JPH0469394A - New transition metal compound and production of syndiotactic poly-alpha-olefin using the same compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula (C5H4 is cyclopentadienyl; A<1> is disubstituted fluorenyl or 4-20C hydrocarbon to bring about crosslinking structure; R<1> and R<2> are halogen, 1-10C alkyl or aryl; M is titanium, zirconium or hafnium). EXAMPLE:Isopropylidene(cyclopentadienyl-2,7-di-tertiarybutyl-9-f-luore nyl) zirconium chloride. USE:A catalyst for producing syndiotactic poly-alpha-olefins. PREPARATION:For example, 2,7-di-tertiarybutylfluorene is dissolved in THF, a solution of methyllithium in an ether at -78 deg.C is dripped into the solution, the reaction temperature is raised to room temperature, the reaction is carried out, then 6,6-dimethylfulvene at -78 deg.C is dripped into the reaction solution. The reaction temperature is raised to room temperature for advance of reaction and the reaction solution is further reacted with zirconium tetrachloride to give a compound shown by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel transition metal compound and a process for producing sondiotactic Fukubori α-olefin using the same as a component of a catalyst.

[Prior Art] A method using a vanadium compound as a catalyst for producing syndiotactic poly-α-olefin has been known for a long time. However, polymers obtained using conventional catalysts consisting of vanadium compounds and organic aluminum have poor syndiotactic properties and cannot be said to exhibit the characteristics of syndiotactic poly-α-olefins.

On the other hand, in Japanese Patent Application Laid-open No. 2-41303, R” (C
p R-) (Cp R'-) M e Q *However, each Cp
is a cyclopentagenyl or substituted cyclopentagenyl ring; each R7, which may be the same or different, is a hydrocarbyl residue having 1 to 20 carbon atoms; each R' is the same or may be different and are hydrocarbyl residues having 1-20 carbon atoms; R'' is a structural bridge between the Cp rings that provides steric rigidity to the catalyst;
Me is a metal of group 4b, 5b, or 6b of the Periodic Table of the Elements; each Q is a hydrocarbyl residue or halogen having 1-20 carbon atoms; 10≧≧3:0≧n≧4;
and 1≧m≧4; and R′ is selected such that (CpR′, ) is sterically different from (CPR, ); It is described that highly syndiotactic polypropylene can be produced by polymerizing α-olefins using the following methods.

However, this publication only describes zirconium and hafnium compounds having isopropylidene (cyclopentadienyl-9-fluorenyl) 5 as a ligand, and the synthesis and synthesis of transition metals having a 2f-substituted fluorenyl group according to the present invention. There is no description of physical properties.

Further, JP-A-64-66214 discloses a method for polymerizing or copolymerizing α-olefins using a compound having at least one fluorenyl group or its derivative as a ligand as a catalyst component. It is not possible to obtain syndiotactic polyα-olefins using these compounds.

[Problem to be solved by the invention]

The transition metal compound having an isopropylidene (cyclopentagenyl-9-fluorenyl) group as a ligand disclosed in the above-mentioned JP-A-2-41303 can be used as a propylene polymerization catalyst in combination with a promoter such as aluminoxane. When used, polypropylene with good activity and high syndiotacticity can be obtained, but the resulting syndiotactic polypropylene has a slow crystallization rate and is difficult to process and mold.

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above problems and to synthesize a novel compound useful as a catalyst component capable of producing a highly active syndiotactic poly-α-olefin. , we have completed the present invention.

That is, the present invention provides - expansion (1) (where C5H4 is a cyclopentagenyl group, A1 is a 2-substituted fluorenyl group, A2 is bonded to the cyclopentagenyl group and the 2-substituted fluorenyl group, and the bridge is R', which represents a hydrocarbon group having 4 to 20 carbon atoms that provides a structure;
We succeeded in obtaining a new transition metal compound represented by R'' (halogen atom, alkyl group having 1 to 10 carbon atoms, or aryl group; 0M is titanium, zirconium, or hafnium) using the synthetic route described below. It was also confirmed through polymerization experiments that the transition metal compound is useful as a catalyst component for the production of syndiotactic poly-α-olefins.

In the formula of the transition metal compound (1) in the present invention, C5H= is a cyclopentadienyl group.

In the formula, A1 is the following formula (n) (where A3 is a chain or branched alkyl group having 1 to 10 carbon atoms, preferably a chain or branched alkyl group having 2 to 6 carbon atoms. ) is a di-substituted fluorenyl group.

Specific examples of AI include 2,7-diethyl 9-fluorenyl group, 2,7-diisopropyl-9-fluorenyl group, 2,7-di-tert-phthyl-9-fluorenyl group, 2,7-dibutyl 9-fluorenyl L
2,7-diisopentyl-9 fluorenyl group, 3,6-
Diethyl-9-fluorenyl group, 3,6-diisopropyl-9-fluorenyl group, 3,6-di-tert-butyl-9-fluorenyl group, 3,6-dibutyl-9
-fluorenyl L 3.6-diisopentyl-9-fluorenyl group, and the like.

A2 is bonded to the cyclopentadienyl group and the disubstituted fluorenyl group, and the bridge represents a hydrocarbon group having 1 to 20 carbon atoms that provides the structure.

A! Specific examples include a methylene group, an ethylidene group, an isopropylidene group, a 2-butylidene group, a cyclopentylidene group, a cyclohexylidene group, and a cyclohexylidene group.

R' and R'' are a halogen atom such as fluorine, chlorine, bromine, or iodine, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a phenyl group, or an aryl group, preferably a chlorine atom or a methyl group. be.

R1 and Rz may be the same or different.

M is titanium, zirconium or hafnium, preferably zirconium or hafnium.

Regarding the synthesis method of the transition metal compound of the present invention, please refer to Japanese Patent Application Laid-Open No.
A method similar to the method for synthesizing a transition metal compound described in JP-41303 can be employed.

That is, the synthetic route of the transition metal compound (+) of the present invention can be abbreviated as follows.

A1□C+ Js÷CH＊Li→A3□C+ JvLi
+CH4-・-(11^"-CsL+A'tC+JtL
i+HC1→A" (C5H5) (A'□C+J7)
+LiC1・−−−−・−−−−−−(2) A” (C
sHs) (A″ICI 38?) +2n-CaLL
i→[A”(CsHa) (A”2C13H&)]
Ljz+2n-CJ+o"'-""(:31[A"
(C5H4) (A'□C+J6)] Li□+MX
, →[A”(Csl(a)(A'zCwH5)]MXz
+2LiX--(4) (X is a halogen atom, A"
, A3, and M have the same meanings as above. ) Disubstituted fluorene^'2 used in the above reaction formula (1)
CI3811 can be produced by employing the known Fr1edel-Crafrs alkylation reaction.

Fulvene compound A2=C used in the above reaction formula (2)
For example, the manufacturing method for 5H is J, O+yg, chem, 4
9.1849 (1984).

A” (C5)15) obtained by the above reaction formula (2) (
A3□C+Ji) is a new compound, obtained as a mixture of and useful as an intermediate for synthesizing the novel transition metal compound of the present invention.

A” (CsHs) (A
3□C+J,) can be reacted with alkyllithium or metallic lithium to form a dilithium salt, which can be used in the next reaction. It can also be used as a dipotassium salt or a disodium salt.

Solvents used when reacting A''(C5H5) (A2fC+zHt) with an alkali metal or an organic alkali metal compound include ethers such as diethyl ether, tetrahydrofuran, and dimethoxyethane, heptane,
Saturated hydrocarbon compounds such as hexane, pentane, etc. can be used.

The ratio of the alkali metal or organic alkali metal compound to A" (CsHs) (A" 150°C1 preferably -90
It is in the range of °C to 90 °C.

[A”(C5H4) (A'2C13H&) ] Li
Examples of the solvent used in the reaction between 2 and -x4 include halogenated hydrocarbons such as chloroform and methylene chloride, saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and quinrene. In addition to hydrogen, ethers such as diethyl ether and tetrahydrofuran can also be used.

Also, when performing the reaction [A”(C5)l,) (A3□C
1JJ] The molar ratio of Li2/gate X4 is 0.9 to 3.0
The zero reaction layer degree, which is preferably 1.0 to 1°5, is -100
It is preferably in the range of -90°C to 50°C.

In addition, [A” (C5H,) (A
X in '□C,3Hh)lnxz is easily substituted with an alkyl group by reacting with an alkyl metal compound such as methyllithium or methylmagnesium bromide. As the solvent used in this case, in addition to ethers such as diethyl ether and tetrahydrofuran, saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene can also be used. . Also, when performing a reaction, [A” (CJ4) (A3□C+zHb) ] MXz
The molar ratio of the alkyl metal compound used is 1.0 to 1.
010 The reaction temperature is preferably between 1.0 and 3.0 -
100″C~100°C3 Preferably 90°C~80°
It is in the range of C.

The produced compound (1) can be purified by recrystallization or sublimation.

The transition metal compound (1) in the present invention is used in combination with a promoter component for the polymerization of α-olefins. The co-catalyst used is aluminoxane or Tokuhyo Sen1-5.
Boron compounds selected from those described in Japanese Patent Publication No. 01950 and Japanese Patent Application Publication No. 11-502036 can be used.

R+A jl! -0-+TA f RZ (where R is a hydrocarbon group having 1 to 4 carbon atoms), especially methylaluminoxane where R is a methyl group, n
is 5 or more, preferably n is 10 or more.

The above-mentioned method for producing aluminoxane is publicly 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. can be exemplified.

As a boron compound, as described in Japanese Patent Publication No. 1,1-501950, the general formula % formula % (where L'-H has Ho, ammonium or up to 3 hydrogen atoms, and 1 to about 20 a substituted ammonium cation, a phosphonium group, substituted by a hydrocarbyl group containing from 1 to about 20 carbon atoms, or a substituted hydrocarbyl group containing from 1 to about 20 carbon atoms, in which one or more hydrogen atoms are replaced by a halogen atom; up to 2 hydrogen atoms are substituted with a hydrocarbyl group containing from 1 to about 20 carbon atoms, or with a substituted hydrocarbyl group containing from 1 to about 20 carbon atoms in which one or more hydrogen atoms are replaced by a halogen atom. B and C are boron and carbon, respectively. X, X' and X'' are hydride groups, halide groups, etc.
Hydrocarbyl groups containing from 1 to about 20 carbon atoms, from 1 to 1 in which one or more hydrogen atoms are replaced by halogen atoms
Hydrocarbyl groups containing about 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 Group TV-A of the Periodic Table of the Elements, etc. a and b are integers of ≧0; C is ≧1;
a+b+c is an even integer from 2 to about 8; m is an integer from 5 to about 22. ) or - expanded % formula %) M "l '- (where L'-H is Ho, ammonium or a hydrocarbyl group containing up to 3 hydrogen atoms and 1 to about 20 carbon atoms, or 1 Substituted ammonium, phosphonium groups containing from 1 to about 20 carbon atoms substituted with substituted hydrocarbyl groups containing from 1 to about 20 carbon atoms, in which up to 3 hydrogen atoms are replaced by halogen atoms; a substituted phosphonium group substituted with a hydrocarbyl group containing atoms or a substituted hydrocarbyl group containing from 1 to about 20 carbon atoms in which one or more hydrogen atoms are replaced by a halogen atom; , M, and H are boron, carbon, transition metal, and hydrogen, respectively; χ3, a substituted hydrocarbyl group containing 1 to about 20 carbon atoms substituted with a halogen atom, each hydrocarbyl substituent of the organic portion of the organic metalloid containing 1 to about 20 carbon atoms;
The metal is a group independently selected from the group consisting of organic metalloid groups selected from Group 1V-A of the Periodic Table of the Elements; ao and bo are the same or different integers ≧0;
C is an integer of ≧2; a' + b' + c'' is from 4 to about 8
m is an integer from 6 to about 12; n is an integer such that 2c'-n=d, and d is an integer ≧1). (Here, L' is a neutral Lewis base; H is a hydrogen atom [L'-
H] is Brønsted acid; B is boron with a valence of 3; ^rl
and Arz may be the same or different aromatic or substituted aromatic hydrocarbon groups containing about 6 to 20 carbon atoms and are linked to each other by a stable bridging group, x: I and x4 are hydride groups, Halide group (with the proviso that either X or X4 is a halide at the same time), 1
a hydrocarbyl group containing ~20 carbon atoms, one or more hydrogen atoms replaced by a halogen atom
substituted hydrocarbyl groups containing from about 20 carbon atoms, each hydrocarbyl substituent group containing from 1 to about 20 carbon atoms;
Examples of these boron compounds include the following: It will be done.

Monohydrocarbyl substituted ammonium salts, such as methylammonium 1-carhetothi' caporate, ethylammonium 1-carbadodecaborate, propylammonium 1-carbadodecaborate, isopropylammonium l-carbadodecaborate, (a-butyl)ammonium 1-carbado Decaborate, ayulinium 1-
Carbadodecaborate, (p-tolyl)ammonium 1
Hydrocarbyl ammonium salts such as carbadodecaborate, such as dimethylammonium 1-rubadoborate, diethylammonium 1-rubadoborate, dipropylammonium 1-rubadoborate, diisopropylammonium 1-rubadoborate, Nitrihydrocarbyl-substituted ammonium salts such as di(a-butyl)ammonium 1-carbadodecaporate, diphenylammonium 1-carbadodecaborate, di(p-tolyl)ammonium 1-carbadodecaporate, e.g. trimethylammonium 1-carbadodecaborate, etc. Carbadodecaborate, triethylammonium 1-carbadodecaborate, tripropylammonium 1-carbadodecaborate, tri(a-butyl)ammonium l-carbadodecaborate, triphenylammonium l-carbadodecaborate, tri[p-tolyl]ammonium These include 1-rubadode porate, N,N-dimethylayulinium 1-rubadode porate, and NN-diethyl aurinium 1-ruba dode borate.

Trialkyl-substituted ammonium salts, such as triethylammoniumtetra(phenyl)boron, triflobylammoniumtetra(pheni/1zllllll), tri(
a-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(P-)lyl)boron, trimethylammoniumtetra(0-tolyl)boron, tributyl, ammoniumtetra(pentafluorophenyl)
Boron, tripropylammonium tetra(0,P-trimethylphenyl)boron, tributylammonium tetra(
aa-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammoniumtetra(0-
) diNN dialkylanilinium salts, such as N,N-dimethylanilinium tetra(phenyl)
Nidialkyl ammonium salts such as boron, N,N-diethylaniliniumtetra(phenyl)boron
pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron, etc.; and triarylphosphonium salts, such as triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)
These include phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, and the like.

The metallocene compound and/or co-catalyst in the present invention may be used as is or supported on a known carrier supporting a Ziegler type catalyst such as SiO□, AlzO3, MgC1z.

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 limitations on the polymerization method and polymerization conditions carried out in the method of the present invention, including a solvent polymerization method using an inert hydrocarbon medium, a bulk polymerization method substantially free of an inert hydrocarbon medium, and a gas phase polymerization method. can also be used, and the polymerization temperature is -100 to 200°C, and the polymerization pressure is normal pressure to 1.
It is common to carry out at 00 kg/CIII. Preferably, the temperature is -50°C to 100" C1 normal pressure to 50 kg/cd.

Examples of the hydrocarbon medium used during polymerization include saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopenkune, and cyclohexane, as well as aromatic hydrocarbons such as \\zene, toluene, and xylene. can also be used.

The α-olefin used in the polymerization reaction includes propylene, 1-butene, 4-methyl-1pentene, 1-
Hexene, ■-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 polymers with 2 carbon atoms such as propylene and ethylene, propylene and 1-butene, etc., can be used as long as they exhibit a syndiotactic structure.
It can also be used to produce copolymers of ethylene or α-olefins with a molecular weight of about 25%.

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

If the crystallization rate is slow, problems occur during processing because it is difficult to crystallize when pelletizing the resin, making it difficult to cut the strands into pellets, and making it difficult to take out the resin from the mold during molding. However, the method of the present invention Poly α obtained with
-Olefins can overcome the traditional drawbacks.

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 [Isopropylidene (cyclopentadiene 2.7-theta-jasso-butyl-9-fluorene)] 27-
tert-butylfluorene 12.0 g (S
synthesized by the method described in Synthesis 335 (1984)) was dissolved in 100d of tetrahydrofuran. Add 44 volumes of methyllithium to this 78 liquid.
mmol was added dropwise at -78°C. After the dropwise addition was completed, the reaction solution was raised to room temperature and stirred at that temperature for 3 hours. To this reaction solution, 4.6 g of 6,6 dimethylfulvene diluted with 50 d of tetrahydrofuran was added dropwise at -78°C.

After the dropwise addition was completed, the reaction temperature was raised to room temperature, and stirring was continued for an additional 10 hours. The reaction was stopped by adding 100 d of 3.6% hydrochloric acid, and the ether layer was washed with water and evaporated to dryness to obtain 16.4 g of a reddish brown viscous liquid.

This viscous liquid was separated and purified by column chromatography to obtain isopropylidene (fuclopentadiene-2, Fuclopentadiene-2, butyl-9-fluorene).

The physical properties of the second compound are shown below.

Elemental analysis value C! 1H34H Calculated value (%) 90.63 9.37 Actual value (%
) 90.51 9.41 [isopropylidene (
cyclopentadiene-2゜7-theta-jatu-butyl-9-fluorenyl)zirconium dichloride]
2,7-theta-butyl-9-fluorene)
By lithiation of 10.0g with n-butyllithium, isopropylidene (cyclopentadiene-2,
The dilithium salt of 7-di-t-phthyl-9-fluorene was prepared.

Next, 6.1 g of zirconium tetrachloride was suspended in 100 d of methylene chloride in a 500 megaglass flask that had been sufficiently purged with nitrogen. To this suspension, 300 ml of a methylene chloride solution of dilithium isopropylidene (cyclopentadienyl-27=dibutyl-9-fluorenyl) dissolved at -78"C was introduced at -78"C.
After stirring at 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 was filtered off, the reddish-brown filtrate was concentrated, and the orange crystals of isopropylidene (cyclopentadienyl-2,7-theta) were obtained by cooling at -30°C for 24 hours. Jasso-Fuchiru 9
-fluorenyl) zirconium dichloride (3.8 g) was obtained.

The physical properties of this compound are shown below.

Elemental analysis value Czq H2, ZrchCHC1 Calculated value (%) 63.97 6.25 13.
0 Actual value (%) 64,13 6.22 12
．． 87H-NMR: Figure 1 Example 2 [Polymerization] After replacing the 2N autoclave with nitrogen, toluene, 1
! was charged, followed by isopropylidene (fuclopentagenyl-2, Fugitive t-butyl-2) synthesized in Example 1.
9-fluorenyl) zirconium dichloride 0.003
7 mmol and 0.2 g of methylaluminoxane (polymerization degree 16.1) manufactured by Tosoh Akzo Corporation were added. Add propylene and maintain the system at 3 kg/c-20"C.
After polymerization for 1 hour, the slurry was taken out, filtered and dried to obtain 137.2 g of syndiotactic polypropylene powder. The scratch limiting viscosity (hereinafter abbreviated as η) of the powder measured in a tetralin solution at 135°C is 0.
．． 96a/g, and the syndiotactic pentad fraction measured by I3C-NMR was 0.92. 10'C
The melting point was determined by differential scanning calorimetry (DSC) at a heating rate of 153°C/min.
The crystallization temperature determined by C was 110°C.

In addition, after melting at 230°C for 5 minutes using DSC, the temperature was maintained at 110°C and the isothermal crystallization rate (T
I/□) was measured and found to be 12 seconds.

Comparative Example 1 Polymerization was carried out in the same manner as [Polymerization method] of Example 1 except that isopropylidene (cyclopentadienyl-9-fluorenyl) zirconium dichloride synthesized according to a conventional method was used as the transition metal compound component. The amount of syndiotactic polypropylene powder obtained was 82.9 g. The powder η is 138 di/g, the syndiotactic pentanode fraction is 0.91, and the melting point is 150 °C.
1 The crystallization temperature was 92°C.

The isothermal crystallization rate (T, 7□) at 110'C measured in the same manner as in Example 2 was 205 seconds.

[Brief explanation of the drawing]

FIG. 1 shows the results of 'H-NMR measurements of isopropylidene (fuclopentadienyl-2, fujterdiary-phthyl-9-fluorenyl) zirconium dichloride obtained in Example 1 of the present specification. FIG. 2 shows a flow sheet of the process for producing polyα-olefin of the present invention. [Effects of the Invention] By using the transition metal compound of the present invention as a catalyst component, a highly active syndiotactic polyα-olefin can be produced, and a syndiotactic polyα-olefin with a fast crystallization rate and a high crystallization temperature can be produced. Otakutic Poly-α-
It can produce olefins and is extremely valuable industrially. Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, C_5H_4 is a cyclopentadienyl group, A
^1 represents a 2-substituted fluorenyl group. A^2 represents a hydrocarbon group having 4 to 20 carbon atoms that is bonded to the cyclopentadienyl group and the disubstituted fluorenyl group to form a bridged structure. R^1 and R^2 represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. M is titanium, zirconium, or hafnium. ) A new transition metal compound represented by (2) Claimed as a transition metal compound in a method for producing a syndiotactic 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. 1. A method for producing a syndiotactic poly-α-olefin, comprising using the transition metal compound according to 1.