JPH08143623A - Polymerization of olefin - Google Patents

Abstract

PURPOSE: To provide a method for producing a polyolefin having a high molecular weight by a high catalyst activity, by coexisting a nickel ylide complex with a specific Lewis acid compound. CONSTITUTION: This polymerization method of olefin is performed in the presence of a catalyst composed of (A) a reaction product of following components (a), (b) and (c) and (B) a lewis acid compound selected from the group of an organic aluminumoxy compound, an organic aluminum compound and an organic boron compound. (a) a zero-valent nickel compound, (b) a ylide compound expressed by R<1> 3 P=CR<2> -C(O)R<3> (R<1> is a 1-12C hydrocarbon group, R<2> and R<3> are each hydrogen or a 1-12C hydrocarbon group) and (c) a phosphorus compound selected from ylides expressed by R<4> 3 P, R<4> 3 PO and R<5> 3 P=CR<6> R<7> (R<4> and R<5> are each a 1-12C hydrocarbon group, R<6> and R<7> are each hydrogen, a 1-12C hydrocarbon group or an SiR3 group).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing olefins using a novel catalyst system.

[0002]

2. Description of the Related Art Heretofore, there has been known a method of polymerizing ethylene using a nickel ylide complex synthesized by reacting a zero-valent nickel compound and an ylide compound. As the nickel ylide complex, for example,
(C ₆ H ₅ ) ₃ P = CR-C (O) R obtained from an ylide compound represented by (C ₆ H ₅ ) ₂ P = CR-C (O) R Positioned nickel ylide complexes have been reported.

For example, Angewandte Chemie, Internal Ed
ition in English, 1978, Volume 17, No.6, page 466, same
1985, Volume 24, No. 7, p. 599, Transition Metal Cat
alyzed Polymerization 2nd, 1986, Cambridge University, Quirk Roderic P, 472 pages, Transition Metal
s and Organometallics as Catalysts for Olefin Poly
merization, 1988, Springer-Verlag Berlin Heidelb
erg, W. Kaminsky and H. Sinn, p. 349.

Further, JP-A-3-131608, 131131, and
6-122720, 122721 and 122722 have (C ₆ H ₅ ) ₃ P = C
In RC (O) R, the substituents on two carbon atoms form monocyclic or polycyclic hydrocarbon groups with each other in the presence of ylide compounds and zero-valent nickel compounds, and in the presence of Lewis bases. A method for producing an ethylene polymer has been proposed.

The Journal of Molecular Catalysis v
ol.41, p123 (1987), bis (cyclooctadiene) nickel and bis (ethylene) (acetylacetonate) were used in the polymerization system in order to highly polymerize ethylene with nickel ylide complex as a catalyst. Although a method of adding a complex such as nickel is known, it is not preferable because a large amount of the transition metal compound residue remains in the polymer.

[0006]

An object of the present invention is to provide an olefin polymerization method capable of giving a high molecular weight polyolefin using a nickel-based catalyst with high catalytic activity.

[0007]

The present invention provides (A) reaction products of the following components (a), (b) and (c), and
(B) A method of polymerizing an olefin in the presence of a catalyst comprising a Lewis acidic compound selected from the group consisting of an organoaluminum oxy compound, an organoaluminum compound and an organoboron compound. (a) Zero-valent nickel compound, (b) Formula R ¹ ₃ P = CR ² -C (O) R ³
(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ represent hydrogen, and a hydrocarbon group having 1 to 12 carbon atoms.), (C) Formula R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ (In the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen, and 1 to 12 carbon atoms. A hydrocarbon compound or a -SiR ₃ group)

The component (A) of the catalyst in the present invention is as follows.
Reaction products of (a), (b) and (c). That is, (a) is a zero-valent nickel compound, (b) is the formula R ¹ ₃ P = CR ² -C (O) R
³ (wherein, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ are hydrogen. Indicating a hydrocarbon group having 1 to 12 carbon atoms) ylide compound represented by, and (c) Formulas R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = C
R ⁶ R ⁷ (in the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶
And R ⁷ is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, or —SiR ₃
Indicates a group. ) A phosphorus compound selected from the represented ylides.

The above-mentioned (a) zero-valent nickel compound means a compound in which various ligands are bound to nickel having a zero oxidation number by a coordinate bond.

In this case, the ligand includes phosphine (eg triphenylphosphine), olefin (eg ethylene, norbornadiene, cyclooctadiene), nitrile (eg acrylonitrile), carbonyl and the like.

Specific examples of the zero-valent nickel compound include:
Bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, bis (triphenylphosphine) (1,5-cyclooctadiene) nickel, nickel (tetracarbonyl), bis (acrylonitrile) nickel, bis (Norbornadiene) nickel can be mentioned.

[0012] As the ylide compound of the above (b), R ¹ ₃ P
= Is a compound represented by ^{CR 2 -C (O) R 3} . R ¹ is a carbon number 1 ~
12 hydrocarbon groups, preferably a phenyl group or a substituted phenyl group. R ² and R ³ are hydrogen and a hydrocarbon group having 1 to 12 carbon atoms. As R ² and R ³ , a monocyclic or polycyclic hydrocarbon group may be formed with two carbon atoms to which R ² and R ³ are bonded.

As a specific example, (C ₆ H ₅ ) ₃ P = CH-C (O) CH ₃ ,
(C ₆ H ₅ ) ₃ P = CH-C (O) (C ₆ H ₅ ), or JP-A-61-2720,
The ylide compounds described in Nos. 122721 and 122722 can be mentioned.

Examples of the above-mentioned (c) ylide compound include R
⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ are ylides. R
⁴ is preferably a hydrocarbon group having 1 to 12 carbon atoms, particularly a phenyl group or a substituted phenyl group. R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, and a phenyl group and an isopropyl group are particularly preferable. R ⁶ and R ⁷ are hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, and trialkylsilyl (—SiR ₃ ).

Specific examples include triphenylmethylenephosphorane (C ₆ H ₅ ) ₃ P = CH ₂ , triisopropylmethylenephosphorane (isoC ₃ H ₇ ) ₃ P = CH ₂ , (isoC ₃ H ₇ ) ₃ P = CH (C ₆ H ₅ ) and the like.

In the present invention, the component (B) is a Lewis acidic compound selected from the group consisting of organic aluminum oxy compounds, organic aluminum compounds and organic boron compounds.

As the organoaluminum oxy compound,
It is a linear or cyclic polymer represented by the general formula (-Al (R ') O-) _m, where R'is a hydrocarbon group having 1 to 10 carbon atoms, and a part of hydrogen, a halogen atom and, or, It also includes those substituted with R'O groups. n is the degree of polymerization and is 3 or more, preferably 10 or more. Particularly, methylalumoxane in which R ′ is a methyl group is preferable.

Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, triphenylaluminum, trioctylaluminum, dimethylethoxyaluminum, diethylethoxyaluminum, diisobutylethoxyaluminum, ethyldiethoxyaluminum, triethoxy. Aluminum can be mentioned.

Examples of the organic boron compound include trimethylboron, triethylboron, tributylboron, triphenylboron, dimethylmethoxyboron, diethylethoxyboron, diphenylethoxyboron and triethoxyboron.

Of the organoaluminum oxy compounds, the organoaluminum compounds and the organoboron compounds, the organoboron compounds are more preferred because they do not reduce the nickel ylide complex to reduce the polymerization activity and the polymer molecular weight. Two or more kinds of these Lewis acidic compounds may be mixed and used.

In the present invention, the nickel ylide complex can be synthesized in the presence of an inorganic compound or an organic polymer compound and used as a supported catalyst. As the inorganic compound as a carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be adopted. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia. 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 porous fine particles are preferred, for example 100-800
It can be heat-treated at ° C and used. The organic polymer compound is preferably one having 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 its side chain.

Specific examples include α-olefin homopolymers and α-olefin copolymers having the above-mentioned functional groups by chemical modification of polyethylene, polypropylene, polybutene, or acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinyl. Mention may be made of homopolymers or copolymers such as benzene, as well as their chemical modifications. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 µ are used.

In the present invention, although not particularly limited,
Olefin can be polymerized by the following method with the above-mentioned catalyst system for olefin polymerization. However, in the present invention, olefin polymerization also includes olefin polymerization and copolymerization between different olefins.

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 non-conjugated diolefin such as dicyclopentadiene, 5-ethylidene-2-norbornene, or 1,5-hexadiene can be copolymerized.

Olefin polymerization is usually carried out by using a supported catalyst in a fluidized or agitated gas phase method, a slurry method in an inert hydrocarbon solvent, a solution method in an inert hydrocarbon solvent at a high temperature, a high temperature / high pressure gravity method. It can be adopted in any legal polymerization method.

The polymerization conditions are, for example, in the gas phase method or the slurry method, a temperature of 5 to 110 ° C., a time of 10 to 360 minutes,
The pressure is preferably atmospheric pressure to 100 kg / cm ² .

In the solution method, the temperature is 100 to 250 ° C. and the time is 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., time 5-600 seconds, the pressure 400 kg /
cm ² or more is preferable.

[0028]

INDUSTRIAL APPLICABILITY In the present invention, it is possible to produce a high molecular weight polyolefin with high catalytic activity by allowing a nickel ylide complex to coexist with a special Lewis acid compound.

[0029]

EXAMPLES In the examples, "polymerization activity" is the polymer yield (kg) per mol of the transition metal used in the polymerization reaction. The molecular weight distribution is the weight average molecular weight Mw and number average molecular weight Mn obtained from GPC using polystyrene as a standard substance.
Was evaluated by the ratio Mw / Mn.

Example 1 300 ml of a toluene solution containing 50 mmol of bis (1,5-cyclooctadiene) nickel was cooled to 0 ° C., 50 mmol of triphenylphosphine and (C ₆ H ₅ ) ₃ P = CH-C (O)
450 ml of a toluene solution in which 50 mmol of (C ₆ H ₅ ) was dissolved was gradually added dropwise, and the mixture was further reacted at 50 ° C. for 2 hours. 50 ° C toluene
Methylalumoxane as a toluene solution in 600 ml
Add 1 mmol in conversion, keep the total pressure with ethylene at 20 kg / cm ² , and add the above reaction solution in a glass ampoule (40% as Ni metal).
(containing μ mol) was destroyed to start polymerization, and ethylene polymerization was continued for 1 hour. Polyethylene with Mw of 5100 and Mw / Mn of 1.9 was obtained with an activity of 92.5 kg / M.Ni.h.

Example 2 Triphenylboron was added in place of methylalumoxane in an amount of 0.
Ethylene was polymerized in the same manner as in Example 1 except that 4 mmol was used. Polymerization activity is 98.7 kg / M.Ni.h and Mw is 75.
00 and Mw / Mn were 2.5.

Comparative Example 1 Ethylene polymerization was carried out in the same manner as in Example 1 except that methylalumoxane was not used. The polymerization activity was 8.7 kg / M.Ni.h, and an oligomer was obtained.

Example 3 300 ml of a toluene solution containing 50 mmol of bis (1,5-cyclooctadiene) nickel was cooled to 0 ° C., and triphenylmethylenephosphorane ((C ₆ H ₅ ) ₃ P = CH was stirred. ₂ ) 50 mmol and (C ₆ H ₅ ) ₃ P = CH—C (O) (CH ₃ ) 50 mmol dissolved in toluene solution 450 ml were gradually added dropwise, and the mixture was further reacted at 50 ° C. for 2 hours. Methylalumoxane as a toluene solution in 0.25 mmol was added to 600 ml of toluene at 50 ° C, the total pressure was maintained at 20 kg / cm ² with ethylene, and the above reaction solution (containing 40 μmol as Ni metal) in a glass ampoule was destroyed. The polymerization was started by continuing the polymerization for 1 hour. Polymerization activity
It was 46.8 kg / M.Ni.h, Mw was 7700, and Mw / Mn was 2.0.

Example 4 In place of methylalumoxane, triphenylboron was added to 0.1%.
Ethylene polymerization was carried out in the same manner as in Example 3 except that 4 mmol was used. Polymerization activity is 41.6kg / M.Ni.h, Mw is 83
00 and Mw / Mn were 2.7.

Comparative Example 2 Ethylene polymerization was carried out in the same manner as in Example 3 except that methylalumoxane was not used. Polymerization activity was 1.8 kg / M.Ni.h, Mw was 7300, and Mw / Mn was 2.2.

Example 5 According to the method described in Example 1 of JP-A-6-12720,
Hexamethyldisilazane was reacted with the yellow solid (melting point 164-170 ° C) obtained by the reaction of 4-naphthoquinone and triphenylphosphine, and then triphenylphosphine oxide and Ni (1,5-cyclooctadiene) ₂ were added. The reaction with heating was carried out to prepare a nickel ylide complex solution. 50 ℃ toluene 600m
Add 0.25 mmol of methylalumoxane as a toluene solution in terms of Al in terms of Al, keep the total pressure at 20 kg / cm ² with ethylene, and destroy the above reaction solution (40 μmol with Ni metal) in the glass ampoule to start polymerization. Then, ethylene polymerization was continued for 1 hour. Polyethylene with Mw of 58700 and Mw / Mn of 9.0 is active
It was obtained at 91.8 kg / M.Ni.h.

Example 6 Triphenylboron was used in place of methylalumoxane in an amount of 0.3.
Ethylene was polymerized in the same manner as in Example 5 except that 4 mmol was used. Polymerization activity is 112 kg / M.Ni.h, Mw is 5900.
0 and Mw / Mn were 7.5.

Example 7 Trimethoxyboron was added in place of methylalumoxane to 0.1%.
Ethylene was polymerized in the same manner as in Example 5 except that 4 mmol was used. Polymerization activity is 54.2 kg / M.Ni.h and Mw is 21.
000 and Mw / Mn were 3.0.

Comparative Example 3 Ethylene polymerization was carried out in the same manner as in Example 5 except that methylalumoxane was not used. The polymerization activity was 50.2 kg / M.Ni.h, Mw was 58700, and Mw / Mn was 6.7.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuhiro Mitani 8-1 Goi Minamikaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Research Institute

Claims (1)

[Claims] 1. (A) The following components (a), (b), and (c)
A method of polymerizing an olefin in the presence of the reaction product of (1) and a catalyst comprising (B) a Lewis acidic compound selected from the group consisting of an organoaluminumoxy compound, an organoaluminum compound and an organoboron compound. (a) Zero-valent nickel compound, (b) Formula R ¹ ₃ P = CR ² -C (O) R ³
(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ represent hydrogen, and a hydrocarbon group having 1 to 12 carbon atoms.), (C) Formula R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ (In the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen, and 1 to 12 carbon atoms. A hydrocarbon group or a -SiR ₃ group), which is a phosphorus compound selected from the ylides represented by.