadienyl] zirconium, diethylgermanylalkyl dichloride bis [2-ethyl-4.mono (4-methoxynaphthyl) cyclopentadienyl] zirconium, diethylidene dichloride Germanium bis [2-n-propyl-4— (4-monomethoxynaphthyl) cyclopentadienyl] chromium, -21-This paper size applies to the Chinese National Standard (CNS) A4 check (210X297 mm) 528758 A7 B7 V. Description of the invention (19) Diethylgermanium dichloride dichloride [2-isopropyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium, dichloride Ethyl germanium alkyl bis [2-n-butyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] chromium 'diethyl germanium alkyl bis [2-isobutyl-1 4-((4-methoxynaphthyl) cyclopentadienyl] chromium, diethylidene dichloride Alkylbis [2-Second-butyl-1 4- (4-methoxynaphthyl) cyclopentadienyl] pin, diethylgermanyldichloride dichloride [2--thirdbutyl-1 4-a . (4-methoxynaphthyl) cyclopentadienyl] zirconium and the like. Y is germanium, R1 is n-propyl, R5 is methoxy, R3, R4, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) R6, R7, R8 and R9 Examples of hydrogen may be di-n-propylgermanylenedichloride dichloride [4-((4-methoxynaphthyl) cyclopentadienyl] chromium), di-n-propylgermanyldichloride dichloride [ 2-methyl-1, 4- (4-methoxynaphthyl) cyclopentadienyl] zirconium, di-n-propylgermanylidene dichloride bis [2-ethyl-4, mono (4-methoxynaphthyl) ) Cyclopentadienyl] Chromium, di-n-propylgermanylidene dichloride bis [2-n-propyl-4 ((4-methoxynaphthyl) cyclopentadienyl] pin, dichloride N-propyl germanium alkylene bis [2-isopropyl-4, 4- (methoxynaphthyl) cyclopentadienyl] chromium, di-n-propyl germanium alkylene dichloride [2-n-butyl A 4-a (4-monomethoxynaphthyl) cyclopentadienyl] chromium, a di-n-propylgermanylidene dichloride bis [2-isobutyl-a 4- (4-methoxynaphthyl) ring Pentadienyl] zirconium, di-n-propylgermanylidene dichloride bis [2-second butyl-4 one (4 Monomethoxynaphthyl) cyclopentadienyl] pin, di-n-propylgermanylidene dichloride [2-third butyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] Wait Y is germanium, R1 is phenyl, R5 is methoxy, R3, R4, R6 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) · 22 _ Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 528758 A7 B7__ 5. Description of the invention (20), R7, R8 and R9 are examples of hydrogen ', which may be diphenylgermanylene dichloride dichloride [4-one (4-methoxynaphthyl) ring Pentadienyl] chromium, diphenyl germanium dichloride bis [2-methyl-4 (4-monomethoxynaphthyl) cyclopentadienyl] zirconium, diphenyl germanium dichloride Alkylbis [2-ethyl-4- (4-methoxynaphthyl) cyclopentadienyl] zirconium, diphenyl germanium dichloride dichloride [2-phenyl-4 4- (1 Oxynaphthyl) cyclopentadienyl] chromium, diphenylgermanylalkyl dichloride bis [2-isopropyl-4 ((4-methoxynaphthyl) cyclopentadienyl] zirconium, dichloro Diphenyl germanium alkylene bis [2-n-butyl-1, 4- (methoxynaphthyl) cyclopentadienyl] zirconium, dibenzyl dichloride, bis [2-isobutyl 4- (1-methoxyzekiyl) cyclopentadienyl] chromium, diphenylene dichloride Germanium bis [2-second butyl-1 4 ((4-methoxynaphthyl) cyclopentadienyl]) chromium, diphenyl germanium dichloride dichloride [2-third butyl-1 Mono (4-monomethoxynaphthyl) cyclopentadienyl] chromium and the like. Y is silicon, R1 is methyl, R5 is ethyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be dimethylsilyl dichloride [4-(4 -ethylnaphthyl) ) Cyclopentadienyl] pin, dimethyl dichloride dichloride, bis [2-methyl-4 ((4-ethylethenyl) cyclopentyl-1 * yl) pin, dimethyl dichloride Silyl bis [2-ethyl-4, 4- (naphthyl) cyclopentadienyl] zirconium, dimethylsilyl dichloride [2-n-propyl-1, 4-, 4-ethyl (Cai Ji) Cyclopentyl-Cycloyl] pin, 1'Chlorinated monomethylsilylbis [2-isopropyl-4 ((4-ethylnaphthyl) cyclopentadienyl]], dichloro Dimethylsilyl bis [2-n-butyl-1—4- (4-ethylnaphthyl) cyclopentadienyl] fluorene, dimethylsilyl dichloride This paper applies Chinese national standards (CNS) Eight 4 Shilo (210X297 mm 1 ~ 〇3-(Please read the precautions on the back to write this page) Binding. Order 528758 A7 B7_ V. Description of the invention (21) bis [2-isobutyl-4 1 '( 4-ethylnaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2 —Second butyl-1 4- (4-ethylnaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2--third butyl-1 4- (4-ethylnaphthyl) Cyclopentadienyl] 鍩, etc. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back ^ fill out this page) Y is silicon, R1 is ethyl, R5 is ethyl, R3, R4 Examples of R6, R7, R8 and R9 being hydrogen may be diethylsilyl dichloride [4-((4-ethylnaphthyl) cyclopentadienyl]) zirconium, diethylsilyl dichloride Bis [2-methyl-1, 4- (4-ethylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride [2-ethyl-1, 4- (4-ethylnaphthyl) Cyclopentadienyl] chromium, diethylsilyl dichloride bis [2-n-propyl-4 (4-ethylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride Bis [2-isopropyl-1, 4- (ethylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride, di- [2-n-butyl-4, 1- (4-ethylnaphthalene) Group) cyclopentadienyl] zirconium, diethylsilyl dichloride [2- Butyl-4 4- (4-ethylzekiyl) cyclopentyl-diphenyl] cone 'diethyl diethylsilyl bis [2-second butyl-1 4- (4-ethylnaphthyl) cyclopentyl Alkenyl] zirconium, diethylsilyl dichloride bis [2-third butyl-4 ((4-ethylnaphthyl) cyclopentanyl)] pin, etc. γ is silicon, R1 is n-propyl R5 is ethyl, R3, R4, Re, R7, R8 and R9 are hydrogen. Examples may be di-n-propylsilyl dichloride [4-mono (4-ethylnaphthyl) cyclopentadienyl ] Chromium, di-n-propylsilyl dichloride [2-methyl-4, 4- (naphthyl) cyclopentadienyl] chromium, di-n-propyl silyl dichloride [2 -Ethyl-4— (4-ethylnaphthyl) cyclopentadienyl] zirconium, di-n-propylsilyl dichloride This paper applies the Chinese National Standard (CNS) A4 Zhuge (210X297 mm) _ 24 Printed by the Consumers 'Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs — 528758 A7 B7 V. Description of the invention (22) Bis [2-n-propyl-4 1' (4-ethylnaphthyl) cyclopentadienyl] chromium, dichloride N-propyl silylidene bis [2-isopropyl-4 4 ( 4 monoethylnaphthyl) cyclopentadienyl] chromium, di-n-propyl silylidene dichloride [2-n-butyl 4- (4-ethylnaphthyl) cyclopentadienyl] chromium, di Di-n-propylsilyl chloride bis [2-isobutyl-1 4- (4-ethylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride di [2—second Butyl-4 mono (4-ethylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyldichloride di [2-third butyl-4 (4-ethylnaphthyl) cyclopentyl Dienyl] pin and so on. γ is silicon, Ri is phenyl, R5 is ethyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be diphenyldiphenylsilylene dichloride [4-(4 -ethylnaphthyl) ) Cyclopentadienyl] chromium, diphenylsalicylidene dichloride [2-methyl-4 (4-ethylnaphthyl) cyclopentadienyl] zirconium, diphenylene dichloride Silyl bis [2-ethyl-1, 4- (naphthyl) cyclopentadienyl] zirconium, diphenyl diphenylsilylidene dichloride, [2-n-propyl-1, 4-a (4-ethylene) Base) Cyclopentyl-storage base] Pin '1 ^ Chlorinated monobenzylsilylbis [2-isopropyl-4 4- (4-ethylnaphthyl) cyclopentadienyl] cone, dichloride Phenylsilylbis [2-n-butyl-4 (4-ethylnaphthyl) cyclopentadienyl] zirconium, diphenyldialkylsilylbis [2-isobutyl-4-1 ( 4 monoethylnaphthyl) cyclopentadienyl] fluorene, diphenyl diphenylarsinyl bis [2-second butyl-4 mono (4-ethylnaphthyl) cyclopentadienyl] chromium, Diphenylsilyl dichloride dichloride. [2-Third-butyl-4, 4- (ethylnaphthyl) cyclopentadienyl] chromium and the like. γ is germanium, Ri is methyl, R5 is ethyl, R3, R4, R6, this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -25-(Please read the notes on the back first to write this Page) 'Pack-book 528758 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (23) Examples of R7, R8 and R9 being hydrogen may be dimethyl germanium dichloride dichloride [4 Mono (4-ethylnaphthyl) cyclopentadienyl] chromium, dimethylgermanium dichloride, bis [2-methyl-4 ((4-ethylethenyl) cyclopentadienyl)], Dimethyl germanium dichloride bis [2-ethyl-4, 4- (ethylnaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride bis [2-n-propyl A 4-a (4-ethylnaphthyl) cyclopentadienyl] chrome 'dimethyl digermanylene alkylene bis [2-isopropyl-4 4- (ethyl 4-naphthyl) cyclopentadienyl Alkenyl] zirconium, dimethyl germanium dichloride bis [2-n-butyl-4, 4- (ethylnaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride Bis [2-isobutyl-1,4- (ethylnaphthyl) cyclopentane Yl] zirconium 'dimethyl germanium dichloride bis [2-second butyl-1 4-mono (4-ethylnaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride Bis [2-Third-Butyl-1, 4- (4-EthylCeichyl) cyclopentyl ..: Allyl] pins, etc. Y is germanium, R1 is ethyl, R5 is ethyl, R3, r4, r6, R7, R8 and R9 are hydrogen. Examples may be diethylgermanyl dichloride dichloride [4_ (4 -ethylnaphthyl) ) Cyclopentadienyl] zirconium, diethylgermanyl dichloride bis [2-methyl-1, 4- (naphthyl) cyclopentadienyl] zirconium, diethylidene dichloride Germanium bis [2-ethyl-1-4- (4-ethylnaphthyl) cyclopentadienyl] chromium, diethylgermanium dichloride dichloride [2-n-propyl-4 4- (1-ethyl Naphthyl) cyclopentadienyl] chromium, diethylgermanyl dichloride dichloride [2-isopropyl-4 ((4-ethylnaphthyl) cyclopentadienyl]) zirconium, dichloride Ethyl germanium alkyl bis [2-n-butyl fluorene-4— (4-ethylnaphthyl) cyclopentadienyl] zirconium, diethyl germanium alkyl bis [2-isobutyl-1 4 Mono (4-ethylnaphthyl) cyclopentadienyl] zirconium, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 26 · (Please read the precautions on the back first ^ write this page) 濉 528758 A7 ____ Β7 _ V. Description of the invention (24) Diethylgermanyl dichloride dichloride [2 — Dibutyl-1 4- (4-ethylnaphthyl) cyclopentadienyl] pin, diethylgermanyl dichloride di [2-third butyl-4 (4-ethylnaphthyl) ring Pentadienyl] chromium and the like. Y is germanium, R1 is n-propyl, R5 is ethyl, R3, R4, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, and R7, R8 and R9 are hydrogen. Examples include di-n-propylgermanium dichloride. Alkyl bis [4-mono (4-ethylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanium dichloride dichloride [2-methyl-1 4- (4-ethylnaphthyl) ring Pentadienyl] chromium, di-n-propylgermanylene dichloride dichloride [2-ethyl-4 (4-ethylnaphthyl) cyclopentadienyl] chromium, di-n-propyl dichloride Germanium bis [2-n-propyl-4 ((4-ethylidene) cyclopentyl)] pin 'di-n-propyl germanium dichloride dichloride [2 -isopropyl-4 1 ( 4 monoethylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanylidene dichloride bis [2-n-butyl_ 4 1 (4-ethylethenyl) cyclopentyl * storage base] pin 'Di-n-propylgermanylidene dichloride [2-isobutyl-4 (4-ethylnaphthyl) cyclopentadienyl] pin, di-n-propylgermanyldichloro dichloride [ 2-Second-Butyl-4 (1-ethylidene) cyclopentyl-yl Bis [2 - a 4-tert-butyl (4-ethyl-naphthyl) cyclopentadienyl] zirconium. Y is germanium, R1 is phenyl, R5 is ethyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be diphenylgermanium dichloride dichloride [4 1 (4 Monoethylnaphthyl) cyclopentadienyl] chromium, diphenylgermanylidene dichloride bis [2-methyl-4- (4-ethylnaphthyl) cyclopentadienyl] zirconium, dichloride Diphenylgermanylalkylbis [2-ethyl-4-((4-ethylnaphthyl) cyclopentadienyl]] fluorene, diphenylgermanyldichloride dichloride [2--original paper size applicable to China National Standard (CNS) A4 Chu Luo (210X297 mm) -27-528758 Printed by the Central Standard Staff Consumer Cooperative of the Ministry of Economic Affairs A7 ____B7______ V. Description of the invention (25) Propyl-4 1 (4-ethylnaphthyl) cyclopentyl Dienyl] Chromium 'diphenylgermanium dichloride bis [2-isopropyl-4,4- (ethylnaphthyl) cyclopentadienyl] chromium, diphenylgermanyl dichloride Bis [2-n-butyl-1,4- (naphthyl) cyclopentadienyl] chromium, diphenylgermanium dichloride, bis [2-isobutyl-1, 4- (4-ethyl) (Cai Ji) cyclopentyl-refined base] pin 'diphenylgermanium dichloride Bis [2-Second-butyl-1 4- (4-ethylnaphthyl) cyclopentadienyl] chromium 'dichloride-monophenylgermanium Monoethylnaphthyl) cyclopentadienyl] zirconium and the like. Y is silicon, R1 is methyl, R5 is isopropyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be dimethylsilyl dichloride [4 1 (4-isopropyl Naphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2-methyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] pin, dimethyl dichloride Silylidenebis [2-ethyl-4, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2-n-propyl-1, 4-1 (4 Monoisopropylnaphthyl) cyclopentadienyl] zirconium, dimethylsilyl dichloride di [2-isopropyl-4, 4- (isopropylnaphthyl) cyclopentadienyl] zirconium, di Dimethylsilyl chloride bis [2-n-butyl-4- (isopropylnaphthyl) cyclopentadienyl] chromium, dimethylsilyl dichloride [2-isobutyl One 4 one (4 isopropylnaphthyl) cyclopentadienyl] zirconium, dimethylsilyl dichloride [2-second butyl one 4 one (4 isopropyl naphthyl) cyclopentadiene Alkenyl] chromium, dimethylsilyl dichloride bis [2-third butyl-1 4- (isopropylnaphthyl) ring ( Notes on the back read write Page) loading chromium-set]

In the evening, R 1 is ethyl, R paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 28-printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 B7 V. Description of the invention (26) Examples of R7, R8, and R9 being argon may be diethylsilyl dichloride [4- (4-isopropylzepyl) cyclopentyl · canyl] cone, and mono ^ ethyl sulfite Nominal bis [2-methyl-1, 4- (isopropylnaphthyl) cyclopentyl-1,4] chromium, diethylsilyl dichloride di [2 -isopropyl-1,4-(isopropyl Propylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride di [2-n-propyl-4 ((4-isopropylnaphthyl) cyclopentadienyl] zirconium, dichloride Diethylsalinidine bis [2-ethyl_ 4 mono (4-isopropylnaphthyl) cyclopentadienyl] chromium, diethyl diethylsilyl dichloride [2-n-butyl-1 4 Mono (4-isopropylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride [2-isobutyl-4 4- (isopropylnaphthyl) cyclopentadienyl] Zirconium, diethylsilyl dichloride [2-second butyl 1 4 (4-isopropylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride [2-third butyl-1 4-(4-isopropylnaphthyl) cyclopentadiene Alkenyl] chromium and the like. Y is silicon, R1 is n-propyl, R5 is isopropyl, R3, R4, R6, R7, R8 and R9 are hydrogen Monoisopropylnaphthyl) cyclopentadienyl] zirconium, di-n-propylsilyl dichloride di [2-methyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, di Di-n-propylsilyl chloride bis [2-ethyl-4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl chloride bis [2-n-propyl chloride 4-Ci- (4-isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride di- [2-isopropyl-4 4- (isopropylnaphthyl) cyclopentyl Dienyl] zirconium, di-n-propyl silylidene dichloride [2-n-butyl-1, 4- (isopropylnaphthyl) cyclopentadiene] This paper is in accordance with China National Standard (CNS) A4 specifications (210X297mm) _ 29-(Please read the precautions on the back first ^ Fill this page)

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, 1T. 528758 A7 B7__ V. Description of the invention (27) Base] Chromium, di-n-propylsilyl dichloride di 2- (2-isobutyl-4 4 (4 1-iso) Propylnaphthyl) cyclopentadienyl] chromium, di-n-propyl silylidene dichloride [2-second butyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, di Di-n-propylsilyl chloride bis [2-third butyl-4 (4-isopropylnaphthyl) cyclopentadienyl] chromium and the like. Y is silicon, R1 is phenyl, R5 is isopropyl, R3, R4, R6, R7, R8, and R9 are hydrogen. For example, dichloro. Diphenylsilylidene bis [4 a ( 4 monoisopropylnaphthyl) cyclopentadienyl] pin, diphenyldiphenylsilylene dichloride [2-methyl-4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, di Diphenylsilyl chloride bis [2-ethyl-4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, diphenylsilyl chloride di [2-n-propyl-1 4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, diphenyldiphenylsilyl dichloride [2-isopropyl-1,4- (isopropylnaphthyl) cyclopentadienyl] ] Chromium, diphenylsilyl dichloride [2 ~ n-butyl-4 (isopropylnaphthyl) cyclopentadienyl] zirconium, diphenylsilyl dichloride [2 -Isobutyl-1,4- (isopropylnaphthyl) cyclopentadienyl] zirconium, diphenyldiphenylsilylidenebis [2-second butyl-1, 4- (isopropylnaphthyl) ) Cyclopentadienyl] Chromium, Diphenylsilyl dichloride [2- -Third-butyl-1, 4- (isopropylnaphthyl) ring Pentadienyl] chromium and the like. Y is germanium, R1 is methyl, R5 is isopropyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be dimethyl germanium dichloride dichloride [4 1 (4 1 iso Propylnaphthyl) cyclopentadienyl] chromium, dimethylgermanyl dichloride dichloride [2-methyl-4 4- (isopropylnaphthyl) cyclopentadiene] This paper applies Chinese national standards (CNS) A4 specification (210X297mm) -30 · '(Please read the precautions on the back to write this page} • Packing-Order 528758 A7 B7 V. Description of the invention (28) Base] Chromium, dimethyl dichloride Germanium alkyl bis [2-ethyl-1, 4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride dichloride [2-n-propyl-1, 4- ( 4-Isoisocylenyl) cyclopentadienyl] pin, dimethylgermanylene dichloride bis [2-isopropyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium , Dimethyl germanium alkylene dichloride [2-n-butyl-4 mono (4-isopropylnaphthyl) cyclopentadienyl] chromium, dimethyl germanium dichloride di [2 -Isobutyl-1. 4- (isopropylnaphthyl) cyclopentadienyl] zirconium, dimethyl dichloride Germanium bis [2-Second-butyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] zirconium, dimethylgermanium dichloride di [2--third-butyl-4 Mono (4-isopropylnaphthyl) cyclopentadienyl] zirconium, etc. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, Y is germanium, R1 is ethyl, R5 is isopropyl, R3, R4, R6, R7 Examples of R8 and R9 being hydrogen may be diethylgermanyl dichloride bis [4-((4-isopropylnaphthyl) cyclopentadienyl] pin), diethylgermanyl dichloride Bis [2-methyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] zirconium, diethylgermanyl dichloride bis [2-ethyl-1, 4- (isopropylnaphthalene) Group) cyclopentadienyl] pin, diethylgermanyl dichloride bis [2-n-propyl-4 1 (4-isocyanenyl) cyclopentanyl] cone, dichloride Ethyl germanium alkyl bis [2-isopropyl-1,4- (isopropylnaphthyl) cyclopentadienyl] chromium, diethyl germanium alkyl dibis [2-n-butyl-1 4-((1-isopropylnaphthyl) cyclopentadienyl] chromium, diethylgermanyl dichloride dichloride [2 — Butyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] zirconium, diethylgermanyldichloride dichloride [2 -second butyl-1, 4-isopropylnaphthyl) Cyclopentadienyl] zirconium, diethyl dichloride This paper applies Chinese National Standard (CNS) A4 Zhuge (210X297 mm) _ 31-528758 A7 B7 V. Description of the invention (29) [2-Third-butyl-4- (4-isopropylnaphthyl) cyclopentadienyl] chromium, etc. Y is germanium, R1 is n-propyl, R5 is isopropyl, R3, R4, k6, R7 Examples of R8 and R9 being hydrogen may be di-n-propylgermanyldichloride dichloride [4-((4-isopropylnaphthyl) cyclopentadienyl] chromium), di-n-propylgermanium dichloride Alkyl bis [2-methyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanylalkylene dichloride [2-ethyl-1, 4-(4- Isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanylidene dichloride bis [2-n-propyl-1,4- (isopropylnaphthyl) cyclopentadienyl] chromium, Di-n-propylgermanylidene dichloride bis [2-isopropyl-1,4- (isopropylnaphthyl) cyclopentyl Alkenyl] zirconium, di-n-propylgermanylidene dichloride bis [2-n-butyl-4 mono (4-isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propyl dichloride Germanium bis [2-isobutyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] pin, di-n-propyl germanium dichloride dichloride [2-second butyl-1, 4 Mono (4-isopropylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanylalkylene dichloride [2-third butyl-1, 4- (isopropylnaphthyl) cyclopentadiene Alkenyl] chromium and the like. Y is germanium, R1 is phenyl, R5 is isopropyl, R3, R4, R6, R7, R8 and R9 are hydrogen. Examples may be diphenyl germanium dichloride dichloride [4 1 (4 1 iso Propylnaphthyl) cyclopentadienyl] chromium, diphenyldiphenylgermanylalkyl dichloride [2-methyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, dichloride Diphenylgermanylalkylbis [2-ethyl-1, 4- (isopropylnaphthyl) cyclopentadienyl] chromium, diphenylgermanyl dichloride, bis [2-n-propyl- 4 (Isopropylnaphthyl) cyclopentadienyl] zirconium, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) _ 32 · (Please read the precautions on the back first 3 Write this page )-Deaf and wood, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed 528758 A7 B7 V. Description of the invention (30) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed with diphenyl germanium monochloride. 2 — isopropyl — 4 — (4-isopropylnaphthyl) cyclopentadienyl] diphenylgermanium dichloride dichromium [2 —n-butyl-1 4 1 (4 1-iso Naphthyl) cyclopentadienyl] zirconium diphenyldiphenylgermanium dichloride bis [2-isobutyl-4- (4-isopropylnaphthyl) pentadienyl] > dichloride Diphenylgermanium bis [2-second butyl-4— (4-isopropylnaphthyl) cyclopentadienyl] diphenylgermanylalkylbis (2-third — 4 — · (4-isopropylnaphthyl) cyclopentadienyl] Chromium, etc. 〇Y is silicon > R 1 is f methyl,] R '1 &; No .: Butyl, R 3 & gt R 4 R 6, R 7, R 8 and R 9 are examples of hydrogen may be dimethylsilyl dichloride (4-(4 -tert-butylnaphthyl) cyclopentadienyl] dichloride Methylsilylene based bis [2 —methyl-4 (4-tert-butylnaphthyl) cyclopentadienyl] dimethylsilyl dichloride [2 —ethyl — 4 — (4- Tributylnaphthyl) cyclopentadienyl] dimethylsilyl dichloride [2 mono-n-propyl 4- (4-Second-Butylnaphthyl) cyclopentadienyl] j Dichloromethylene dichloride bis (2-isopropyl-4- (4-tert-butylnaphthyl) cyclopentadienyl) ] Zirconium dimethyl dichloride silicon bis (2-n-butyl-4-(4-tertiary butyl naphthyl) cyclopentadienyl pin Isobutyl — 4 — (4 —Second-butylnaphthyl) cyclopentadienyl] Chromium dichloromethylene dichloride bis (2 -2nd butyl — 4-(4 -3rd butylnaphthyl) pentyl Dienyl] pinyl dichloride dimethylsilyl bis [2-3rd butyl — 4 — (4-3rd n-butylnaphthyl) cyclopentadienyl] pin, etc. Y is silicon, R1 is ethyl , R5 is the third butyl, R3, R4, (Please read the notes on the back to write this page first) • Packing · 1T This paper size is applicable to the Chinese National Standard (CNS) Α4 Zhuge (210 × 297 mm) -33- 528758 A7 B7___ V. Description of the invention (31) R6 For example, R7, R8 and R9 are hydrogen. Diethylsilyl dichloride [4-((4-tertiary-butylnaphthyl) cyclopentadienyl]], diethyl dichloride dichloride Bis [2-methyl-4 mono- (4-tertiary-butylnaphthyl) cyclopentadienyl] zirconium, diethylsilyl dichloride bis [2-ethyl 4-tertiary (4-tertiary-butylnaphthyl) ring Pentadienyl] chromium, diethylsilyl dichloride, bis [2-n-propyl-4, (4-tert-butylnaphthyl) cyclopentadienyl] pin, diethylsilyl dichloride Bis [2-isopropyl-4, 4- (3rd-butylnaphthyl) cyclopentadienyl] chromium, diethylsilyl dichloride [2--n-butyl-4, 4 (3rd Butylnaphthyl) cyclopentadienyl] chromium, diethyldiethylsilyldichloride [2-isobutyl-4 ((tetra-n-butylnaphthyl) cyclopentadienyl] pin), diethyl dichloride Silylene bis [2-Second-butyl-1, 4- (4-Third-butylnaphthyl) cyclopentadienyl] zirconium, diethylsilyl dichloride [2-Third-butyl-1, 4- ( 4 a third butyryl) cyclopentadienyl] chromium and the like. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Y is silicon, R1 is n-propyl, R5 is third butyl, R3, R4, R6, R7, R8 and Examples of R9 being hydrogen may be di-n-propylsilyldichloride dichloride [4-((4-tert-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyldichloride dichloride [2 — Methyl-4, 4- (3rd-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilylidene dichloride, [2-ethyl-4, 4- (3rd-butylnaphthyl) cyclopentadiene] Yl] hydrazone, di-n-propyl silylidene dichloride [2-n-propyl-1, 4- (tertiary-butylnaphthyl) cyclopentadienyl] chromium, di-n-propyl silylidene dichloride [2-Isopropyl-4, 4- (3-tert-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride [2-n-butyl-4, 4- (tert-butyl) Naphthalene This paper scale applies the Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) _ 34-528758 A7 _ B7 __ V. Description of the invention (32) Cyclopentadienyl] Chromium, 'Dichloride Di-n-propyl silane Bis [2-isobutyl-1, 4- (tertiary-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylsilyl dichloride di [2 -second butyl-1, 4-1 (4- The third n-butylnaphthyl) cyclopentadienyl] zirconium, the di-n-propylsilylidene dichloride [2-third butyl-4- (4-tert-butylnaphthyl) cyclopentadienyl] zirconium and the like. γ is silicon, Ri is phenyl, R5 is third butyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be diphenyldichlorosilyl dichloride [4 a (4 a Tributylnaphthyl) cyclopentadienyl] chromium, diphenyldiphenylsilylidenebis [2-methyl-1,4- (3rd-butylnaphthyl) cyclopentadienyl] chromium, dichlorodiphenyl Silylene bis [2-ethyl-1, 4- (3rd-butylnaphthyl) cyclopentadienyl] pin, diphenyldiphenylsilyl dichloride [2-n-propyl-4, 4-1 Tributylnaphthyl) cyclopentadienyl] chromium, diphenyldiphenylsilylidenebis [2-isopropyl-1,4- (3rd-butylnaphthyl) cyclopentadienyl] pin, diphenyl dichloride Silylidenebis [2-n-butyl-4- (4-t-butylnaphthyl) cyclopentadienyl] pyrene, diphenyldiphenylsilyldichloride [2-isobutyl-4-1 (economic Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China (please read the notes on the back to write this page) 4-Tertiary butadienyl) cyclopentadienyl] chromium, diphenyldiphenylsilyl dichloride [2-2nd Butyl-4 4 (4 1 Tributyl-naphthyl) cyclopentadienyl] zirconium dichloride, diphenylmethylene-bis [Silicon alkyl 2 - a 4-tert-butyl (4-butoxy a third-naphthyl) cyclopentadienyl] chromium. Y is germanium, R1 is methyl, R5 is third butyl, R3, R4, R6, R7, R8, and R9 are hydrogen. Examples may be dimethylgermanium dichloride dichloride [4 one (4 one Third napthyl) cyclopentadienyl] zirconium, dichloride This paper applies Chinese national standards (CNS> A4 size (210x297 mm) ~ -35- 528758 A7 B7__ 5. Description of the invention (33) Germanium bis [2-· methyl-1 4 ((4-tert-butylnaphthyl) cyclopentadienyl] chromium), dimethyl germanium dichloride dichloride [2 -ethyl-1 4 1 (4- Third napthyl) cyclopentadienyl] chromium, dimethyl dimethylsulfinyl dichloride bis [2-n-propyl-4- (4-second butynyl) cyclopentadienyl] zirconium, two Dimethylgermanyl chloride bis [2-isopropyl-4 4- (3rd-butylnaphthyl) cyclopentadienyl] pin, dimethylgermanium dichloride bis [2-n-butyl -4_ (4-Second-butylzekiyl) cyclopentanyl] chromium, dimethylgermanyl dichloride bis [2-isobutyl-1 4-mono (4-tert-butylnaphthyl) cyclopentadiene Alkenyl] chromium, dimethyl germanium dichloride bis [2-second butyl 4 mono (4-tert-butylnaphthyl) cyclopentadienyl] zirconium, dimethylgermanyl dichloride bis [2-tert-butyl-1 4-tri (4-tert-butylnaphthyl) cyclopentadienyl ] Zirconium, etc. Y is germanium, R1 is ethyl, R5 is third butyl, R3, R4, printed by R6, R7, R8, and R9 are hydrogen in the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Examples include dichloride. Diethylgermanylalkylbis [4-mono (4-tert-butylnaphthyl) cyclopentadienyl] zirconium, diethylgermanyldichloride dichloride [2-methyl-1 Butylnaphthyl) cyclopentadienyl] chromium, diethylgermanyl dichloride dichloride [2-ethyl-4 (4-third butadienyl) cyclopentadienyl] pin, diethyl dichloride Germanium alkylene bis [2-n-propyl-4 (4-tert-butylnaphthyl) cyclopentadienyl] zirconium, diethylgermanium dichloride di [2-isopropyl-1 4 one ( 4 —Third-butylnaphthyl, cyclopentadienyl] chromium, diethylgermanyldichloride dichloride [2-n-butyl-4 (4-t-butylnaphthyl) cyclopentadienyl] Chromium, diethylgermanyl dichloride bis [2-isobutyl-1 4 One (4-three-butylnaphthyl) cyclopentadienyl] zirconium, diethylgermane dichloride The paper size is applicable to the Chinese National Standard (CNS) A4 Zhuge (210X297 mm) -36-528758 A7 B7___ 5 2. Description of the invention (34) based bis [2-second butyl-1'4- (4-third-butylnaphthyl) cyclopentadienyl] zirconium, diethylgermanylalkyl dichloride [2--3rd Butyl-1,4- (3rd-butylnaphthyl) cyclopentadienyl] chromium, etc. Y is germanium, R1 is n-propyl, R5 is third butyl, R3, R4, R6, R7, R8 and R9 are Examples of hydrogen may be di-n-propylgermanylenedichloride dichloride [4-((tertiary-n-butylnaphthyl) cyclopentadienyl] zirconium], di-n-propylgermanylalkyl dichloride [2-- Methyl-4 .— (4-tert-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylgermanylidene dichloride bis [2-ethyl-1,4- (tertiary-butylnaphthyl) cyclopentyl Dienyl] zirconium, di-n-propylgermanylidene dichloride bis [2-n-propyl-1, 4- (tertiary-butylnaphthyl) cyclopentadienyl] chromium, di-n-propylidene dichloride Germanium bis [2-isopropyl-4— (4-tributylene ) Cyclopentadienyl] Chromium, di-n-propylgermanylidene dichloride bis [2-n-butyl-4 4- (tetra-n-butylnaphthyl) cyclopentadienyl] pin, di-n-dichloride Propyl germanium alkylene bis [2-isobutyl-1,4- (tertiary-butylnaphthyl) cyclopentadienyl] chromium, di-n-propyl germanium alkylene dichloride [2-second butyl One 4 one (4 one third-butaphthyl) cyclopentadienyl] chromium, di-n-propyl germanium dichloride dichloride [printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2 —Third butyl 4— 4 a third butadienyl) cyclopentadienyl] zirconium Y is germanium, R1 is phenyl, R5 is a third butyl, R3, R4, R6, R7, R8 and R9 are hydrogen Phenylgermanylalkylbis [4-mono (4-tert-butylnaphthyl) cyclopentadienyl] chromium, diphenylgermanylalkyl dibis [2-methyl- 4- (4-tert-butylnaphthyl) ) Cyclopentadienyl] zirconium, diphenyl germanium alkylene dichloride [2-ethyl-4] This paper size applies to the Chinese National Standard (CNS) A4 Zhuge (210X297 mm) _ 37-Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 528758 A7 B7 V. Description of the invention (35)-(4-3rd-naphthyl-cyclopentadienyl] zirconium, diphenyl germanium alkyl dichloride [2-n-propyl 1-4-1 Tributylnaphthyl) cyclopentadienyl], diphenyl germanium dichloride, bis [2-iso-n-propyl-1, 4- (2nd-butylenyl) cyclopentyl-1, methyl] cone, Monochloro- · benzylgermanylidenebis [2-n-butyl-1, 4- (tertiary-butylnaphthyl) cyclopentadienyl] chromium, diphenylgermanylalkyl dichloride [2 — Isobutyl-1, 4- (3rd-butylnaphthyl) cyclopentadienyl] chromium., Diphenyldiphenylgermanylidene dichloride [2-2nd-butyl-1, 4-1 (4-3rd-butylnaphthyl) Cyclopentadienyl] chromium, diphenyl germanium dichloride dichloride [2-third butyl-4-(third-butadienyl) cyclopentadienyl] zirconium and the like. In addition to the compound examples shown above, in the above (1), the compound in which M is replaced by titanium or a compound, and another halogen atom or a Ci-C2Q hydrocarbon group may be used in place of X1 and / or X2 chlorine. The metal stilbene compound of formula (1) can be sequentially prepared by the following method. That is, it includes the steps of reacting a naphthylcyclopentadienyl compound with a metal salt type base to anionize it, reacting an anionized naphthylcyclopentadienyl compound with a crosslinking agent, and crosslinking the naphthylcyclopentadienyl compound. A step of two molecules, a step of reacting a cross-linked bis (4-naphthylcyclopentadienyl) compound with a metal salt base to make it dianionized to make a dianionized bis (4-zeolylcyclopentadiene) Base) compound reacts with a metal halide compound, performs intramolecular cross-linking steps to close the ring, and separates the racemic metal dioxin compound of formula (1). The size of this paper applies to the Chinese National Standard (CNS) A4 specification (210X297). (Centi) ΓΤβΓ — (Please read the notes on the back to write this page)

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs I 528758 A7 ____B7_ V. Description of Invention (36). In the above method, the naphthylcyclopentadienyl compound is a substituted or unsubstituted naphthylcyclopentadiene represented by the formula (2). R7

(Wherein 1 ^ 2, 1 ^ 3, 1 ^ 4, 115, feet 6,117, 1 ^ 8 and 1 ^ 9 respectively independently represent hydrogen, halogen atom, Ci ~ C2. Alkyl group, C7 ~ C20 aralkyl group, Ce ~ C2G aryl group, substituted silane group with Ci-Cso hydrocarbon group, Ci-Cs. Alkoxy group, C7 ~ C2G aralkyloxy group, or C6 ~ C20 aryloxy group, and halogen groups can be used to replace each group). Specific examples of each substituent in the formula (2) are the same as those described in the formula (1). Specific examples of the compound of formula (2) may be naphthylcyclopentadiene '1 -methyl-3-naphthylcyclopentadiene, 1-ethyl-3 -naphthylcyclopentadiene, 1-n-propyl 1-naphthylcyclopentadiene, 1-n-butyl-3-naphthylcyclopentadiene, 1-second butyl-3-naphthylcyclopentadiene-1, 1-table tributyl-3 —Naphthylcyclopentadiene, 1-methyl-3- (4-methylnaphthyl) cyclopentadiene, 1-ethyl-3- (4-methylnaphthyl) cyclopentadiene, 1-n-propyl -3-(4-Monaphthyl) cyclopentadiene '1. mono-n-butyl-3-(4-methylnaphthyl) cyclopentadiene, 1-second butyl-3-(4-methyl Naphthyl) cyclopentadiene, 1-Third-Butyl-3— (4-A) This paper size is applicable to Chinese National Standard (CNS) grid (210X297 mm) -39 · (Please read the notes on the back first to write this Page) Pack. Order 528758 A7 B7 V. Description of the invention (37) Naphthyl) cyclopentadiene, 1-methyl-1 3- (4-methoxynaphthyl) cyclopentadiene, 1-ethyl-3- (4-methoxynaphthyl) cyclopentadiene, 1-n-propyl-3-(4-methoxynaphthyl) cyclopentadiene, 1- Butyl-1, 3- (4-methoxymethoxy), cyclopentyl-1, 1-butyl-1, 3-butyl-1, 3- (4-methoxynaphthyl) cyclopentadiene, 1-third-butyl-1, 3— (4-monomethoxynaphthyl) cyclopentadiene, 1-methyl-1, 3- (4-naphthyl) cyclopentadiene, 1-ethyl-3 ((4-fluoronaphthyl)) cyclopentadiene Alkenes, 1-n-propyl-3— (4-fluoronaphthyl) cyclopentadiene, 1-n-butyl-3— (4-fluoronaphthyl) cyclopentadiene, 1—second butyl-3 — (4-fluoronaphthyl) cyclopentadiene, 1—third butyl—3— (4-fluoronaphthyl) cyclopentadiene, 1—methyl-1— (4-ethylnaphthyl) cyclopentadiene Diene, 1-ethyl-3- (4-ethylnaphthyl) cyclopentadiene, 1-n-propyl-3 3- (4-ethylnaphthyl) cyclopentadiene, 1-n-butyl-3 (4-Ethylnaphthyl) cyclopentadiene, 1-second butyl-1, 3- (4-Ethylnaphthyl) cyclopentadiene, 1-Third-butyl-3-(4-Ethylnaphthyl) ring Pentadiene '1-methyl-3- (4-propnaphthyl) cyclopentadiene, 1-ethyl-3- (4-propnaphthyl) cyclopentadiene, 1-propyl-3- ( 4-c Naphthyl) cyclopentadiene, 1-n-butyl-1, 3- (4-propylnaphthyl) cyclopentadiene, 1-second butyl-1, 3- (4-propylnaphthyl) cyclopentadiene, 1 One third butyl-3— (4-propynapthyl) cyclopentadiene, 1 one methyl one—3— (4-butnaphthyl) cyclopentadiene, 1—ethyl-3— (4—butzeyl ) Cyclopentadiene, 1-propyl- 3-(4 -butylnaphthyl) cyclopentadiene '1 -n-butyl- 3-(4-butnaphthyl) cyclopentadiene, 1 -second butyl -3- (4 monobutylnaphthyl) cyclopentyl bis (3) -diphenyl dibutyl-3 This paper size applies Chinese National Standard (CNS) A4 Zhuge (210X297 mm) -40-(Please read the precautions on the back first to write this page ) H 燊. Written by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs. 528758 A7 B7 V. Description of the invention (38) (4 _ butaphthyl) cyclopentadiene etc. Anionization of naphthylcyclopentadienyl compounds and dianionization of these cross-linked bis (4-naphthylcyclopentadienyl) compounds refers to the anionization of each cyclopentadienyl ring, The former is an anionization followed by a reaction with a cross-linking agent to carry out these two molecular cross-links smoothly, and the latter is a step of closing the ring by intramolecular cross-linking for the subsequent reaction with the metal halide compound. The base used for the above anionization and dianionization may be, for example, methyl lithium, third butyl lithium, phenyl lithium, lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium diisopropylamidide, potassium third butoxide , Methyl magnesium iodide, ethyl magnesium iodide, phenyl magnesium bromide, third butyl magnesium bromide, and the like. In addition, for the anionization of naphthylcyclopentadienyl compounds, amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tertiary butylamine, aniline, ethylenediamine, etc. can be used together with a base. Primary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, etc. , Trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, triphenylamine, N, N-xylylamine, N, N, N ', N'-tetra Tertiary amines such as methylethylenediamine, N-methylpyrrolidine, 4-dimethylamine pyridine. The cross-linking agent which cross-links two molecules of the anionic naphthylcyclopentadienyl compound is represented by the formula (3). This paper size applies Chinese National Standard (CNS) Α4 Zhuge (2! 〇χ297 mm) _41 (Please read the precautions on the back before filling out this page)-Pack-Order 528758 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (39)

X

I

Rl—Y—R1 (3)

I

X (where Y represents carbon, silicon, germanium or tin 'R1 represents hydrogen, halogen atom' Ci-Cs. Alkyl, C7 ~ c2. Aralkyl, c6 ~ C2Q aryl, substituted silane with Cl ~ C2Q hydrocarbon group Group, .Cl ~ C20 alkoxy 'C7 ~ C2. Aralkoxy, or C6 ~ C20 aryloxy, each group can also be replaced with a halogen atom, x represents a halogen atom). Specific examples of each substituent in the formula (3) are the same as those described in the formula (1). Specific examples of the crosslinking agent of the formula (3) include dichlorodimethylsilane, dichloro = ethanesilane, dichlorodi-n-propylsilane, dichlorodi-n-butylsilane, dichlorodiphenylsilane, dibromodimethylsilane, and dichlorosilane. Bromodiethylsilane, dibromodi-n-propylsilane, dibromodi-n-butylsilane, dibromodiphenylsilane, dichlorodimethylgermanium, dichlorodiethylgermanium, dichlorodi-n-propylgermanium, dichlorodisilane N-butyl germanium, dichlorodiphenyl germanium, dibromodimethyl germanium, dibromodiethyl germanium, dibromodi-n-propyl germanium, dibromodi-n-butyl germanium, dibromodiphenyl germanium, etc. By anionizing the naphthylcyclopentadienyl compound and its subsequent reaction with a cross-linking agent, these two molecules are cross-linked to form formula (4). This paper size applies the Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) -42 _ (Please read the precautions on the back and write this page first) Binding and binding 528758 A7 B7 V. Description of invention U〇) R7

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (where Y, R1'R2, R3, R4, R5, r6, r7, R 8 and R 9 are as defined above) and their mirrors are different The structure is formed into a bis (4-naphthylcyclopentadienyl) compound. The anionization and cross-linking reaction of naphthylcyclopentadienyl compounds is usually in an organic solvent at a reaction temperature of -100 ° C to below the boiling point of the solvent, preferably between 70 ° C and 100 ° C. Range. The organic solvent used in the reaction may be used without any particular limitation as long as it does not react with the above-mentioned raw material compounds and reaction products, and does not decompose them. However, it is preferable to use ethers, halogenated hydrocarbons, and aromatic compounds. . The ethers are preferably lower molecular weight ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dimethoxyethane. The halogenated hydrocarbon is preferably dichloromethane. The aromatic compounds are preferably toluene, anisole, xylene. A mixture of two or more of the above may be used. After adding mixed water to the reaction mixture obtained in the above reaction, leave it to stand so that the paper size is applicable to the Chinese National Standard (CNS) A4 Zhuge (21 ×: 297 mm) _ 43 528758 A7 B7 V. Description of the invention (41) Layer with water solution. The double (solution is used in the next step. Double adopts, for example, distillation chromatography, etc., to make the above-mentioned metal salt-type base intermolecularly interspersed with its mirror phase isomer. The closed system is double. Secondly, the next step is (4-naphthyl ring de-solvent purification, and the resulting double reaction is used in combination with (4, 2 anion, closed ring, and racemic gold naphthyl ring). Mononaphthylcyclopentadienyl) can be crystallized, distilled, and columned dienyl) compounds can be directly used in the separation method obtained after the separation, but compounds are usually from the solution of pentadienyl). The next step is better. The naphthylcyclopentadienyl group is converted into a compound and then halogenated to form a compound of the formula (1 is a dipentanyl compound, pentadienyl). Metal halide materials (please read the precautions on the back to write this page) Pack-(5) Printed by X X1 \ / Μ / \ X X2 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Formula M means titanium, chromium or Bell, X 1 and X 2 are each independently halogen Atom or Ci-CsQ hydrocarbon group, and X represents a halogen atom). Specific examples of the halogenated metal of the formula (5) include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrafluoride, and methyl titanium trichloride. , Methyl titanium bromide, methyl titanium triiodide, methyl titanium trifluoride, chromium tetrachloride, zirconium tetrabromide, zirconium tetrahalide, chromium tetrafluoride, tetrachloride, tetrabromide Give, tetraiodide, tetrafluoride, etc. The reaction of the dianionized bis (4-naphthylcyclopentadienyl) compound with the metal halide is to dissolve or suspend the metal halide in the solvent, and mix the paper size Applicable to China National Standard (CNS) A4 Zhuge (210X297 mm) _44 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 ___B7 V. Description of the invention (42) Dianionized bis (4-'naphthylcyclopentadiene) Alkenyl) compounds are reacted. As long as the reaction solvent is a bis (4-naphthylcyclopentadienyl) compound which is anionized with di and the metal bismuth produced, it will not react or decompose them. It can be used with special restrictions, but it is preferred to use ethers, halogenated hydrocarbons, and aromatics. Group compounds. The ethers are preferably lower molecular ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dimethoxyethane. The halogenated hydrocarbons are preferably dichloromethane. The aromatic compounds are toluene and benzyl. Ether and xylene are suitable. In addition, two or more of the above may be used. Finally, the racemic-metallic stilbene compound is isolated from the above reaction solution according to a conventional method, and the compound of formula (1) and its mirror phase are obtained after purification. Isomers of racemic metal stilbene compounds. The isolation and purification of these racemic metal stilbene compounds can be removed by solvent distillation, extraction with a suitable solvent, adsorption, filtration, recrystallization, etc. Usually, the method is refined by recrystallization. In the formula (1), M is a pin, Y is silicon, X1 and X2 are chlorine, R1 and R2 are methyl, and all compounds of 3,114,115,116,117,118, and 1 ^ 9 are hydrogen, That is, dimethylsilyl dichloride di (2-methyl-4-naphthylcyclopentadienyl) zirconium dichloride is taken as an example, and the synthetic reaction process is shown below. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 45-(Please read the precautions on the back to write this page)-Binding and binding 528758 A7 B7 V. Invention description U3) Reaction process

Anionization step Cross-linking step (please read the notes on the back to write this page first) Installation and reaction process 2 Orders

Compounds (1) and (2) Closed-loop steps This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 46-528758 A7 ____B7 V. Description of the invention (44) The compound of formula (1.) 'of the present invention A racemic metal dioxin compound (hereinafter referred to as a metal dioxin compound) formed from its mirror isomer can be isolated in the above manufacturing method, or it can be used as a catalyst for olefin polymerization without being separated. . When the above-mentioned metal stilbene compound is used as a catalyst for olefin polymerization, it can be used with olefin polymerization, for example, one or more selected from alumoxane, and react with the metal stilbene compound to form an ion complex. It can be used together with compounds of Lewis acid. In addition, when used as a catalyst for olefin polymerization, a metal duplex compound can be used alone, or it can be supported on a particulate carrier together with other components, and the particulate carrier system has a particle size of 5 to 3 0 / / m, preferably 1 0 to 2 0 0 // m of granular or spherical inorganic or organic solid fine particles. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, which can be polymerized by using the catalyst containing the metal duplex compound of the present invention, olefin-based ethylene, propylene, 1-butene, 4-methyl-1, 1-pentene, 1-hexane Suspect, 1 pentamate, 1-decane, 1-12 dodecene, 1 tetradecene, 1 hexadecene, 1 octadecene, 1 monocarbene, etc. -Olefins, 3-methyl-1, butene, 4-methyl-1, 1-pentene, 2-methyl-1, 1-pentene and other branched α-olefins, and mixtures of two or more of these. The metal stilbene compound of the present invention is used as a catalyst. The olefin polymer obtained by polymerization is not only a separate polymer of the above-mentioned olefins, but also a copolymer combined with other olefins, such as ethylene and propylene, and propylene. Combined with two-components such as 1-butene, or ethylene, propylene, and 1-butene-47- This paper size applies to China National Standard (CNS) Α4 Zhuge (210X297 mm) 528758 Employees of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 printed by the consumer cooperative. V. Description of the invention (45) The co-polymer formed by the three-component combination can be a block copolymer that changes the type of olefins supplied in multi-stage polymerization. In addition, by using the metal dioxin compound of the present invention as a catalyst, it is also possible to polymerize cyclic olefins, dienes, styrenes, other polymerizable monomers having a double bond, or polymerization with α-olefins. Copolymerization. Cyclic olefins are, for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, orthobornene, 5-methyl-2-orthobornene, 5-ethyl-ortho-norbornene, benzene Protoporbornene, indenyl probornene and the like. Dienes are, for example, 5-methylene-2—orthobornyl dilute, 5-ethylidene-2—orthobornyl, 5-propylidene-5—orthobornylene, cyclopentadiene, 5-vinyl A cyclic diene such as 2-norbornene, 1,3-butadiene, isoprene, 1,4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl -1,4 -hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 1,7-octadiene, 6-methyl-1,7 —Octadiene '7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene and other chain diene. The styrenes may be, for example, styrene, p-chlorostyrene, p-methylstyrene, p-third butylstyrene, α-methylstyrene 'vinylnaphthalene, and the like. Other polymerizable monomers with double bonds are ethylene cyclohexane, ethylene chloride, 4-trimethylsilyloxy-1,6-heptadiene, and 5- (N'N-diisopropylamino) -pentene. , Methyl methacrylate, ethyl acrylate, etc. The polymerization method of the olefins using the metal stilbene compound of the present invention as a catalyst may be either liquid phase polymerization or gas phase polymerization. Liquid phase polymerization can also use inert hydrocarbons as a solvent, liquefied propylene can be used, liquefaction 1-This paper size applies to China National Standard (CNS) 8 4 specifications (2i × 297mm) (Please read the precautions on the back before (Fill in this page) Binding and binding 528758 A7 B7 V. Description of the invention (46) (Please read the note on the back to write this page first) Liquefied olefins such as butene itself are used as solvents. Polymerization solvents can be aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecyl Aliphatic hydrocarbons such as alkane, cyclopentane, methylcyclopentane, cyclohexane, cycloheptane, cyclooctane and other aliphatic hydrocarbons, gasoline, kerosene, light oil, petroleum fractions, etc. The polymerization method can be any one of batch method, semi-continuous method and continuous method, and the reaction conditions can be changed into two or more stages for polymerization. In the polymerization method using the metal duplex compound of the present invention as a catalyst, although the concentration of the metal duplex compound in the polymerization reaction system is not particularly limited, the transition metal concentration is 10- 2 to 10- 1. Moore / liter range is appropriate. The pressure of the polymerization olefin is not particularly limited, but it is preferably in the range of normal pressure to 50 k g / cm 2. The polymerization temperature is not particularly limited, but is usually in the range of 50 to 250 ° C, and preferably in the range of 30 to 100 ° C. The molecular weight during the polymerization can be adjusted by known means, for example, by selecting a temperature or introducing hydrogen. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The following examples illustrate the present invention in more detail. All the reactions in the following examples were carried out in an inert gas atmosphere, and the reaction solvent was dried beforehand. Example 1 Synthesis of dimethylsilyl dichloride di (2-methyl-1,4-naphthylcyclopentadienyl) chromium This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm)- 49-528758 A7 B7 V. Description of the invention (47) A · The synthesis of the ligand is at 0 · 1 0. 1 dry ice-mixture / < stirring 1 to cool the ear) dimethanol bath for an hour, dry, over 5 0 0 0 mol 0 mol dropwise add n-butyl in the methanol bath to obtain the suspension of methyl disulfide. Take out the pale yellow filter and reduce the amount of m1 into the glass reaction vessel. 21) 1 monomethyl-1 3-naphthyl ring Pentadiene 0 0 m 1 in 30 minutes • 3 g) tetramethyl ethyl, to obtain 2 cooling to 6 2 m 1 (lithium n-hexane light yellow precipitate to-4 0 ℃ chlorosilane 5 The solution was kept in a room color. 0 g (yield 2-methyl-4-naphthylcyclopentane) was distilled off under reduced pressure. Diamine and 278 ° C. 0.10 solution. From this suspension, add 60 mM, stir and wash the agent with water. 90% of the tube is dienyl), 12g (isopropyl ether, here at millimoles), 1.6 mol dry. Ice- Remove from methanol bathThen in dry ice • 7 g (0 THF solution for 8 hours, the liquid was refined by column chromatography to refine the yellow liquid silane. Construct a methanol bath • 0 5 2 Mo. Repeat the reflux from dry ice to dry the reaction with 1 2 sodium sulfate Mixed dimethyl bis (Please read the precautions for NMR, then fill in this page. Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The metal bismuth complex is synthesized in a 500ml glass reaction container. 11 · 9g (2.5 mmol) dimethylbis (2-methyl-1,4-naphthylcyclopentadienyl) silane and 100 m 1 THF, cooled in a dry ice-methanol bath to -20 t: A solution of 5 1 ml (53 mmol) of 1.0 lithium mole of diethyl ether was dropped into this mixture over 30 minutes. Take out from the dry ice-methanol bath and stir at room temperature. 18 hours to get a yellow transparent solution. The paper size is in accordance with Chinese National Standards (CNS) A4 specifications (210X297 mm) _50. Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, 528758 A7 B7. 5. Description of the invention (48). Add this solution to an additional 5.9 g (25 mmol) ) 200 ml of THF solution of chromium tetrachloride. This solution was slowly warmed to room temperature. Stirred for 18 hours. After filtering, it was dried under reduced pressure and recrystallized from dichloromethane-hexane to give 3.1 g ( Yield: 20%) racemic dimethylsilyl dichloride bis (2-methyl-1,4-naphthylcyclopentadienyl) chromium. The obtained racemic dimethylsilyl dichloride. The 1-NMR data of (2-methyl-4naphthylcyclopentadienyl) fluorene is shown below.

SiMe; 0.89 (6H, s), CpMe; 2.16 (6H, s), aCpH; 5.80 (2H, d), cold CpH; 7.20 (2H, d), CpNp; 7.28-7. 5 4 (7 H M) Example 2 Synthesis of dimethylsilyl dichloride (2-methyl-1, 4-naphthylcyclopentadienyl) dichloride, and a synthetic metal duplex compound in a 500 ml glass reaction container, Add 11.9 g (2.5 mmol) of bis (2-methyl-1,4-naphthylcyclopentadienyl) dimethylsilane and 100 m 1 THF, and cool in a dry ice-methanol bath to -2 0 ° C. A solution of 5 1 ml (53 mmol) of 1.04 mole of methyl lithium in diethyl ether was added dropwise to the mixture over a period of 30 minutes. Take out from the dry ice-methanol bath and stir at room temperature for 18 hours to get a yellow transparent solution. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm). 51-(Please read the precautions on the back first \ ^^ write This page) Binding · Binding 528758 A7 B7 V. Description of the invention (49) fluid. To this solution was added a separately prepared 8. Og (25 millimolar) tetrachloride to give a 200 m 1 T H F solution. This solution was slowly warmed to room temperature. Stir for 18 hours. It was filtered, dried under reduced pressure, and recrystallized from dichloromethane-hexane to obtain 2.5 g (yield 10%) of racemic dimethylsilyldichlorobis (2-methyl-4naphthyl). Cyclopentadienyl) give. Example 3 Synthesis of dimethylgermanium dichloride di (2-methyl-1,4-naphthylcyclopentadienyl) chromium dichloride. A 500 ml glass reaction vessel was charged with 21 · 3 g (Employee of the Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative (1 · 10 moles) 1-methyl-3-naphthylcyclopentadiene, 12g (0 · 10 moles) of tetramethylethylenediamine and 200ml of diisopropyl ether in a dry ice-methanol bath Intercooling is -78 ° C. To this mixture, 62 ml (0. 10 mmol) of 1.66 mol of n-butyllithium in n-hexane was added dropwise to the mixture over a period of 30 minutes. Remove from dry ice-methanol bath and stir for 1 hour to obtain a pale yellow precipitated suspension. The suspension was cooled in a dry ice-methanol bath to a temperature of 40 ° C, and a solution of 9.0 g (0.52 mol) of dimethyldichlorosilane in 50 ml of THF was added. Remove from dry ice-methanol bath, and keep stirring at room temperature for 18 hours, then reflux for 12 hours to obtain a pale yellow liquid. This liquid was washed with water, and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure. This reaction mixture was purified by column chromatography to obtain 43.4 g (yield 85%) of dimethylbis (2-methyl-4naphthylcyclopentadienyl) dimethyl germanium as a yellow liquid. This paper size applies Chinese National Standard (CNS) A4 Zhuge (210 X 297 mm) _ 52-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 528758 A7 B7 V. Description of the invention (50) Synthesis of the compound In a 500 ml glass reaction vessel, 12 · 7 g (25 mmol) of bis (2-methyl-4 4-naphthylcyclopentadienyl) dimethyl germanium and 100 ml of THF were added, and the mixture was dried on ice. Cool in a methanol bath to a temperature of 20 ° C. To this mixture was added dropwise 51 ml (53 mmol) of a 1.04 mole of methyl lithium diethyl ether solution over 30 minutes. It was taken out of the dry ice-methanol bath and stirred at room temperature for 18 hours to obtain a yellow transparent solution. The previously obtained yellow permeable liquid was added to a separately prepared solution of 5.9 g (25 mmol) of tetrachloride in 200 ml of THF. This solution was slowly warmed to room temperature. Stir for 18 hours. It was filtered and dried under reduced pressure, and recrystallized from dichloromethane-hexane to obtain 2.5 g (yield 10%) of racemic dimethylgermanylalkyl dichloride di (2-methyl-1 4 A naphthylcyclopentyl group. Application Example 1 · Polymerization of propylene In a 100 ml glass container substituted with nitrogen, 4 m 1 (6 mmol of aluminum per unit) of methylalumoxane-toluene solution (manufactured by Tosohichi Acuso) was added, and 1 ml of racemic was added. Dichlorosilyl bis (2-methyl-4-naphthylcyclopentadienyl) chromium-toluene dichloride solution was stirred at room temperature for 30 minutes. This solution was put in a SUS autoclave containing 1 < (〇.56x10-6 mol) toluene and heated to 30 t :. Propylene was introduced thereinto at a pressure of 0.3 MP a and polymerized for 1 hour. After polymerization, the polypropylene was filtered, and the catalyst component was divided into 2 < hydrochloric methanol. Filter in order, this paper size applies Chinese National Standard (CNS) A4 Zhuge (210X297 mm) · 53-(Please read the notes on the back first to write this page) • Equipment · 528758 A7 B7 Staff of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative. 5. Description of the invention (51) Wash and dry to obtain 2 9 polypropylene. According to the calculation, the polymerization activity of each unit of zirconium is 5 1 kg — PP / mmole z r_h. The obtained polypropylene was Mw = 186,000, Mw / Mn = 1.70, mmmm = 〇.877, Mp = 145.00CO. Comparative application example 1: Polymerization of propylene. Dichlorination was synthesized in the same manner as in Example 1. Racemate of dimethylsilylbisindenyl zirconium. Instead of dimethylsilyl dichloride (2-methyl-4naphthylcyclopentadienyl) chromium-toluene solution, use 1 ml (2.23X10-6 mole) of dimethylsilyl dichloride The solution of bisindenyl chromium in toluene was adjusted to 14 ml of methylaluminoxane-toluene solution (22 millimoles per unit of aluminum) (other than Tosoh-8 (made by 115) Co., Ltd.), which was the same as that of Application Example 1. Polymerization of propylene was carried out under the conditions to obtain 40 g of polypropylene, and the polymerizability per unit of chromium was 18 kg — PP / millole-Z r -h. The obtained polypropylene was Mw = 41,900 M w / M η = 2 · 02, mmmm = 0 · 930, Μρ = 145 · 10C ο Comparative Application Example 2: · Polymerization of Propylene The same method as in Example 1 was used to synthesize dimethyl dichlorite sand-based bis (2 ' 4 Dimethylnaphthylcyclopentadienyl) racemate of zirconium. Instead of digassed monomethyl sulfinyl (2-methyl-4 4-naphthylcyclopentadienyl) (Please read first Note on the back ^: write this page)-The paper size of the binding and binding is applicable to the Chinese National Standard (CNS) A4 Zhuge (210X297 mm) -54 · 528758 A7 ______B7 V. Description of the invention (52) (Please read first Note on this page) Use 1ml (1.98x1 0_6 mole) dichlorosilyl bis (2,4-dimethylcyclopentadienyl) chromium toluene solution for chromium-toluene solution The others were polymerized with propylene under the same conditions as in Application Example 1, and 35 · 5 g of polypropylene was obtained, and the polymerizability per unit of chromium was i8kg_ PP / mmole-Zr- h. The obtained polypropylene-based Mw = 99000 Mw / Mn = 1 · 9 1 〇 Industrial applicability As shown in the above application example, the metal double-coated fluorene compound having a bis (4-naphthylcyclopentadienyl) ligand of the present invention is used as an olefin such as propylene. The catalyst component during polymerization can have a higher polymerization activity than the conventionally known metal dioxin compounds, and can obtain a polyolefin having a high molecular weight. The present invention can provide a suitable main component as a catalyst for olefin polymerization The metal double-coated compound and its manufacturing method are of great industrial significance. The paper printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) Α4 Zhuge (210X297 mm) -55-

Claims (1)

528758 Gaomu A8 B8 C8 D8 VI. Application for Patent Scope 1 · A racemic compound with a bis (4-naphthylcyclopentadienyl) ligand formed by a compound represented by the formula (1) 'and its mirror isomer Metal Duplex Compound, R7 Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives (where M represents titanium, chromium, or carbon dioxide, Υ represents carbon, silicon, germanium, or tin, and X1 and X2 are independently halogen atoms or CiACs, respectively. Hydrocarbon groups, feet 1,112 , 113, 114, 115, 1 ^ 6, 117, ruler 8 and ruler 9 independently represent hydrogen, halogen atom, Cl ~ C2Q alkyl group, C7 ~ C20 aromatic compound group, C6 ~ C2Q aryl group, with Cl ~ C2 ( ) The alkyl group is substituted by a sand group, Ci-C " alkoxy 'C7 ~ C2Q aralkoxy or c6 ~ C 2 0 aryloxy, and each group can be replaced by a halogen atom). 2 · If the compound in the first item of the patent application scope, where M is chromium, X1 and χ2 are chlorine, γ is silicon or germanium, and R1 is Ci ~ in the formula (丄) This paper applies Chinese national standard (CNS) A4 Specifications (210X297 mm) • 56- 528758 A8 B8 C8 _______D8 6. Application scope of patent C4 alkyl or phenyl, R2 series hydrogen or Ci ~ c4 alkyl group and R3 ~ R9 series hydrogen. 3. The compound according to item 1 in the scope of patent application, wherein M is chromium, X 1 and X 2 are chlorine, γ is silicon or germanium, r 1 is c 1 to C 4 alkyl or phenyl in formula (1), R2 is hydrogen or Cl ~ C4 alkyl, R5 is fluorine, Ci ~ C4 alkyl or Ci ~ C4 alkoxy, and R3 ~ R4 and R6 ~ R 9 are ammonia. 4. A method for producing a racemic metal stilbene compound having a bis (4-naphthylcyclopentadienyl) ligand, characterized in that it sequentially comprises the formula (2) R7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (where r2, r3, r4, r5, r6, r7, r7, r8 & R9 respectively represent hydrogen, halogen atom, Ci-Czo alkyl, C7 ~ c2. Alkyl group, c6 ~ C2. Aryl group, Ci ~ C2. Substituted silyl group of alkyl group, Ci ~ C2Q alkoxy group, C7 ~ C2Q aralkyloxy group, or C6 ~ C20 aryloxy group, each halogen atom can also be used to replace each Step of reacting the naphthylcyclopentadienyl group with a base to anionize it to react the anionized naphthylcyclopentadienyl compound with a crosslinking agent represented by formula (3). Standard (CNS) A4 specification (210X297 mm) _ 57-528758 Α8 Β8 C8 D8 VI. Patent application scope XI R1—Y—R1 (3) IX (where Y represents carbon, silicon, germanium or tin, and X represents halogen Atom, R1 represents hydrogen, halogen atom, Cl ~ C2 ◦ radical, C7 ~ C2G aromatic radical, C6 ~ C2Q aromatic radical, with Ci-Cs. Hydrocarbyl substituted silyl, Ci ~ C2Q alkoxy, C7 ~ C2Q Aralkyloxy, or C6 ~ C2. Aryloxy, these groups can also be substituted with halogen atoms) to crosslink naphthylcyclopentadienyl The two-molecule step of the compound is a step of reacting the obtained bis (4-naphthylcyclopentadienyl) compound of formula (4) with a base to perform dianionization. (Please read the precautions on the back before filling this page ) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, R7 R8 and R9 are the same as defined above). The bis (4-naphthylcyclopentadienyl) compound which anionized anion and the size of this paper apply Chinese National Standard (CNS) A4 specification (210X297 mm) 58- 528758 A8 B8 C8 D8 VI. Patent Application Formula (5) X X1 / / MX X2 (5) (Formula M represents titanium, chromium, or X, X1 and X2 are independently halogen atoms or Ci ~ C2Q hydrocarbon groups, X represents halogen Atomic) reaction of halogenated metal compounds to make intramolecular cross-linking and closed-loop steps, and single ionization (1) (Please read the precautions on the back before filling this page) R7 (1), R 3, R 4, R 5, R 6, R 7, R 8 and R 9 are as defined above) and a bis (4-naphthylcyclopentadienyl) complex formed by a compound of the compound and its specular isomer This is the result of a step of a racemic metal double-coated compound. 5 · The method according to item 4 of the scope of patent application, where M in the formula (χ) is wrong, X1 and X2 are chlorine, γ is silicon or germanium, and rule 1 is (1 ~ 04) This paper standard is applicable to China Standard (CNS) A4 specification (210X297 mm) -59- Order • 1% 528758 A8 B8 C8 D8 6. Application scope of patents: alkyl or phenyl, R2 is hydrogen or Ci-Cd alkyl and R3 ~ R9 is hydrogen. 6. The method according to item 4 of the scope of patent application, wherein in the formula (1), M is chromium, X1 and X2 are chlorine, Y is silicon or germanium, R1 is alkyl or phenyl, R2 is hydrogen or Ci ~ C4 Alkyl, R5 based fluorine, (^ ~ C4 alkyl or Ci-Ca alkoxy, and R3 ~ R4 and R6 ~ R9 based hydrogen (please read the precautions on the back before filling this page) Staff of the Central Bureau of Standards, Ministry of Economic Affairs The paper size printed by the consumer cooperative is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 60 _