JPH0485310A - Production of syndiotactic poly-alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a syndiotactic poly-alpha-olefin of a high crystallization rate in high activity by polymerizing an alpha-olefin in the presence of a specified catalyst and using a specified new transition metal compound as a component of this catalyst. CONSTITUTION:A process for obtaining a poly-alpha-olefin by polymerizing an alpha-olefin (e.g. propylene) in the presence of a catalyst comprising a transition metal compound and a promoter selected from between an aluminoxane and a boron compound (e.g. methylaluminoxane), wherein a new transition metal compound of the formula [wherein A<1> is (substituted) cyclopentadienyl; A<2> is (substituted) fluorenyl; A<3> is 4-20C hydrocarbondiylidene; R<1> and R<2> are each halogen, H, 1-100C aryl or alkyl; and M is Ti, Zr or Hf] is used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Prior Art] As an olefin polymerization catalyst containing a metallocene compound as an essential component, a so-called Kaminski type catalyst consisting of aluminoxane and a metallocene compound is known.

JP-A-58-19309 discloses (cyclopentagenyl) zMeRHal (here,
R is cyclopentadienyl, C1-C6 alkyl, halogen, Me is a transition metal compound, Hal is halogen) in the presence of a catalyst consisting of aluminoxane and ethylene and/or α-
A method for polymerizing or copolymerizing olefins is described.

JP-A-60-35008 describes that poly-α-olefins having a wide molecular weight distribution can be produced by using a catalyst consisting of at least two metallocene compounds and aluminoxane.

JP-A-61-130314 describes that polypropylene with a high degree of isotacticity can be obtained by polymerizing propylene in the presence of a catalyst consisting of a sterically fixed zircon-chelate compound and aluminoxane.

JP-A-1-275609 describes that isotactic polypropylene can be obtained by polymerizing propylene in the presence of a catalyst consisting of a metallocene compound crosslinked with heteroatoms and aluminoxane.

JP-A-1-301704 discloses that isotactic polypropylene is obtained by polymerizing propylene in the presence of a catalyst consisting of a bis-substituted cyclopentadienyl transition metal compound cross-linked with silicon, germanium, or tin and aluminoxane. It is stated that.

Special Publication No. 1-501950, Special Publication No. 1-50203
Publication No. 6 describes a method for polymerizing or copolymerizing ethylene and/or α-olefin in the presence of a catalyst consisting of a metallocene compound having at least one substituent that can react with protons and a substituted ammonium salt of a special boron compound. ing.

JP-A-2-41303 discloses that highly syndiotactic polypropylene is obtained by polymerizing propylene in the presence of a catalyst consisting of a structurally crosslinked metallocene compound having sterically different substituents and aluminoxane. It is stated that. The publication describes that syndiotactic poly-α-olefins having a wide range of molecular weights can be produced by using two or more of the above metallocene compounds.

However, no transition metal compound having two transition metal atoms in one molecule useful as an olefin polymerization catalyst has been synthesized to date.

[Problem to be solved by the invention]

The method disclosed in JP-A-2-41303 is an excellent method in which the activity per transition metal is good and the syndiotacticity of the obtained polymer is high. Chic polypropylene had a slow crystallization rate and was difficult to process and mold.

In addition, since the catalyst system using a hafnium compound described in JP-A-2-41303 has extremely low polymerization activity at low temperatures, a catalyst system containing a mixture of a zirconium compound and a hafnium compound is used to create a zindiotactic compound with a wide molecular weight distribution. To effectively produce olefins, it was necessary to polymerize them at high temperatures. Therefore, there was a problem that the syndiotacticity of the obtained polymer was reduced.

In the present invention, a method of producing syndiotactic polypropylene having a fast crystallization rate and good processability, and, if necessary, efficiently producing syndiotactic poly-α-olefin having a wide molecular weight distribution, was investigated.

[Means to solve the problem]

The present inventors have conducted intensive studies on a method for solving the above problems and producing poly-α-olefin with high activity and high syndiotacticity with good productivity.
Syndiotactic polypropylene with a high crystallization rate can be obtained by using a new transition metal compound having two transition metal atoms as a component of the catalyst, and syndiotactic polypropylene can be obtained by mixing it with other metallocene compounds. The present inventors have discovered that poly-α-olefins having a high molecular weight and a wide molecular weight distribution can be produced, and have completed the present invention.

That is, the present invention provides (1) a method for producing a poly-α-olefin by polymerizing an α-olefin in the presence of a catalyst consisting of a transition metal compound and a cocatalyst selected from aluminoxane or a boron compound. (However, AI represents a cyclopentadienyl group or a substituted cyclopentadienyl group, A2 represents a fluorenyl group or a substituted fluorenyl group, A3 represents a hydrocarbon diylidene group having 4 to 20 carbon atoms, and R1 and R2 represent a halogen atom. , a hydrogen atom, an aryl group having 1 to 10 carbon atoms, or an alkyl group (0M is titanium, zirconium, or hafnium). manufacturing method.

Further, in a method for producing a poly-α-olefin by polymerizing an α-olefin in the presence of a catalyst consisting of a transition metal compound and a cocatalyst selected from aluminoxane or a boron compound, it is described as a transition metal compound in claim (1). transition metal compound and general formula (If) (where, AI represents a cyclopentadienyl group or a substituted cyclopentagenyl group, A2 represents a fluorenyl group or a substituted fluorenyl group, and A4 represents an alkylidene having 4 to 20 carbon atoms. R1.R1 is an aryl group, an alkyl group, a cycloalkyl group, or a halogen atom, a hydrogen atom, or a silyl group.
A method for producing a syndiotactic poly-α-olefin using two types of transition metal compounds represented by (M is titanium, zirconium, or hafnium).

It has been confirmed that the method is useful as a method, and the present invention has been achieved.

Novel transition metal compounds used in the method of the invention (
1) is a novel metallocene compound having two transition metal atoms in one molecule.

A1 may be any from an unsubstituted cyclopentadienyl group to a 4-substituted cyclopentadienyl group, and A2 may be any from an unsubstituted fluorenyl group to an 8-substituted fluorenyl group.

A3 represents a hydrocarbon diylidene group having 4 to 20 carbon atoms.

Specific examples of A3 include, for example, 2.3-butanediylidene group, 2.4-pentadienyl group, 1.3-cyclopenkune diylidene group, 4-cyclopentene-1,3-diylidene group, and 2.5-hexane. Diylidene group, 1.4-
Cyclohexanediylidene group, 6-methyl-2,4-hebutanediylidene group, bicyclo(3,3,0)octane-3,7-diylidene group, bicyclo(3,3,1)nonane-3,7-diylidene group , 9.10-anthracene diylidene group, and the like.

R1 and R2 are halogen atoms such as fluorine, chlorine, bromine, and iodine, hydrogen atoms, methyl groups, ethyl groups, isopropyl groups, t-butyl groups, phenyl groups, and aryl groups or alkyl groups having 1 to 10 carbon atoms. , particularly preferably a chlorine atom or a methyl group.

R1 and p2 may be the same or different.

M is titanium, zirconium, or hafnium, preferably zirconium or hafnium, and may be the same or different.

For example, the synthetic route for the novel transition metal compound (1) of the present invention is shown below in the case of 1,4-cyclohedondiylidenebis ((cyclopentadienyl-9-fluorenyl)zirconium dihalide). It will be done.

CJsO□+2CsL-Cth)Is(=Cs11.
)z+21(g.

CJs(=CsHa)t+2LiC+Jq+2HCI
→ C, H Shun ((C5H5) CI3H? ] z+2L
icIC&HI ((CsHs)C+J*) 2 +
4nBuLi→ CJ@ ((LiCsHJLiC+
Js ) z +4CaH+.

CaHs ((LiCsH4)LiCsH4) z +
22rL" CbHe ((CsHs) (C+Js)
Z,)h]z+4LiX (X is a halogen atom) Sarani, above CJI C(C5H5) (C+sH@)
ZrXz) z is RLi or RMgCl (R is 1 carbon number
A compound in which at least one of X is substituted with R can be obtained by reacting with a metal alkyl compound of Group IA of the Periodic Table or Group 11A of the Periodic Table, such as 1 to 10 alkyl groups).

Specific examples of the novel transition metal compound (1) of the present invention include:
For example, 2,3-butanediylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride], 2,3-butanediylidenebis[(cyclopentadienyl-9-fluorenyl)hafnium dichloride]
, 2,3-butanediylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dimethyl], 2
．． 3-phthanediylidenebisC(cyclopencdiuni-9-fluorenyl)hafniumdimethyl], 2,5-
Hexacdiylidenebis [(cyclopentadienyl-9
-fluorenyl)zirconium dichloride], 2.5-
Hexacdiylidenebis [(cyclopentadienyl-9
-fluorenyl) hafnium dichloride], 2,5-hexacdiylidene bis[(cyclopentadienyl-9-
fluorenyl)zirconium dimethyl], 2,5-hexacdiylidenebis[(cyclopentadienyl-9-fluorenyl)hafniumdimethyl], 1,4-cyclohexanediylidenebis[(cyclopentadienyl-9-
fluorenyl) zirconium dichloride], 1.4-cyclohexanediylidene bis[(cyclopentagenyl-9-fluorenyl) hafnium dichloride], 1.4
-Cyclohexanediylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dimethyl], 1
．． 4-Cyclohexanediylidenebis[(cyclopentadienyl-9-fluorenyl)hafniumdimethyl L6
-Methyl-2,4-hebutanediylidene bis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride], 6-methyl-2,4-hebutanediylidene bis[(cyclopentadienyl-9-fluorenyl) ) hafnium dichloride], 6-methyl-2,4-hebutanediylidenebis[(cyclopentagenyl-9-fluorenyl)zirconium dimethyl], 6-methyl-2,4-
heptanediylidenebis [(cyclopentadienyl-9
-fluorenyl) hafnium dimethyl], bicyclo[3
3,0] octane-3,7-diylidenebis[(cyclopentagenyl-9-fluorenyl)zirconium dichloride], bicyclo(3,3,0)octane-3, fudiylidenebis[(cyclopecgenyl-9 -fluorenyl) hafnium dichloride], bicyclo(3,3,
0) Octane-3,7-diylidenebis((cyclopentadienyl-9-fluorenyl)zirconium dimethyl), bicyclo(3,30]octane-3,7-diylidenebis[(cyclopentadienyl-9-fluorenyl)
hafnium dimethyl], bicyclo(3,3,1)nonane-3,7 diylidenebis[(cyclopentagenyl-9
-fluorenyl)zirconium dichloride], bicyclo(3,3,1)nonane-3,7-diylidenebis[(cyclopentagenyl-9-fluorenyl)hafnium dichloride], bicyclo(3,3,1)nonane-3,7 −
Diylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dimethyl], bicyclo(3,3,
1) Nonane-3,7-diylidenebis [(cyclopentadienyl-9-fluorenyl)hafnium dimethyl)
, 9.10-anthrasecdiylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride], 9.10-anthrasecdiylidenebis[(cyclopentagenyl-9-fluorenyl)hafnium dichloride], 9 .10-andhrasecdiylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dimethyl), 9.10-anthrasecdiylidenebis[(cyclopentagenyl-9-fluorenyl)hafniumdimethyl), 1.4 -cyclohexacdiylidenebis[(tetramethylcyclopentadienyl-9-
fluorenyl) zirconium dichloride), 1,4-cyclohexacdiylidene bis[(tetramethylcyclopentagenyl-9-fluorenyl)hafnium dichloride), 1,4-cyclohexacdiylidene bis[(tetramethylcyclopentagenyl- 9-fluorenyl)
zirconiumdimethyl], 1,4-cyclohexacdiylidenebis[(tetramethylcyclopentadienyl-
9-fluorenyl)hafnium dimethyl), 1,4-cyclohexacdiylidenebis[(cyclopentadienyl-27-cyt-phthyl-9-fluorenyl)zirconium dichloride), 1,4-cyclohexacdiylidenebis[(cyclo pentagenyl-2,7-di-t-butyl-9-fluorenyl) hafnium dichloride),
1.4-Cyclohexacdiylidenebis[(cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl)zirconium dimethyl) + 1.4-cyclohexacdiylidenebis[(cyclopentadienyl 2. 7-
t-phthyl-9-fluorenyl) hafnium dimethyl), 1,4-cyclohexacdiylidene bis[
(Tetramethylcyclopentadienyl-2,7-t-
9-fluorenyl) zirconium dichloride)
, 1.4-cyclohexacdiylidenebis[(tetramethylcyclopentadienyl-2,7-di-t-phthyl-9-fluorenyl)hafnium dichloride), 1.4
-Cyclohexacdiylidenebis[(tetramethylcyclopentadienyl-2,7-butyl-9-fluorenyl)zirconium dimethyl), 1,4-cyclohexacdiylidenebis[(tetramethylcyclopentadienyl-2 , 7-di-t-butyl-9-fluorenyl) hafnium dimethyl].

These compounds can be synthesized according to the above reaction formula, and specifically, can be synthesized by a method analogous to the example of the present invention.

In the transition metal compound of general formula (II) used in the method of the present invention, A1, A2, A3, ill, R'' and gates are exemplified by those of general formula (1), and A4 has 1 to 20 carbon atoms. alkylidene group, cycloalkylidene group, silylene group,
It is a substituted silylene group, and specific examples include isopropylidene group, cyclopentylidene group, cyclohexylidene group,
Examples include dimethylsilylene group.

Specific examples of general formula (I[) include isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentajenyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentajenyl-9-fluorenyl) -fluorenyl)
Zirconium dimethyl, isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dimethyl,
Cyclopentylidene (cyclopentajenyl-9-fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentajenyl-9-fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentajenyl-9-fluorenyl) zirconium dimethyl, cyclopentylidene Cyclohexylidene (cyclopentajenyl-9-fluorenyl) hafnium dimethyl, cyclohexylidene (cyclopentajenyl-9-fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentajenyl-9-fluorenyl) hafnium dichloride, cyclohexylidene ( cyclopentagenyl-9-fluorenyl) zirconium dimethyl, cyclohexylidene (cyclopentagenyl-9-fluorenyl) hafnium dimethyl, isopropylidene (cyclopentagenyl, 2,
7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentajenyl-2,7-di-t-phthyl-9-fluorenyl) hafnium dichloride, isopropylidene (cyclopentagenyl-2,7-fluorenyl) t-phthyl-9-fluorenyl
Zirconium dimethyl, isopropylidene (cyclopentadienyl-2,7-di-butyl-9-fluorenyl), dimethylsilylene (cyclopentadienyl-9-fluorenyl), zirconium dichloride, dimethylsilylene (cyclopentadienyl) -9-
fluorenyl) hafnium dichloride, dimethylsilylene (cyclopentajenyl-9-fluorenyl) zirconium dimethyl, dimethylsilylene (cyclopentagenyl-9-fluorenyl) hafnium dimethyl, and the like.

In addition to known aluminoxanes, cocatalysts used with transition metal compounds during polymerization include
Although boron compounds such as those described in Japanese Patent Publication No. 1950 and Japanese Patent Publication No. 1950-1502036 can be used as co-catalysts, aluminoxanes are preferred from the viewpoint of activity and ease of availability.

Aluminoxanes are compounds represented by the general formula % (where R is a hydrocarbon group having 1 to 3 carbon atoms, and n is an integer of 2 or more), especially methylaluminoxane where R is a methyl group. Those in which n is 5 or more, preferably 10 or more are used. The above aluminoxanes may contain some alkylaluminum compounds.

Methods for producing the above aluminoxanes are known, such as a method in which trialkylaluminum is added to salts containing water of crystallization (copper sulfate hydrate, magnesium chloride hydrate, etc.) in a hydrocarbon solvent and reacted; Examples include a method in which trialkylaluminium and water are directly reacted in an organic compound solvent.

In addition, boron compounds that can be used as co-catalysts in combination with the transition metal compounds of the present invention are listed in Japanese Patent Application Publication No. 1-5
Boron compounds described in Japanese Patent Publication No. 01950 and Japanese Patent Application Publication No. Hei 1-502036 can be used.

The boron compound described in Japanese Patent Application Publication No. 1-501950 has the general formula % (where L"-H is H'", ammonium or up to 3 hydrogen atoms, and 1 to about 20 carbon atoms). or substituted ammonium cations, phosphonium groups, up to 3 hydrogen atoms, substituted hydrocarbyl groups containing from 1 to about 20 carbon atoms, in which one or more hydrogen atoms are replaced by halogen atoms. Substituted phosphonium groups whose atoms are substituted with hydrocarbyl groups containing from 1 to about 20 carbon atoms or substituted hydrocarbyl groups containing from 1 to about 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. B and C are boron and carbon, respectively; X, X' and X'' are hydride, halide, hydrocarbyl groups containing from 1 to about 20 carbon atoms,
1 where more than one hydrogen atom is replaced by a halogen atom
Hydrocarbyl groups containing ~20 carbon atoms, organic metalloid groups in which each hydrocarbyl substituent of the organic moiety contains 1 to about 20 carbon atoms, and the metal is selected from Groups V-A of the Periodic Table of the Elements, etc. a and b are integers of ≧0; C is ≧
is an integer of 1; a + c is an even integer from 2 to about 8; m is an integer from 5 to about 22. ) or the general formula %) (where L'-H is H, ammonium or a hydrocarbyl group containing up to 3 hydrogen atoms and 1 to about 20 carbon atoms, or one or more hydrogen atoms Substituted ammonium, phosphonium groups, substituted hydrocarbyl groups containing from 1 to about 20 carbon atoms, up to 3 hydrogen atoms substituted by halogen atoms, hydrocarbyl groups containing from 1 to about 20 carbon atoms or 1
1 where more than one hydrogen atom is replaced by a halogen atom
~ Any substituted phosphonium group substituted with a substituted hydrocarbyl group containing about 20 carbon atoms; B
, C, M, H are respectively boron, carbon, transition metal and hydrogen; x3, x4, X is a hydride group, a halide group, a hydrocarbyl group having from 1 to about 20 carbon atoms, one or more a substituted hydrocarbyl group containing from 1 to about 20 carbon atoms in which a hydrogen atom is replaced by a halogen atom, each hydrocarbyl substituent of the organic portion of the organometalloid containing from 1 to about 20 carbon atoms, and the metal is in the elemental period It is a group independently selected from the group consisting of organic metalloid groups selected from Group 1 V-A of the Table of Contents; a゛ and bo are the same or different integers ≧0; c゛ is ≧2. Integer; a' + b' + c' is an even integer from 4 to about 8; + is an integer from 6 to about 12;
n is an integer such that 2c'-n=d, and d is an integer of ≧1).

In addition, the boron compound described in Japanese Patent Publication No. 11-502036 has the general formula %) (where Lo is a neutral Lewis base; H is a hydrogen atom; [L'
-〇) is Brønsted acid; B is valent boron; Ar,
and Ar2 may be the same or different aromatic or substituted aromatic hydrocarbon groups containing from about 6 to 20 carbon atoms and are linked to each other by a safe bridging group, and x and x4 are hydride groups, halide groups. (At the same time, X, or
, with the condition that one of them is Khalid), 1~
a hydrocarbyl group containing about 20 carbon atoms, from 1 to 1 in which one or more hydrogen atoms are replaced by a halogen atom;
Substituted hydrocarbyl groups containing about 20 carbon atoms, each hydrocarbyl substituent containing from 1 to about 20 carbon atoms, and the metal being selected from Groups V-A of the Periodic Table of the Elements (organometalloids) The following compounds can be mentioned as specific examples of the boron compounds described in JP-A-1-501950.

Monohydrocarbyl substituted ammonium salts, such as methylammonium 1-carbadodecaborate, ethylammonium 1-carbadodecaborate, propylammonium 1-carbadodecaborate, isopropylammonium 1-carbadodecaborate, (a-butyl)ammonium 1-carbadodecaborate , ayulinium 1-rubadodecaporate, (p-)lyl)ammonium 1-
dihydrocarbyl-substituted ammonium salts such as carbadodecaborate, such as dimethylammonium 1-carbadodecaborate, diethylammonium 1-carbadodecaborate, dipropylammonium 1-carbadodecaborate, diisopropylammonium 1-carbadodecaborate, di(a -butyl)ammonium 1-carbadodecaborate, diphenylammonium 1-carbadodecaborate, di(p-)lyl)ammonium 1-carbadodecaborate, etc. nitrihydrocarbyl-substituted ammonium salts, such as trimethylammonium 1-carbadodecaborate, triethylammonium 1-carbadodecaborate, tripropylammonium 1-carbadodecaborate, tri(a-butyl)ammonium l-carbadodecaborate, triphenylammonium l-carbadodecaborate, tri(P-tolyl)ammonium 1-carbadodecaborate , N,N-dimethylayulinium carbarbadodecaborate, N,N-diethylayulinium 1-carbadodecaporate, and the like.

The boron compounds described in JP-A-502036 include trialkyl-substituted ammonium salts, such as triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(a-butyl)
Ammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammoniumtetra(0-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(0,P-dimethylphenyl)
Boron, tributylammoniumtetra(a,a-dimethylphenyl)boron, tributylammoniumtetra(p
-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-methyl)ammoniumtetra(0-tolyl)boron, etc.: N,N-dialkylanilinium salts, such as N,N-dimethylanilinium Nidialkylammonium salts such as niumtetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-2,4,6-bentamethylaniliniumtetra(phenyl)boron, etc. -propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron, etc.: and triarylphosphonium salts, such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphoniumtetra Examples include (phenyl)boron, tri(dimethylphenyl)phosphoniumtetra(phenyl)boron, and the like.

The metallocene compound and/or cocatalyst in the present invention may be used as is or supported on a known carrier supporting a Ziegler type catalyst such as SiO2, 61203 or MgClt.

In the present invention, the ratio of aluminoxane to the transition metal compound used is 10 to 10,000 times by mole, usually 50 times
~5000 times the mole.

There are no particular restrictions on the polymerization method and polymerization conditions carried out in the method of the present invention, and known methods for polymerizing α-olefins may be used, such as solvent polymerization using an inert hydrocarbon medium or substantially inert carbon Bulk polymerization method and gas phase polymerization method without hydrogenation medium can also be used, and the polymerization temperature is -100 to 200 degrees Celsius, and the polymerization pressure is normal pressure to 10 degrees Celsius.
It is common to carry out at 0 kg/cffl. Preferably, the temperature is -50°C to 100°C and normal pressure to 50 kg/d.

Examples of hydrocarbon media used during polymerization include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane, as well as aromatic hydrocarbons such as Hensen, toluene, and xylene. can be used.

The α-olefin used in the polymerization reaction includes propylene, 1-butene, 4-methyl-1-pentene, 1
-hexene, 1-octene, 1-decene, 1-dodecene,
Examples include α-olefins having 3 to 25 carbon atoms, such as 1-tetradecene, 1-hexadecene, and 1-octadecene.

In the present invention, not only homopolymerization of α-olefins but also copolymers of ethylene or α-olefins having about 2 to 25 carbon atoms, such as propylene and ethylene, propylene and 1-butene, etc. It can also be used when manufacturing.

The polypropylene obtained by the method of the present invention is characterized by a high crystallization temperature and a fast crystallization rate.

If the crystallization speed is slow, it will be difficult to crystallize the resin when pelletizing it, and it will be difficult to cut the strands into pellets.
When molding resin, it is difficult to take it out of the mold and problems occur during processing, but the polypropylene obtained by the method of the present invention can overcome the conventional drawbacks.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 Synthesis of metallocene compound C1,4-biscyclopentadienylidenecyclohexane] 15 g of 1,4-cyclohexanedione and 36 g of cyclopentadiene were placed in a 500 m four-bottle flask that was sufficiently purged with nitrogen.
Methanol 2001111! dissolved in. To this solution, 34 ml of pyrrolidine was added dropwise at 0°C over 30 minutes, and the mixture was returned to room temperature and stirred for 30 minutes. The reaction was stopped by adding 21d of acetic acid, and the solid was filtered, washed with methanol, and dried to obtain 39 g of brown 1,4-biscyclopentajunylidenecyclohexane.

C1,4-biscyclopentagenyl-1,4-bifluorenylcyclohexane] 16.6 g of fluorene was added to 150 Id of tetrahydrofuran in a 500 Id four-bottle flask that was sufficiently purged with nitrogen. A tetrahydrofuran solution of fluorenyllithium was obtained by dissolving and lithiation with methyllithium. To this solution, 1.4 g of 1,4-biscyclopentadienylidenecyclohexane synthesized above was added to 2 g of tetrahydrofuran.
The solution diluted with 00d was added dropwise at -10°C over 30 minutes. After the completion of the dropwise addition, the reaction temperature was raised to room temperature and stirring was continued for an additional 15 hours.

The reaction was stopped by charging 200 m of 3.6% hydrochloric acid water, and the formed solid was separated by filtration and washed with ether.

By drying, a white powder of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane 1 is obtained.
8.5g was obtained.

[1,4-Cyclohexacdiylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride] 1,4-biscyclopentadienyl 1.4 synthesized above
A tetralithium salt of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane was prepared by lithiation of -bifluorenylcyclohexane with n-butyllithium. Next, the nitrogen was replaced sufficiently.
6.1 g of zirconium tetrachloride in a 00d glass flask
was suspended in 100 d of methylene chloride. 300 d of a methylene chloride solution of 0,013 mol of the tetralithium salt of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane dissolved at -78 DEG C. was introduced into this suspension. After stirring at -78°C for 4 hours, the temperature was raised to room temperature, and the reaction was continued at that temperature for an additional 15 hours. The reddish-brown solution containing a white precipitate of lithium chloride is filtered off, concentrated and -
By cooling at 30''C for 24 hours, 3.1 g of orange 1,4-cyclohexacdiylidene bis[(cyclopangenyl-9-fluorenyl)zirconium dichloride] was obtained.

The elemental analysis values of the product are shown below.

CwtX HwtX ClwtX ZrwtX analysis value 5B, 6 3.72 16.5 21.2
Calculated value 58.1 3.78 16.7 20.
4. The measurement results of the 'H-NMR spectrum of this compound are shown in FIG.

The SUS autoclave of Polymerization Method 21 was purged with nitrogen, then charged with 11 toluene, and the above-prepared 1,4-cyclohexacdiylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride] 3.0■, East Methylaluminoxane manufactured by ThorAkzo (degree of polymerization 17.7) 0
．． 4 g was added. Add propylene to the system to 3kg/
Polymerization was carried out at 20°C for 1 hour while maintaining the temperature at edG.

After polymerization, the slurry was taken out, filtered, and dried to obtain 100.0 g of syndiotactic polypropylene powder.

Further, toluene in the filtrate was distilled off under reduced pressure to obtain 1.1 g of a toluene-soluble component.

The intrinsic viscosity (hereinafter abbreviated as η) of the powder measured in a tetralin solution at 135 °C is 0.60 dl/g,
GPC (gel, permeation chromatography)
The molecular weight distribution index (Mw/Mn) measured by was 2.7. "C-NMR was measured, and the syndiotactic pentand fraction determined from the peak attributed to the methyl group at about 2o, 2ppm was 0.91. The syndiotactic polypropylene obtained was heated at 230°C. The isothermal half-crystallization rate (t'A) measured by melting at 110° C. and cooling to 110° C. was 1 minute 22 seconds.

Example 2 After purging the SuS autoclave of 21 with nitrogen, L4-cyclohexacdiylidene bis [(
cyclopentadienyl-9-fluorenyl)zirconium dichloride) 2.0■, methylaluminoxane 0
．． 13 g was added. 400 g of liquid propylene was introduced into the system, and polymerization was carried out at 50° C. for 1 hour. 197.0 by purging unreacted propylene and drying under reduced pressure.
g of syndiotactic polypropylene powder was obtained.

The powder η is 0.52 cll/g, (Mw/Mn
) is 2.6, and the syndiotactic pentad fraction is 0.
83, t'/2 was 1 minute 12 seconds.

Comparative Example 1 Impropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride 3 synthesized by a conventional method
．． Polymerization was carried out in the same manner as in the [polymerization method] of Example 1 except that 0■ was used as the metallocene compound component. The obtained syndiotactic polypropylene powder was 126.
4g, toluene available fn 0.7g. The powder had η of 1.39 dl/g, (Mw/Mn) of 2.2, syndiotactic pentad fraction of 0.91, and t% of 3 minutes and 42 seconds.

Example 3 2.0 g of 1,4-cyclohexacdiylidene bis[(cyclopentadienyl-9-fluorenyl)zirconium dichloride] synthesized in Example 1 and isopropylidene (cyclopentadienyl- Example 1 except that a mixture with 1.0 μm of 9-fluorenyl)zirconium dichloride was used as the metallocene compound component.
Polymerization was carried out in the same manner as in [Polymerization method]. The obtained syndiotactic polypropylene powder weighed 84.3 g.
) The toluene soluble content was 0.3 g. Powder η is 0
．． 96 dl/g, (MH/Mn) was 6.2, syndiotactic pentad fraction was 0.91, and t% was 3 minutes 42 seconds.

Comparative Example 2 Isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride 1 synthesized in Comparative Example 1
．． [Polymerization method] was carried out in the same manner as in Example 1, except that a mixture of 0 ■ and 3.0 ■ of isopropylidene (cyclopentadienyl-9-fluorenyl) hafnium dichloride synthesized by a conventional method was used as the metallocene compound component. As a result of polymerization, 39.2 g of syndiotactic polypropylene powder, 0.4 g of luene soluble content
I got it. The powder η is 1.42d17 g, (M
u/Mn) was 2.5, the syndiotactic pentad fraction was 0.89, and tz was 3 minutes 26 seconds.

As mentioned above, it has not been possible to obtain a syndiotactic poly-α-olefin having a wide molecular weight distribution by the method of polymerizing at 20° C. using a known catalyst containing a mixture of a zirconium compound and a hafnium compound.

Comparative Example 3 Polymerization was carried out in the same manner as Comparative Example 2 except that the polymerization temperature was 50°C. The resulting syndiotactic polypropylene powder weighed 67.7 g, with a total weight of 1. It was Og. Powder η is 2.10 dl/g
, (Mw/Mn) was 6.4, the syndiotactic pentanod fraction was 0.78, and tz was 3 minutes 26 seconds.

Although it was possible to obtain syndiotactic polypropylene having a wide molecular weight distribution in the above method, the syndiotacticity was significantly reduced.

Example 4 Synthesis of metallocene compound 1.4-
A tetralithium salt of biscyclopentadienyl-1,4-bifluorenylcyclohexane was prepared.

Next, in a 500 ml glass flask that was sufficiently purged with nitrogen, 2.2 g of zirconium tetrachloride and 3,0
g was suspended in 100+ wl of methylene chloride solution. To this suspension, 300 ml of a methylene chloride solution of the tetralithium salt of 1,4-biscyclopentadienyl-1,4-bifluorenylcyclohexane synthesized above was charged at -78°C, and the mixture was heated at -78°C. After stirring for 4 hours, the temperature was raised to room temperature, and the reaction was further continued at room temperature for 15 hours.

The reddish-brown solution containing a white precipitate of lithium chloride was filtered, the filtrate was concentrated, and a solid was precipitated by cooling at −30° C. for 24 hours. By filtering and drying, 2.6 g of an orange solid was obtained.

The elemental analysis values of the above orange solid are C52,16χ, )I 3.21χ, Cj! 14,3
3χZr 9.04χ, l(f 20.50χ.

Polymerization test results 2I! After replacing the SUS autoclave with nitrogen,
2.0 mg of the orange solid synthesized above and 0.2 g of methylaluminoxane were added, and then 400 g of liquefied propylene was charged into an autoclave and polymerized at 50°C for 1 hour.

By purging unreacted propylene and drying the resulting polymer under reduced pressure, 116.2 g of powder was obtained. η of this powder was 0.93 dl/g, and (Mw/Mu) was 6.
．． 8. Syndiotactic pentad fraction is 0.82,
t% was 1 minute 46 seconds.

Example 5 Synthesis of metallocene compound Lithium salt of 27-di-t-butylfluorene and 6゜6
-Isopropylidene (cyclopentadiene-2,7-di-t-
Butylfluorene) was lithiated with n-butyllithium and reacted with zirconium tetrachloride to produce isopropylidene (cyclopentadienyl-2,7-di-t).
-butylfluorenyl) zirconium dichloride was obtained.

After purging the SUS autoclave of Polymerization Test Result 21 with nitrogen, 2.0 mg of (1,4-cyclohexacdiylidenebis[(cyclopentagenyl-9-fluorenyl)zirconium dichloride) synthesized in Example 1 and the above Isopropylidene (cyclopentadiene-2,7-di-t-butylfluorenyl) zirconium dichloride 1 synthesized in
Polymerization was carried out in the same manner as in Example 1, except that a mixture with OLlg and OLlg was used as the metallocene compound.

84.3 g of the resulting syndiotactic polypropylene powder and 0.1 g of toluene soluble content were obtained.

The obtained powder has η of 0.72 dl/g, (Mw/
Mn) was 4.7, syndiotactic pentad fraction was 0.92, and L% was 24 seconds.

[Brief explanation of the drawing]

Figure 1 shows 1,4-sochlorohexacdiylidene bis[(cyclopentadienyl-9-
'H-NMR of fluorenyl)zirconium dichloride
The measurement results are shown below. FIG. 2 shows a flow sheet of the poly-α-olefin manufacturing process of the present invention. (Effects of the Invention) By carrying out the method of the present invention, syndiotactic polypropylene with a fast crystallization rate can be produced with high activity, and the metallocene compound of the present invention can be used with conventional syndiotactic polypropylene. - Syndiotactic poly-α- effectively has a wide molecular weight distribution when used in combination with metallocene compounds for olefin production.
It can produce olefins and is extremely valuable industrially. Patent applicant Mitsui Toatsu Chemical Co., Ltd. Procedural amendment (method) November 2, 1990 as shown in the attached sheet? Day

Claims (2)

[Claims] (1) In a method for producing poly-α-olefin by polymerizing α-olefin in the presence of a catalyst consisting of a transition metal compound and a cocatalyst selected from aluminoxane or a boron compound, General formula (I) General formula ▲ Mathematical formula , chemical formulas, tables, etc.▼(I) (However, A^1 indicates a cyclopentadienyl group or substituted cyclopentadienyl group, A^2 indicates a fluorenyl group or substituted fluorenyl group. A^3 indicates Hydrocarbon diylidene group having 4 to 20 carbon atoms; R^1 and R^2 represent a halogen atom, a hydrogen atom, an aryl group or an alkyl group having 1 to 10 carbon atoms; M is titanium, zirconium, or hafnium) A method for producing a syndiotactic poly-α-olefin, which comprises using a novel transition metal compound represented by: (2) Claim (1) as a transition metal compound in a method for producing a poly-α-olefin by polymerizing an α-olefin in the presence of a catalyst consisting of a transition metal compound and a cocatalyst selected from aluminoxane or a boron compound. Transition metal compounds and general formula (II) described in ▲Mathematical formulas, chemical formulas, tables, etc.▼General formula (II) (However, A^1 represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and A ^2 represents a fluorenyl group or a substituted fluorenyl group.A^4 represents an alkylidene group having 1 to 20 carbon atoms, a cycloalkylidene group, a silylene group, or a substituted silylene group.R^1 and R^2 are A halogen atom, a hydrogen atom, an aryl group having 1 to 10 carbon atoms, an alkyl group, and M is titanium, zirconium, or hafnium. A method for producing syndiotactic poly-α-olefin.