JPH03131611A - Production of ethylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having high molecular weight from ethylene and comonomers consisting of various kinds of terminal-unsaturated compounds over a wide polymerization condition range in high efficiency by using a new catalyst consisting of a combination of a zero-valent Ni compound and two specific kinds of compounds. CONSTITUTION:The objective polymer is produced by polymerizing ethylene and an ethylenic unsaturated monomer copolymerizable therewith in contact with a catalyst consisting of a combination of (A) a zero-valent nickel compound [preferably tetrakis(triphenylphosphine)nickel, etc.], (B) a compound of formula (R<1> to R<4> are H, 1-5C alkyl, etc.; Ar is 6-12C aryl) and (C) a compound of formula R<5>R<6>R<7>P=O (R<5> to R<7> are 1-20C alkyl, 6-12C aryl, etc.) (e.g. trimethylphosphine oxide). The component B is preferably produced by reacting the corresponding 1,4-naphthoquinone with triphenylphosphine.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Field of Industrial Application The present invention relates to a novel nickel-catalyzed process for the production of copolymers of ethylene and comonomers of terminally unsaturated compounds.

<Prior Art> Polyolefins such as polyethylene have almost no polarity, are chemically inactive, and have the disadvantage of poor adhesive ability and dyeing ability.

As a way to improve these drawbacks of polyolefins,
Attempts have been made to copolymerize α-olefins and polar vinyl compounds. For example, in Japanese Patent Application Laid-Open No. 59-43003, TiC1-(CH) A
A method for copolymerizing 3252 propylene and unsaturated carboxylic acid esters using a lCl catalyst has been proposed. Further, JP-A-61-155408 and JP-A-62-86009 propose a method of copolymerizing ethylone and ethyl acrylate in the presence of a Lewis acid. However, these methods require an equal or larger amount of Lewis acid than the unsaturated carboxylic ester during the two-copolymerization reaction, making it difficult to put them to practical use as an industrial production method. There is a problem that.

And, in U.S. Patent No. 4,698,403,
A method has been proposed in which ethylene and a comonomer having a polar group are copolymerized using a nickel chelate compound catalyst. However, to our knowledge, the activity of the catalysts used therein is quite low. Moreover, the inventor of this U.S. patent invention himself has reported that the molecular weight of polymers using the nickel chelate compound catalyst is low [Journal of Polymer Science Part, A (Klabunde, et al. al J
, PolymerScl, Part A) 25.198
9 (1987)).

Furthermore, JP-A No. 59-46293 proposes a nickel-based polymerization catalyst containing a compound represented by the following formula as one component, but this catalyst is effective only for the polymerization of olefins, and is effective only for the polymerization of other olefins. copolymerization of various terminally unsaturated compounds with comonomers could not be achieved.

[Summary of the invention]

<Summary> The purpose of the present invention is to solve the above-mentioned problems with nickel-based catalysts and to produce high-molecular-weight ethylene copolymers using nickel-based catalysts. Catalysts in combination with compounds aim to achieve this objective.

That is, the method for producing an ethylene copolymer according to the present invention is as follows:
It is characterized by copolymerizing ethylene and an ethylenically unsaturated monomer copolymerizable with ethylene by contacting a catalyst consisting of a combination of (A), (B) and (C> below). be.

Catalyst component (A) Zero-valent nickel compound component (B) Compound represented by the following general formula (1) (where R1-R4 are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, a carbon number 6 to 12 aryl groups,
Represents an alkoxy group having 1 to 5 carbon atoms or an aryloxy group having 6 to 12 carbon atoms, Ar represents an aryl group having 6 to 12 carbon atoms) Component (C) Compound R5R represented by the following general formula (n) "R7P-0 (old) (However, R5-R7 independently has a carbon number of 1 to
20 alkyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 39 carbon atoms, or an alkaryl group having 7 to 39 carbon atoms) <Effects of the Invention> According to the present invention, a novel nickel By using a system catalyst, ethylene and ethylenically unsaturated monomers that can be copolymerized with it can be polymerized with high efficiency under a wide range of polymerization conditions from low temperature and low pressure to high temperature and high pressure, resulting in high molecular weight copolymers. can be obtained.

[Detailed description of the invention]

(1) Catalyst The catalyst according to the present invention is a combination of the following components (A) to (C).

Ingredient (A)〉 Component (A) is a zero-valent nickel compound.

Here, the zero-valent nickel compound means a compound in which nickel is bonded to various substituents (ie, ligands) not through covalent bonds but through coordinate bonds. Ligands in this case include phosphines (e.g. triarylphosphines), olefins (e.g. ethylene, cyclooctadiene, norbornadiene), nitriles (e.g. alkyl-, alkenyl- or aryl-nitriles) carbonyl (Co), etc. There is. Zero-valent nickel compounds are known compounds, such as those published in Nihon Kagaku Complete Edition: "New Experimental Chemistry Course", Volume 12 (Organometallic Chemistry),
(Marukubi, 1978), pages 211-230, for details.

Specific examples of preferred Nf(0) compounds for use in the present invention include tetrakis(triphenylphosphine)nickel, bis(1,5-cyclooctadiene)nickel, bis(acrylonitrile)nickel, bis(norbornadiene)nickel. and nickel (tetracarbonyl).

Component (B)> Component CB) is a compound represented by the following general formula (I).

In the formula, R1-R4 and Ar each have the following meanings.

R1-R4 are each independently hydrogen, carbon number 1-5,
an alkyl group preferably having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, or an alkyl group having 6 to 12 carbon atoms,
Preferably 6 to 9 aryloxy groups are shown. Ar represents an aryl group having 6 to 12 carbon atoms.

The compound represented by this general formula (1) has the corresponding 1.4-
The known method from naphthoquinone and triphenylphosphine (M, Arhad et al.).

Tetrahedron, 23.2203 (1986)
) can be synthesized by

Component (C)> Component (C) is a compound represented by the following formula (II).

R5R6R7P-0(n) In the formula, R5 to R7 each have the following meanings.

R5-R7 are each independently an alkyl group having 1 to 20 carbon atoms, preferably 1=12, an aryl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms, and preferably 7 to 37 carbon atoms. is an aralkyl group of 7 to 10, or a carbon number of 7 to 39
, preferably 7 to 10 alkaryl groups.

Specific examples of the phosphine oxide represented by the formula (II) include trimethylphosphine oxyto, triphenylphosphine oxyto, methyldiphenylphosphine oxyto, trioctylphosphine oxyto, tri(
p-tolyl) phosphine oxyto, and the like.

Preparation of Catalyst> The catalyst of the present invention is a combination of (A), (B) and each catalyst component, and basically these components are mixed in a polymerization reactor or outside the polymerization reaction system. - Formed by contacting at one time, stepwise, or divided into multiple times.

Specifically, for example, component (A) and component (B) may be brought into contact with each other in advance, and this mixture and component (C) may be separately placed in a polymerization reaction vessel. Alternatively, components (A), (B
), (C) may all be brought into contact with each other in advance, and this mixture may be placed in a polymerization reaction vessel.

The usage ratio of (A) to (C) in the catalyst is CB)/(A)
The molar ratio is 0.5-20, preferably 1-5. Further, the (C)/(A) molar ratio is 0.01 to 500, preferably 1 to 200. It is.

(n) Use of catalyst/copolymerization of ethylene In the present invention, the catalyst is used to copolymerize ethylene and an ethylenically unsaturated comonomer copolymerizable therewith.

Ethylene As the ethylene, ordinary high-purity ethylene gas is used.

Comonomer> The comonomer copolymerized with ethylene is generally a terminally unsaturated compound represented by the following formula (III).

In the formula, n, R8 and X each have the following meanings.

neo or a natural number (preferably up to 20) R8: hydrogen, alkyl group having 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, X: vinyl, -OH.

-OR" Co2R, where a is an integer of 0 to 3, R9 and R10 are each independently a halogen, an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 8, and/or carbon Number 6~
1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, optionally substituted with 12, preferably 6 to 9, aryloxy groups
, an alkyl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms,
an aryl group having 7 to 32 carbon atoms, preferably 7 to 10 carbon atoms,
or an aralkyl group having 7 to 32 carbon atoms, preferably 7 to 32 carbon atoms
- Indicates the alkaryl group of 10.

Specific examples of the terminally unsaturated compound represented by formula (m) include (a) allyl alcohol, 4-pentene-
Alcohols such as 1-ol and 10-undecen-1-ol; (b) ethers such as 5-methoxy-1-pentene and ethyl vinyl ether; (c) acrylic esters such as methyl acrylate and ethyl acrylate. , (d)
Methyl 4-pentenoate, ethyl 10-undecenoate, 1
Unsaturated carboxylic acid esters such as phenyl 0-undecenoate, (e) unsaturated carboxylic acid amides such as acrylamide, N,N dimethylundecenoic acid amide, (f) 5-
Higher α-olefins such as dimethylamino-1-pentene and 10-dimethylamino-1-undecene, (trimethoxyvinylsilane, 4-()ethoxysilyl)
Unsaturated silanes such as -1-butene can be mentioned. These can be used in combination within each group or between groups.

The amount of these terminally unsaturated compounds to be used can be arbitrarily selected.

-Copolymerization Reaction> The polymerization reaction can be carried out by bringing ethylene and the comonomer into contact with a catalyst, preferably in a solvent, under a wide range of polymerization temperatures and pressures. That is, even under conditions of low temperature and low pressure, a high molecular weight ethylene copolymer can be produced with high efficiency, and of course, a high molecular weight ethylene copolymer can be produced under high temperature and high pressure conditions.

Here, it is preferable to use an inert solvent as the solvent [2].

As this inert solvent, any solvent commonly used in the art can be used, and in particular, aliphatic and aromatic hydrocarbons having 4 to 20 carbon atoms and halogenated hydrocarbons can be used. More specific examples include pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, chlorobenzene, and the like.

Polymerization conditions are not particularly limited, but for example, polymerization temperature 2
The polymerization pressure is in the range of 0 to 300°C and 1 to 200 kg/cdG.

EXPERIMENTAL EXAMPLES> The present invention will be explained in more detail with the following experimental examples. The present invention is not limited in any way by these experimental examples.

The molecular weight of the produced polymer was determined by gel permeation chromatography (
n1 was determined by GPC), and the weight average molecular weight MW and dispersity Q value are shown in the following experimental examples.

Quantitation of ester groups in the product was determined by 0.1. This was done based on the results of infrared (IR) spectrum measurements of a compression-molded sheet with a thickness of 1 mm.

In addition, the melting point of the produced polymer was determined by phase difference calorimeter (DSC) 6
The melting peak temperature is shown in the following examples.

Example 1 (1) Preparation of catalyst (No. 1) 1.4-naphthoquinone/triphenylphosphine adduct (hereinafter abbreviated as NQTPP) 1356I! 1 g and 895a+g of triphenylphosphine oxide (hereinafter abbreviated as TPPO) were weighed into a flask, and after purging the inside of the flask with nitrogen, 340 ml of dry toluene was added and the whole was stirred. In a separate flask, under nitrogen atmosphere
86 rIIg bis(1,5-cyclooctadiene)
Weigh nickel (hereinafter abbreviated as N1 (cod)2), make it into a solution using 1.00 ml of dry toluene,
After adding this to the above mixture, the whole was heated to 80°C for 20 hours.
Catalyst No. 1 was prepared by heating for a minute.

(2) Copolymerization of ethylene and methyl 4-pentenoate Dry toluene (300 ml) and 1.65 g of methyl 4-pentenoate were added to a 1 liter autoclave under a nitrogen atmosphere, and then 20 ml of catalyst No. 1 was added. 60℃,
The polymerization reaction was carried out for 2 hours at an ethylene pressure of 5 g/C.

After purging unreacted ethylene, the reaction mixture was taken out and
Pour into 00 ml of methanol and add concentrated hydrochloric acid (1 ml).
After the addition treatment, the precipitate was separated by filtration, further washed with methanol, and then vacuum-dried to obtain 10.5 g of a colorless polymer.

Catalyst activity 1240g:/gNi molecular weight Mw
18.000 (Q value 2.6) Melting point 126
．． 5°C Ester content 0.85 mol% Example 2 Copolymerization of ethylene and ethyl 10-undecenoate Instead of methyl 4-pentenoate, ethyl 10-undecenoate 3
．． A copolymerization reaction was carried out in the same manner as in Example 1 (2) except that 07 g was used.

Polymer yield 13.3g Molecular weight Mw95.000 (Q value 15.5)
Point 129°C Ester content 10.90 mol% Example 3 Copolymerization of ethylene and 10-undecenyl alcohol Experimental example except that 1.97 g of 10-undecenyl alcohol was used instead of methyl 4-pentenoate. 1 (2)
A copolymerization reaction was carried out in the same manner.

Polymer acid j19.0゜Molecular weight Mw128.000 (Q value 19.3) Melt
Point 130°C Example 4 (1) Preparation of catalyst (No. 2) NQTPP (1.86 g) and Ni (cod) 2 (1
, 22 g) and 450 ml of toluene, Catalyst No.

2 was prepared.

(2> Into an autoclave containing 1 liter of copolymer of ethylene and 10-ethyl undecenoate, dry toluene (300 ml) under a nitrogen atmosphere,) A solution of lyoctylphosphine oxide (3.86 g) in toluene (25 ml) and 10
- Add 4.24 g of ethyl undecenoate, catalyst No. 2
The polymerization operation was carried out in the same manner as in Example 1 (2) using the following.

Polymer yield 18.9g Molecule fil Mw 102,000 (Q value 18.3)
Excitation point: 12 g, 5°C Ester content: 1.05 mol% Example 5 Copolymerization of ethylene and 7,8-epoxy-1-octene Instead of 10-ethyl undecenoate, 7,8-epoxy-1-octene (2 A colorless polymer was obtained by carrying out the same operation as in (2) of Example 4, except that 52 g) was used.

Polymer yield 2.9g Molecule i1 Mw24.000 (Q value 2.9) Melting
Point: 131°C Comparative Example 1 (1) Preparation of catalyst (No. 3) Instead of NQTTP, 673 mg of p-benzoquinone-triphenylphosphine adduct, TPPO, N
Catalyst No. 3 was prepared in the same manner as in Example 1 (1) using 510 mg, 500 mg, and 300 ml of toluene.

(2) Example 1 (2) except that 1.38 g of methyl 4-pentenoate and 20 ml of the above catalyst (No. 3) were used.
), no polymer was obtained at all.

Comparative Example 2 The same operation as in Comparative Example 2 was performed except that ethyl 10-undecenoate (2.52 g) was used instead of methyl 4-pentenoate, but no polymer was obtained.

Claims (1)

[Claims] 1. Polymerization by bringing ethylene and an ethylenically unsaturated monomer copolymerizable therewith into contact with a catalyst consisting of a combination of the following (A), (B), and (C). , a method for producing a characterized ethylene copolymer. Catalyst component (A) Zero-valent nickel compound component (B) Compound represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (However, R^1 to R^4 are mutually exclusive. independently, hydrogen;
An alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 6 to 1 carbon atoms
(Ar represents an aryl group having 6 to 12 carbon atoms) Component (C) A compound represented by the following general formula (II) R^5R^6R^7P=0(II) (However, R^5 to R^7 are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms,
Aralkyl group having 7 to 39 carbon atoms, or 7 to 39 carbon atoms
2. The ethylenically unsaturated monomer has the following general formula (III)
The method for producing an ethylene copolymer according to claim 1, characterized in that the compound is a compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (However, n is 0 or an approximately natural number, R^8 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and X is vinyl, -OH, -OR
^9, -CO_2R^9, -CONR^9R^1^0▲ Formula,
There are chemical formulas, tables, etc. ▼, -NR^9R^1^0, -Si(OR^9)_3_-_a(R^1^0)_a,
-OSi(OR^9)_3_-_a(R^1^0)_a
Or indicates -BR^9_2. Here, a represents an integer of 0 to 3. R^9 and R^1^0 are each independently a carbon atom which may be substituted with a halogen, an alkoxy group having 1 to 10 carbon atoms, and/or an aryloxy group having 6 to 12 carbon atoms; (represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 32 carbon atoms, or an alkaryl group having 7 to 32 carbon atoms)