JPH1053611A - Olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst high in polymerization activity and capable of giving a polymer excellent in copolymerizability, etc., on the polymerization of an olefin by combining a compound having a specific structure and containing a transition metal belonging to the group IV in the periodic table with an aluminoxane, etc. SOLUTION: This catalyst for polymerizing an olefin is obtained from (A) a compound containing a transition metal belonging to the group IV in the periodic table and represented by formulae I to IV (M is the transition metal belonging to the group IV; X is H, a halogen, a 1-12C hydrocarbon group, a 1-12C hydrocarbon amide group, etc.; Y is H, a 1-20C hydrocarbon substituent, etc.; R is H, a 1-12C hydrocarbon group; R' is a 2-12C hydrocarbon group) and (B) an aluminoxane or an ionic compound capable of reacting with the component A to produce a cationic transition metal compound. The ionic compound includes the ionic compound of tetrakis(pentafluorophenyl)borate anion with an active proton-bearing amine cation. Thereby, an olefinic (co)polymer narrow in mol.wt. distribution and excellent in mechanical physical properties can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and highly active catalyst for olefin polymerization.

[0002]

2. Description of the Related Art In recent years, Ti, Zr, Hf, V, and the like, which are highly active as olefin polymerization catalysts, have narrow molecular weight distributions of formed polymers and narrow composition distributions in copolymerization, and can provide olefin polymers having excellent physical properties. Attention has been focused on metallocene-type homogeneous catalysts. These complex catalysts are well known as catalyst systems using an ionic compound capable of forming a non-coordinating anion by reacting with an organoaluminum oxy compound such as methylalumoxane or a metallocene as a cocatalyst.

Recently, metallocene complexes having a Lewis base functional group containing a nitrogen atom in the cyclopentadienyl ligand are well known. Meanwhile, Organometallics, 1994,
Volume 13, pages 4140-4142 propose that titanocene having a Lewis base functional group containing a nitrogen atom in a cyclopentadienyl ligand as shown in formula (5) can be used as an olefin polymerization catalyst. .

[0004]

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[0005]

The above-mentioned transition metal compounds as homogeneous catalysts are all expensive, and there is a demand for the development of a new inexpensive catalyst system having polymerization performance that can be industrially employed. I have.

[0006]

According to the present invention, there is provided (A) a compound represented by the following general formula:
An olefin obtained from a transition metal compound belonging to Group IV of the periodic table represented by any of (1) to (4) and (B) an aluminoxane or an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound It relates to a catalyst system for polymerization.

[0007]

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Wherein M is a Group IV transition metal, X is hydrogen,
Halogen, hydrocarbon group having 1 to 12 carbon atoms, 1 to 12 carbon atoms
12 is a hydrocarbon amide group or a hydrocarbon oxy group having 1 to 12 carbon atoms, and Y is hydrogen or a hydrocarbon substituent having 1 to 20 carbon atoms, which itself forms a ring with a cyclopentadienyl group. R may be hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and R 'may be a hydrocarbon group having 2 to 12 carbon atoms. )

The transition metal of Group IV of the periodic table of the present invention is Ti,
Zr or Hf. X is hydrogen, halogen, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon amide group having 1 to 12 carbon atoms, or a hydrocarbon oxy group having 1 to 12 carbon atoms. X
As preferred, a chlorine atom as a halogen, methyl, benzyl, neopentyl group as a hydrocarbon group, diethylamide as a hydrocarbon amide group, di-t-butylamide,
Examples of the dioctylamide group and the hydrocarbon oxy group include methoxy, ethoxy, and isopropoxy groups.

Y is hydrogen or a hydrocarbon substituent having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl and benzyl; and silicon such as trimethylsilyl. Hydrocarbon groups containing atoms are also included. Y attached to the cyclopentadienyl ring can form a polycyclic group such as an indenyl group and a fluorenyl group together with the cyclopentadienyl ring. Further, in the formulas (1) and (3), two kinds of cyclopentadienyl rings are linked to each other by a bridging group such as a Me ₂ Si group, a dimethylmethylene group, a methylphenylmethylene group, a diphenylmethylene group, an ethylene group, and a substituted ethylene group. Also included are those joined by. R is a hydrocarbon group having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, and benzyl. Further, R may be different from each other. R '
Is a hydrocarbon group having 2 to 12 carbon atoms, such as ethyl, propyl, isopropyl, butyl, t-butyl, phenyl, and benzyl.

Specific examples of the transition metal compounds of Group IV of the periodic table represented by the formulas (1) to (4) of the present invention include the following formula (6)
~ (14). Here, the transition metal of M is preferably Ti or Zr.

[0012]

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[0013]

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Compound of the formula (6) wherein M is Ti: cyclopentadienyl ((2-dimethylaminoethyl) cyclopentadienyl) titanium dichloride Compound of the formula (7) wherein M is Ti: cyclopentadienyl (Tetramethyl (2-dimethylaminoethyl) cyclopentadienyl) titanium dichloride Compound of the formula (8) wherein M is Ti: pentamethylcyclopentadienyl ((2-dimethylaminoethyl) cyclopentadienyl) titanium dichloride Compound of the formula (9) wherein M is Ti: ((2-diethylaminoethyl) cyclopentadienyl) titanium trichloride Compound of the formula (10) wherein M is Ti: (tetramethyl (2-diethylaminoethyl) cyclopentane Dienyl) titanium trichloride A compound of the formula (11) wherein M is Ti: cyclopentadienyl ( o- dimethylaminobenzyl) cyclopentadienyl) titanium dichloride formula (12) by M is Ti compound: cyclopentadienyl ((o- dimethylamino cumyl) cyclopentadienyl)
Titanium dichloride Compound of the formula (13) wherein M is Ti: ((o-dimethylaminobenzyl) cyclopentadienyl) titanium trichloride Compound of the formula (14) wherein M is Ti: ((o-dimethylaminocumyl ) Cyclopentadienyl) titanium trichloride

The transition metal compound of the present invention can be prepared, for example, by the method described in Organometallics, 1994, Vol. 13, pages 4140-4142, or by the following synthesis method.

The compound represented by the formula (1) is represented by R ₂ NCH ₂ CH ₂ Cl
And CpNa to R ₂ NCH ₂ CH ₂ CpH and then NaH to R ₂ NCH ₂
It is converted to CH ₂ CpNa and finally obtained by reaction with CpMCl ₃ .

The compound represented by the formula (3) is Li (o-NR ₂ C
₆ H ₄ ) with substituted or unsubstituted fulvene to react with CpCR ₂ (o-NR ₂
The cyclopentadienyl derivative of C ₆ H ₄ ) is first synthesized and obtained by reaction with CpMCl ₃ after conversion to an alkali metal salt.

The compound represented by the formula (2) or (4)_TwoNC
H_TwoCH_TwoCpLi or Cp (Li) CR_Two(o-NR_TwoC₆H _Four) Me_ThreeBy SiCl
Methylsilylated cyclopentazinyl ligand and MCl
_Four Can be synthesized by the reaction with

In the present invention, the periodic rule represented by the equations (1) to (4)
Table IV transition metal compounds with alumoxane and / or
Reacts with a transfer metal compound to form a cationic complex
Polymerization of olefins in combination with ionic compounds
Can be. The alumoxane in the present invention has the general formula (-
Al (R) O-)_nIs a linear or cyclic polymer represented by
(R is a hydrocarbon group having 1 to 10 carbon atoms;
And those substituted with an RO atom and / or RO group. n is
Degree of polymerization, 5 or more, preferably 10 or more)
It is an aluminum oxy compound. R is methyl,
Ethyl, propyl and isobutyl groups.
Preferred is a thiol group. Reacts with transition metal compounds and becomes cationic
Examples of ionic compounds capable of forming a complex include metallocene
Tetrakis (pentafluorophene) well known in catalyst systems
Nyl) borate anion, for example (CH_Three)_TwoN (C₆H_Five) H⁺
An amine cation having an active proton such as (C₆H_Five)
_ThreeC ⁺Trisubstituted carbonium cations such as carborane
Has cation, metal carborane cation, transition metal
Use of an ionic compound with ferrocenium cation
Can be.

In the present invention, a conjugated diene is polymerized in combination with a metal hydride compound, an organometallic compound of a main element metal of Groups I to III of the periodic table, an organometallic halogen compound, and a hydrogenated organometallic compound. can do.
As the metal hydride compound, for example, NaH, LiH, Ca
H ₂ , LiAlH ₄ , NaBH ₄ , as the organometallic compound of the main element metal, for example, methyl lithium, butyl lithium, phenyl lithium, dibutyl magnesium, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl Aluminum, as an organometallic halogen compound,
For example, ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride,
Diethyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride,
Examples of the hydrogenated organometallic compound include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In the present invention, the transition metal compound and / or
Alternatively, an ionic compound can be used by being supported on an inorganic compound or an organic polymer compound. As the inorganic compound as the carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonate and sulfate can also be used. Particularly preferred are inorganic oxides, silica, alumina, magnesia, titania, zirconia,
Calcia and the like. These inorganic oxides have an average particle size of 5 to 150 μ and a specific surface area of 2 to 800 m ² / g
The porous fine particles are preferably used, for example, after being heat-treated at 100 to 800 ° C. The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring, or a functional group such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom in a side chain. As specific examples, ethylene, propylene, α-olefin homopolymer having the functional group by chemical modification such as polybutene, α-olefin copolymer, acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, homopolymer such as divinylbenzene, Copolymers and their chemically modified products can be mentioned. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used. By supporting the transition metal compound and / or the ionic compound, contamination due to adhesion of the catalyst to the polymerization reactor can be prevented.

In the present invention, olefin polymerization includes copolymerization of different olefins. The polymerization can be carried out by contacting the olefin as a solution or a slurry of hydrocarbons or halogenated hydrocarbons of each component, or, for example, after contacting in advance in the absence of olefin, and then polymerizing the olefin.

Examples of the hydrocarbon solvent for dissolving and slurrying each component include inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene, and halogenated hydrocarbon solvents. Examples include chloroform, methylene chloride, dichloroethane, chlorobenzene and the like.

In the above, the contact of each component is usually from 0 to
Perform at 100 ° C for 10 to 180 minutes. The molar ratio of the aluminoxane / transition metal compound is usually 10 to 10,000, preferably 100 to 3000, and the molar ratio of the ionic compound / transition metal compound is usually 0.01 to 100, preferably 0.1 to 10. is there. Further, when the organometallic compound is shared, the molar ratio of the organometallic compound / transition metal compound is usually from 0.1 to 10,000.
, Preferably 1 to 1000.

The olefin polymerization in the present invention is usually carried out by a fluidized or stirred gas phase method using a supported catalyst, a slurry method in an inert hydrocarbon solvent, a solution method in an inert hydrocarbon solvent at high temperature, High-temperature / high-pressure polymerization method can be adopted for any polymerization method. The polymerization conditions are, for example, in the gas phase method or the slurry method, the temperature is 5 to 110 ° C., the time is 10 to 360 minutes,
Atmospheric pressure to 100 kg / cm ² pressure, the solution process, the temperature from 100 to 250
° C., time 1 to 60 minutes, the pressure in 10~300kg / cm ² under a high-temperature high-pressure polymerization processes, a temperature 120 to 300 ° C., 5 to 600 seconds, the pressure
It is performed at 400 kg / cm ² or more.

In addition, the polymerization activity is improved, the shape of the solid catalyst of the produced polymer is maintained, the catalyst is easily introduced into the polymerization reactor, the catalyst is prevented from adhering to the polymerization reactor, and the fluidity in the gas phase reactor is improved. For the purpose, for example, an olefin that has been preliminarily polymerized according to the above various polymerization methods can be used as a catalyst in the main polymerization. The prepolymerization is performed, for example, in a slurry method in an inert hydrocarbon solvent, usually at 5 to 80 ° C. for 5 to 60 minutes, under conditions in which 1 to 100 g of an olefin polymer can be obtained per 1 mg atom of the transition metal of the metallocene. Can be.

Specific examples of the olefin in the present invention include:
Ethylene, propylene, butene-1, 4-methylpentene
1, acyclic monoolefins such as hexene-1 and octene-1, and cyclic monoolefins such as cyclopentene, cyclohexene and norbornene. Also,
In the above-mentioned olefin polymerization and copolymerization, a small amount of a non-conjugated diolefin such as dicyclopentadiene, 5-ethylidene-2-norbornene or 1,5-hexadiene can be further copolymerized.

[0028]

The catalyst system of the present invention has a high polymerization activity, and the obtained (co) polymer has a narrow copolymerizability and a narrow molecular weight distribution.
Excellent mechanical properties.

[0029]

EXAMPLES In the examples, "polymerization activity" refers to the yield (g) of polymer per 1 mmol of transition metal of the transition metal compound catalyst used in the polymerization reaction. The molecular weight distribution was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.

Example 1 [Synthesis of transition metal compound] A Ti complex represented by the formula (6) was synthesized by the following method. Me ₂ NCH ₂ CH ₂ OH and SO in CHCl ₃ solvent
Me ₂ NCH ₂ CH ₂ Cl.HCl is produced by reaction with Cl ₂ and Me ₂ NCH ₂ CH ₂ Cl is obtained by NaOH treatment, and then Me ₂ NCH ₂ C is formed by reaction with CpNa.
After generating Me ₂ NCH ₂ CH ₂ CpNa metal salt with H ₂ Cp and further NaH, finally reacting CpTiCl ₄ to obtain the target red
Cp (Me ₂ NCH ₂ CH ₂ Cp) TiCl ₂ was obtained. The complex melted and decomposed at 168-170 ° C.

[Polymerization of ethylene] To 200 ml of toluene, 10 mmol of methylalumoxane (manufactured by Tosoh Akzo) is added as a toluene solution, and the solution is kept at 40 ° C. Ethylene
While flowing at a rate of 1000 ml / min., 5 μmol of the above-mentioned Cp (Me ₂ NCH ₂ CH ₂ Cp) TiCl ₂ as a transition metal compound was added as a toluene solution, and polymerization was carried out for 1 hour. The polymerization was stopped with an ethanol solution containing HCl, filtered and dried to obtain a white ethylene polymer. The activity was 550 (g / mmol.Ti.h.atm).

Example 2 [Synthesis of transition metal compound] A Ti complex represented by the formula (7) was synthesized by the following method. Synthesis was performed in the same manner as in the transition metal compound of Example 1 except that Et ₂ NCH ₂ CH ₂ OH was used instead of Me ₂ NCH ₂ CH ₂ OH as a raw material. Red Cp (Et ₂ NCH ₂ CH
₂ Cp) TiCl ₂ was obtained. The complex melted and decomposed at 167-169 ° C.

[Polymerization of ethylene] Ethylene was polymerized in the same manner as in Example 1. The activity was 40 (g / mmol.Mhatm).

Example 3 (C) as an ionic compound instead of methylalumoxane
Ethylene was polymerized in the same manner as in Example 1 except that 7.50 μmol of ₆ H ₅ ) ₃ C ⁺ B (C ₆ F ₅ ) ₄ ^- and 1 mmol of triisobutylaluminum were added as a toluene solution. Activity is 950 (g / mmo
lMhatm).

Example 4 [Synthesis of transition metal compound] BrC ₆ H ₄ NH ₂ was converted with Me ₂ SO ₄ .
BrC ₆ H ₄ conversion to NMe _2, to give a LiC ₆ H ₄ NMe ₂ from BuLi, fulvene, cyclopentadienyl derivatives CpCM by water treatment
e ₂ C ₆ H ₄ NMe ₂ was synthesized. Next, K (THF) is used for KCpCMe ₂ C ₆ H ₄ NMe ₂
After forming the metal salt, finally, CpTiCl ₄ was reacted to obtain Cp (CpCMe ₂ C ₆ H ₄ NMe ₂ ) TiCl ₂ as a target substance. The results of elemental analysis were as follows: 61.46% carbon (calculated value 61.14%), 6.19% hydrogen (6.10%
%) And nitrogen was 3.31% (3.41%).

[Polymerization of Ethylene] Ethylene was polymerized under the same polymerization conditions as in Example 1 except that the above compound was used as the transition metal compound. The activity is 102 (g / mmol.Mha
tm). Mw was 1440000 and Mw / Mn was 2.9.

Claims (1)

[Claims] 1. A (A) transition metal compound of Group IV of the Periodic Table represented by the general formulas (1) to (4) and (B) an aluminoxane or the transition metal compound to react with the cationic transition metal compound. An olefin polymerization catalyst system obtained from the ionic compound that can be formed. Embedded image (Wherein, M is a Group IV transition metal, X is hydrogen, halogen, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon amide group having 1 to 12 carbon atoms, or a hydrocarbonoxy group having 1 to 12 carbon atoms) , Y
Is hydrogen or a hydrocarbon substituent having 1 to 20 carbon atoms, which may itself form a ring with a cyclopentadienyl group, and R is hydrogen or a hydrocarbon group having 1 to 12 carbon atoms;
R 'is a hydrocarbon group having 2 to 12 carbon atoms. )