JPH11292918A - Production of olefin-polar monomer copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject copolymer by copolymerization between an olefin and a polar monomer using a specific nickel complex catalyst. SOLUTION: This copolymer is obtained by copolymerization between an olefin (e.g. ethylene) and a polar monomer (e.g. acrylic acid) using a catalyst comprising a nickel complex of formula I (X is a halogen; R<1> to R<5> are each H or a hydrocarbon), wherein the catalyst to be used is pref. such one as to be prepared by contacting the complex compound of formula I with an ionized ionic compound (pref. an anionic compound metal salt such as silver triflate). The copolymerization is carried out pref. at -100 to 100 deg.C and normal pressure to 30 MPa for 10-1,440 min. The complex compound of formula I is prepared, for example, by reaction of a nickel complex compound of formula II with an alkyllithium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin / polar monomer copolymer such as an ethylene / methyl acrylate copolymer using a nickel complex catalyst.

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to propose a method for efficiently producing an olefin / polar monomer copolymer using a specific nickel complex catalyst.

[0003]

The present invention provides a compound represented by the following general formula (1):
An olefin / polar monomer copolymer obtained by copolymerizing an olefin and a polar monomer using a catalyst comprising a nickel complex compound represented by the following formula, preferably a catalyst comprising the nickel complex compound and an ionized ionic compound. It is a manufacturing method of.

[Formula 2] [Wherein, X represents a halogen atom. R ¹ and R ² are the same or different and each represent a hydrogen atom or a hydrocarbon group.
R ³ and R ⁴ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ⁵ represents a hydrogen atom or a hydrocarbon group. Further, two or more of R ¹ , R ² , R ³ and R ⁴ may be mutually connected to form a ring. ]

The olefin copolymerized by the method of the present invention includes ethylene, propylene, 1-butene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene, 3-methyl-1-butene, 4
And α-olefins having 2 to 20 carbon atoms such as -methyl-1-pentene. These olefins can be used alone or in combination of two or more.
It is desirable that the proportion of the olefin in all the monomers is 0.5 to 99.5 mol%, preferably 1 to 99 mol%.

The polar monomers copolymerized by the method of the present invention include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, bicyclo (2,2,1) -5-heptene-
Α, β-unsaturated carboxylic acids such as 2,3-dicarboxylic acid, and metal salts thereof such as sodium, potassium, lithium, zinc, magnesium, and calcium; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacryl Α, β-unsaturated carboxylic esters such as isobutyl acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and maleic anhydride and their acid anhydrides; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, Vinyl laurate, vinyl stearate, vinyl trifluoroacetate Vinyl esters such as; glycidyl acrylate, glycidyl methacrylate,
And unsaturated glycidyl group-containing monomers such as itaconic acid monoglycidyl ester.

[0006] These polar monomers can be used alone or in combination of two or more.
The ratio of the polar monomer in all the monomers is 0.5 to 99.5
%, Preferably 1 to 99 mol%.

In the present invention, in addition to the olefin and the polar monomer, other copolymerizable monomers such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, Conjugated or non-conjugated dienes such as 9-decadiene; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornadiene and dicyclopentadiene can also be copolymerized. These other monomers can be used alone,
Two or more of them can be used in combination. The proportion of the polar monomer in all the monomers is at most 80 mol%, preferably at most 70 mol%.

Specific examples of the olefin / polar monomer copolymer obtained by the production method of the present invention include α-olefin / acrylic acid copolymer, α-olefin / methyl acrylate copolymer, α-olefin / acrylic Isopropyl acrylate copolymer, α-olefin / n-butyl acrylate copolymer, α-olefin / isobutyl acrylate copolymer, α-olefin / 2-ethylhexyl acrylate copolymer, α-olefin / methacrylic acid copolymer Polymer, α-
Olefin / methacrylic acid copolymer, α-olefin
Methyl methacrylate copolymer, α-olefin / isopropyl methacrylate copolymer, α-olefin / n-butyl methacrylate copolymer, α-olefin / isobutyl methacrylate copolymer, α-olefin / methacrylic acid 2
-Ethylhexyl copolymer, α-olefin / vinyl acetate copolymer, α-olefin / vinyl propionate copolymer, α-olefin / ethyl acrylate / maleic anhydride copolymer, α-olefin / ethyl acrylate / Examples include glycidyl methacrylate copolymer, α-olefin / vinyl acetate / glycidyl methacrylate copolymer, and α-olefin / glycidyl methacrylate copolymer.

The olefin / polar monomer copolymer obtained by the production method of the present invention preferably has a polymer in which the number of carbon atoms serving as branch points is in the range of 0 to 20 per 1,000 carbon atoms.

The nickel complex compound used as a catalyst component in the present invention is represented by the following general formula (1).

Specific examples of the atoms or groups represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) include a hydrogen atom;
Methyl group, ethyl group, n-propyl group, isopropyl group,
a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms such as n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group; phenyl group, naphthyl group, etc. An aryl group having 6 to 20 carbon atoms; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-
Examples include an aryl group in which 1 to 5 substituents such as a butyl group, a tert-butyl group, a pentyl group, and a hexyl group are substituted. R ¹ and R ² may be the same or different.

R ¹ , R ² , R3 and R ⁴ in the general formula (1) are 2
Two or more, preferably adjacent groups may be connected to each other to form a ring.

Specific examples of the atom or group represented by R ⁵ in the general formula (1) include a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. -A linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms such as butyl group, tert-butyl group, pentyl group, hexyl group, allyl group; 6 to 9 carbon atoms such as phenyl group and mesityl group And the like.

Specific examples of the atom represented by X in the general formula (1) include fluorine, chlorine, bromine and iodine.

Specific examples of the nickel complex compound represented by the general formula (1) include the following compounds.

Embedded image

[Formula 4]

The nickel complex compound represented by the general formula (1) is obtained by using a nickel complex compound represented by the following general formula (2) as a raw material and an alkyl metal compound such as Grignard reagent, alkyllithium, alkylzinc or alkylaluminum. Or a nickel complex compound represented by the following general formula (2) as a raw material, Grignard reagent,
It can be synthesized by a method of reacting with an alkyl metal compound such as alkyl lithium, alkyl zinc, or alkyl aluminum, and then reacting with a hydrogen halide such as hydrogen fluoride, hydrochloric acid, hydrogen chloride, bromine chloride, or hydrobromic acid.

[0017]

[Formula 5] [Wherein, X ¹ and X ² are the same or different, and represent a halogen atom. R ¹ and R ² are the same or different,
Shows a hydrogen atom or a hydrocarbon group. R ³ and R ⁴ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ⁵ represents a hydrogen atom or a hydrocarbon group. Also R ¹ ,
Two or more of R ² , R ³ and R ⁴ may be mutually connected to form a ring. ]

Examples of the ionized ionic compound used in the present invention include an ionic compound, a borane compound, a carborane compound and the like. Among them, a metal salt of an anion compound is preferably used.

Examples of the anionic compound used in the ionized ionic compound include carboxylic acids such as acetic acid and trifluoroacetic acid, sulfonic acids such as triflate and methanesulfonate, tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, and the like. And boron compounds such as tetrakis (3,5-bistrifluoromethylphenyl) borate. Other examples in which such an ionic compound is obtained include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, and tris (pentafluoro) Boron, Tris (p-
Examples include (tril) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron. Still other examples include N, N-dialkylanilinium salts, such as N, N-dimethylanilinium tetra (phenyl) boron.

Preferred examples of the metal used for the ionized ionic compound include lithium, sodium, potassium, magnesium, silver and the like.

Specific examples of the ionized ionic compound include silver triflate, sodium tetrafluoroborate, sodium tetraphenylborate, and sodium tetrakis (3,5-bistrifluoromethylphenyl) borate.

In the present reaction, it is particularly preferable to copolymerize an olefin and a polar monomer with a catalyst obtained by bringing a nickel complex compound represented by the general formula (1) into contact with an ionized ionic compound.

The reaction conditions for the copolymerization are as follows:
Preferably, the temperature is 100 ° C., the time is 10 to 1440 minutes, and the pressure is normal pressure to 30 MPa.

The reaction medium used in the copolymerization includes, for example, inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, toluene and xylene; and halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and chlorobenzene. Can be

[0025]

According to the present invention, it is possible to efficiently produce a copolymer of an olefin and a polar monomer by using a catalyst comprising the above nickel complex compound and a catalyst obtained from the catalyst and an ionized ionic compound. it can.

[0026]

Embodiments of the present invention will be described below. Example 1 [Synthesis of Compound I]

[Formula 6] Under an argon atmosphere, dibromo [diacetyl-bis (2,6-) was added to a 100 ml (mL) flask equipped with a magnetic stir bar.
Isopropylphenylimine)] nickel (II) (4.2 g) and diethyl ether (150 ml, mL) were added, and the mixture was stirred at -78 ° C. To this, a solution of 0.65 g of dimethylmagnesium dissolved in 30 ml (mL) of diethyl ether was added dropwise at -78 ° C. After continuing stirring at the same temperature for 2 hours, the whole was filtered at -78 ° C. The filtrate was stirred at −78 ° C. while adding a 0.25 M solution of hydrogen chloride in diethyl ether.
3.5 ml (mL) was added dropwise, and stirring was continued for 2 hours at the same temperature. After the whole was filtered at -78 ° C, the solvent of the filtrate was distilled off to obtain 1.6 g of dark blue crystals. FD-MS: 484 (M ⁺ , 20%), 486 (M ⁺ +2, 8%) Example 2 [Synthesis of Compound II]

Embedded image Under an argon atmosphere, dibromo [diacetyl-bis (2,6-) was added to a 100 ml (mL) flask equipped with a magnetic stirrer.
Isopropylphenylimine)] nickel (II) (4.2 g) and tetrahydrofuran (500 ml, mL) were added and sufficiently dissolved. 30 mL (mL) of methylmagnesium bromide in diethyl ether (3.0 M) at -78 ° C
Was dropped. After continuing stirring at the same temperature for 2 hours,
The whole was filtered at -78 ° C. The solvent in the filtrate was distilled off to obtain 2.6 g of dark blue crystals. FD-MS: 556 (M ⁺ , 30%), 558 (M ⁺ +2, 32%) Examples 3, 4 [Synthesis of Compounds III and IV]
V was synthesized according to compound II.

[Formula 8] Compound III, FD-MS: 484 (M ⁺ , 22%), 486 (M ⁺ +2, 17%) Compound IV, FD-MS: 528 (M ⁺ , 31%), 530 (M ⁺ +2, 35 %) Example 5 [Copolymerization of Ethylene / Methyl Acrylate] After a 200 ml (mL) container equipped with a magnetic stirrer was purged with argon, 100 μmol (μmol) of compound II was added, and the whole was -78%. After cooling to ° C., the inside of the vessel was replaced with ethylene. While maintaining the temperature at −78 ° C., 70 ml (mL) of dry dichloromethane was added, and the mixture was stirred at the same temperature for 30 minutes. Then, a dichloromethane solution (3.3 M) of sodium tetrakis (3,5-bistrifluoromethyl) borate (3.3 M) was added thereto. Milliliter (mL) was added at -78 ° C. After stirring at the same temperature for 10 minutes,
Add 1.0 milliliter (mL) of methyl acrylate, and add
After the temperature was raised to, stirring was continued at the same temperature for 24 hours while supplying ethylene. 100 mL of methanol (mL) was added, and the resulting polymer was filtered, washed with acetone, and 697 mg.
Was obtained. Example 6-15 A copolymerization reaction was carried out in the same manner as in Example 5, except that the nickel complex compound, the ionized ionic compound, the reaction temperature, the time, the solvent, and the methyl acrylate concentration were changed. The results are shown in Table 1. However, * 1 in the table
* 2 was based on the following. * 1: Polyethylene equivalent * 2: By ¹³ C NMR analysis, polymer branch <6 (carbon atoms / 10
00 carbon atoms).

[Table 1]

Claims (2)

[Claims] 1. A method for producing an olefin / polar monomer copolymer, comprising copolymerizing an olefin and a polar monomer using a catalyst comprising a nickel complex compound represented by the following general formula (1). [Formula 1] [Wherein, X represents a halogen atom. R ¹ and R ² are the same or different and each represent a hydrogen atom or a hydrocarbon group.
R ³ and R ⁴ are the same or different and each represent a hydrogen atom or a hydrocarbon group. R ⁵ represents a hydrogen atom or a hydrocarbon group. Further, two or more of R ¹ , R ² , R ³ and R ⁴ may be mutually connected to form a ring. ] 2. A method for producing an olefin / polar monomer copolymer, comprising using a catalyst comprising a nickel complex compound represented by the general formula (1) and an ionized ionic compound.