JP2021169631A - Polar group-containing olefin copolymer - Google Patents

Abstract

To provide a novel polar group-containing olefin copolymer that uses a vinylidene comonomer, allowing a wide range of practical applications, and a method for producing the same.SOLUTION: A polar group-containing olefin copolymer contains a structural unit derived from ethylene and/or C3-10 α-olefin, and a structural unit derived from at least one selected from polar group-containing monomers represented by formulas (1), (2) and (3) of 20-0.001 mol% [FG is a halogen atom, a hydroxy group, a C6-20 aryl group, a C1-20 alkoxy group, a C1-20 alkylthio group, a substituted amino, cyano or carboxyl group having a C1-20 hydrocarbon group, an ester group having a C1-20 hydrocarbon group or an acyloxy group having a C1-20 hydrocarbon group].SELECTED DRAWING: None

Description

The present invention relates to an olefin copolymer containing a polar group-containing monomer having a specific structure as a constituent component. Specifically, the present invention relates to an ethylene and / or α-olefin monomer and a polar group-containing monomer having a specific structure (polar group). It relates to a novel polar group-containing olefin copolymer having a unique structure obtained by copolymerizing a vinylidene monomer having a specific structure.

Among resin materials, olefin polymers are excellent in various properties such as physical properties and moldability, and are highly economical and compatible with environmental problems, and are extremely versatile and important industrial materials.
However, since the olefin polymer does not have a polar group, it is difficult to apply it to applications that require adhesiveness to other materials, printability, or compatibility with fillers and the like. As an improved material, a copolymer of ethylene produced by a high-pressure radical polymerization process and a polar group-containing vinyl monomer has been used as a simple substance or as a composition with another resin (Patent Document 1 and Patent). Document 2). However, due to the polymer multi-branched structure, it is inferior in low elastic modulus and mechanical properties, and its application range is limited not only when it is used alone but also when it is used as a composition with other resins. It was.

On the other hand, in the method for producing an olefin polymer using a metallocene catalyst, which is generally used in the past, when ethylene and a polar group-containing monomer are copolymerized, the catalytic polymerization activity is lowered and it is difficult to copolymerize. A method of reacting an organoaluminum compound or an organozinc compound with a polar comonomer (masking of a polar functional group) and then copolymerizing with an olefin has been reported (Patent Documents 3 and 4). However, this method has a problem that a large amount of metal salt is precipitated at the same time as the copolymer is formed, and is not widely used from the viewpoint of the cost of the organoaluminum compound.
By the way, in recent years, an attempt to copolymerize an olefin and a polar comonomer by using a so-called post-metallocene, a late-period transition metal complex catalyst, without using a masking agent such as an organoaluminum compound has been energetically promoted. Has been done. So far, acrylic acid esters (Patent Documents 5 to 10), acrylonitrile (Non-Patent Document 1), and vinyl ethers (Non-Patent Documents 1) have been used as polar comonomeres, while having the characteristic of obtaining a linear copolymer with few branches as a copolymer structure. Patent documents 2) and the like have been reported.

Japanese Patent No. 279292 Japanese Unexamined Patent Publication No. 3-229713 Japanese Unexamined Patent Publication No. 2003-327627 Japanese Unexamined Patent Publication No. 03-207707 Special Table 2002-521534 Japanese Unexamined Patent Publication No. 6-184214 Japanese Unexamined Patent Publication No. 2008-22301 Japanese Unexamined Patent Publication No. 2010-150246 Japanese Unexamined Patent Publication No. 2010-150532 Japanese Unexamined Patent Publication No. 2010-20647

K. Nozaki et al. , J. Am. Chem. Soc. , 2007, 129, 8948-8949. R. Jordan et al. , J. Am. Chem. Soc. , 2007, 129, 8946-8947.

However, among the polar commonomers, the vinylidene compound, which is a 1,1-disubstituted olefin, is lower in polymerizability by the late-period transition metal complex catalyst than the vinyl compound, which is a mono-substituted olefin, and therefore is co-located with the olefin. It was difficult to polymerize.
In view of such circumstances, an object of the present invention is to provide a polar group-containing olefin copolymer using a novel linear vinylidenecomonomer and a method for producing the same.

The present inventors have made various searches in the production of polar group-containing olefin copolymers with the aim of solving the above-mentioned problems of the present invention.
As a result, they have found that the above problems can be solved by using a specific vinylidenecomonomer as a polymerization catalyst having a specific structure, and have completed the invention. Based on these results, the following inventions are provided.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been generally described. Therefore, the overall configuration of the present invention can be summarized as follows [1]. ] To [16].
Here, the polar group-containing olefin copolymer having a specific structure in [1] is configured as the basic invention [1], and each of the inventions below [2] adds ancillary requirements to the basic invention, or It shows the embodiment. The inventions [4] to [16] define additional requirements relating to the method for producing a polar group-containing olefin copolymer having a specific structure of the present invention. All invention units are collectively referred to as an invention group.

［式（１）、（２）及び（３）中、ＦＧは、ハロゲン原子、水酸基、炭素原子数６〜２０のアリール基、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０のアルキルチオ基、炭素原子数１〜２０の炭化水素基を有する置換アミノ基、シアノ基、カルボキシル基、炭素原子数１〜２０の炭化水素基を有するエステル基、または炭素原子数１〜２０の炭化水素基を有するアシルオキシ基である。
Ｒは、炭素原子数１〜１０のアルキル基、ハロゲン原子で置換された炭素原子数１〜１０のアルキル基、ハロゲン原子、またはシアノ基であり、ＦＧとの間で環状構造を形成しても良い。］ [1]
Structural units derived from ethylene and / or α-olefins with 3 to 10 carbon atoms,
Polar group-containing olefin containing 20 to 0.001 mol% of structural units derived from at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2) and (3). It is a copolymer and
And,
¹³ A polar group-containing olefin copolymer having a methyl branching degree calculated by C-NMR analysis of 20 or less per 1,000 carbons of the copolymer.

[In the formulas (1), (2) and (3), FG has a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkylthio group, substituted amino group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having 1 to 20 carbon atoms, or hydrocarbon having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, and even if a cyclic structure is formed with the FG. good. ]

[2]
The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and an ester group having a hydrocarbon group having 1 to 20 carbon atoms. , Or the polar group-containing olefin copolymer according to [1], which is an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms.

[3]
The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms. The polar group-containing olefin copolymer according to [2].

[4]
The method for producing a polar group-containing olefin copolymer according to any one of [1] to [3].
A method for producing a polar group-containing olefin copolymer, which comprises polymerizing using a compound containing a transition metal of groups 8 to 10.

[5]
The compound containing the transition metal of Group 8 to 10 is a metal complex obtained by reacting a carben precursor compound with a complex precursor of a transition metal compound of Group 8 to 10 [4]. The method for producing a polar group-containing olefin copolymer according to.

［一般式（４）及び一般式（５）において、Ｚは、ＯＲ^３、ＳＲ^３、ＳＯ_３Ｒ^３、Ｎ＝ＣＲ^３Ｒ^４、ＣＲ^３＝ＮＲ^４、Ｎ（Ｒ^３）_２、Ｐ（Ｒ^３）_２、ＣＯ_２Ｒ^３、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^３）_２、Ｃ（Ｏ）Ｒ^３、ＳＯ_２Ｒ^３、ＳＯＲ^３、ＯＳＯ_２Ｒ^３、Ｐ（Ｏ）（ＯＲ^３）_２−ｙ（Ｒ^４）_ｙ、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^３）_２Ｍ’、Ｐ（Ｒ^３）_２（Ｏ）を表す。（ここで、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を表し、Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はホスホニウムを表し、ｙは０〜２の整数を表す）。Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はヘテロ原子を含有してもよい炭素数１〜４０の炭化水素基である。Ｘ^１は、炭素数３〜９の飽和又は不飽和な二価の炭化水素基を表し、Ｘ^１が形成する環上に置換基を有していてもよい。Ｒａは、水素原子又はヘテロ原子を含有してもよい炭素数１〜１０の炭化水素基であり、Ｘ^１から成る環の一部と縮環してもよい。Ａ⁻は、カウンターアニオンを表し、任意の陰イオンを表す。Ｅ^１及びＥ^２は、それぞれ独立に、炭素原子又は窒素原子を表す。ｎは、０又は１の整数を表す。］ [6]
The method for producing a polar group-containing olefin copolymer according to [5], wherein the carbene precursor compound is represented by the following general formula (4) or general formula (5).

[In the general formula (4) and the general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P ( R ³ ) ₂ , CO ₂ R ³ , CO ₂ M', C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) represents a _{^{(OR 3) 2-y (}} R 4) y, SO 3 M ', PO 3 M' 2, P (O) (OR 3) 2 M ', P (R 3) 2 (O). (Here, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M'is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium. Represents, y represents an integer from 0 to 2). R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by ^{X 1.} Ra is a hydrocarbon group having carbon atoms of 1 to 10 also contain hydrogen atom or a hetero atom, it may be condensed with a part of the ring of X ^1. A ⁻ represents a counter anion and represents an arbitrary anion. E ¹ and E ² independently represent a carbon atom or a nitrogen atom, respectively. n represents an integer of 0 or 1. ]

［一般式（６）又は一般式（７）において、Ｘ^２は、炭素数３〜９の飽和又は不飽和な二価の炭化水素基を表す。Ｘ^２が形成する環上に置換基を有していてもよい。Ａ⁻、Ｚ、Ｒ^１、Ｒ^２、Ｘ^１、Ｅ^１及びＥ^２は、［６］に記載した通りである。］ [7]
The method for producing a polar group-containing olefin copolymer according to [6], wherein the carbene precursor compound is represented by the following general formula (6) or general formula (7).

[In the general formula (6) or the general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. It may have a substituent on the ring formed by ^{X 2.} A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in [6]. ]

［一般式（８）又は一般式（９）において、Ｒ^５〜Ｒ^９は、ハロゲン原子又はヘテロ原子含有基又はヘテロ原子を含有していてもよい炭素数１〜４０の炭化水素基を表す。Ａ⁻、Ｚ、Ｒ^１、Ｒ^２、Ｅ^１及びＥ^２は、［６］に記載した通りである。］ [8]
The method for producing a polar group-containing olefin copolymer according to [7], wherein the carbene precursor compound is represented by the following general formula (8) or general formula (9).

[In the general formula (8) or the general formula (9), R ^{5 to} R ⁹ represent a halogen atom or a hetero atom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in [6]. ]

［一般式（１０）又は一般式（１１）において、Ｒ^１０は、ハロゲン原子又はヘテロ原子含有基又はヘテロ原子を含有していてもよい炭素数１〜４０の炭化水素基を表す。Ａ⁻、Ｚ、Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６、Ｅ^１及びＥ^２は、［６］又は［８］に記載した通りである。］ [9]
The method for producing a polar group-containing olefin copolymer according to [6], wherein the carbene precursor compound described above is represented by the following general formula (10) or general formula (11).

[In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom or a heteroatom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in [6] or [8]. ]

[10]
In the general formulas (4) to (11), the Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P (R ^3). ) ₂ , P (O) (OR ³ ) _2-y (R ⁴ ) _y The preparation of the polar group-containing olefin copolymer according to any one of [6] to [9]. Method.

［一般式（１２）又は一般式（１３）において、Ｍ^１は、周期表の８〜１０族に属する遷移金属を表す。Ｌ^１及びＬ^２は、Ｍ^１に配位子したリガンドを表し、それぞれ独立に、ハロゲン原子、水素原子、ヘテロ原子を含有する炭素数１〜２０の炭化水素基を表す。Ｌ^１及びＬ^２は、互いに連結して環を形成してもよい。
Ｚは、ＯＲ^３、ＳＲ^３、ＳＯ_３Ｒ^３、Ｎ＝ＣＲ^３Ｒ^４、ＣＲ^３＝ＮＲ^４、Ｎ（Ｒ^３）_２、Ｐ（Ｒ^３）_２、ＣＯ_２Ｒ^３、ＣＯ_２Ｍ’、Ｃ（Ｏ）Ｎ（Ｒ^３）_２、Ｃ（Ｏ）Ｒ^３、ＳＯ_２Ｒ^３、ＳＯＲ^３、ＯＳＯ_２Ｒ^３、Ｐ（Ｏ）（ＯＲ^３）_２−ｙ（Ｒ^４）_ｙ、ＳＯ_３Ｍ’、ＰＯ_３Ｍ’_２、Ｐ（Ｏ）（ＯＲ^３）_２Ｍ’、Ｐ（Ｒ^３）_２（Ｏ）を表す。（ここで、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は炭素数１〜２０の炭化水素基を表し、Ｍ’は、アルカリ金属、アルカリ土類金属、アンモニウム、４級アンモニウム又はホスホニウムを表し、ｙは０〜２の整数を表す）。Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はヘテロ原子を含有してもよい炭素数１〜４０の炭化水素基である。Ｘ^１は、炭素数３〜９の飽和又は不飽和な二価の炭化水素基を表し、Ｘ^１が形成する環上に置換基を有していてもよい。Ｒａは、水素原子又はヘテロ原子を含有してもよい炭素数１〜１０の炭化水素基であり、Ｘ^１から成る環の一部と縮環してもよい。Ａ⁻は、カウンターアニオンを表し、任意の陰イオンを表す。Ｅ^１及びＥ^２は、それぞれ独立に、炭素原子又は窒素原子を表す。ｎは、０又は１の整数を表す。Ａ^＋はカウンターカチオンを表し、任意の陽イオンを表す。］ [11]
The preparation of the polar group-containing olefin copolymer according to [4], wherein the compound containing the transition metal of Groups 8 to 10 is represented by the following general formula (12) or general formula (13). Method.

[In the general formula (12) or the general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent ligands ligandd to M ¹ , and independently represent hydrocarbon groups having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, and a hetero atom. L ¹ and L ² may be connected to each other to form a ring.
Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P (R ³ ) ₂ , CO ₂ R ³ , CO ₂ M' , C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) (OR ³ ) _2-y (R ⁴ ) _y , SO _{3 M ', PO 3 M'} 2, P (O) (OR 3) 2 M ', represent a _{^{P (R 3) 2 (O}} ). (Here, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M'is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium. Represents, y represents an integer from 0 to 2). R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by ^{X 1.} Ra is a hydrocarbon group having carbon atoms of 1 to 10 also contain hydrogen atom or a hetero atom, it may be condensed with a part of the ring of X ^1. A ⁻ represents a counter anion and represents an arbitrary anion. E ¹ and E ² independently represent a carbon atom or a nitrogen atom, respectively. n represents an integer of 0 or 1. A ⁺ represents a counter cation and represents an arbitrary cation. ]

[12]
The method for producing a polar group-containing olefin copolymer according to [11], wherein M ^{1 is a transition metal belonging to Group 10 of the periodic table.}

［式（Ｃ１）中、
Ｍは周期表第１０族の金属原子を表し、
Ｘはリン原子（Ｐ）または砒素原子（Ａｓ）を表し、
Ｙ^１は、水酸基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のエステル基、シリル基、及びハロゲン原子から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜７０の２価の炭化水素基を表し、
Ｑは、Ｙ^１［−Ｓ（＝Ｏ）_２−Ｏ−］Ｍ、Ｙ^１［−Ｃ（＝Ｏ）−Ｏ−］Ｍ、Ｙ^１［−Ｐ（＝Ｏ）（−ＯＨ）−Ｏ−］ＭまたはＹ^１［−Ｓ−］Ｍの「［ ］」の中に示される２価の基を表し（ただし、両側のＹ^１、Ｍは基の結合方向を示すために記載している。）、
Ｒ^１５は、水素原子、ハロゲン原子、炭素原子数１〜３０の炭化水素基、ハロゲン原子で置換された炭素原子数１〜３０の炭化水素基、炭素原子数１〜１０のアルコキシ基で置換された炭素原子数２〜３０の炭化水素基、炭素原子数６〜２０のアリールオキシ基で置換された炭素原子数７〜３０の炭化水素基、炭素原子数２〜１０のアミド基で置換された炭素原子数３〜３０の炭化水素基、炭素原子数１〜３０のアルコキシ基、炭素原子数６〜３０のアリールオキシ基、及び炭素原子数２〜１０のアシロキシ基からなる群より選ばれる置換基を表し、
Ｒ^１６及びＲ^１７はそれぞれ独立して、水素原子、アルコキシ基、アリールオキシ基、シリル基、アミノ基、またはハロゲン原子、アルコキシ基及びアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜１２０の炭化水素基を表し、Ｒ^１６及びＲ^１７の少なくとも一方が、炭素原子数１〜１０のアルキル基または炭素原子数４〜１０６のシクロアルキル基である。また、Ｒ^１６またはＲ^１７はＹ^１と結合して環構造を形成してもよい。
Ｌは電子供与性配位子を表し、
ｑは０、１／２、１または２である。］ [13]
The method for producing a polar group-containing olefin copolymer according to [4], wherein the compound containing the transition metal of Groups 8 to 10 is a metal complex represented by the following general formula (C1).

[In equation (C1),
M represents a metal atom of Group 10 of the periodic table,
X represents a phosphorus atom (P) or an arsenic atom (As),
Y ¹ may be substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. Represents a divalent hydrocarbon group from 1 to 70
Q is Y ¹ [-S (= O) _2- O-] M, Y ¹ [-C (= O) -O-] M, Y ¹ [-P (= O) (-OH) -O- ] M or Y ¹ [-S-] M represents a divalent group shown in "[]" (however, Y ¹ and M on both sides are described to indicate the bonding direction of the group. ),
R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and an alkoxy group having 1 to 10 carbon atoms. It was substituted with a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. Substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an asyloxy group having 2 to 10 carbon atoms. Represents
R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. It represents a hydrocarbon group having 1 to 120 carbon atoms, ^{and at least one of R 16} and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may ^{be combined with Y 1} to form a ring structure.
L represents an electron donating ligand
q is 0, 1/2, 1 or 2. ]

[14]
In the general formula (C1), Q is -S _{(= O)} 2 -O- (although, S is bound to ^{Y 1,} O is bound to M.), Containing polar group according to [13] A method for producing an olefin copolymer.

［式（Ｃ２）中、Ｒ^１１２〜Ｒ^１１５は水素原子、ハロゲン原子、炭素原子数１〜２０の炭化水素基、炭素原子数１〜８のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、シリル基またはハロゲン原子で置換された炭素原子数１〜２０の炭化水素基を表す。Ｍ、Ｘ、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｌ及びｑは一般式（Ｃ１）の記載と同じ意味を表す。］
で示される金属錯体である、［１３］に記載の極性基含有オレフィン共重合体の製造方法。 [15]
The compound represented by the general formula (C1) is the general formula (C2).

[In the formula (C2), R ^{112 to} R ¹¹⁵ are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and aryloxy groups having 6 to 20 carbon atoms. , Represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in the general formula (C1). ]
The method for producing a polar group-containing olefin copolymer according to [13], which is a metal complex represented by.

［式（Ｃ３）中、３つのＲ^１１６はそれぞれ独立して、水素原子または炭素原子数１〜８の炭化水素基を表し、それぞれ同じであっても異なっていてもよい。Ｍ、Ｘ、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１１３、Ｒ^１１４、Ｒ^１１５、Ｌ及びｑは一般式（Ｃ２）の記載と同じ意味を表す。］
で示される金属錯体である、［１５］に記載の極性基含有オレフィン共重合体の製造方法。 [16]
The compound represented by the general formula (C2) has a general formula (C3) in which ^{R 112 is a silyl group.}

[In the formula (C3), ^{each of the three R 116s} independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meanings as described in the general formula (C2). ]
The method for producing a polar group-containing olefin copolymer according to [15], which is a metal complex represented by.

In the present invention, a novel polar group-containing olefin copolymer using a specific vinylidenecomonomer is provided.
Further, in the present invention, it is possible to produce a polar group-containing olefin copolymer by using a post-metallocene complex catalyst having a specific structure.
The polar group-containing olefin copolymer provided by the present invention has a wide range of applications and is very useful.

Hereinafter, the polar group-containing olefin copolymer of the present invention, and further, the method for producing the copolymer, its use, and the like will be described in detail for each item.
[1] Polar Group-Containing Monomer of the Present Invention (1) Polar Group-Containing Monomer The polar group-containing monomer used in the present invention is
It is at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2) and (3).

[In the formulas (1), (2) and (3), FG has a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkylthio group, substituted amino group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having 1 to 20 carbon atoms, or hydrocarbon having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, and even if a cyclic structure is formed with the FG. good. ]

(2) Specific Examples of Polar Group-Containing Monomers In the formulas (1), (2) and (3), the FG is preferably a halogen atom, an aryl group having 6 to 20 carbon atoms, and 1 to 20 carbon atoms. It is a substituted amino group having a hydrocarbon group, a cyano group, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms, more preferably a halogen. It is an atom, an aryl group having 1 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms.

Here, FG will be described in detail.
The halogen atom is not particularly limited. The halogen atom preferably includes chlorine, fluorine, bromine and iodine.

Specifically, the aryl group having 6 to 20 carbon atoms includes a phenyl group, a methylphenyl group, an n-propylphenyl group, an i-propylphenyl group, an n-butylphenyl group, an i-butylphenyl group, and an s-butyl. Preferable examples include a phenyl group, a t-butylphenyl group, an n-hexylphenyl group, a trimethylphenyl group, a pentamethylphenyl group, a biphenyl group, a naphthyl group and the like.

Specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, and n-. Preferable examples include hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-detoxy and the like.

Specifically, the alkylthio group having 1 to 20 carbon atoms includes a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, an s-butylthio group, a t-butylthio group, a pentylthio group and a hexylthio. Groups, decylthio groups, dodecylthio groups and the like can be preferably mentioned.

Specific examples of the substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms include a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, and a monophenylamino group. A group, a diphenylamino group, a bis (trimethylsilyl) amino group, a morpholinyl group and the like can be preferably mentioned.

Specific examples of the ester group having a hydrocarbon group having 1 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Preferred examples thereof include a group, a (4-hydroxybutyl) carbonyl group, a (4-glycidylbutyl) carbonyl group, a phenoxycarbonyl group, a succinic acid anhydride group, and a succinateimide group.

Specific examples of the acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms include an acetyloxy group, a propionyloxy group, a (meth) acryloyloxy group, and a benzoyloxy group.

Next, R will be described in detail.
In formulas (1), (2) and (3), R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group. Yes, an annular structure may be formed with the FG.
Specifically, R, which is an alkyl group having 1 to 10 carbon atoms, has a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, and the like. 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl Group, isobutyl group, 1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group, 3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group, 4- Heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl Groups, 1-adamantyl groups, 2-adamantyl groups and the like can be preferably mentioned.
The R, which is an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, preferably includes a structure in which the above-mentioned hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen atom. A specific preferred example is a trifluoromethyl group.
Preferred specific examples of R, which is a halogen atom, are fluorine, chlorine, and bromine. Of these, a more preferred substituent is chlorine.

[2] α-olefin in the present invention The α-olefin used in the present invention is ethylene and / or an α-olefin having 3 to 10 carbon atoms. Preferred specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene and 4-methyl-1-pentene, which are particularly preferable. A specific example is ethylene. Further, one type of α-olefin may be used, or a plurality of types may be used in combination.

[3] Copolymer composition (composition of polar group-containing olefin copolymer)
The polar group-containing olefin copolymer in the present invention preferably has a structural unit amount of 0.001 to 10.000 mol% derived from the polar group-containing monomer in the polar group-containing olefin copolymer. Of these, it is particularly preferable to select in the range of 0.010 to 5.000 mol%.
The amount of this structural unit can be controlled by selecting a catalyst, the amount of polar group-containing monomer added at the time of polymerization, and the pressure and temperature at the time of polymerization. As specific means for increasing the amount of structural unit derived from the polar group-containing monomer in the copolymer, it is effective to increase the amount of polar group-containing monomer added at the time of polymerization, reduce the olefin pressure at the time of polymerization, and increase the polymerization temperature. be. For example, it is required to regulate these factors to control the copolymer region of interest.

The polar group-containing olefin copolymer in the present invention has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) determined by gel permeation chromatography (GPC) in the range of 1.5 to 3.5. It is preferable to have. Of these, the range is more preferably 1.6 to 3.3, and particularly preferably 1.7 to 3.0.
When Mw / Mn satisfies this range, various processability including molding of the laminated body becomes sufficient, and the adhesive strength becomes excellent. Mw / Mn can be controlled by selecting the catalyst to be used.

The melting point of the polar group-containing olefin copolymer in the present invention is not particularly limited. The melting point is preferably 50 ° C to 138 ° C. Of these, the temperature is particularly preferably 60 ° C. to 135 ° C., and even more preferably 70 ° C. to 135 ° C. If this range is satisfied, heat resistance and adhesiveness will be excellent.
This melting point can be controlled by selecting the catalyst to be used and the amount of the polar group-containing monomer added at the time of polymerization. As specific means for increasing the melting point of the polar group-containing olefin copolymer, it is effective to reduce the amount of the polar group-containing monomer added at the time of polymerization, increase the olefin pressure at the time of polymerization, and lower the polymerization temperature. For example, it is required to regulate these factors to control the copolymer region of interest.

The polar group-containing olefin copolymer in the present invention is a linear random copolymer having a methyl branching degree of 20 or less per 1,000 carbons of the copolymer calculated by ^{13 C-NMR analysis.} This degree of methyl bifurcation is preferably 18 or less per 1,000 carbons of the copolymer.
When the methyl branch satisfies this value, the elastic modulus is high and the mechanical strength of the molded product is also high.
This degree of methyl bifurcation can be controlled by selecting the catalyst to be used and the polymerization temperature. A reduction in the polymerization temperature is effective as a specific means for reducing the degree of methyl bifurcation of the copolymer. For example, it is required to regulate these factors to control the copolymer region of interest.

[4] Compounds Containing Transition Metals As an example of the method for producing a polar group-containing olefin copolymer of the present invention, there is a method of polymerizing using a compound containing a transition metal of groups 8 to 10.
Specific examples of preferable transition metals include vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, manganese atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, palladium atom and the like. .. Of these, vanadium atom, iron atom, cobalt atom, nickel atom and palladium atom are preferable, and nickel atom and palladium atom are particularly preferable. These metals may be single or in combination of two or more.

The compound containing the transition metal of Group 8 to 10 is preferably a metal complex obtained by reacting the carben precursor compound with the complex precursor of the transition metal compound of Group 8 to 10.

The carbene precursor compound is preferably a compound represented by the following general formula (4) or general formula (5). These compounds are N-heterocyclic carbene precursors.

In the general formula (4) and the general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ _{) 2} , P (R). ³ ) ₂ , CO ₂ R ³ , CO ₂ M', C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) ( _{^{OR 3) 2-y (R}} 4) y, SO 3 M ', PO 3 M' 2, P (O) (OR 3) 2 M ', represent a _{^{P (R 3) 2 (O}} ). (Here, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M'is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium. Represents, y represents an integer from 0 to 2). R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by ^{X 1.} Ra is a hydrocarbon group having carbon atoms of 1 to 10 also contain hydrogen atom or a hetero atom, it may be condensed with a part of the ring of X ^1. A ⁻ represents a counter anion and represents an arbitrary anion. E ¹ and E ² independently represent a carbon atom or a nitrogen atom, respectively. n represents an integer of 0 or 1.

The N-heterocyclic carbene precursor represented by the general formula (4) or the general formula (5) of the present invention is, as a typical example, a 1,3 diazole ring (5-membered imidazole) having two nitrogen atoms. The 5-membered ring is fused with another ring, and the condensed ring contains one nitrogen atom to form a carbene at the carbon atom of the condensed ring. That is, it is an N-heterocyclic carbene precursor in which the ring structure is linked to the 5-membered ring structure that generates carbene, and the ring structure is linked so as to contain nitrogen atoms in the 5-membered ring structure that generates carbene. ing.

In the N-heterocyclic carbene precursor represented by the general formula (4) or the general formula (5), the ring condensed into a 5-membered ring may be further condensed, and those precursors are as follows. It is represented by the general formula (6) or the general formula (7).

In the general formula (6) or the general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. It may have a substituent on the ring formed by ^{X 2.} A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in the general formula (4) or the general formula (5).

The precursor compound represented by the general formula (6) or the general formula (7) is more specifically a precursor compound represented by the following general formula (8) or the general formula (9).

In the general formula (8) or the general formula (9), R ^{5 to} R ⁹ represent a halogen atom or a hetero atom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in the general formula (4) or the general formula (5).

The precursor compound represented by the general formula (8) or the general formula (9) is specifically exemplified below together with the synthesis method thereof. The detailed contents are described in Japanese Patent Application Laid-Open No. 2016-135777.

The precursor compound (b) is 2- (2,6-diisopropylphenyl) imidazole [1,5-a] quinolinium-9-olate.

The precursor compound (c) is 2- (2,6-dibenzhydryl-4-methylphenyl) imidazole [1,5-a] quinolinium-9-olate.

Other examples of N-heterocyclic carbene precursors represented by the general formula (4) or the general formula (5) are represented by the following general formula (10) or the general formula (11).

In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom or a heteroatom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in the general formula (4) or the general formula (8).

Here, a typical example of the carbene precursor compound of the present invention is as follows.

In the general formulas (4) to (11), Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P (R ^3). ) ₂ , CO ₂ R ³ , CO ₂ M', C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) (OR) _{^{3) 2-y (R 4}} ) y, SO 3 M ', PO 3 M' 2, P (O) (OR 3) 2 M ', represent a _{^{P (R 3) 2 (O}} ).

Specific examples of Z include OH, OCH ₃ , OCH ₂ CH ₃ , SH, SCH ₃ , SCH ₂ CH ₃ , SO ₃ H, SO ₃ CH ₃ , SO ₃ CH ₂ CH ₃ , N = CH ₂ , N = CHCH ₃ , N = CHCH ₂ CH ₃ , N = CH (Dip), CH = NH, CH = NCH ₃ , CH = NCH ₂ CH ₃ , CH = N (Dip), C (CH ₃ ) = N (Dip) _{, NH 2, N (CH 3} ) 2, N (CH 2 CH 3) 2, PH 2, P (CH 3) 2, P (CH 2 CH 3) 2, P i Pr 2, PPh 2, CO 2 H , CO ₂ CH ₃ , CO ₂ CH ₂ CH ₃ , CO ₂ K, C (O) NH ₂ , C (O) N (CH ₃ ) ₂ , C (O) N (CH ₂ CH ₃ ) ₂ , C ( O) H, C (O) CH ₃ , C (O) CH ₂ CH ₃ , SO ₂ H, SO ₂ CH ₃ , SO ₂ CH ₂ CH ₃ , SOH, SOCH ₃ , SOC ₂ CH ₃ , OSO ₂ H, OSO ₂ CH ₃ , OSO ₂ CH ₂ CH ₃ , P (O) (OH) (CH ₃ ), P (O) (OCH ₃ ) (CH ₃ ), SO ₃ Na, SO ₃ K, PO ₃ Na ₂ , PO ₃ K ₂ , P (O) (OH) ₂ Na, P (O) (OCH ₃ ) ₂ K, P ( ^t Bu) ₂ (O), P ( ⁱ Pr) ₂ (O), PPh ₂ (O) ) Etc. are exemplified. Here, Dip 2,6-diisopropylphenyl group, Ph refers to a phenyl ^group, i Pr is an isopropyl ^group, t Bu denotes a tertiary butyl group.

R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. Here, specific examples of hydrocarbon groups having 1 to 40 carbon atoms that may contain a hetero atom include C (O) CH ₃ , C (O) CH ₂ CH ₃ , CH ₂ OCH ₃ , and CH ₂ OCH. ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH _{2, and the} like are exemplified.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 33 carbon atoms, and is an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples are 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, Tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 2,4,6-trimethylphenyl group, 2,6-diisopropylphenyl group, 2,6-dibenzhydryl- 4-Methylphenyl group and the like.

Ra is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a hetero atom, and is CH ₃ , CH ₂ CH ₃ , C (O) CH ₃ , C (O) CH ₂ CH ₃ , CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH _{2, and the} like are exemplified.
A ⁻ represents a counter anion, and COO ⁻ , Cl ⁻ , and Br ⁻ are exemplified as arbitrary anions. In the above-mentioned Z, there is a substituent in which the leaving group is removed and the charge is negatively monovalent. In this case, A ⁻ is not required because it becomes electrically neutral in the molecule.

Examples of the halogen atom or the heteroatom-containing group or the hydrocarbon group having 1 to 40 carbon atoms which may contain the heteroatom in the general formulas (8) to (11) include a fluorine atom, a chlorine atom and a bromine atom. , CH ₃ , CH ₂ CH ₃ , C (O) CH ₃ , C (O) CH ₂ CH ₃ , CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ NH ₂ , CH ₂ CH ₂ NH ₂ , NO _{2 and the} like are exemplified.
More specifically, the hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, or an aryl group. Preferred specific examples are 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, These include a tricyclohexylmethyl group, a 1,1-dimethyl-2-phenylethyl group, an isopropyl group, a 1-dimethylpropyl group, a phenyl group, a biphenyl group, an anthracenyl group, a 2,4,6-trimethylphenyl group and the like.

[5] Metal complex [5.1] Metal complex (first example)
In the first example of the metal complex used in the present invention, the carben precursor compound according to any one of the general formulas (4) to (11) is reacted with the complex precursor of the transition metal compound of Group 8 to 10 of the periodic table. It is a metal complex characterized by being obtained.

Examples of such a metal complex include compounds represented by the following general formula (12) or general formula (13).

In the general formula (12) or the general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent ligands ligandd to M ¹ , and independently represent hydrocarbon groups having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, and a hetero atom. L ¹ and L ² may be connected to each other to form a ring. Z, R ¹ , R ² , X ¹ , n, Ra, E ¹ and E ² are as described in the general formula (4) or the general formula (5). A ⁺ represents a counter cation, and K ⁺ and Na ⁺ are exemplified as arbitrary cations. Depending on the valence of M ^{1 and the types of Z, L 1} and L ² , the complex as a whole may be negatively charged, in which case the counter cation A ⁺ is required. Here, ^{the valence of M 1} means a formal oxidation number used in organometallic chemistry.
^{Examples of the transition metal M 1} in the general formula (12) or the general formula (13) include Fe, Co, Ni, Pd, and Pt. Examples of the ligands L ¹ and L ² include a halogen atom, a methyl group, a phenyl group, a benzyl group, pyridine, 2,6-lutidine and the like.

The metal complex represented by the general formula (12) or the general formula (13) is exemplified below together with a method for synthesizing the metal complex. The detailed contents are described in Japanese Patent Application Laid-Open No. 2016-135777.
The complex synthesis reaction may be carried out in a reactor used for polymerization or copolymerization of α-olefins, or may be carried out in a container different from the reactor. After complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation.

This metal complex is formed from 2- (2,6-diisopropylphenyl) imidazole [1,5-a] quinolinium-9-olate and chloro (methyl) (1,5-cyclooctadiene) palladium. ..

This metal complex consists of 2- (2,6-diisopropylphenyl) imidazole [1,5-a] quinolinium-9-olate and Ni (cod) ₂ (where cod is 1,5-cyclooctadiene). Has been formed.

[5.2] Metal complex (second example)
A second example of the metal complex used in the present invention will be described below.
The structure of the second example of the metal complex is represented by the general formula (C1).

In the formula, M represents a metal atom of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and carbon. It represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted with one or more groups selected from an ester group having 2 to 10 atoms, a silyl group, and a halogen atom, and Q is Y. ¹ [-S (= O) _2- O-] M, Y ¹ [-C (= O) -O-] M, Y ¹ [-P (= O) (-OH) -O-] M or Y ^{1 [-S-]} represents a divalent group shown in the "[]" of M (where both sides of the Y ^1, M is described to show the coupling direction of the group.).

R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and an alkoxy group having 1 to 10 carbon atoms. It was substituted with a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. Substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an asyloxy group having 2 to 10 carbon atoms. Represents.

R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. It represents a hydrocarbon group having 1 to 120 carbon atoms, ^{and at least one of R 16} and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may ^{be combined with Y 1} to form a ring structure.
L represents an electron donating ligand, and q is 0, 1/2, 1 or 2.
In addition, in this specification, "hydrocarbon" includes saturated, unsaturated aliphatic hydrocarbon, and aromatic hydrocarbon. It also includes a chain structure and a cyclic structure.

Hereinafter, the structure of the general formula (C1) will be described.
M represents a metal atom of Group 10 of the periodic table. Examples of the metal atom of Group 10 of the periodic table include Ni, Pd, and Pt. From the viewpoint of catalytic activity and the molecular weight of the obtained polymer, Ni and Pd are preferable, and Pd is more preferable.
X is a phosphorus atom (P) or an arsenic atom (As), and has a two-electron coordination with the central metal M. As X, P is preferable from the viewpoint of easy availability and catalyst cost.

R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and an alkoxy group having 1 to 10 carbon atoms. It was substituted with a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. Substitution selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms. Represents a group.

Preferred specific examples of the halogen atom represented by R ¹⁵ are a fluorine atom, a chlorine atom and a bromine atom. Of these, a more preferred substituent is the chlorine atom.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹⁵ is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 13 carbon atoms, and is an alkyl group or cycloalkyl. It is a group or an aryl group.
Preferred specific examples are methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group and 1-decyl group. , T-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropyl group, 1,1-diethylpropyl group, 1-Phenyl-2-propyl group, Isobutyl group, 1,1-Dimethylbutyl group, 2-Pentyl group, 3-Pentyl group, 2-Hexyl group, 3-Hexyl group, 2-Ethylhexyl group, 2-Heptyl group, 3-Heptyl group, 4-Heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group , Cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbonyl group, 2-bicyclo [2.2.2] octyl group, nopinyl group, decahydronaphthyl group, Mentil group, neomentyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xsilyl group, benzyl group, p-ethylphenyl group and the like can be mentioned.
Among these, more preferable substituents are a methyl group and a benzyl group, and particularly preferably a methyl group.

The hydrocarbon group having 1 to 30 carbon atoms substituted with the halogen atom represented by R ¹⁵ is preferably substituted by substituting the above-mentioned hydrocarbon group having 1 to 30 carbon atoms with a fluorine atom, a chlorine atom, or a bromine atom. Specific preferred examples of the group include a trifluoromethyl group and a pentafluorophenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with the alkoxy group having 1 to 10 carbon atoms represented by R ¹⁵ preferably contains the above-mentioned hydrocarbon group having 1 to 30 carbon atoms as a methoxy group, an ethoxy group, or the like. It is a substituent substituted with an isopropoxy group, a 1-propoxy group, a 1-butoxy group, or a t-butoxy group. More preferably, it is a hydrocarbon group having 2 to 6 carbon atoms substituted with a methoxy group or an ethoxy group, specifically, a 1- (methoxymethyl) ethyl group, a 1- (ethoxymethyl) ethyl group, 1-. Examples include (phenoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, di (ethoxymethyl) methyl group, and di (phenoxymethyl) methyl group. Be done. Particularly preferred are a 1- (methoxymethyl) ethyl group and a 1- (ethoxymethyl) ethyl group.

The hydrocarbon group having 7 to 30 carbon atoms substituted with the aryloxy group having 6 to 20 carbon atoms represented by R ^{15 preferably has the above-mentioned hydrocarbon group having 1 to 30 carbon atoms as a phenoxy group, 4} -Methylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethylphenoxy group, 2,6-di-t-butylphenoxy group substituted substituent. More preferably, it is a hydrocarbon group having 1 to 6 carbon atoms substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferably a 1- (phenoxymethyl) ethyl group or 1- (2,6). -Dimethylphenoxy group Methyl) Ethyl group.

The hydrocarbon group having 3 to 30 carbon atoms substituted with the amide group having 2 to 10 carbon atoms represented by R ^{15 preferably has the above-mentioned hydrocarbon group having 1 to 30 carbon atoms as an acetamide group or propionylamino.} It is a substituent substituted with a group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, and a benzoylamino group. A 2-acetamidophenyl group, a 2-propionylaminophenyl group, a 2-valerylaminophenyl group, and a 2-benzoylphenyl group are more preferable, and a 2-acetamidophenyl group is particularly preferable.

The alkoxy group having 1 to 30 carbon atoms represented by R ¹⁵ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and a preferable specific example is a methoxy group. These include an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a t-butoxy group. Among these, a more preferable substituent is a methoxy group, an ethoxy group, or an isopropoxy group, and a particularly preferable one is a methoxy group.

The ^{aryloxy group having 6 to 30 carbon atoms represented by R 15} is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples are a phenoxy group, a 4-methylphenoxy group, and a 4-methoxyphenoxy group. , 2,6-Dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a more preferable substituent is a phenoxy group or a 2,6-dimethylphenoxy group, and a particularly preferable one is a phenoxy group.

The asyloxy group having 2 to 10 carbon atoms represented by R ¹⁵ is preferably an acyloxy group having 2 to 8 carbon atoms, and preferred specific examples are an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. , Valeryloxy group, isovaleryloxy group, pivaloyloxy group, benzoyloxy group.
Among these, more preferable substituents are an acetyloxy group, a propionyloxy group and a benzoyloxy group, and particularly preferably an acetyloxy group and a propionyloxy group.

Among the preferred groups as these R ^15, more preferably, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, an alkoxy having 1 to 20 carbon atoms Specific examples of the group, particularly preferable, include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group and an acetyloxy group.

R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. It represents a hydrocarbon group having 1 to 120 carbon atoms. However, ^{at least one of R 16} and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may ^{be combined with Y 1} to form a ring structure.

The ^{alkoxy group represented by R 16} and R ¹⁷ is preferably one having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The ^{aryloxy group represented by R 16} and R ¹⁷ is preferably one having 6 to 24 carbon atoms, and examples thereof include a phenoxy group. Examples of the silyl group represented by R ¹⁶ and R ^{17 include a trimethylsilyl group.} Examples of the amino group represented by R ¹⁶ and R ¹⁷ include an amino group, a methyl amino group, and a dimethyl amino group. Specific examples of the hydrocarbon group having 1 to 120 carbon atoms which may be substituted with one or more groups selected from the halogen atom, alkoxy group and aryloxy group represented by R ¹⁶ and R ^{17 include a methyl group.} Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, n-hexyl Group, 2-hexyl group, 3-hexyl group, 2-heptyl group, 3-heptyl group, 4-heptyl group, 2-methyl-4-heptyl group, 2,6-dimethyl-4-heptyl group, 3-methyl -4-Heptyl group, Cyclopropyl group, Cyclobutyl group, Cyclopentyl group, Cyclohexyl group, Cycloheptyl group, Cyclooctyl group, 1-adamantyl group, Trifluoromethyl group, benzyl group, 2'-methoxybenzyl group, 3'- Methoxybenzyl group, 4'-methoxybenzyl group, 4'-trifluoromethylbenzyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3 , 5-Dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group , 2,4,6-triisopropylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl Group, 3,5-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis (trifluoromethyl) Phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl group, 2', 6'-dimethoxy-2-biphenyl group, 2'-methyl-2-biphenyl group, 2', 4 ', 6'-triisopropyl-2-biphenyl group and the like can be mentioned.

Further, R ¹⁶ and R ¹⁷ may be the same or different. Further, R ¹⁶ and R ¹⁷ may be combined to form a ring structure. R ¹⁶ and / or R ¹⁷ may ^{combine with Y 1} to form a ring structure.

At ^{least one of R 16} and R ¹⁷ represents an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group are preferable. Examples of the cycloalkyl group having 4 to 106 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, and the cycloalkyl group represented by the following general formula (5) is used. Especially preferable.

In the formula, R represents an alkylene group having 1 to 14 carbon atoms which may have a substituent, and R ¹⁹ , R ¹¹⁰ and R ¹¹¹ are independently hydrogen atom, alkoxy group, aryloxy group, respectively. Represents a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group, of R ⁹ and R ¹⁰ . At least one of them is not a hydrogen atom, and R ¹⁹ , R ¹¹⁰ , R ¹¹¹ and the alkylene group R may be bonded to each other to form a ring structure. In the formula, the bond between the carbon atom and X in the general formula (C1) is also shown.

Further, both R ¹⁶ and R ¹⁷ are preferably cycloalkyl groups represented by the general formula (5) for ease of synthesis.

As described above, in the general formula (5), ^{at least one of R 19} and R ¹¹⁰ is not a hydrogen atom. It is considered that the substituent R ¹⁹ or R ^{110 that} is not a hydrogen atom suppresses the chain transfer of the polymer due to β-hydrogen desorption during the polymerization reaction and improves the molecular weight of the obtained polymer. An ^{alkoxy group represented by R 19} , R ¹¹⁰ and R ¹¹¹ , an aryloxy group, a silyl group, an amino group, or a carbon atom which may be substituted with one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group. Specific examples of the hydrocarbon groups of Nos. 1 to 30 include the same as the specific examples of R ¹⁶ and R ¹⁷ described above.
The alkylene group R preferably has 2 to 6 carbon atoms, and more preferably 4 carbon atoms.

At ^{least one of R 19} and R ¹¹⁰ is preferably an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. Further, it is preferable that at least one of ^{R 19} and R ^{110 is an isopropyl group.}

Hereinafter, specific examples ^{of the X-R 16} or X-R ^{17 site when R 16} or R ¹⁷ represents a group represented by the general formula (5) will be given. Incidentally, Me represents a methyl group, the bond X and M, X and Y ¹ are omitted.

Among these, R ¹⁶ and R ¹⁷ are preferably 2-isopropyl-5-methylcyclohexyl groups (mentyl groups) represented by the following formulas. Further, it is more preferable that both ^{R 16} and R ^{17 are menthyl groups.}

In the general formula (C1), Q is represented by −S (= O) ₂ -O−, −C (= O) −O−, −P (= O) (−OH) −O−, or −S−. It represents a divalent group and is a site that coordinates one electron with M. The left side of each of the above equations ^{is bound to Y 1} and the right side is bound to M. Among these, −S (= O) _2- O− is particularly preferable from the viewpoint of catalytic activity.

In Y 1 ^-Q site, greater oxygen atom or a sulfur atom electronegativity is 1 e-coordinated to the metal atom M. Bonding electrons between Y ¹ -Q-M is ^formally, can be indicated as a ^Y 1 -Q anion state, the M cation state.

In the general formula (C1), Y ¹ is substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. It represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be present.
Examples ^{of the silyl group as the substituent on Y 1} include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a triisopropylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group and the like. In particular, a trimethylsilyl group and a triethylsilyl group are preferable.
The alkoxy group having 1 to 10 carbon atoms, which is a substituent on Y ^{1, is preferably an alkoxy group having 1 to 6 carbon atoms.} Preferred specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a phenoxy group and the like, and a methoxy group and a phenoxy group are particularly preferable.
The ester group having 2 to 10 carbon atoms, which is a substituent on Y ¹ , is preferably an ester group having 2 to 8 carbon atoms, and preferred specific examples are a methoxycarbonyl group, an ethoxycarbonyl group, and an n-propoxycarbonyl. Group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy) carbonyl group, (4-glycidylbutoxy) carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinateimide The group is mentioned. Preferred examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group and a succinic acid anhydride group, and particularly preferably a methoxycarbonyl group and a succinic acid anhydride group.
Examples of the halogen atom as the substituent on Y ¹ include fluorine, chlorine, bromine and the like, and fluorine and chlorine are particularly preferable.
The hydrocarbon group having 1 to 70 carbon atoms is preferably a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group, an arylene group or the like, and an arylene group is particularly preferable.

Y ¹ is a cross-linking site that connects the X and Q sites. Specific examples of Y ¹ showing X in P atomic below. Here, the plurality of R ^104s may be the same or different, and have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 6 to 20 carbon atoms. Represents a hydrocarbon group having 1 to 20 carbon atoms substituted with an aryloxy group, a silyl group or a halogen atom. However, the upper limit of the number of carbon atoms as ^{Y 1 is 70.}

Halogen atom R ¹⁰⁴ represents an alkoxy group, specific examples of the aryl group and the silyl group are the same as those described in Y ^1. Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰⁴ and the hydrocarbon group having 1 to 20 carbon atoms substituted with halogen atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-. Butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbonyl group, endo-norbonyl group, menthyl group, neomentyl group, Trifluoromethyl group, benzyl group, 4'-trifluoromethylbenzyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5- Dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,6-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2, 4,6-Triisopropylphenyl group, 2-t-butylphenyl group, 2-cyclohexylphenyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis (trifluoro) Methyl) Phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, 2-biphenyl group, 2'-methyl-2-biphenyl group, 2', 4', 6'-triisopropyl-2-biphenyl Examples thereof include a group, a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, a cinnamyl group, a styryl group, an anthrasenyl group and a fluorenyl group.

Substituents ^{R 16} or ^{R 17} may form a ring structure bound to ^{Y 1} site. Specifically, the structure shown below can be mentioned. The following example illustrates the case where the substituent R ¹⁶ and Y ¹ site is to form a ring structure.

Among the metal complexes represented by the general formula (C1), those represented by the following general formula (C2) are particularly preferable.

In the general formula (C2), R ^{112 to} R ¹¹⁵ are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and aryloxy groups having 6 to 20 carbon atoms. , Represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. These specific examples are the same as those described in ^{R 104.} M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in the general formula (C1).

In the general formula (C2), those represented by the following general formula (C3) in which ^{R 12 is a silyl group are preferable.}

In the formula, each of the three independent R- ^116s may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meanings as described in the general formula (C2).

In the general formula (C3), R ¹¹⁶ is preferably a hydrocarbon group having 1 to 4 carbon atoms, and it is particularly preferable that all ^{three R 116 are methyl groups.} R ¹¹³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, an isopropyl group, or a phenyl group. R ¹¹⁴ and R ¹¹⁵ are preferably hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms, and particularly preferably hydrogen atoms.

The metal complex of the catalyst represented by the general formula (C1) can be synthesized by the same method as described in known literature (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a 0-valent or divalent M source with a ligand in the general formula (C1).

Compound represented by the general formula (C2) and the general formula (C3) is a ^{Y 1} and Q In the formula (C1), that the particular group corresponding to the general formula (C2) and the general formula (C3) Can be synthesized by.

Examples of the zero-valent M source include tris (dibenzylideneacetone) dipalladium as a palladium source, and tetracarbonyl nickel (0): Ni (CO) ₄ , bis (1,5-cyclooctadiene) as a nickel source. Nickel is mentioned.

The divalent M source is, as a palladium source, (1,5-cyclooctadiene) (methyl) palladium chloride, palladium chloride, palladium acetate, bis (acetoformer) dichloropalladium: PdCl ₂ (CH ₃ CN) ₂ , bis ( Benzonitrile) dichloropalladium: PdCl ₂ (PhCN) ₂ , (N, N, N', N'-tetramethylethylenediamine) dichloropalladium (II): PdCl ₂ (TMEDA), (N, N, N', N' -Tetramethylethylenediamine) Dimethylpalladium (II): PdMe ₂ (TMEDA), Bis (acetylacetonato) Palladium (II): Pd (acac) ₂ (acac = acetylacetonato), (Palladium (II) trifluoromethanesulfonate) : Pd (OSO ₂ CF ₃ ) ₂ as a nickel source, (allyl) nickel chloride, (allyl) nickel bromide, nickel chloride, nickel acetate, bis (acetylacetonato) nickel (II): Ni (acac) ₂ , (1,2-Dimethoxyethane) dichloronickel (II): Nickel ₂ (DME), nickel trifluoromethanesulfonate (II): Ni (OSO ₂ CF ₃ ) ₂ .

The metal complex represented by the general formula (C1) can be isolated and used, but the metal source containing M and the ligand precursor are brought into contact with each other in the reaction system without isolating the complex. Can be subjected to polymerization as it is (in situ). ^{In particular, when R 15} in the general formula (C1) is a hydrogen atom, after reacting a metal source containing 0-valent M with a ligand precursor, the complex can be directly subjected to polymerization without isolation. preferable.

The ligand precursor in this case is the case of the general formula (C1).

(The symbols in the formula have the same meaning as above.)
Indicated by.

The ratio ((C1 ligand) / M) of the M source (M) and the ligand precursor (C1-1) (C1 ligand) in the general formula (C1) is 0.5 to 2.0. It is preferable to select in the range of 1.0 to 1.5.

When isolating the metal complex of the general formula (C1), one obtained by coordinating and stabilizing the electron-donating ligand (L) in advance can also be used. In this case, q is 1/2, 1 or 2. When q is 1/2, it means that one divalent electron donating ligand is coordinated to two metal complexes. q is preferably 1/2 or 1 in the sense of stabilizing the metal complex catalyst. When q is 0, it means that there is no ligand.

The electron donating ligand (L) is a compound having an electron donating group and capable of coordinating with the metal atom M to stabilize the metal complex.
Examples of the electron donating ligand (L) include dimethyl sulfoxide (DMSO) as having a sulfur atom. As those having a nitrogen atom, a trialkylamine having 1 to 10 carbon atoms of an alkyl group, a dialkylamine having 1 to 10 carbon atoms of an alkyl group, pyridine, and 2,6-dimethylpyridine (also known as 2,6-lutidine). ), Aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N, N, N', N'-tetramethylethylenediamine (TMEDA), 4- (N, N-dimethylamino) pyridine (DMAP), Examples thereof include acetonitrile, benzonitrile, quinoline and 2-methylquinoline. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoint of stability and catalytic activity of the metal complex, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), N, N, N', N'-tetramethylethylenediamine ( TMEDA) is preferred, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (also known as 2,6-lutidine) are more preferred.

[6] Polymerization catalyst The polymerization catalyst in the present invention is a copolymer of α-olefin such as ethylene and (meth) acrylic acid ester or allyl monomer, which has good catalytic activity, high molecular weight and high comonomer content. It is a catalyst that enables production.
This catalyst has the above-mentioned metal complex as a main catalyst component (A), and as the component (B), a compound or an ion-exchangeable layered silicate that reacts with the component (A) to form an ion pair is used. It is used, and if necessary, the organoaluminum compound of the component (C) is used.

Specific examples of the component (B) include the following (B-1) to (B-3).
(B-1) An ionic compound or a Lewis acid (B-3) solid acid capable of reacting with the aluminum oxy compound (B-2) component (A) to convert the component (A) into a cation.

(B-1) In the aluminum oxy compound, it is well known that the aluminum oxy compound can activate the post-metallocene complex, and specific examples of such a compound include the following general formulas (II) to (IV). Examples thereof include compounds represented by.

In each of the above general formulas, ^Ra represents a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Further, a plurality of R ^a may each be the same or different. Further, p represents an integer of 0 to 40, preferably 2 to 30. Of the general formulas, the compounds represented by the first and second formulas are compounds also called aluminoxane, and among these, methylaluminoxane or methylisobutylaluminoxane is preferable. It is also possible to use a plurality of types of the above-mentioned aluminoxane in combination within each group and between each group. The above aluminoxane can be prepared under various known conditions.
The compound represented by the third of the general formula is 10: 1 to 10: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and ^{alkylboronic acid represented by the general formula RBB} (OH) _2. It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula, R ^b represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

The compound (B-2) is an ionic compound or Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation, and such an ionic compound includes carbonium. Examples thereof include a complex of a cation such as a cation or an ammonium cation and an organic boron compound such as triphenylboron, tris (3,5-difluorophenyl) boron or tris (pentafluorophenyl) boron.
Further, examples of the Lewis acid as described above include various organic boron compounds such as tris (pentafluorophenyl) boron. Alternatively, metal halogen compounds such as aluminum chloride and magnesium chloride are exemplified.
In addition, a certain kind of Lewis acid described above can be grasped as an ionic compound capable of reacting with the component (A) and converting the component (A) into a cation.

Examples of the solid acid of (B-3) include alumina, silica-alumina, and silica-magnesia.

The polymerization catalyst of the present invention comprises a carbene precursor compound or a phosphorus sulfonic acid compound represented by the general formulas (4) to (11) and a group 8 to 10 (late cycle type; Fe, Co, Ni, Pd, etc.). It is an α-olefin polymerization catalyst obtained by reacting with a transition metal compound.
The synthesis of the catalyst composition can generally be carried out by contacting a transition metal compound of Group 8-10 with a novel carbene precursor compound or phosphorus sulfonic acid compound in a solution or slurry.
The transition metal compound is preferably a Group 10 transition metal compound, which is bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, palladium sulfate, palladium acetate, bis (allyl palladium chloride), palladium chloride, bromide. Palladium, (cyclooctadien) palladium (methyl) chloride, dimethyl (tetramethylethylenediamine) palladium, bis (cyclooctadien) nickel, nickel chloride, nickel bromide, (tetramethylethylenediamine) nickel (methyl) chloride, dimethyl (tetra) It is synthesized using methylethylenediamine) nickel, (cyclooctadien) nickel (methyl) chloride, and the like.

The complex formation reaction may be carried out in a reactor used for copolymerization with an α-olefin, or may be carried out in a container different from the reactor. After the complex is formed, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation. Further, it can be carried out in the presence of a porous carrier described later.
Further, as the catalyst composition of the present invention, one kind may be used alone, or a plurality of kinds of catalyst compositions may be used in combination. In particular, for the purpose of widening the molecular weight distribution and the comonomer content distribution, it is useful to use these two kinds of catalyst compositions in combination.

The polymerization catalyst of the present invention may be used alone or may be supported on a carrier. As the usable carrier, any carrier can be used as long as the gist of the present invention is not impaired.
In general, inorganic oxides and polymer carriers can be preferably used. Specific examples thereof include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof, and SiO ₂ −Al ₂ O ₃ , SiO _2- V ₂ O ₅ , SiO _2- TIO ₂ , SiO _2- MgO, SiO _2- Cr ₂ O ₃ and other mixed oxides can also be used, and inorganic silicates, polyethylene carriers, polypropylene carriers, etc. Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers and the like can be used.
As for these carriers, the particle size, particle size distribution, pore volume, specific surface area and the like are not particularly limited, and any carrier can be used.

The catalyst for olefin polymerization of the present invention can be prepared by bringing the above components (A) and (B) into contact with each other in the presence or absence of a monomer to be polymerized inside or outside the polymerization tank.
That is, the components (A) and (B) and the component (C) may be introduced separately into the polymerization tank if necessary, or the components (A) and (B) may be brought into contact with each other in advance and then introduced into the polymerization tank. You may. Further, the component (C) may be impregnated with a mixture of the components (A) and (B) and then introduced into the polymerization tank.
The contact of each of the above components may be carried out in an inert gas such as nitrogen in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is preferably a temperature in the range of −20 ° C. to the boiling point of the solvent, particularly preferably a temperature in the range of room temperature to the boiling point of the solvent. The catalyst prepared in this manner may be used without washing after preparation, or may be used after washing. Further, after preparation, a new combination of components may be used as needed.

The catalyst component may be prepolymerized in the polymerization tank or outside the polymerization tank in the presence of an olefin. The olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene. There is no limitation, and a mixture of these and other olefins may be used. It is preferably an olefin having 2 or 3 carbon atoms. As the olefin supply method, any method can be used, such as a supply method for maintaining the olefin in the reaction vessel at a constant speed or a constant pressure state, a combination thereof, and a stepwise change.

[7] Copolymerization Reaction The copolymerization reaction in the present invention comprises hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, and methylcyclohexane, and liquefied α-olefins. Liquids such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formylamide, acetonitrile, methanol, isopropyl alcohol, ethylene glycol, etc. It is carried out in the presence or absence of such a polar solvent. Moreover, you may use the mixture of the liquid compound described here as a solvent. The above-mentioned hydrocarbon solvent is more preferable in order to obtain high polymerization activity and high molecular weight.

In the copolymerization in the present invention, the copolymerization can be carried out in the presence or absence of a known additive. As the additive, a radical polymerization inhibitor or an additive having an action of stabilizing the produced copolymer is preferable. For example, a quinone derivative, a binder phenol derivative and the like are examples of preferable additives.
Specifically, monomethylether hydroquinone, 2,6-di-t-butyl4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT, and a reaction product of tetravalent titanium alcoxide and BHT. Things can be used.
Inorganic and / or organic fillers may be used as additives, and the polymerization may be carried out in the presence of these fillers.

In the present invention, the polymerization form is not particularly limited. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in a medium, bulk polymerization using the liquefied monomer itself as a medium, vapor phase polymerization performed in a vaporized monomer, or a polymer produced in a monomer liquefied at high temperature and high pressure. High-pressure ion polymerization or the like in which at least a part of the above is dissolved is preferably used.
Further, the polymerization mode may be any of batch polymerization, semi-batch polymerization, and continuous polymerization.

The unreacted monomer or medium may be separated from the produced copolymer and recycled for use. Upon recycling, these monomers and media may be purified and reused, or may be reused without purification. Conventionally known methods can be used for separating the produced copolymer from the unreacted monomer and the medium. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

The copolymerization temperature, copolymerization pressure, and copolymerization time are not particularly limited, but usually, the optimum setting can be made in consideration of productivity and process capacity from the following ranges.
That is, the copolymerization temperature is usually −20 ° C. to 290 ° C., preferably 0 ° C. to 250 ° C., the copolymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 90 MPa, and the copolymerization time is 0. It can be selected from the range of 1 minute to 50 hours, preferably 0.5 minutes to 40 hours, and more preferably 1 minute to 30 hours.
In the present invention, the copolymerization is generally carried out in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferably used. A small amount of oxygen or air may be mixed.

The supply of the catalyst and the monomer to the copolymerization reactor is not particularly limited, and various supply methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to take a method in which a predetermined amount of monomer is supplied to the copolymerization reactor in advance and a catalyst is supplied to the copolymerization reactor. In this case, additional monomers and additional catalysts may be supplied to the copolymerization reactor. Further, in the case of continuous polymerization, a method can be adopted in which a predetermined amount of the monomer and the catalyst are continuously or intermittently supplied to the copolymerization reactor to carry out the copolymerization reaction continuously.

Regarding the control of the composition of the copolymer, a method of supplying a plurality of monomers to the reactor and controlling the composition by changing the supply ratio can be generally used. In addition, there are a method of controlling the copolymer composition by utilizing the difference in the monomer reactivity ratio due to the difference in the structure of the catalyst, and a method of controlling the copolymer composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. ..
A conventionally known method can be used for controlling the molecular weight of the copolymer. That is, a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, a method of controlling the molecular weight using a chain transfer agent, and a method of controlling the ligand structure in the transition metal complex. The molecular weight can be controlled according to the above.
When a chain transfer agent is used, a conventionally known chain transfer agent can be used. For example, hydrogen, metal alkyl and the like can be used.

Hereinafter, the present invention will be specifically described with reference to Examples, and the rationality, significance, usefulness, and excellence of the present invention over the prior art will be demonstrated.

[1] Method for Analyzing Polymer Structure [1-1] Copolymer Content of Copolymer The comonomer content of the copolymer obtained in Examples was determined by NMR analysis using Ascend 500 manufactured by Bruker. Using 1,1,2,2-tetrachloroethane-d ₂ as a solvent, the molar ratio of ethylene: comonomer was determined by ¹ H-NMR measurement at 120 ° C., and incorp. It is shown in Table 1 with the notation (%). incorp. (%) Means the comonomer content (mol%).
[1-2] Amount of methyl branching 200 mg of a sample is inner diameter together with o-dichlorobenzene / benzene dehydrohydrogenated (C6D5Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane which is a reference substance for chemical shift. It was placed in a 10 mmφ NMR sample tube, replaced with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. For the NMR measurement, an NMR apparatus AVANCE III400 of Bruker Biospin Co., Ltd. equipped with a cryoprobe having a diameter of 10 mm was used.
The amount of methyl branch is 1 with the average of the integrated intensities of the characteristic signals of 20.0 ppm and 33.2 ppm when the sum of the integrated intensities of the signals in the range of 10 to 180 ppm is normalized to 1,000 in the ^{13 C-NMR spectrum.} It was determined as the number of methyl branches per 000 C.

[2] Number average molecular weight (Mn) and weight average molecular weight (Mw)
Using a high-temperature GPC device manufactured by Tosoh Corporation, HLC-8121GPC / HT, equipped with a TSKgel-GMHHR-H (S) HT column manufactured by Tosoh Corporation (two 7.8 mm ID x 30 cm in series). It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) using monodisperse polystyrene as a standard substance of molecular weight.
In Table 1 described later, Mw / Mn is indicated by the notation PDI.

Unless otherwise specified in the following synthesis examples, the operation was carried out in a purified argon atmosphere, and the solvent used was dehydrated and deoxidized. The metal complex 1 and the metal complex 2 used as the catalyst are described in Non-Patent Document 3; K.K. Nozaki et al. , J. Am. Chem. Soc. , 2015, 137, 10934-10937, Non-Patent Document 11; Synthesized according to Japanese Patent Application Laid-Open No. 2014-219220. Examples of the comonomer include methyl methacrylate (Methyl methyllate (MMA); Kanto Chemical Co., Inc.), α-methylstyrene (α-MS); TCI), and β-metharyl chloride (MACl); TCI. ), Methyl butenyl acetate (MBAc); Aldrich, and methylyl phenyl ether (MAPE); Alfa Aesar). All of these comonomer were distilled and used. Among these comonomer, the structural formulas of methyl methacrylate (MMA), methylbutenyl acetate (MBAc), α-methylstyrene (α-MS), and metallicylphenyl ether (MAPE) are shown below.

[3] Synthesis of Polar Group-Containing Olefin Copolymers of Examples 1, 2, 4, 5, 6, 8, 9, 10, 11 and 12 Under an argon atmosphere, the following catalyst (metal complex 1) was added in a predetermined amount (metal complex 1). In a 50 mL autoclave manufactured by Pressure Resistant Glass Industry Co., Ltd. (the amount shown in Table 1), a predetermined amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each copolymer (Table 1). (Listed inside) was added. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was dried under reduced pressure to obtain a copolymer.

[4] Synthesis of Polar Group-Containing Olefin Copolymers of Examples 3 and 7 In a 50 mL autoclave manufactured by Pressure-Resistant Glass Industry Co., Ltd. containing a predetermined amount (the amount shown in Table 1) of the metal complex 1 under an argon atmosphere. A fixed amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each copolymer (listed in Table 1) were added. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was placed in a Soxhlet extractor and washed with methyl ethyl ketone for 5 days. Then, it was dried under reduced pressure to obtain a copolymer.

[5] Synthesis of Polar Group-Containing Olefin Copolymer of Example 13 Under an argon atmosphere, in a 50 mL autoclave manufactured by Pressure Resistant Glass Industry Co., Ltd. containing a predetermined amount (the amount shown in Table 1) of the following catalyst (metal complex 2). To a predetermined amount (amount shown in Table 1) of toluene and a predetermined amount (amount shown in Table 1) of each copolymer (listed in Table 1) were added. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was dried under reduced pressure to obtain a copolymer.

[6] Results and discussion Table 1 shows the experimental results. It was confirmed that a polar group-containing olefin copolymer could be obtained in any of the examples. According to this embodiment, a novel polar group-containing olefin copolymer that exhibits adhesiveness, printability, or physical properties compatible with a filler or the like is provided. Further, according to this example, the polar group-containing olefin copolymer is efficiently produced.
^{It was confirmed that the methyl branching degree of the olefin copolymer calculated by 13} C-NMR analysis was 20 or less per 1,000 carbons of the copolymer as a linear random copolymer.

The present invention is not limited to the embodiments detailed above, and various modifications or modifications can be made within the scope of the claims of the present invention.

According to the present invention, a novel polar group-containing olefin copolymer having good adhesiveness and printability, or exhibiting good compatibility with a filler or the like is provided, which contains a novel polar group. Since it is an olefin copolymer, it can be used in a wide range of applications. This olefin copolymer can be produced by the production method of the present invention and has high industrial applicability.
In particular, the olefin copolymer of the present invention can be suitably used for applications that require physical properties such as adhesiveness to other materials, printability, or compatibility with fillers and the like.

［式（１）中、ＦＧは、ハロゲン原子、水酸基、炭素原子数６〜２０のアリール基、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０のアルキルチオ基、炭素原子数１〜２０の炭化水素基を有する置換アミノ基、シアノ基、または炭素原子数１〜２０の炭化水素基を有するアシルオキシ基である。
式（２）及び（３）中、ＦＧは、ハロゲン原子、水酸基、炭素原子数６〜２０のアリール基、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０のアルキルチオ基、炭素原子数１〜２０の炭化水素基を有する置換アミノ基、シアノ基、カルボキシル基、炭素原子数１〜２０の炭化水素基を有するエステル基、または炭素原子数１〜２０の炭化水素基を有するアシルオキシ基である。
Ｒは、炭素原子数１〜１０のアルキル基、ハロゲン原子で置換された炭素原子数１〜１０のアルキル基、ハロゲン原子、またはシアノ基であり、ＦＧとの間で環状構造を形成しても良い。］ [1]
Structural units derived from ethylene and / or α-olefins with 3 to 10 carbon atoms,
Polar group-containing olefin containing 20 to 0.001 mol% of structural units derived from at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2) and (3). It is a copolymer and
And,
¹³ A polar group-containing olefin copolymer having a methyl branching degree calculated by C-NMR analysis of 20 or less per 1,000 carbons of the copolymer.

[In the formula (1), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is a substituted amino group having 20 hydrocarbon groups, a cyano group, or an acyloxy group having 1 to 20 carbon atoms.
In formulas (2) and (3), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and a carbon atom. Substituent amino group having a hydrocarbon group of 1 to 20, cyano group, carboxyl group, ester group having a hydrocarbon group of 1 to 20 carbon atoms, or acyloxy group having a hydrocarbon group of 1 to 20 carbon atoms Is.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, and even if a cyclic structure is formed with the FG. good. ]

[2]
In the formula (1), the FG has a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, or a cyano group having 1 to 20 carbon atoms. Ri acyloxy der having a hydrocarbon group,
In the formulas (2) and (3), the FG has a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and 1 carbon atom. polar group-containing olefin copolymer according to said acyloxy group der Rukoto [1] having an ester group or a hydrocarbon group having 1 to 20 carbon atoms, with a 20 hydrocarbon group.

[3]
In the formula (1), wherein FG is Ri acyloxy der having a halogen atom, an aryl group having 6 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms,
In the formulas (2) and (3), the FG has a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an ester group having 1 to 20 carbon atoms. polar group-containing olefin copolymer according to said acyloxy group der Rukoto having a hydrocarbon group [2].

[In the formula (1), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. It is a substituted amino group having 20 hydrocarbon groups, a cyano group, or an acyloxy group having 1 to 20 carbon atoms.
In formulas (2) and (3), FG is a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and a carbon atom. Substituent amino group having a hydrocarbon group of 1 to 20, cyano group, carboxyl group, ester group having a hydrocarbon group of 1 to 20 carbon atoms, or acyloxy group having a hydrocarbon group of 1 to 20 carbon atoms Is.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, and even if a cyclic structure is formed with the FG. good. ]

(2) Specific Example of Polar Group-Containing Monomer Preferably, in the formula (1), the FG is a substituted amino having a halogen atom, an aryl group having 6 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. A acyloxy group having a group, a cyano group, or a hydrocarbon group having 1 to 20 carbon atoms.
In the formulas (2) and (3), the FG has a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and 1 carbon atom. An ester group having a hydrocarbon group of ~ 20, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms.
More preferably, in the formula (1), the FG is an acyloxy group having a halogen atom, an aryl group having 6 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms.
In the formulas (2) and (3), the FG has a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an ester group having 1 to 20 carbon atoms. It is an acyloxy group having a hydrocarbon group.

In the general formula ^(C2), those represented by the following general formula ^{R 1 1 2} is a silyl group (C3) is preferred.

In the following, the present invention experimental examples specifically described, reasonableness of construction of the present invention, significance, usefulness, demonstrating excellence over the prior art.
Experimental Examples 1 to 7 are reference examples, and Experimental Examples 8 to 13 are Examples.

[3] Under an argon atmosphere of the polar group-containing olefin copolymer of experimental example 1,2,4,5,6,8,9,10,11,12, a predetermined amount of catalyst (metal complex 1) below In a 50 mL autoclave manufactured by Pressure Resistant Glass Industry Co., Ltd. (the amount shown in Table 1), a predetermined amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each copolymer (Table 1). 1) was added. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was dried under reduced pressure to obtain a copolymer.

[4] Under an argon atmosphere of the polar group-containing olefin copolymer of experimental examples 3 and 7, a predetermined amount of a metal complex 1 in Taiatsu Co. 50mL autoclave containing (amount shown in Table 1), A predetermined amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each copolymer (listed in Table 1) were added. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was placed in a Soxhlet extractor and washed with methyl ethyl ketone for 5 days. Then, it was dried under reduced pressure to obtain a copolymer.

[5] Under an argon atmosphere of the polar group-containing olefin copolymer of Experiment Example 13, a predetermined amount of catalyst (metal complex 2) below (amounts shown in Table 1) Taiatsu containing Co. 50mL autoclave A predetermined amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each copolymer (listed in Table 1) were added thereto. After filling a predetermined amount (the amount shown in Table 1) of ethylene, the autoclave was stirred at a predetermined temperature (the temperature shown in Table 1) for a predetermined time (the time shown in Table 1). After cooling to room temperature, methanol (about 20 mL) was added into the autoclave. The resulting copolymer was recovered by filtration. The copolymer was dissolved in ODCB (ortho-dichlorobenzene) and then reprecipitated in methanol. Then, it was dried under reduced pressure to obtain a copolymer.

[6] Results and discussion Table 1 shows the experimental results. Polar group-containing olefin copolymer that is obtained has been confirmed in any of the experimental example. According to the present experiment example, adhesion and printability, or to express the properties of compatibility, such as a filler, the novel polar group-containing olefin copolymer are provided. Further, according to this experiment example, the polar group-containing olefin copolymer can be efficiently produced.
^{It was confirmed that the methyl branching degree of the olefin copolymer calculated by 13} C-NMR analysis was 20 or less per 1,000 carbons of the copolymer as a linear random copolymer.

Claims (16)

Structural units derived from ethylene and / or α-olefins with 3 to 10 carbon atoms,
Polar group-containing olefin containing 20 to 0.001 mol% of structural units derived from at least one selected from the group consisting of polar group-containing monomers represented by the following general formulas (1), (2) and (3). It is a copolymer and
And,
¹³ A polar group-containing olefin copolymer having a methyl branching degree calculated by C-NMR analysis of 20 or less per 1,000 carbons of the copolymer.

[In the formulas (1), (2) and (3), FG has a halogen atom, a hydroxyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkylthio group, substituted amino group having 1 to 20 carbon atoms, cyano group, carboxyl group, ester group having 1 to 20 carbon atoms, or hydrocarbon having 1 to 20 carbon atoms It is an acyloxy group having a group.
R is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, a halogen atom, or a cyano group, and even if a cyclic structure is formed with the FG. good. ] The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and an ester group having a hydrocarbon group having 1 to 20 carbon atoms. The polar group-containing olefin copolymer according to claim 1, further comprising an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms. The FG is a halogen atom, an aryl group having 6 to 20 carbon atoms, an ester group having a hydrocarbon group having 1 to 20 carbon atoms, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms. The polar group-containing olefin copolymer according to claim 2. The method for producing a polar group-containing olefin copolymer according to any one of claims 1 to 3, wherein the polymer is polymerized using a compound containing a transition metal of groups 8 to 10. A method for producing a contained olefin copolymer. The claim is characterized in that the compound containing the transition metal of Group 8 to 10 is a metal complex obtained by reacting a carben precursor compound with a complex precursor of a transition metal compound of Group 8 to 10. 4. The method for producing a polar group-containing olefin copolymer according to 4. The method for producing a polar group-containing olefin copolymer according to claim 5, wherein the carbene precursor compound is represented by the following general formula (4) or general formula (5).

[In the general formula (4) and the general formula (5), Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P ( R ³ ) ₂ , CO ₂ R ³ , CO ₂ M', C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) represents a _{^{(OR 3) 2-y (}} R 4) y, SO 3 M ', PO 3 M' 2, P (O) (OR 3) 2 M ', P (R 3) 2 (O). (Here, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M'is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium. Represents, y represents an integer from 0 to 2). R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by ^{X 1.} Ra is a hydrocarbon group having carbon atoms of 1 to 10 also contain hydrogen atom or a hetero atom, it may be condensed with a part of the ring of X ^1. A ⁻ represents a counter anion and represents an arbitrary anion. E ¹ and E ² independently represent a carbon atom or a nitrogen atom, respectively. n represents an integer of 0 or 1. ] The method for producing a polar group-containing olefin copolymer according to claim 6, wherein the carbene precursor compound is represented by the following general formula (6) or general formula (7).

[In the general formula (6) or the general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. It may have a substituent on the ring formed by ^{X 2.} A ⁻ , Z, R ¹ , R ² , X ¹ , E ¹ and E ² are as described in claim 6. ] The method for producing a polar group-containing olefin copolymer according to claim 7, wherein the carbene precursor compound is represented by the following general formula (8) or general formula (9).

[In the general formula (8) or the general formula (9), R ^{5 to} R ⁹ represent a halogen atom or a hetero atom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. A ⁻ , Z, R ¹ , R ² , E ¹ and E ² are as described in claim 6. ] The method for producing a polar group-containing olefin copolymer according to claim 6, wherein the carbene precursor compound described above is represented by the following general formula (10) or general formula (11).

[In the general formula (10) or the general formula (11), R ¹⁰ represents a halogen atom or a heteroatom-containing group or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. A ⁻ , Z, R ¹ , R ² , R ⁵ , R ⁶ , E ¹ and E ² are as described in claim 6 or 8. ] In the general formulas (4) to (11), the Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P (R ^3). ) ₂ , P (O) (OR ³ ) _2-y (R ⁴ ) The method for producing a polar group-containing olefin copolymer according to any one of claims 6 to 9, characterized in that it is _y. The preparation of the polar group-containing olefin copolymer according to claim 4, wherein the compound containing the transition metal of Groups 8 to 10 is represented by the following general formula (12) or general formula (13). Method.

[In the general formula (12) or the general formula (13), M ¹ represents a transition metal belonging to groups 8 to 10 of the periodic table. L ¹ and L ² represent ligands ligandd to M ¹ , and independently represent hydrocarbon groups having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom, and a hetero atom. L ¹ and L ² may be connected to each other to form a ring.
Z is OR ³ , SR ³ , SO ₃ R ³ , N = CR ³ R ⁴ , CR ³ = NR ⁴ , N (R ³ ) ₂ , P (R ³ ) ₂ , CO ₂ R ³ , CO ₂ M' , C (O) N (R ³ ) ₂ , C (O) R ³ , SO ₂ R ³ , SOR ³ , OSO ₂ R ³ , P (O) (OR ³ ) _2-y (R ⁴ ) _y , SO _{3 M ', PO 3 M'} 2, P (O) (OR 3) 2 M ', represent a _{^{P (R 3) 2 (O}} ). (Here, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M'is an alkali metal, an alkaline earth metal, ammonium, a quaternary ammonium or a phosphonium. Represents, y represents an integer from 0 to 2). R ¹ and R ² are hydrocarbon groups having 1 to 40 carbon atoms, which may independently contain a hydrogen atom or a hetero atom. X ¹ represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms, and may have a substituent on the ring formed by ^{X 1.} Ra is a hydrocarbon group having carbon atoms of 1 to 10 also contain hydrogen atom or a hetero atom, it may be condensed with a part of the ring of X ^1. A ⁻ represents a counter anion and represents an arbitrary anion. E ¹ and E ² independently represent a carbon atom or a nitrogen atom, respectively. n represents an integer of 0 or 1. A ⁺ represents a counter cation and represents an arbitrary cation. ] The method for producing a polar group-containing olefin copolymer according to claim 11, wherein M ^{1 is a transition metal belonging to Group 10 of the periodic table.} The method for producing a polar group-containing olefin copolymer according to claim 4, wherein the compound containing the transition metal of Groups 8 to 10 is a metal complex represented by the following general formula (C1).

[In equation (C1),
M represents a metal atom of Group 10 of the periodic table,
X represents a phosphorus atom (P) or an arsenic atom (As),
Y ¹ may be substituted with one or more groups selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, a silyl group, and a halogen atom. Represents a divalent hydrocarbon group from 1 to 70
Q is Y ¹ [-S (= O) _2- O-] M, Y ¹ [-C (= O) -O-] M, Y ¹ [-P (= O) (-OH) -O- ] M or Y ¹ [-S-] M represents a divalent group shown in "[]" (however, Y ¹ and M on both sides are described to indicate the bonding direction of the group. ),
R ¹⁵ is substituted with a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, and an alkoxy group having 1 to 10 carbon atoms. It was substituted with a hydrocarbon group having 2 to 30 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide group having 2 to 10 carbon atoms. Substituent selected from the group consisting of a hydrocarbon group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an asyloxy group having 2 to 10 carbon atoms. Represents
R ¹⁶ and R ¹⁷ are each independently substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. It represents a hydrocarbon group having 1 to 120 carbon atoms, ^{and at least one of R 16} and R ¹⁷ is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 106 carbon atoms. Further, R ¹⁶ or R ¹⁷ may ^{be combined with Y 1} to form a ring structure.
L represents an electron donating ligand
q is 0, 1/2, 1 or 2. ] In the general formula (C1), Q is -S _{(= O)} 2 -O- (although, S is bound to ^{Y 1,} O is bound to M.), Containing polar group according to claim 13 A method for producing an olefin copolymer. The compound represented by the general formula (C1) is the general formula (C2).

[In the formula (C2), R ^{112 to} R ¹¹⁵ are hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and aryloxy groups having 6 to 20 carbon atoms. , Represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a silyl group or a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described in the general formula (C1). ]
The method for producing a polar group-containing olefin copolymer according to claim 13, which is a metal complex represented by. The compound represented by the general formula (C2) has a general formula (C3) in which ^{R 112 is a silyl group.}

[In the formula (C3), ^{each of the three R 116s} independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , L and q have the same meanings as described in the general formula (C2). ]
The method for producing a polar group-containing olefin copolymer according to claim 15, which is a metal complex represented by.