JPH0892309A - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

(57) [Summary] [Structure] [A] At least one transition metal compound represented by the following general formula [1]: And [B] an olefin polymerization catalyst comprising an organoaluminum compound and / or an organoboron compound. [Effect] By using the catalyst of the present invention, an olefin polymer can be produced with high activity and is industrially extremely useful.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel olefin polymerization catalyst and a method for producing an olefin polymer in the presence of the catalyst, more specifically, a specific transition metal compound and an organoaluminum compound and / or The present invention relates to an olefin polymerization catalyst comprising an organic boron compound and a method for producing an olefin polymer in the presence of this catalyst.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an α-olefin polymer, ethylene has been used in the presence of a titanium catalyst composed of a titanium compound and an organoaluminum compound or a vanadium catalyst composed of a vanadium compound and an organoaluminum compound. There is known a method of copolymerizing a vinyl ester with an α-olefin. Generally, an ethylene / α-olefin copolymer obtained with a titanium-based catalyst has a wide molecular weight distribution and composition distribution, and is inferior in transparency, surface non-adhesiveness and mechanical properties. In addition, the ethylene / α-olefin copolymer obtained with the vanadium catalyst has a narrower molecular weight distribution and composition distribution than those obtained with the titanium catalyst, and has improved transparency, surface non-adhesiveness and mechanical properties. However, the activity of the catalyst was not sufficient, and it was essential to remove the catalyst residue from the produced polymer.

On the other hand, a catalyst composed of a metallocene compound and an aluminoxane has recently been proposed as a new catalyst for olefin polymerization. For example, JP-A-58-19309, JP-A-60-35006, and JP-A-61-13
It is described in Japanese Patent Application No. 0314 and Japanese Patent Application Laid-Open No. 2-41303 that the catalyst system is highly active in the polymerization of olefins. Further, a catalyst system using a transition metal compound other than the metallocene compound is disclosed in JP-A-4-185614.
JP-A-5-155923, JP-A5-25-25
Although described in each of JP-A-30133, the activity is not sufficient, and the appearance of a catalyst having higher activity is desired.

[0004]

An object of the present invention is to provide a catalyst for olefin polymerization which comprises a transition metal compound and an organoaluminum compound and / or an organoboron compound and has excellent polymerization activity. Furthermore, it is an object to provide a method for polymerizing an olefin in the presence of this catalyst.

[0005]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that a catalyst composed of a specific transition metal compound and an organoaluminum compound and / or an organoboron compound is used in the polymerization of olefins. The inventors have found that they exhibit high activity and arrived at the present invention. That is,
The present invention provides [A] at least one transition metal compound represented by the following general formula [1]

[0006]

[Chemical 3]

(In the formula, each A and B may be the same or different.
Good aromatic hydrocarbon residue, or halogen or silicon containing
Group, nitrogen-containing group, sulfur-containing group, phosphorus-containing group, halogen
Hydrocarbon water having 1 to 20 carbon atoms which may have a substituent
Is it a group consisting of elementary groups, alkoxy groups and aryloxy groups?
A substituted aromatic hydrocarbon residue having a substituent selected from
Each X¹, X²May be the same or different O, S
Or NR⁰And R ⁰Is no hydrogen atom or carbon number 1
20 hydrocarbon groups. Also, M is the number of the periodic table
A metal of groups 3, 4, 5, 6 and R¹Are the same but different
Optionally hydrogen, halogen, silicon-containing groups, halogen
Carbon atoms having 1 to 20 carbon atoms, which may have a substituent
Indicates a hydrogen group, an alkoxy group or an aryloxy group
You ), And [B] an organoaluminum compound and /
Or catalyst for olefin polymerization consisting of organic boron compound
The present invention also relates to olefin polymerization using the above catalyst.
It is a method of manufacturing a united body.

The olefin polymerization catalyst and the method for producing the olefin polymer of the present invention will be specifically described below. In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymer but also copolymer. Sometimes used in a sense. [Transition Metal Compound] The transition metal compound [A] used in the present invention is a transition metal compound represented by the following general formula [1].

[0009]

[Chemical 4]

Here, each of A and B has an aromatic hydrocarbon residue which may be the same or different, or has a halogen, a silicon-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group or a halogen substituent. And a substituted aromatic hydrocarbon residue having a substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group and an aryloxy group. Specifically, A and B are as follows.

[0011]

[Chemical 5]

Here, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ and R ⁹ may be the same or different and are hydrogen, a halogen atom, SiR ₃ ¹⁰ , NR ₂ ¹⁰ and SR ¹⁰ (R
¹⁰ is hydrogen which may be the same or different, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group or an aryloxy group. ), A hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group or an aryloxy group. Each X ¹ and X ² are O, S or NR ⁰ which may be the same or different, R ⁰ is hydrogen, methyl group, ethyl group, normal propyl group, isopropyl group,
It is a hydrocarbon group having 1 to 20 carbon atoms such as a normal butyl group, a tert-butyl group, an isobutyl group and a phenyl group.

M is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or the like metal of Group 3, 4, 5 and 6 of the periodic table, especially titanium and zirconium. Hafnium is preferred. R ¹
May be the same or different, hydrogen, halogen, trimethylsilyl group, triphenylsilyl group, silicon-containing substituents such as trimethoxysilyl group, trifluoromethyl group,
Methyl group, ethyl group, isopropyl group, tert-butyl group, hydrocarbon group which may have a halogen substituent such as phenyl group, methoxy group, ethoxy group, butoxy group,
It is an alkoxy group such as a phenoxy group or an aryloxy group. Specific examples of the above-mentioned transition metal compounds are as follows, taking titanium as an example.

[0014]

[Chemical 6]

Further, a mixture of these compounds may be used. Next, the organoaluminum compound and the organoboron compound used in the present invention will be described in detail. Examples of the organoaluminum compound used in the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, diethylaluminum monochloride, diethylaluminum monomethoxide, halogen such as diethylaluminum monohydride. , Aluminoxanes such as alkoxy- or hydrogen-containing alkylaluminum, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and chloroaluminoxane, among which aluminoxanes are particularly preferable.

Examples of the organic boron compound used in the present invention include tetraphenylboron, tri (pentafluorophenyl) boron, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-). Trialkyl-substituted ammonium salts such as butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (q-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron; N, N- Dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6
-N, N-dialkylanilinium salts such as pentamethylanilinium tetra (phenyl) boron, di (1-propyl) ammonium tetra (pentafluorophenyl)
Boron, dialkylammonium salts such as dicyclohexylammonium tetra (phenyl) boron, triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra And triarylphosphonium salts such as (phenyl) boron. As a method for obtaining a polymerization catalyst from the components [A] and [B], the molar ratio of the transition metal atom in the component [A] to the aluminum atom and / or boron atom in the component [B] is 1: 0. 1-1000
It is preferably 0000, particularly 1: 0.5 to 1,000,000. In addition, two or more kinds of organic aluminum compounds and organic boron compounds may be used at the same time.

[Polymerization Method] The olefin polymerization method according to the present invention comprises the above-mentioned [A] transition metal compound,
[B] The olefin is polymerized in the presence of the organoaluminum compound and / or the organoboron compound. As a method for bringing the component [A] and the component [B] into contact with each other, the components may be contacted with each other in a separate vessel in advance, or may be contacted with each other in the polymerization reactor before or during the polymerization. good. This contact may be carried out in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is -20 ° C. to the boiling point of the solvent, preferably room temperature to the boiling point of the solvent.

The olefins applicable to the polymerization method of the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-hexene, 3-methyl-1-butene and 4-methyl. -1-Pentene, 1-octene, 1-decene, 1-dodecene, vinylcycloalkane, styrene or derivatives thereof;
Cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cyclohexene, norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene and the like; and non-conjugated polyene having 5 to 20 carbon atoms such as 1,4-pentadiene and 1,5-hexadiene. Further, the polymerization can be suitably applied to not only homopolymerization but also generally known random copolymerization and block copolymerization.

It is also possible to preliminarily polymerize the above-mentioned olefins such as ethylene, propylene, 1-butene, 1-hexene, etc. before the polymerization and wash them if necessary, and use them as a catalyst. This preliminary polymerization is preferably carried out under a mild condition in an inert solvent, and 0.01 g per 1 g of the catalyst is used.
It is desirable to carry out so as to produce ˜1000 g, preferably 0.1 to 100 g of polymer. In the present invention, the polymerization is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but normal pressure to about 2000 kg · f / c is preferable.
It is in the range of m ² . Further, hydrogen may be present as a molecular weight modifier in the polymerization system.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples without departing from the gist thereof. Also,
FIG. 1 is a flow chart diagram for helping understanding of the technical contents included in the present invention, and the present invention is not restricted by the flow chart diagram unless it deviates from the gist thereof.

<Example 1>(6,6'-dimethyl-
Synthesis of 1,1′-biphenyl-2,2′-dioxy-titanium dichloride) TiCl ₄ (TH
F) 1.33 g of ₂ is transferred and dissolved in 5 ml of dry THF. Then, the reaction system was cooled to -55 ° C, and 0.73 g of 6,6'dimethyl-2,2'-dihydroxybiphenyl was added thereto.
Using a Teflon cannula, 5 ml of a dry THF solution of
Drip over about 20 minutes. The reaction solution becomes a red suspension solution. The temperature of the mixture was slowly raised to room temperature, and the solvent was distilled off under reduced pressure to obtain 2.6 g of a red tar-like solid. This solid was washed 6 times with 5 ml of dry ether and dried under vacuum to obtain 1.01 g of 6,6'-dimethyl-1,1'-biphenyl-2,2'-dioxy-titanium dichloride as an orange solid.

<Example 2> (Polymerization of Ethylene) Tare of a Schlenk reaction vessel sufficiently replaced with nitrogen was weighed,
6,6'-dimethyl-1,1'-biphenyl-2,2 '
-Dioxy-titanium dichloride 0.06mmo
1 Weighed precisely. After adding 20 ml of dry toluene to the solution and dissolving it well, 6.38 ml of a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo) (12 in terms of Al atom)
mmol) was added. Next, ethylene gas was blown into this solution through a glass bubbler to initiate polymerization. Then, after continuing the supply of ethylene gas for 10 minutes,
Polymerization was stopped by adding 1 ml of methanol to obtain a white solid. This is further added with hydrochloric acid-methanol (methanol 500
After thoroughly washing with (ml + hydrochloric acid 1 ml), it was dried to obtain 0.33 g of an ethylene polymer.

<Example 3> (Polymerization of ethylene) Polymerization of ethylene was carried out in the same manner as in Example 2 except that 0.6 mmol of triethylaluminum was used in place of methylaluminoxane. 0.15g of coalescence was obtained. <Example 4> (Polymerization of ethylene) Polymerization of ethylene was carried out in the same manner as in Example 2 except that 0.084 mmol of dimethylphenylammonium tetra (pentafluorophenyl) boron was used in place of methylaluminoxane. As a result, 0.21 g of an ethylene polymer was obtained.

<Example 5> (Polymerization of ethylene) The tare of a Schlenk reaction vessel sufficiently nitrogen-substituted was weighed,
6,6'-dimethyl-1,1'-biphenyl-2,2 '
-Dioxy-titanium dichloride 0.011 mm
ol was precisely weighed. After adding 10 ml of dry toluene to the solution and dissolving it well, 1.2 ml of a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo Co., Ltd.) (2.
2 mmol) was added. Next, the temperature of the reaction system was raised to 50 ° C. with stirring, and 3.0 ml of dry styrene was added to initiate polymerization. After 4 hours, 1 ml of methanol was added to terminate the polymerization. The produced white solid was further thoroughly washed with hydrochloric acid-methanol (500 ml of methanol + 1 ml of hydrochloric acid) and then dried to obtain 1.52 g of a styrene polymer. Then, the obtained white solid was put into a cylindrical filter paper, and Soxhlet extraction was carried out for 12 hours using methyl ethyl ketone as a solvent to obtain 0.73 g of syndiotactic polystyrene. From this, the syndiotactic selectivity was 48%.

[0025]

EFFECTS OF THE INVENTION By using the catalyst of the present invention, an olefin polymer can be produced with high activity and is industrially very useful.

[Brief description of drawings]

FIG. 1 is a flowchart showing a catalyst system of the present invention.

Claims (4)

[Claims] 1. A small amount represented by the following general formula [1]:
At least one transition metal compound(In the formula, each A and B may be the same or different.
Hydrocarbon residue, halogen, silicon-containing group, nitrogen-containing
Has a group, a sulfur-containing group, a phosphorus-containing group, a halogen substituent
Optionally substituted hydrocarbon group having 1 to 20 carbon atoms, alco
A unit selected from the group consisting of an oxy group and an aryloxy group.
A substituted aromatic hydrocarbon residue having a substituent, each X¹,
X²May be the same or different, O, S or NR⁰so
Oh, R ⁰Is a hydrogen atom or carbonization having 1 to 20 carbon atoms
It is a hydrogen group. M is the third, fourth, fifth, sixth of the periodic table
Group metals, R¹May be the same or different
Has hydrogen, halogen, silicon-containing groups, halogen substituents
Optionally substituted hydrocarbon group having 1 to 20 carbon atoms, alco
An oxy group or an aryloxy group is shown. ), And [B]
Organic aluminum compound and / or organic boron compound
Olefin polymerization catalyst consisting of a product. 2. The catalyst for olefin polymerization according to claim 1, wherein the organoaluminum compound in the catalyst component [B] is an aluminoxane. 3. A small amount represented by the following general formula [1]:
At least one kind of transition metal compound(In the formula, each A and B may be the same or different.
Hydrocarbon residue, halogen, silicon-containing group, nitrogen-containing
Has a group, a sulfur-containing group, a phosphorus-containing group, a halogen substituent
Optionally substituted hydrocarbon group having 1 to 20 carbon atoms, alco
A group selected from the group consisting of xy group and aryloxy group.
A substituted aromatic hydrocarbon residue having a substituent, each X¹,
X²May be the same or different, O, S or NR⁰so
Oh, R ⁰Is a hydrogen atom or carbonization having 1 to 20 carbon atoms
It is a hydrogen group. M is the third, fourth, fifth, sixth of the periodic table
Group metals, R¹May be the same or different
Has hydrogen, halogen, silicon-containing groups, halogen substituents
Optionally substituted hydrocarbon group having 1 to 20 carbon atoms, alco
An oxy group or an aryloxy group is shown. ), And [B]
Organic aluminum compound and / or organic boron compound
Of Olefin Polymer Using a Catalyst System Consisting of Oxides
Law. 4. The method for producing an olefin polymer according to claim 3, wherein the organoaluminum compound in the catalyst component [B] is an aluminoxane.