JP2020158686A - Method for producing polyolefin copolymer - Google Patents

Abstract

To provide a method for producing a polyolefin copolymer having a structural unit derived from a methacrylate in a side chain, under mild polymerization conditions.SOLUTION: A method for producing a polyolefin copolymer includes polymerizing a methacrylate represented by formula (1) and/or formula (2) and an α-olefin represented by formula (3), with a transition metal catalyst represented by formula (4).SELECTED DRAWING: None

Description

The present invention relates to a method for producing a polyolefin-based copolymer. Specifically, the present invention relates to a method for producing a polyolefin-based copolymer having a structural unit derived from a methacrylic acid ester in the side chain.

Polyolefins typified by polyethylene and polypropylene are general-purpose resins used in a wide range of fields from packaging materials to molding members. By giving the polyolefin a polar substituent or a branched structure, it is expected to impart compatibility and flexibility not found in conventional polyolefins. For example, various studies have been conducted on a copolymerization method of a methacrylic acid ester having a polar substituent and ethylene as one of the methods for producing a polyolefin-based copolymer.

A high-pressure radical polymerization method is known as a conventional technique for producing a polyolefin-based copolymer by copolymerizing a methacrylic acid ester having a polar substituent. In recent years, nickel- or palladium-catalyzed coordination polymerization has been disclosed (Patent Document 1 and Non-Patent Document 1). Patent Document 1 reports a copolymerization method of ethylene and methyl methacrylate using a palladium catalyst, and methyl methacrylate is randomly introduced into the main chain of polyolefin. On the other hand, in Non-Patent Document 1, when ethylene and methyl methacrylate were reacted in the presence of a diphosphazan monooxide palladium catalyst, random copolymerization did not occur and 2,1 methyl methacrylate was added to the polymerization terminal of polyethylene. It has been reported that a polyolefin-based polymer having an enoart structure is produced. However, a method for producing a polyolefin-based copolymer having a structural unit derived from methyl methacrylate in the side chain has not yet been established.

JP-A-2018-141138

M, Chen. C, Chen. Angew. Chem. , Int. Ed. 2018, 57, 3094-3098.

An object of the present invention is to provide a method for producing a polyolefin-based copolymer having a structural unit derived from a methacrylic acid ester in a side chain under mild polymerization conditions.

The inventors examined the copolymerization of methyl methacrylate and α-olefin using a diimine palladium catalyst with reference to the prior art, and found that a polyolefin-based copolymer in which a structural unit derived from methyl methacrylate was introduced into the side chain. The present invention was completed based on the finding, that is, the present invention provides the following [1] to [4].
[1] The methacrylic acid ester represented by the formula (1) and / or the formula (2) and the α-olefin represented by the formula (3) are polymerized with a transition metal catalyst represented by the formula (4). A method for producing a polyolefin-based copolymer.

[In formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms. ]

[In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 or more and 10 or less. ]

[In formula (3), R ³ is an alkyl group having 1 to 12 carbon atoms. ]

[In formula (4), M is a transition metal atom of Group 10 of the periodic table, X is a monovalent organic anion composed of multiple atoms including a boron atom or an aluminum atom, and R ⁴ is a hydrogen atom and a halogen atom. , An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 42 carbon atoms, a substituted silyl group, an alkoxy group having 1 to 20 carbon atoms, and 7 to 7 carbon atoms. 12 aralkyloxy group or an aryloxy group having a carbon number of 6-42, independently ^{R 5} and ^{R 6} are each an aryl group having a carbon number of 6-42, ^{R 7} and ^{R 8,} Independently, they are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 42 carbon atoms, or R ⁷ and R ⁸ are linked to each other and have 1 to 30 carbon atoms. It is a divalent base. ]

[2] The transition metal catalyst is a transition metal catalyst produced by contacting a catalyst precursor represented by the formula (5) with one or more compounds selected from the group consisting of organoaluminum compounds and boron compounds. The manufacturing method according to [1].

[In formula (5), M, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are synonymous with the above, and R ⁹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and carbon. Aralkyl group with 7 to 12 atoms, aryl group with 6 to 42 carbon atoms, substituted silyl group, alkoxy group with 1 to 20 carbon atoms, aralkyloxy group with 7 to 12 carbon atoms, or 6 to 6 carbon atoms It is an aryloxy group of 42. ]

[3] The production method according to [2], wherein the catalyst precursor is represented by the formula (6).

[In formula (6), R ⁴ , R ⁷ , R ⁸ and R ⁹ are synonymous with the above, and R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independent hydrogen atoms. , A halogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 1 to 12 carbon atoms. ]

[4] A polyolefin-based copolymer produced by the method according to any one of [1] to [3].

According to the present invention, it is possible to provide a polyolefin-based copolymer having a structural unit derived from a methacrylic acid ester in the side chain under mild polymerization conditions.

Hereinafter, the present invention will be described in detail.
[Method for producing polyolefin-based copolymer]
In the method for producing a polyolefin-based copolymer according to the present invention, a methacrylic acid ester represented by the formula (1) and / or the formula (2) described later and an α-olefin represented by the formula (3) described later are used. Is polymerized with a transition metal catalyst described later.

The methacrylic acid ester in the present invention is a compound represented by the following formulas (1) and (2).

In the formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms.

Alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group and n. Examples thereof include −hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopentyl group and cyclohexyl group.
Moreover, the alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a hydroxy group, an acetoxy group, a nitro group, a sulfonyl group, a silyl group, a substituent such as a cyano group and the like.

From the viewpoint of ease of manufacture and availability, R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group or an acetoxyethyl group. , Methyl group is more preferable.

In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 or more and 10 or less.

Examples of the alkyl group having 1 to 12 carbon atoms in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and n. -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

From the viewpoint of availability, R ² is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. n is preferably 0 or more and 5 or less, and more preferably 0 or more and 2 or less.

The α-olefin in the present invention is a compound represented by the following formula (3).

In formula (3), R ³ is an alkyl group having 1 to 12 carbon atoms.

Alkyl groups having 1 to 12 carbon atoms in the formula (3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group and n. -Pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like can be mentioned.

From the viewpoint of availability and handling properties, ^{R 3} is n- butyl, n- pentyl, n- hexyl, n- heptyl, n- octyl group, n- nonyl or n- decyl Preferably, n -Butyl group or n-octyl group is more preferable.

<Transition metal catalyst>
The transition metal catalyst in the present invention is a compound represented by the following formula (4).

In the formula (4), M is a transition metal atom of Group 10 of the periodic table, and X is a monovalent organic anion composed of multiple atoms including a boron atom or an aluminum atom.

In formula (4), M is preferably nickel or palladium, more preferably palladium.

In the formula (4), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an aryl group having 6 to 42 carbon atoms, and a substituted silyl group. It is an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, or an aryloxy group having 6 to 42 carbon atoms, and R ⁵ and R ⁶ are independent of each other and have 6 carbon atoms. They are aryl groups of ~ 42, and R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 42 carbon atoms. Further, R ⁷ and R ⁸ may be divalent groups having 1 to 30 carbon atoms linked to each other.

Examples of the halogen atom represented by R ⁴ in the formula (4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these, a chlorine atom or a bromine atom is preferable.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ in the formula (4) include a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. As a linear alkyl group, a methyl group, an ethyl group, an n-butyl group, etc.; as a branched alkyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, etc.; as a cyclic alkyl group, a cyclohexyl group. , Cyclooctyl group and the like. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like. Among them, a linear unsubstituted alkyl group having 1 to 20 carbon atoms is preferable, a linear unsubstituted alkyl group having 1 to 12 carbon atoms is more preferable, and a methyl group is more preferable.

The aralkyl group having a carbon number of 7 to 12 represented by R ⁴ in the formula (4), a benzyl group and a phenethyl group. The aralkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like. Of these, an unsubstituted aralkyl group having 7 to 12 carbon atoms is preferable, and a benzyl group is more preferable.

Examples of the aryl group having 6 to 42 carbon atoms represented by R ⁴ in the formula (4) include a phenyl group, a naphthyl group, a 4-tolyl group, a mesitylene group, and a 4-biphenyl group. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like. Among them, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group, 4-tolyl group, or mesitylene group is more preferable.

The substituted silyl group represented by R ⁴ in the formula (4) includes a methylsilyl group, an ethylsilyl group, a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, and a tri-n-propyl group. Cylyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri Examples thereof include an -n-hexylsilyl group, a tricyclohexylsilyl group and a triphenylsilyl group.

The alkoxy group having 1 to 20 carbon atoms represented by the formula (4) ^{R 4} in, methoxy group, ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, sec- butoxy group, tert- butoxy Examples thereof include groups, n-pentyloxy groups, neopentyloxy groups, n-hexyloxy groups, n-octyloxy groups, n-dodecyloxy groups, n-pentadecyloxy groups, n-eicosyloxy groups and the like.

The aralkyloxy group having a carbon number of 7 to 12 represented by ^{R 4} in the formula (4), benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl ) Methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3) , 4-Dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3) , 6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2) , 3,4,5-Tetramethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) ) Methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) ) Phenyl group, naphthylmethoxy group and the like. The aralkyloxy group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like. Among them, an aralkyloxy group having 7 to 10 carbon atoms is preferable, and a benzyloxy group is more preferable.

Examples of the aryloxy group having a carbon number of 6-42 represented by ^{R 4} in the formula (4), a phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy Group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-3 Methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-tert-butyl-3,4- Dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-tert-butyl-3-methylphenoxy group, 2- tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group , 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,4,6-trimethylphenoxy group, 2,6- Di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert -Butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n- Examples thereof include a hexylphenoxy group, an n-octylphenoxy group, an n-decylphenoxy group, a naphthoxy group, an anthrasenoxy group and the like. The aryloxy group may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like. Of these, an aryloxy group having 6 to 20 carbon atoms is preferable.

R ⁴ in the formula (4) is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 42 carbon atoms, and more preferably a hydrogen atom or a halogen atom. Alternatively, it is a linear unsubstituted alkyl group having 1 to 12 carbon atoms, and is particularly preferably a methyl group.

In formula (4), R ⁵ and R ⁶ are independently aryl groups having 6 to 42 carbon atoms. The aryl group may have a substituent such as a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group and a cyano group.

Examples of the aryl group having 6 to 42 carbon atoms include a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a 2-isopropylphenyl group, and a 2-n-butylphenyl group. 2-isobutylphenyl group, 2-n-hexylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,6-diethylphenyl group, 2,6-di-n-propylphenyl group, 2, 6-diisopropylphenyl group, 2,6-di-n-butylphenyl group, 2,6-diisobutylphenyl group, 2,6-di-n-hexylphenyl group, 2-methyl-6-ethylphenyl group, 2- Methyl-6-n-propylphenyl group, 2-methyl-6-isopropylphenyl group, 2-methyl-6-butylphenyl group, 2-ethyl-6-n-propylphenyl group, 2-ethyl-6-isopropylphenyl Group, 2-ethyl-6-n-butylphenyl group, 2-n-propyl-6-isopropylphenyl group, 2-n-propyl-6-n-butylphenyl group, 2-isopropyl-6-n-butylphenyl group Group, 2,4,6-trimethylphenyl group, 2,4-dimethyl-6- (2-methylphenyl) phenyl group, 2,4-dimethyl-6- (2-ethylphenyl) phenyl group, 2,4- Dimethyl-6- (2-n-propylphenyl) phenyl group, 2,4-dimethyl-6- (2-isopropylphenyl) phenyl group, 2,4-dimethyl-6- (2,6-dimethylphenyl) phenyl group , 2,4-Dimethyl-6- (2,6-diethylphenyl) phenyl group, 2,4-dimethyl-6- (2,6-di-n-propylphenyl) phenyl group, 2,4-dimethyl-6 -(2,6-diisopropylphenyl) phenyl group, 2,4-dimethyl-6- (2-methyl-6-ethylphenyl) phenyl group, 2,4-dimethyl-6- (2-methyl-6-n-) Phenyl phenyl) phenyl group, 2,4-dimethyl-6- (2-methyl-6-isopropylphenyl) phenyl group, 2,4-dimethyl-6- (2-ethyl-6-n-propylphenyl) phenyl group, Examples thereof include a 2,4-dimethyl-6- (2-ethyl-6-isopropylphenyl) phenyl group and a 2,4-dimethyl-6- (1-naphthyl) phenyl group. Among them, an aryl group having 6 to 30 carbon atoms is preferable, and a 2,4,6-trimethylphenyl group is more preferable.

In formula (4), R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 42 carbon atoms, or R ⁷ and R. It is a divalent group having 1 to 30 carbon atoms formed by linking ⁸ . Further, these alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 42 carbon atoms, and divalent groups having 1 to 30 carbon atoms may have substituents. Examples of the substituent include a halogen atom, a hydrocarbon oxy group, a nitro group, a sulfonyl group, a silyl group, a cyano group and the like.
Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cyclic alkyl group and the like. As a linear alkyl group, a methyl group, an ethyl group, an n-butyl group, etc.; as a branched alkyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, etc.; as a cyclic alkyl group, a cyclohexyl group. , Cyclooctyl group and the like. Among them, a linear alkyl group having 1 to 20 carbon atoms is preferable, a linear alkyl group having 1 to 12 carbon atoms is more preferable, and a methyl group or an ethyl group is more preferable. It is preferably a methyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a 4-tolyl group, a mesitylene group and the like. Among them, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 12 carbon atoms is more preferable, and a phenyl group or a mesitylene group is more preferable.

In the formula (4), the divalent group having 1 to 30 carbon atoms formed by linking R ⁷ and R ⁸ is any of an aliphatic group, an alicyclic group, an aromatic group, and a combination thereof. There may be. Specific divalent groups include 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, ethene-1,2-diyl group, propene-1,3-diyl group, 1 -Buten-1,4-diyl group, 2-butene-1,4-diyl group, 1,3-butadiene-1,4-diyl group, cyclohexane-1,2-diyl group, cyclopentene-3,5-diyl Group, norbornan-1,2-diyl group, butane-2,3-diyl group, 2,3-dimethylbutane-2,3-diyl group, pentane-2,4-diyl group, 1,2-phenylene group, Examples thereof include a naphthalene-1,8-diyl group, and a naphthalene-1,8-diyl group is preferable.

(Method for producing a transition metal catalyst represented by the formula (4))
The transition metal catalyst represented by the above formula (4) is formed by contact between the catalyst precursor represented by the formula (5) described later and one or more compounds selected from the group consisting of organoaluminum and boron compounds described later. Can be produced and manufactured.
The method of contacting may be simply mixing or stirring as appropriate. Further, each of the catalyst precursor and one or more compounds selected from the group consisting of organoaluminum compounds and boron compounds may be dissolved in a solvent and used as a solution.
The temperature at the time of contact is not particularly limited, but is, for example, −50 to 60 ° C., preferably 0 to 30 ° C., and more preferably around room temperature (for example, 5 to 30 ° C.).

The concentration of the transition metal catalyst represented by the above formula (4) in the polymerization solution is usually 0.01 to 500 mmol / L, preferably 0.05 to 100 mmol / L, and more preferably 0.05 to 0.05 to L. It is 50 mmol / L.
Hereinafter, the catalyst precursor represented by the formula (5), one or more compounds selected from the group consisting of organoaluminum and boron compounds, and the solvent will be described.

(A) Catalyst precursor represented by the formula (5) The catalyst precursor used in the production of the transition metal catalyst represented by the above formula (4) is the catalyst precursor represented by the formula (5).

In the formula (5), M, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meanings as described above, and are as described in the above formula (4).

In formula (5), R ⁹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 42 carbon atoms, a substituted silyl group, and carbon. It is an alkoxy group having 1 to 20 atoms, an aralkyloxy group having 7 to 12 carbon atoms, or an aryloxy group having 6 to 42 carbon atoms. A preferred example of R ^{9 is the same as} a preferred example of R ⁴ . However, R ⁹ and R ⁴ may be the same or different.

(A-1) Catalyst precursor represented by the formula (6) As the catalyst precursor represented by the above formula (5), a compound represented by the formula (6) may be used from the viewpoint of reactivity. preferable.

In the formula (6), R ⁴ , R ⁷ , R ⁸ and R ⁹ have the same meanings as described above, and are as described with respect to the above formulas (4) and (5). Further, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independently hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, or aralkyl having 1 to 12 carbon atoms. It is the basis.

Examples of the halogen atom represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ in the formula (6) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl groups having 1 to 12 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ in the formula (6) include linear alkyl groups, branched alkyl groups and cyclic alkyl groups. The group and the like can be mentioned. As the linear alkyl group, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Decil group, n-undecyl group, n-dodecyl group, etc .; isopropyl group, sec-butyl group, isobutyl group, tert-butyl group, neopentyl group, etc. as branched alkyl groups; cyclohexyl group as cyclic alkyl group , Cyclooctyl group and the like.

Examples of the aralkyl group having 1 to 12 carbon atoms represented by R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ in the formula (6) include a benzyl group and a phenethyl group.

(B) One or more compounds selected from the group consisting of organoaluminum compounds and boron compounds The organoaluminum compounds and boron compounds may be used in combination or alone.

(B-1) Organoaluminium compound The organoaluminum compound in the present invention may be a known compound. Examples of the organoaluminum compound include each compound represented by the following formula (X1), formula (X2), or formula (X3), and a combination of two or more thereof.

Formula (X1): Organoaluminium compound represented by E ¹ _d AlZ _3-d (X2) Formula: {-Al (E ² ) -O-} Cyclic aluminoxane represented by _e (X3) Formula: E ^{3 _{{-Al (E 3) -O-}}} f AlE 3 linear aluminoxane represented by _2, however, in the above (X1) ~ (X3) ^formula, E 1, ^{E 2} and ^{E 3} are each independently carbonized Representing a hydrogen group, if there are multiple E ¹ , multiple E ² or multiple E ³ , they may be the same or different from each other. Z represents a hydrogen atom or a halogen atom, and when there are a plurality of Z atoms, they may be the same or different from each other. d represents a number satisfying 0 <d ≦ 3, e is an integer of 2 or more, preferably an integer of 2 to 40, and f is an integer of 1 or more, preferably an integer of 1 to 40. ..

The hydrocarbon group represented by E ¹ , E ² and E ³ is preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the organic aluminum compound represented by the above formula (X1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride and dipropylaluminum chloride. , Dialkylaluminum chloride such as diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum Examples thereof include dialkylaluminum hydrides such as hydrides, diisobutylaluminum hydrides, and dihexylaluminum hydrides. Among them, trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

Examples of E ² and E ³ in the formulas (X2) and (X3) include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and neopentyl group. A group and the like can be exemplified. Of these, a methyl group or an isobutyl group is preferable.

The annular and linear aluminoxane represented by the above equations (X2) and (X3) can be produced by various methods. The production method thereof is not particularly limited, and a known production method may be used. As a production method, a method of producing by contacting a solution of trialkylaluminum such as trimethylaluminum in a suitable organic solvent such as benzene and an aliphatic hydrocarbon with water, or trialkylaluminum such as trimethylaluminum. , A method of producing by contacting with a metal salt containing water of crystallization such as copper sulfate hydrate can be exemplified.

(B-2) Boron Compound The boron compound in the present invention may be a known compound. Examples of the boron compound include compounds represented by the following formulas (Y1), (Y2), or (Y3), and combinations of two or more thereof.

Formula (Y1): Boron compound represented by BQ ¹ Q ² Q ³ ;
Equation (Y2): Boron compound represented by G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- ; and Equation (Y3): (J-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Boron compounds to be
However, in the above formula (Y1) ~ (Y3), B represents a boron ^atom, Q 1 to Q ⁴ are each independently a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a silyl group, siloxy group, Represents an alkoxy group, an amino group, an amide group, or an imide group, G ⁺ represents an inorganic or organic cation, J represents a neutral Lewis base, and (JH) ⁺ represents a blended acid.

(Y1) ^Q 1 ~Q ⁴ in ~ (Y3) formula is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, C 1 -C ~ 20 silyl group, siloxy group, amino group substituted with 2 to 20 carbon atom group, amide group substituted with 2 to 20 carbon atom number hydrocarbon group, or 2 to 20 carbon atom number It is an imide group substituted with the above-mentioned hydrocarbon group, more preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, still more preferably. , A fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably a fluorinated aryl group having 6 to 20 carbon atoms containing at least one fluorine atom.

Examples of the boron compound represented by the above formula (Y1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluoro). Examples thereof include phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane and the like.

Examples of G ⁺ , which is an inorganic cation in the boron compound represented by the above formula (Y2), include alkali metal cations, preferably lithium ions, sodium ions, potassium ions, silver cations, ferrothenium cations, and alkyl-substituted ferro. Examples thereof include senium cations. Examples of G ⁺ , which is an organic cation, include triphenylmethyl cation, tetraalkylphosphonium cation, tetraarylphosphonium cation, tetraalkylammonium cation, trialkylsulfonium cation, diaryliodonium cation, and triarylcarbenium cation. it can.

^{(Y2) (BQ 1 Q 2} Q 3 Q 4) in the formula ^- include tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4 , 5-Tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, Tetrakis (2,3,4-trifluorophenyl) borate, Phenyltris (pentafluorophenyl) borate, Tetrakis [ 3,5-bis (trifluoromethyl) phenyl] borate and the like can be exemplified.

Examples of the boron compound represented by the above formula (Y2) include lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, and potassium tetrakis. [3,5-bis (trifluoromethyl) phenyl] borate, silver tetrakis (pentafluorophenyl) borate, ferrosenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrosenium tetrakis (pentafluorophenyl) Bolate, Triphenylmethylcation, Tetrabutylphosphonium tetrakis (pentafluorophenyl) borate, Tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, Tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylsulfonium tetrakis (pentafluorophenyl) borate, Examples thereof include diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenyl carvenium tetrakis (pentafluorophenyl) borate, and triphenyl carbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate. Of these, sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate is most preferred.

As (JH) ⁺ in the formula (Y3), trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like can be exemplified, and (BQ ¹ Q ² Q ³ Q ^4). ) ^- , The same as above can be exemplified.

Examples of the boron compound represented by the above formula (Y3) include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, and the like. Tri (n-butyl) ammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) ) Borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, diisopropyl Ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium Tetrakis (pentafluorophenyl) borate and the like can be exemplified.

The boron compound in the present invention is preferably a boron compound represented by the above formula (Y2), and particularly preferably sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

For the production of the catalyst, one or more compounds selected from the group consisting of organoaluminum compounds and boron compounds can be used, but from the viewpoint of handling, boron compounds are preferable, and sodium tetrakis [3,5-bis (3,5-bis) is particularly preferable. Trifluoromethyl) phenyl] borate.

(C) Solvent for Dissolving Catalyst Precursor, etc. Each of the catalyst precursor in the present invention and one or more compounds selected from the group consisting of organoaluminum compounds and boron compounds may be used as solutions. Examples of the solvent of the solution include methylene chloride, chloroform, toluene, pentane, hexane, heptane and the like. Of these, methylene chloride, chloroform, or toluene is preferable.
The concentration of the catalyst precursor in the solution is usually 0.01 to 500 mmol / L, preferably 0.05 to 100 mmol / L, and more preferably 0.05 to 50 mmol / L.

<Other ingredients>
In the method for producing a polyolefin-based copolymer according to the present invention, other components such as an internal standard substance and a reaction terminator such as triethylsilane may be used as long as the effects of the present invention are not impaired.

<Quantitative relationship of each component>
In the polyolefin-based copolymer of the present invention, the molar ratio of one selected from the group consisting of methacrylic acid esters represented by the formulas (1) and (2) and the α-olefin represented by the formula (3). {[Methacrylic acid ester] / [α-olefin]} is not particularly limited, but from the viewpoint of polymer yield, the molar ratio is, for example, 0.1 to 20, preferably 0.2 to 10, and more preferably 0. .5-5, more preferably 1-5.

In the polyolefin-based copolymer of the present invention, the molar ratio of the transition metal catalyst to the α-olefin represented by the formula (3) {[transition metal catalyst] / [α-olefin]} is not particularly limited, but the molar ratio is not particularly limited. The ratio is, for example, 0.001 to 0.1, preferably 0.001 to 0.05, and more preferably 0.001 to 0.02.
In the production of the transition metal catalyst represented by the formula (4), the molar ratio of one or more compounds selected from the group consisting of organoaluminum and boron compounds to the catalyst precursor represented by the formula (5) {[Al. The B-containing compound] / [catalyst precursor]} is not particularly limited, but when an organoaluminum compound is used, the molar ratio is preferably 0.1 to 10000 in order to obtain sufficient polymerization activity, which is more preferable. Is 5 to 2000. When a boron compound is used, the molar ratio is preferably 0.1 to 10, more preferably 0.5 to 10, in order to obtain sufficient polymerization activity.

<Polymerization conditions>
The polymerization method of the present invention is not particularly limited, and examples thereof include solution polymerization and bulk polymerization. Moreover, both the batch method and the continuous method can be adopted. Each monomer used in the polymerization of the present invention may be charged all at once before the start of the copolymerization reaction, but there may be a monomer to be added during the copolymerization reaction. Solvents used for solution polymerization include saturated hydrocarbon solvents such as hexane, heptane, butane, octane, and isobutane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene. System solvent: Halogen-based solvent such as methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform and the like can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be used in combination. A halogen-based solvent such as methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and chloroform is preferable because of the solubility of the product.

The polymerization temperature in the present invention is preferably −50 to 80 ° C., more preferably 0 to 50 ° C. The polymerization time is preferably 1 to 200 hours. Further, the polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.

[Polyolefin-based copolymer]
The polyolefin-based copolymer in the present invention is produced by the above-mentioned production method.
In the polyolefin-based copolymer of the present invention, the introduction rate of the methacrylic acid ester represented by the formula (1) and / or the formula (2) is preferably 0.1 to 1 from the viewpoint of expressing the function of the substituent. It is 50%, more preferably 0.5 to 50%.
Here, the molar ratio of the unit of the methacrylic acid ester represented by the formula (1) and / or the formula (2) to the unit of the α-olefin represented by the formula (3) in the polymer is the former: the latter =. Assuming i: j, the introduction rate of the methacrylic acid ester is 100 × (i / (i + j)). Specifically, the introduction rate can be measured by the measuring method described in the examples.
The number average molecular weight ( _Mn ) of the polyolefin-based copolymer is not particularly limited, but is preferably 1,000 to 1,000,000, and more preferably 3,000 to 5,000,000.
The molecular weight distribution (M _w / M _n ) of the polyolefin-based copolymer is not particularly limited, but is preferably 1.0 to 100, more preferably 1.0 to 50, and even more preferably 1.00 to 20.
The melting point of the polyolefin-based copolymer is preferably −50 to 100 ° C., more preferably 0 to 90 ° C., and even more preferably 0 to 80 ° C.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
Each evaluation method of the polyolefin-based copolymer adopted in the following Examples and Comparative Examples is shown below.

<Introduction rate of methacrylic acid ester>
The introduction rate of the methacrylic acid ester in the polymer was calculated from the integrated intensity of the signal obtained by ¹ H NMR spectrum measurement of the polyolefin-based copolymer as a product. For example, if the molar ratio of the unit of methacrylic acid ester to the unit of α-olefin in the polymer is the former: the latter = i: j, the introduction rate of the methacrylic acid ester is 100 × (i / (i + j)). is there.

For ¹ H NMR spectrum measurement of the polymer, AVANCE III (400 MHz) manufactured by Bruker biospin and AVANCE III HD type (500 MHz) manufactured by Bruker biospin were used. ^{For the 13} C NMR spectrum measurement, AVANCE III (100 MHz) manufactured by Bruker biospin and AVANCE III HD type (125 MHz) manufactured by Bruker biospin were used. ¹ H NMR spectrum measurement uses 1,1,2,2-tetrachloroethane-d ₂ (C ₂ D ₂ Cl ₄ ) and the remaining 1,1,2,2-tetrachloroethane signal (5.91 ppm). Was used as the internal standard. ¹³ C NMR spectrum measurement used 1,1,2,2-tetrachloroethane-d ₂ (C ₂ D ₂ Cl ₄ ) and signal derived from 1,1,2,2-tetrachloroethane-d ₂ (74. 2ppm) was used as the internal standard.

<Number average molecular weight (M _n ) and molecular weight distribution (M _w / M _n )>
HLC-8220GPC manufactured by TOSOH is used, tetrahydrofuran (THF, flow velocity: 0.36 mL / min, temperature: 40 ° C., sample concentration: 0.1 wt / vol%) is used as the mobile phase, and the differential refractometer is used as the detector. A detector (RID, manufactured by JASCO Corporation, RI-2031) was used. For the calibration curve, standard polystyrene (manufactured by TOSOH) was referred to, and the number average molecular weight (M _n ) and the weight average molecular weight (M _w ) were determined. From these values, the molecular weight distribution (M _w / M _n ) was calculated. As the column, TSKgel SuperMultipore HZ-M and TOSOH super H-RC manufactured by TOSOH were used.

<Melting point>
The melting point was determined by differential scanning calorimetry using a DSC822e manufactured by METTLER. The measurement was carried out under a nitrogen gas stream, and the temperature conditions were as shown below. The temperature was raised from room temperature to 180 ° C. at 10 ° C./min, and then lowered to −50 ° C. at 20 ° C./min. Then, the measurement was carried out while raising the temperature from −50 ° C. to 180 ° C. at 10 ° C./min. The temperature of the inflection point of the measurement curve was read and used as the melting point.

[Example 1]
In a 25 mL Schlenk tube, a palladium-catalyzed precursor (11.5 mg) represented by the formula (7) (where Me is a methyl group) and tetrakis [3,5-bis (trifluoromethyl) phenyl] sodium borate (21.3 mg) was added, vacuum dried, and then nitrogen substitution was performed. Methylene chloride (2.0 mL) is added, and the mixture is stirred at 25 ° C. for 2 minutes (stirr dimensions: length 10 mm × φ4 mm, rotation speed: 500 rpm), and then methyl methacrylate (400 mg), 1-decene (280 mg), Naphthalene (40 mg) was added as an internal standard substance, and stirring was continued. After the reaction started, the reaction solution was sampled, ¹ H NMR measurement was performed, and it was confirmed from the integral ratio of the protons derived from the olefin of naphthalene and each monomer that the conversion rate of the monomer was saturated, and 0.4 mL of triethylsilane was added. The reaction was stopped by adding. The reaction solution was poured into a large excess of methanol and the solid content was filtered off to obtain 45.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (1523H, m, polyethylene part)
δ = 3.59 ppm (3H, s, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 2]
The procedure was the same as in Example 1 except that methyl methacrylate (200 mg) was used instead of methyl methacrylate (400 mg) to obtain 33.4 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (1414H, m, polyethylene part)
δ = 3.59 ppm (3H, m, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 3]
The procedure was the same as in Example 1 except that methyl methacrylate (801 mg) was used instead of methyl methacrylate (400 mg) to obtain 11.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (1235H, m, polyethylene part)
δ = 3.59 ppm (3H, m, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 4]
The procedure was the same as in Example 1 except that the reaction temperature was set to 0 ° C. instead of 25 ° C. to obtain 96.1 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (2842H, m, polyethylene part)
δ = 3.59 ppm (3H, m, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 5]
The procedure is the same as in Example 1 except that the palladium complex (13.2 mg) represented by the formula (8) is used instead of the palladium catalyst precursor represented by the formula (7) as the catalyst precursor. This was done to give 24.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (3985H, m, polyethylene part)
δ = 3.59 ppm (3H, m, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 6]
The procedure was the same as in Example 1 except that isoprenyl methacrylate (619 mg) was used instead of methyl methacrylate (400 mg) to obtain 41.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (699H, m, polyethylene part)
δ = 1.71 ppm (3H, m, CH ₃ )
δ = 2.28 ppm (2H, m, CCH ₂ )
δ = 4.02 ppm (2H, m, OCH ₂ )
δ = 4.69, 4.75 ppm (2H, m, CH ₂ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.29 ppm (CH ₃ )
δ = 32.78 ppm (CH ₂ )
δ = 39.84ppm (CH)
δ = 62.68 ppm (OCH ₂ )
δ = 177.0ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 7]
The procedure was the same as in Example 1 except that 1-hexene (168 mg) was used instead of 1-decene (280 mg) to obtain 62.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (346H, m, polyethylene part)
δ = 3.59 ppm (3H, m, OCH ₃ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.22 ppm (CH ₃ )
δ = 32.79 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 177.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 8]
The procedure was the same as in Example 1 except that acetoxyethyl methacrylate (689 mg) was used instead of methyl methacrylate (400 mg) to obtain 70.0 mg of the polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (1318H, m, polyethylene part)
δ = 4.00-4.30ppm (4H, m, OCH ₂ CH ₂ O)
δ = 2.10 ppm (3H, m, CH ₃ COO)
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.20 ppm (CH ₃ )
δ = 20.93 ppm (CH ₃ COO)
δ = 32.80 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 61.99, 62.44 ppm (OCH ₂ CH ₂ O)
δ = 176.4ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 9]
The procedure was the same as in Example 1 except that tert-butyl methacrylate (569 mg) was used instead of methyl methacrylate (400 mg) to obtain 75.0 mg of the polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (1985H, m, polyethylene part)
^{δ = 1.39ppm (9H, s,} O t Bu)
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.20 ppm (CH ₃ )
δ = 32.80 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 28.35, 80.69 ppm (tert-Bu)
δ = 176.2ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 10]
The procedure was the same as in Example 1 except that −n-butyl methacrylate (569 mg) was used instead of methyl methacrylate (400 mg) to obtain 60.0 mg of polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80 ppm (1414H, m, polyethylene part, CH ₂ CH ₂ CH ₃ )
δ = 3.90 ppm (2H, m, OCH ₂ )
The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 70 ° C.).
δ = 17.20 ppm (CH ₃ )
δ = 32.80 ppm (CH ₂ )
δ = 39.67ppm (CH)
δ = 13.77, 19.37, 30.90, 64.58 ppm (n-Bu)
δ = 177.0ppm (COO)
The results of the above evaluation are shown in Table 1.

[Example 11]
The procedure was the same as in Example 1 except that allyl methacrylate (505 mg) was used instead of methyl methacrylate (400 mg) to obtain 6.7 mg of the polymer.
The ¹ H NMR spectrum of the polymer was as follows (400 MHz, C ₂ D ₂ Cl ₄ , 70 ° C).
δ = 0.70-1.80ppm (91H, m, polyethylene part)
δ = 1.89 ppm (3H, s, CH ₃ (methacryloyl group))
δ = 4.07 ppm (2H, t, OCH ₂ )
δ = 5.47, 6.02 ppm (2H, s, CH ₂ (methacryloyl group))
The results of the above evaluation are shown in Table 1.

[Reference example 1]
A reference example is J. Am. Chem. Soc. , 2018, 140, 1876-1883. It was carried out with reference to.
Under an argon atmosphere, a palladium catalyst (5.7 mg) represented by the formula (9), toluene (4.0 mL), and methyl methacrylate (4.0 mL) were added to a 50 mL autoclave manufactured by Pressure Resistant Glass Industry Co., Ltd. .. It was filled with ethylene at 1.0-2.0 MPa and stirred at 120 ° C. for 15 hours. After cooling to room temperature, methanol (20 mL) was added to the autoclave, and the resulting copolymer was recovered by filtration. The copolymer was dissolved in ortho-dichlorobenzene and then reprecipitated in methanol. Then, it was dried under reduced pressure to obtain 101 mg of a copolymer.

The ¹³ C NMR spectrum from the methacrylic acid ester moiety in the polymer was as follows (125 MHz, C ₂ D ₂ Cl ₄ , 120 ° C.).
δ = 21.3 ppm (CH ₃ )
δ = 39.1 ppm (CH ₂ )
δ = 45.9ppm (C)
δ = 177.5ppm (COO)
δ = 50.8 ppm (OCH ₃ )

From the results in Table 1, by using the method for producing a polyolefin-based copolymer of the present invention, it is possible to obtain a polyolefin into which a methacrylic acid ester has been introduced under mild conditions in both temperature and pressure. In order to determine the primary structure of the polyolefin-based copolymer according to Examples 1 to 10, J. Am. Chem. Soc. , 2018, 140, 1876-1883. Was referred to. This reference shows the ¹³ C NMR chemical shifts of various esters as model compounds. According to this, the chemical shift differs depending on the site where the methacrylic acid ester is introduced into the polyolefin. The ¹³ C NMR chemical shifts of the polymers described in Examples 1-10 were in good agreement with the chemical shifts of methyl 2-methylpentaneate cited as an example of the model compound. This suggests that the primary structure of the polyolefin-based copolymers described in Examples 1 to 10 has a structure as shown in the formula (10) in which the methacrylic acid ester is present at the end of the polymer chain. On the other hand, the chemical shift of ¹³ C NMR in Reference Example 1 showed good agreement with the chemical shift of methyl 2-hexyl-2-methyldecanoate cited as an example of the model compound. From this, the primary structure of Reference Example 1 suggests that the methacrylic acid ester is introduced inside the polymer main chain.

[In the formula (10), R ¹⁶ is an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 24 carbon atoms. ]

In ¹ H NMR of the polymer described in Example 11, a signal of a methacryloyl group was observed, and a signal derived from OCH ₂ (4.07 ppm) was split in triplicate. Therefore, the primary structure thereof is of the formula (11). It is suggested to take such a structure.

INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to produce a polyolefin-based copolymer containing a methacrylic acid ester unit under mild polymerization conditions. Further, since the polyolefin-based copolymer obtained in the present invention has a low melting point and has polar and non-polar portions in the side chain, it exhibits excellent adhesiveness to an organic / inorganic base material, for example, hot. It can be applied to melt bonding and the like. It can also be used as a matrix resin for fiber reinforced plastics.

Claims (4)

A polyolefin obtained by polymerizing a methacrylic acid ester represented by the formulas (1) and / or the formula (2) and an α-olefin represented by the formula (3) with a transition metal catalyst represented by the formula (4). A method for producing a system copolymer.

[In formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms. ]

[In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 or more and 10 or less. ]

[In formula (3), R ³ is an alkyl group having 1 to 12 carbon atoms. ]

[In formula (4), M is a transition metal atom of Group 10 of the periodic table, X is a monovalent organic anion composed of multiple atoms including a boron atom or an aluminum atom, and R ⁴ is a hydrogen atom and a halogen atom. , An alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 42 carbon atoms, a substituted silyl group, an alkoxy group having 1 to 20 carbon atoms, and 7 to 7 carbon atoms. 12 aralkyloxy group or an aryloxy group having a carbon number of 6-42, independently ^{R 5} and ^{R 6} are each an aryl group having a carbon number of 6-42, ^{R 7} and ^{R 8,} Independently, they are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or aryl groups having 6 to 42 carbon atoms, or R ⁷ and R ⁸ are linked to each other and have 1 to 30 carbon atoms. It is a divalent base. ] Claimed that the transition metal catalyst is a transition metal catalyst produced by contacting a catalyst precursor represented by the formula (5) with one or more compounds selected from the group consisting of organoaluminum compounds and boron compounds. Item 1. The manufacturing method according to Item 1.

[In formula (5), M, R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are synonymous with the above, and R ⁹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and carbon. Aralkyl group with 7 to 12 atoms, aryl group with 6 to 42 carbon atoms, substituted silyl group, alkoxy group with 1 to 20 carbon atoms, aralkyloxy group with 7 to 12 carbon atoms, or 6 to 6 carbon atoms It is an aryloxy group of 42. ] The production method according to claim 2, wherein the catalyst precursor is represented by the formula (6).

[In formula (6), R ⁴ , R ⁷ , R ⁸ and R ⁹ are synonymous with the above, and R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independent hydrogen atoms. , A halogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 1 to 12 carbon atoms. ] A polyolefin-based copolymer produced by the method according to any one of claims 1 to 3.