JP7213504B2 - Polar group-containing olefin copolymer - Google Patents

Description

The present invention relates to an olefin copolymer comprising a polar group-containing monomer having a specific structure as a constituent component, and more specifically, 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 comonomer having a

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

On the other hand, in the conventional method for producing an olefin polymer using a metallocene catalyst, when ethylene and a polar group-containing monomer are copolymerized, the catalytic polymerization activity is lowered and the copolymerization is difficult. A method of reacting an organoaluminum compound or an organozinc compound with a polar comonomer (masking a polar functional group) and then copolymerizing it 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 produced.
In recent years, efforts have been vigorously made to copolymerize an olefin and a polar comonomer using a so-called post-metallocene, late transition metal complex catalyst, without using a masking agent such as an organoaluminum compound. It is So far, while having the feature of obtaining a linear copolymer with less branching as a copolymer structure, as a polar comonomer, acrylic acid ester (Patent Documents 5 to 10), acrylonitrile (Non-Patent Document 1), vinyl ether (Non- Patent Document 2) and the like have been reported.

Japanese Patent No. 2792982 JP-A-3-229713 JP 2003-327627 A JP-A-03-207707 Japanese Patent Publication No. 2002-521534 JP-A-6-184214 Japanese Patent Application Laid-Open No. 2008-223011 JP 2010-150246 A JP 2010-150532 A JP 2010-202647 A

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 comonomers, vinylidene compounds, which are 1,1-disubstituted olefins, are less polymerizable with late transition metal complex catalysts than vinyl compounds, which are monosubstituted olefins. It was difficult to polymerize.
In view of such circumstances, an object of the present invention is to provide a novel polar group-containing olefin copolymer using a linear vinylidene comonomer and a method for producing the same.

In order to solve the problems of the present invention described above, the present inventors conducted various searches in the production of polar group-containing olefin copolymers.
As a result, the present inventors have found that the above problems can be solved by using a polymerization catalyst having a specific structure and using a specific vinylidene comonomer, 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. ] to [16].
Here, the polar group-containing olefin copolymer having a specific structure in [1] is constituted as the basic invention [1], and each invention below [2] adds incidental requirements to the basic invention, or It shows an embodiment thereof. The inventions [4] to [16] define additional requirements relating to the method for producing the polar group-containing olefin copolymer having the specific structure of the present invention. All invention units are collectively referred to as an invention group.

［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]
a structural unit derived from ethylene and/or an α-olefin having 3 to 10 carbon atoms;
A polar group-containing olefin containing 20 to 0.001 mol% of a structural unit 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) is a copolymer,
And,
A polar group-containing olefin copolymer characterized by being a linear random copolymer having a degree of methyl branching of 20 or less per 1,000 carbon atoms of the copolymer as calculated by ¹³ C-NMR analysis.

[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 a A substituted amino group having 20 hydrocarbon groups, a cyano group, or an acyloxy group having a hydrocarbon 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. a substituted amino group having a hydrocarbon group of 1 to 20, a cyano group, a carboxyl 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 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 may form a cyclic structure with FG. good. ]

[2]
In formula (1), 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, or a cyano group having 1 to 20 carbon atoms. an acyloxy group having a hydrocarbon group ,
In formulas (2) and (3), FG is a substituted amino group having a halogen atom, an aryl group having 6 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and 1 carbon atom. The polar group-containing olefin copolymer according to [1], which is an ester group having a hydrocarbon group of up to 20 or an acyloxy group having a hydrocarbon group of 1 to 20 carbon atoms .

[3]
In formula (1), 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 formulas (2) and (3), 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 a The polar group-containing olefin copolymer according to [2], which is an acyloxy group having a hydrocarbon group .

[4]
A 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, comprising polymerizing a compound containing a Group 8-10 transition metal.

[5]
[4], wherein the compound containing a transition metal of Groups 8 to 10 is a metal complex obtained by reacting a carbene precursor compound with a complex precursor of a transition metal compound of Groups 8 to 10; The method for producing the polar group-containing olefin copolymer according to 1.

［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 general formulas (4) and (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 (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 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M′ represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium. and y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. 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 1 to 10 carbon atoms which may contain a hydrogen atom or a heteroatom, and may be fused with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. 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 general formula (6) or general formula (7), X ² represents a saturated or unsaturated divalent hydrocarbon group having 3 to 9 carbon atoms. The ring formed by X ² may have a substituent. 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 general formula (8) or general formula (9), R ⁵ to R ⁹ represent a halogen atom, 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 , 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 general formula (10) or (11), R ¹⁰ represents a halogen atom, 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 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 , P(O)(OR ³ ) _2-y (R ⁴ ) _y , production 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]
Production of the polar group-containing olefin copolymer according to [4], wherein the compound containing a Group 8-10 transition metal is represented by the following general formula (12) or general formula (13): Method.

[In general formula (12) or (13), M ¹ represents a transition metal belonging to Groups 8 to 10 of the periodic table. L ¹ and L ² each represent a ligand attached to M ¹ and each independently represents a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom or a heteroatom. L ¹ and L ² may be linked together 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', P(R ³ ) ₂ (O). (Here, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M′ represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium. and y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. 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 1 to 10 carbon atoms which may contain a hydrogen atom or a heteroatom, and may be fused with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1; A ⁺ represents a counter cation and represents any cation. ]

[12]
The method for producing a polar group-containing olefin copolymer according to [11], wherein the M1 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 a Group 8-10 transition metal is a metal complex represented by the following general formula (C1).

[In the formula (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 is the number of carbon atoms optionally 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 of 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 represents a divalent group shown in "[ ]" of [-S-]M (Y ¹ and M on both sides are described to indicate the bonding direction of the group. ),
R ¹⁵ is 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, or an alkoxy group having 1 to 10 carbon atoms. 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. a 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 acyloxy group having 2 to 10 carbon atoms; represents
each of R ¹⁶ and R ¹⁷ is 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; 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. Also, R ¹⁶ or R ¹⁷ may combine 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- (where S is bonded to Y ¹ and O is bonded to M.), containing the polar group described in [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 represented by the general formula (C2)

[In the formula (C2), R ¹¹² to R ¹¹⁵ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, , represents a silyl group or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described for 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) is the general formula (C3) in which R ¹¹² is a silyl group

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

The present invention provides a novel polar group-containing olefin copolymer using a specific vinylidene comonomer.
Moreover, in the present invention, it is possible to produce a polar group-containing olefin copolymer 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, as well as the production method and use of the copolymer, will be described specifically and 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 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 a A substituted amino group having 20 hydrocarbon groups, a cyano group, or an acyloxy group having a hydrocarbon 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. a substituted amino group having a hydrocarbon group of 1 to 20, a cyano group, a carboxyl 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 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 may form a cyclic structure with FG. good. ]

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

Here, FG will be described in detail.
Halogen atoms are not particularly limited. Halogen atoms are preferably chlorine, fluorine, bromine and iodine.

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

Alkoxy groups having 1 to 20 carbon atoms are specifically methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n- Preferred examples include hexoxy, cyclopropoxy, cyclopentoxy, cyclohexoxy, n-octoxy, n-dethoxy and the like.

Alkylthio groups having 1 to 20 carbon atoms are specifically methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio and hexylthio. , a decylthio group, a dodecylthio group, and the like.

Substituted amino groups having a hydrocarbon group having 1 to 20 carbon atoms are specifically monomethylamino group, dimethylamino group, monoethylamino group, diethylamino group, monoisopropylamino group, diisopropylamino group, monophenylamino group. group, diphenylamino group, bis(trimethylsilyl)amino group, morpholinyl group, and the like.

Ester groups having a hydrocarbon group having 1 to 20 carbon atoms are specifically methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl and t-butoxycarbonyl. group, (4-hydroxybutyl)carbonyl group, (4-glycidylbutyl)carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide group and the like.

Acyloxy groups having a hydrocarbon group of 1 to 20 carbon atoms are preferably exemplified by acetyloxy, propionyloxy, (meth)acryloyloxy, benzoyloxy and the like.

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, and may form a ring structure with FG.
R, which is an alkyl group having 1 to 10 carbon atoms, is specifically a 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, 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 group, 1-adamantyl group, 2-adamantyl group and the like can be preferably mentioned.
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. Among 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, and are particularly preferred. A specific example is ethylene. Also, one type of α-olefin may be used, or a plurality thereof may be used in combination.

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

The polar group-containing olefin copolymer in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio determined by gel permeation chromatography (GPC) in the range of 1.5 to 3.5. Preferably. Among them, the range of 1.6 to 3.3 is more preferable, and the range of 1.7 to 3.0 is particularly preferable.
When Mw/Mn satisfies this range, various workability including molding of a laminate becomes sufficient, and 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 between 50°C and 138°C. Among these, the range of 60°C to 135°C is particularly preferred, and the range of 70°C to 135°C is more preferred. When this range is satisfied, excellent heat resistance and adhesiveness can be obtained.
This melting point can be controlled by selecting the catalyst to be used and the amount of the polar group-containing monomer added during polymerization. Effective means for increasing the melting point of the polar group-containing olefin copolymer include reducing the amount of the polar group-containing monomer added during polymerization, increasing the olefin pressure during polymerization, and lowering the polymerization temperature. For example, it is required to adjust these factors to control the desired copolymer region.

The polar group-containing olefin copolymer in the present invention is a linear random copolymer having a degree of methyl branching of 20 or less per 1,000 carbon atoms of the copolymer as calculated by ¹³ C-NMR analysis. The degree of methyl branching 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.
The degree of methyl branching can be controlled by selecting the catalyst to be used and the polymerization temperature. Lowering the polymerization temperature is effective as a specific means for lowering the degree of methyl branching of the copolymer. For example, it is required to adjust these factors to control the desired copolymer region.

[4] Compound Containing Transition Metal As an example of the method for producing the polar group-containing olefin copolymer of the present invention, there is a method of polymerizing using a compound containing a Group 8-10 transition metal.
Specific examples of preferred 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, and palladium atom. . Among these, vanadium atom, iron atom, cobalt atom, nickel atom and palladium atom are preferred, and nickel atom and palladium atom are particularly preferred. These metals may be used singly or in combination.

The compound containing a Group 8-10 transition metal is preferably a metal complex obtained by reacting a carbene precursor compound with a complex precursor of a Group 8-10 transition metal compound.

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 general formulas (4) and (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 , ^CO2R3 , _CO2M ', C(O)N ⁽ R3) ₂ , _C (O)R3 ^{, SO2R3 ,} _SOR3 , _OSO2R3 ^, P(O)( represents 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 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M′ represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium or phosphonium. and y represents an integer from 0 to 2). R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. 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 1 to 10 carbon atoms which may contain a hydrogen atom or a heteroatom, and may be fused with a part of the ring consisting of X ¹ . A ⁻ represents a counter anion and represents any anion. E ¹ and E ² each independently represent a carbon atom or a nitrogen atom. n represents an integer of 0 or 1;

A typical example of the N-heterocyclic carbene precursor represented by the general formula (4) or (5) of the present invention is a 1,3 diazole ring (5-membered imidazole) having two nitrogen atoms. wherein the 5-membered ring is fused to another ring and the fused ring includes one nitrogen atom to form a carbene at the carbon atom of the fused ring. That is, it is an N-heterocyclic carbene precursor in which a ring structure is linked to a carbene-generating five-membered ring structure, and the ring structure is linked to include a nitrogen atom in the carbene-generating five-membered ring structure. ing.

In the N-heterocyclic carbene precursor represented by general formula (4) or general formula (5), the ring condensed to the 5-membered ring may be further condensed, and these precursors are represented by the following It is represented by general formula (6) or general formula (7).

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

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

In general formula (8) or general formula (9), R ⁵ to R ⁹ represent a halogen atom, 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 , E ¹ and E ² are as described in general formula (4) or general formula (5).

Precursor compounds represented by general formula (8) or general formula (9) are specifically exemplified below together with their synthesis methods. Detailed contents are described in JP-A-2016-135777.

Precursor compound (b) is 2-(2,6-diisopropylphenyl)imidazo[1,5-a]quinolinium-9-oleate.

Precursor compound (c) is 2-(2,6-dibenzhydryl-4-methylphenyl)imidazo[1,5-a]quinolinium-9-oleate.

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

In general formula (10) or general formula (11), R ¹⁰ represents a halogen atom, 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 general formula (4) or general formula (8).

Here, representative examples of the carbene precursor compound of the present invention are as follows.

In 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 ) represents _2-y (R ⁴ ) _y , SO ₃ M', PO ₃ M' ₂ , P(O)(OR ³ ) ₂ M', P(R ³ ) ₂ (O);

Specific examples of Z include OH, OCH3, _OCH2CH3 , SH, _SCH3 , _SCH2CH3 , _{SO3H , SO3CH3 , SO3CH2CH3 ,} N _{= CH2 ,} N _{= CHCH3} , N= _CHCH2CH3 , N ₌ CH(Dip), CH=NH, CH= _NCH3 , CH= _NCH2CH3 , CH=N(Dip), C _{( CH3} )=N(Dip) , _NH2 , N( _CH3 ) ₂ , N _{( CH2CH3} ) ₂ , _{PH2, P(CH3)2 , P ( CH2CH3 ) 2} , _PiPr2 , ^PPh2 , _CO2H , _{CO2CH3 , CO2CH2CH3} , _CO2K , C(O) _NH2 , C(O)N( _CH3 ) ₂ , C(O)N _{( CH2CH3} ) _{2 , C} ( O)H, _C (O) _CH3 , _{C (} O) _{CH2CH3 , SO2H , SO2CH3} , _SO2CH2CH3 , SOH, _SOCH3 , _SOCH2CH3 , _OSO2H , _OSO2CH3 , OSO2CH2CH3, P(O)(OH)( _CH3 ) _, P(O) ₍ OCH3) _{( CH3} ) _{, SO3Na , SO3K , PO3Na2} , _{PO3K2 ,} P ₍ O)(OH)2Na, P(O)( ^OCH3 ) _{2K, P(tBu)2 (} O), P(iPr) _{2 (} O), ^PPh2 ₍ O ) and the like are exemplified. Here, Dip represents a 2,6-diisopropylphenyl group, Ph represents a phenyl group, ⁱ Pr represents an isopropyl group, and ^t Bu represents a tertiary butyl group.

R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom. Specific examples of the hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom include C(O)CH ₃ , C(O)CH ₂ CH ₃ , CH ₂ OCH ₃ and CH ₂ OCH. _2CH3 , _{CH2NH2 , CH2CH2NH2} and the _{like are exemplified} .
The hydrocarbon group is preferably a hydrocarbon group having 1 to 33 carbon atoms, such as 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- and a 4-methylphenyl group.

Ra is a hydrocarbon group having 1 to 10 carbon atoms which may contain a hydrogen atom or a heteroatom, and is CH ₃ , CH ₂ CH ₃ , C(O)CH ₃ , C(O)CH ₂ CH ₃ , _{CH2OCH3 , CH2OCH2CH3 , CH2NH2 , CH2CH2NH2 etc. are illustrated} .
A ⁻ represents a counter anion, and examples of arbitrary anions are COO ⁻ , Cl ⁻ and Br ⁻ . Among Z mentioned above ^, there is a substituent which becomes negatively charged by removing the leaving group.

Examples of the halogen atom, heteroatom-containing group, or hydrocarbon group having 1 to 40 carbon atoms which may contain a heteroatom in the general formulas (8) to (11) include a fluorine atom, a chlorine atom, and a bromine atom. , _CH3 , _CH2CH3 , _{C (} O) _{CH3 , C (} O) _{CH2CH3 , CH2OCH3 , CH2OCH2CH3} , _CH2NH2 , _CH2CH2NH2 , _{NO 2} and the like are exemplified.
More specifically, the hydrocarbon group is preferably a hydrocarbon group having 1 to 30 carbon atoms, such as 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, phenyl group, biphenyl group, anthracenyl group, 2,4,6-trimethylphenyl group and the like.

[5] Metal complex [5.1] Metal complex (first example)
A first example of the metal complex used in the present invention is obtained by reacting a carbene precursor compound represented by any one of the general formulas (4) to (11) with a complex precursor of a transition metal compound of groups 8 to 10 of the periodic table. It is a metal complex characterized by being obtained by

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

In general formula (12) or (13), M ¹ represents a transition metal belonging to Groups 8 to 10 of the periodic table. L ¹ and L ² each represent a ligand attached to M ¹ and each independently represents a hydrocarbon group having 1 to 20 carbon atoms containing a halogen atom, a hydrogen atom or a heteroatom. L ¹ and L ² may be linked together to form a ring. Z, R ¹ , R ² , X ¹ , n, Ra, E ¹ and E ² are as described in general formula (4) or general formula (5). A ⁺ represents a counter cation, and arbitrary cations are exemplified by K ⁺ and Na ⁺ . 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 a counter cation A ⁺ is required. Here, the valence of M1 means ^a formal oxidation number used in organometallic chemistry.
Examples of the transition metal M1 in the general formula (12) or ( ¹³ ) include Fe, Co, Ni, Pd, and Pt. L ¹ and L ² of the ligand include halogen atoms, methyl groups, phenyl groups, benzyl groups, pyridine, 2,6-lutidine and the like.

The metal complex represented by general formula (12) or general formula (13) is exemplified below together with its synthesis method. Detailed contents are described in JP-A-2016-135777.
The complex synthesis reaction may be carried out in the reactor used for the polymerization or copolymerization of the α-olefin, or may be carried out in a vessel separate from the reactor. After the complex formation, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation.

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

This metal complex is prepared from 2-(2,6-diisopropylphenyl)imidazo[1,5-a]quinolinium-9-olate and Ni(cod) ₂ (cod is 1,5-cyclooctadiene). formed.

[5.2] Metal complex (second example)
A second example of the metal complex used in the present invention is described below.
The structure of the second example of the metal complex is shown by 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), Y ¹ represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbon 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; ¹ [-S(=O) ₂ -O-]M, Y ¹ [-C(=O)-O-]M, Y ¹ [-P(=O)(-OH)-O-]M or Y ¹ represents a divalent group shown in "[ ]" of [-S-]M (however, Y ¹ and M on both sides are described to indicate the bonding direction of the group).

R ¹⁵ is 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, or an alkoxy group having 1 to 10 carbon atoms. 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. a 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 acyloxy group having 2 to 10 carbon atoms; represents

each of R ¹⁶ and R ¹⁷ is 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; 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. Also, R ¹⁶ or R ¹⁷ may combine with Y ¹ to form a ring structure.
L represents an electron donating ligand and q is 0, 1/2, 1 or 2.
In this specification, "hydrocarbon" includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons. It also includes chain structures and cyclic structures.

The structure of general formula (C1) is described below.
M represents a metal atom of group 10 of the periodic table. Examples of metal atoms of Group 10 of the periodic table include Ni, Pd, and Pt, but Ni and Pd are preferred, and Pd is more preferred, from the viewpoint of catalytic activity and the molecular weight of the resulting polymer.
X is a phosphorus atom (P) or an arsenic atom (As) and is coordinated to the central metal M with two electrons. As X, P is preferable from the standpoint of easy availability and catalyst cost.

R ¹⁵ is 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, or an alkoxy group having 1 to 10 carbon atoms. 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 ^R15 are a fluorine atom, a chlorine atom and a bromine atom. Among these, a more preferred substituent is a 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, cycloalkyl 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-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, benzyl group, p-ethylphenyl group and the like.
Among these, more preferred substituents are methyl group and benzyl group, and particularly preferred is methyl group.

The halogen-substituted hydrocarbon group having 1 to 30 carbon atoms represented by R ¹⁵ is preferably a substituted is a group, and specific preferred examples thereof include a trifluoromethyl group and a pentafluorophenyl group.

The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms represented by R ¹⁵ is preferably the aforementioned hydrocarbon group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, It is a substituent substituted with an isopropoxy group, 1-propoxy group, 1-butoxy group, or 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. (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 1-(methoxymethyl)ethyl group and 1-(ethoxymethyl)ethyl group.

The hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms represented by R ¹⁵ is preferably a phenoxy group, 4 -methylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethylphenoxy group and 2,6-di-t-butylphenoxy group. More preferably a phenoxy group or a hydrocarbon group having 1 to 6 carbon atoms substituted with a 2,6-dimethylphenoxy group, 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 an amide group having 2 to 10 carbon atoms represented by R ¹⁵ is preferably an acetamide group, propionylamino group, butyrylamino group, isobutyrylamino group, valerylamino group, isovalerylamino group, pivaloylamino group and benzoylamino group. More preferred are 2-acetamidophenyl group, 2-propionylaminophenyl group, 2-valerylaminophenyl group and 2-benzoylphenyl group, and particularly preferred is 2-acetamidophenyl group.

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 preferred specific examples include a methoxy group, Examples include ethoxy, isopropoxy, 1-propoxy, 1-butoxy, and t-butoxy. Among these, more preferred substituents are methoxy group, ethoxy group and isopropoxy group, and particularly preferred is 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 phenoxy group, 4-methylphenoxy group and 4-methoxyphenoxy group. , 2,6-dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, more preferred substituents are phenoxy group and 2,6-dimethylphenoxy group, and particularly preferred is phenoxy group.

The acyloxy 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 acetyloxy group, propionyloxy group, butyryloxy group and isobutyryloxy group. , valeryloxy, isovaleryloxy, pivaloyloxy and benzoyloxy groups.
Among these, more preferred substituents are acetyloxy group, propionyloxy group and benzoyloxy group, and particularly preferred are acetyloxy group and propionyloxy group.

Of these preferred groups for R ¹⁵ , more preferred are a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, and an alkoxy group having 1 to 20 carbon atoms. and particularly preferred examples include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group and an acetyloxy group.

each of R ¹⁶ and R ¹⁷ is 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; represents a hydrocarbon group having 1 to 120 carbon atoms. 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. Also, R ¹⁶ or R ¹⁷ may combine with Y ¹ to form a ring structure.

The alkoxy group represented by R ¹⁶ and R ¹⁷ preferably has 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy and isopropoxy groups. The aryloxy group represented by R ¹⁶ and R ¹⁷ preferably has 6 to 24 carbon atoms, such as a phenoxy group. Examples of the silyl group represented by R ¹⁶ and R ¹⁷ include trimethylsilyl group. The amino group represented by R ¹⁶ and R ¹⁷ includes an amino group, a methylamino group and a dimethylamino group. Specific examples of the hydrocarbon group having 1 to 120 carbon atoms which may be substituted with one or more groups selected from halogen atoms, alkoxy groups and aryloxy groups represented by R ¹⁶ and R ¹⁷ include 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.

Also, R ¹⁶ and R ¹⁷ may be the same or different. Also, R ¹⁶ and R ¹⁷ may combine 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. The alkyl group having 1 to 10 carbon atoms is preferably methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group. 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. Especially preferred.

In the formula, R represents an optionally substituted alkylene group having 1 to 14 carbon atoms, and R ¹⁹ , R ¹¹⁰ and R ¹¹¹ each independently represent a hydrogen atom, an alkoxy group, an aryloxy group, represents a hydrocarbon group having ¹ to 30 carbon atoms optionally 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 ^; At least one of them is not a hydrogen atom, and R ¹⁹ , R ¹¹⁰ , R ¹¹¹ and the alkylene group R may each combine to form a ring structure. In the formula, the bond between the carbon atom and X in 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 general formula (5), at least one of R ¹⁹ and R ¹¹⁰ is not a hydrogen atom. It is believed that this non-hydrogen substituent R ¹⁹ or R ¹¹⁰ suppresses the chain transfer of the polymer due to β-hydrogen elimination during the polymerization reaction and increases the molecular weight of the resulting polymer. A carbon atom optionally substituted by one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a halogen atom, an alkoxy group, and an aryloxy group represented by R ¹⁹ , R ¹¹⁰ and R ¹¹¹ Specific examples of the hydrocarbon group of numbers 1 to 30 are 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, 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. Furthermore, at least one of R ¹⁹ and R ¹¹⁰ is preferably an isopropyl group.

Specific examples of XR ¹⁶ or XR ¹⁷ sites when R ¹⁶ or R ¹⁷ represents a group represented by formula (5) are given below. Me represents ^a methyl group, and the bonds between X and M and between X and Y1 are omitted.

Among these, R ¹⁶ and R ¹⁷ are preferably 2-isopropyl-5-methylcyclohexyl group (menthyl group) represented by the following formula. Furthermore, both R ¹⁶ and R ¹⁷ are more preferably menthyl groups.

In general formula (C1), Q is -S(=O) ₂ -O-, -C(=O)-O-, -P(=O)(-OH)-O-, or -S- It represents a divalent group that is used and is a site that coordinates one electron to M. The left side of ^each of the above formulas is attached to Y1, and the right side is attached to M. Of these, -S(=O) ₂ -O- is particularly preferred from the viewpoint of catalytic activity.

At the Y ¹ -Q site, a highly electronegative oxygen or sulfur atom is one-electron coordinated to the metal atom M. As for the bonding electrons between Y ^{1 -QM, it is also possible to formally express Y 1 -Q} as an anion state and M as a cation state.

In 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. represents a divalent hydrocarbon group having 1 to 70 carbon atoms which may be substituted.
Examples of the silyl group as a substituent on Y ¹ include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group and the like. trimethylsilyl group and triethylsilyl group are particularly preferred.
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 methoxy, ethoxy, isopropoxy and phenoxy groups, with methoxy and phenoxy groups being particularly preferred.
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 include a methoxycarbonyl group, an ethoxycarbonyl group, and n-propoxycarbonyl. group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, (4-hydroxybutoxy)carbonyl group, (4-glycidylbutoxy)carbonyl group, phenoxycarbonyl group, succinic anhydride group, succinimide groups. Preferred are a methoxycarbonyl group, an ethoxycarbonyl group, a (4-hydroxybutoxy)carbonyl group and a succinic anhydride group, and particularly preferred are a methoxycarbonyl group and a succinic anhydride group.
The halogen atom which is a substituent on Y ¹ includes fluorine, chlorine, bromine and the like, and fluorine and chlorine are particularly preferred.
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, etc., and particularly preferably an arylene group.

Y ¹ is the bridging site connecting the X and Q sites. Specific examples of Y ¹ in which X is represented by a P atom are shown below. Here, the plurality of R ¹⁰⁴ may be the same or different, and is 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 represents an aryloxy group, a silyl group or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. However, the upper limit of the ^number of carbon atoms for Y1 is 70.

Specific examples of the halogen atom, alkoxy group, aryloxy group and silyl group represented by R ¹⁰⁴ are the same as those described for Y ¹ . Examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰⁴ include 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, 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, neomenthyl 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 group, vinyl group, allyl group, butenyl group, cyclohexenyl group, cinnamyl group, styryl group, anthracenyl group, fluorenyl group and the like.

Substituent R ¹⁶ or R ¹⁷ may be attached to the Y ¹ site to form a ring structure. Specific examples include the structures shown below. The following example shows the case where the substituent ^R16 and the Y1 site are bonded 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 preferred.

In general formula (C2), R ¹¹² to R ¹¹⁵ are 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 an aryloxy group having 6 to 20 carbon atoms. , represents a silyl group or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. These specific examples are the same as those described for ^R104 . M, X, R ¹⁵ , R ¹⁶ , R ¹⁷ , L and q have the same meanings as described for general formula (C1).

In the general formula (C2), those represented by the following general formula (C3) in which R ¹¹ is a silyl group are preferred.

In the formula, each independent three R ¹¹⁶ may be the same or different and represents 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 general formula (C2).

In general formula (C3), R ¹¹⁶ is preferably a hydrocarbon group having 1 to 4 carbon atoms, and it is particularly preferred 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, particularly preferably a hydrogen atom, isopropyl group or phenyl group. R ¹¹⁴ and R ¹¹⁵ are preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom.

The metal complex of the catalyst represented by general formula (C1) can be synthesized by methods similar to those described in known literature (eg, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a zero- or divalent M source with the ligand in general formula (C1).

In the compounds represented by general formulas (C2) and (C3), Y ¹ and Q in general formula (C1) are specific groups corresponding to general formulas (C2) and (C3). can be synthesized by

The zero-valent M source includes tris(dibenzylideneacetone)dipalladium as a palladium source, and tetracarbonylnickel(0):Ni(CO) ₄ and bis(1,5-cyclooctadiene) as a nickel source. Nickel is mentioned.

Divalent M sources include (1,5-cyclooctadiene)(methyl)palladium chloride, palladium chloride, palladium acetate, bis(acetonitrile)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):NiCl ₂ (DME), and nickel(II) trifluoromethanesulfonate:Ni(OSO ₂ CF ₃ ) ₂ .

The metal complex represented by the general formula (C1) can be used after being isolated. can also be subjected to polymerization in situ. In particular, when R ¹⁵ in general formula (C1) is a hydrogen atom, after reacting a metal source containing zero-valent M with a ligand precursor, the complex can be directly subjected to polymerization without isolation. preferable.

In this case, the ligand precursor is, in the case of general formula (C1),

(The symbols in the formula have the same meanings as described above.)
is indicated by

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

When isolating the metal complex of the general formula (C1), it can be stabilized by previously coordinating it with an electron-donating ligand (L). In this case q will be 1/2, 1 or 2. That q is 1/2 means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1/2 or 1 in order to stabilize the metal complex catalyst. In addition, 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.
The electron-donating ligand (L) includes dimethylsulfoxide (DMSO) as one having a sulfur atom. Nitrogen atom-containing trialkylamines having alkyl groups of 1 to 10 carbon atoms, dialkylamines having alkyl groups of 1 to 10 carbon atoms, pyridine, 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), Acetonitrile, benzonitrile, quinoline, 2-methylquinoline and the like. Those having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoint of metal complex stability and catalytic activity, dimethylsulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (also known as 2,6-lutidine), N,N,N',N'-tetramethylethylenediamine ( TMEDA) is preferred, and dimethylsulfoxide (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 an α-olefin such as ethylene and a (meth)acrylic acid ester or an allyl monomer, which has good catalytic activity, a high molecular weight and a high comonomer content. It is the catalyst that makes the production possible.
This catalyst contains the aforementioned metal complex as a main catalyst component (A), and a compound or ion-exchange layered silicate that reacts with component (A) to form an ion pair as component (B). If necessary, the organoaluminum compound of component (C) is used.

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

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

In each general formula above, R ^a 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. Moreover, a plurality of R ^a may be the same or different. In addition, p represents an integer of 0-40, preferably 2-30. Among the general formulas, the compounds represented by the first and second formulas are compounds also called aluminoxanes, and among these, methylaluminoxane and methylisobutylaluminoxane are preferred. A plurality of types of the above aluminoxanes may be used in combination within each group and between each group. And the above aluminoxanes can be prepared under various known conditions.
The compound represented by the _third general ^formula is a 10:1 to 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 a Lewis acid capable of reacting with the component (A) to convert the component (A) into a cation. Examples include complexes of cations such as cations and ammonium cations and organic boron compounds such as triphenylboron, tris(3,5-difluorophenyl)boron, and tris(pentafluorophenyl)boron.
Further, examples of Lewis acids as described above include various organoboron compounds such as tris(pentafluorophenyl)boron. Alternatively, metal halide compounds such as aluminum chloride and magnesium chloride are exemplified.
Some of the above Lewis acids can also be understood as ionic compounds capable of reacting with the component (A) to convert the component (A) into cations.

Examples of the solid acid (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 It is an α-olefin polymerization catalyst obtained by reacting with a transition metal compound.
Synthesis of the catalyst composition can generally be carried out by contacting the Group 8-10 transition metal compound with the novel carbene precursor compound or phosphorus sulfonic acid compound in solution or slurry.
The transition metal compound is preferably a group 10 transition metal compound such as bis(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, palladium sulfate, palladium acetate, bis(allylpalladium chloride), palladium chloride, bromide. Palladium, (cyclooctadiene)palladium(methyl)chloride, dimethyl(tetramethylethylenediamine)palladium, bis(cyclooctadiene)nickel, nickel chloride, nickel bromide, (tetramethylethylenediamine)nickel(methyl)chloride, dimethyl(tetra methylethylenediamine)nickel, (cyclooctadiene)nickel(methyl)chloride, etc.

The complex formation reaction may be carried out in the reactor used for copolymerization with the α-olefin, or may be carried out in a vessel separate from the reactor. After forming the complex, the metal complex may be isolated and extracted and used as a catalyst, or may be used as a catalyst without isolation. Furthermore, it is also possible to carry out in the presence of a porous carrier, which will be described later.
In addition, the catalyst composition of the present invention may be used singly or in combination of plural kinds of catalyst compositions. In particular, for the purpose of broadening the molecular weight distribution and comonomer content distribution, it is useful to use a plurality of such catalyst compositions in combination.

The polymerization catalyst of the present invention may be used alone or supported on a carrier. Any carrier can be used as long as it does not impair the gist of the present invention.
In general, inorganic oxides and polymeric supports are suitable for use. Specific examples 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 can also be used, inorganic silicates, polyethylene supports, polypropylene supports, Polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, polyimide carriers and the like can be used.
There are no particular restrictions on the particle size, particle size distribution, pore volume, specific surface area, etc. of these carriers, and any carrier can be used.

The olefin polymerization catalyst of the present invention can be prepared by contacting the above components (A) and (B) in the presence or absence of the monomers to be polymerized inside and outside the polymerization tank.
That is, the components (A) and (B) and, if necessary, the component (C) may be separately introduced into the polymerization tank, or the components (A) and (B) may be contacted in advance and then introduced into the polymerization tank. You may Alternatively, the mixture of components (A) and (B) may be introduced into the polymerization tank after impregnating component (C).
The above components may be contacted in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene in an inert gas such as nitrogen. The contact temperature is preferably -20° C. to the boiling point of the solvent, particularly room temperature to the boiling point of the solvent. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, after preparation, new components may be used in combination as needed.

The catalyst components may be prepolymerized in the presence of an olefin either inside the polymerization vessel or outside the polymerization vessel. 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. Mixtures of these with other olefins may also be used without limitation. Olefins having 2 or 3 carbon atoms are preferred. The method of supplying the olefin may be any method such as a method of supplying the olefin to the reaction vessel at a constant rate or maintaining a constant pressure, a combination thereof, or a stepwise change.

[7] Copolymerization reaction The copolymerization reaction in the present invention is carried out using hydrocarbon solvents such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, and methylcyclohexane, and liquefied α-olefins. liquids, 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. Mixtures of the liquid compounds described herein may also be used as solvents. In order to obtain high polymerization activity and high molecular weight, the above hydrocarbon solvents are more preferable.

Copolymerization in the present invention can be carried out in the presence or absence of known additives. As the additive, a radical polymerization inhibitor and an additive having an effect of stabilizing the produced copolymer are preferable. Examples of preferred additives include quinone derivatives and hindered phenol derivatives.
Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl 4-methylphenol (BHT), reaction products of trimethylaluminum and BHT, reaction products of tetravalent titanium alkoxide and BHT things can be used.
Inorganic and/or organic fillers may also be used as additives and the polymerization may be carried out in the presence of these fillers.

In the present invention, there are no particular restrictions on the polymerization method. Slurry polymerization in which at least a part of the produced polymer becomes a slurry in the medium, bulk polymerization in which the liquefied monomer itself is used as the medium, gas-phase polymerization conducted in the vaporized monomer, or polymer produced in the liquefied monomer at high temperature and high pressure. High-pressure ion polymerization in which at least a part of is dissolved is preferably used.
Moreover, as the polymerization mode, any of batch polymerization, semi-batch polymerization, and continuous polymerization may be used.

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

Although the copolymerization temperature, copolymerization pressure and copolymerization time are not particularly limited, they can usually be optimally set within the following ranges in consideration of productivity and process capability.
That is, the copolymerization temperature is generally −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; It can be selected from the range of 1 minute to 50 hours, preferably 0.5 minutes to 40 hours, more preferably 1 minute to 30 hours.
In the present invention, copolymerization is generally carried out under an inert gas atmosphere. For example, nitrogen or argon atmosphere can be used, and nitrogen atmosphere is preferably used. In addition, a small amount of oxygen or air may be mixed.

There are no particular restrictions on the supply of the catalyst and monomers to the copolymerization reactor, and various supply methods can be adopted depending on the purpose. For example, in the case of batch polymerization, it is possible to supply a predetermined amount of monomers in advance to a copolymerization reactor, and then supply the catalyst there. In this case, additional monomer or additional catalyst may be fed to the copolymerization reactor. Further, in the case of continuous polymerization, a method of continuously or intermittently supplying predetermined amounts of monomers and a catalyst to a copolymerization reactor to carry out the copolymerization reaction continuously can be adopted.

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

In the following, the present invention will be specifically explained by experimental examples, and the rationality, significance, usefulness, and superiority of the configuration of the present invention over the prior art will be demonstrated.
Experimental Examples 1 to 7 and 10 are reference examples, and Experimental Examples 8 to 9 and 11 to 13 are examples.

[1] Analysis method of polymer structure [1-1] Comonomer content of copolymer The comonomer content of the copolymers 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, ¹ H-NMR measurements at 120° C. determine the molar ratio of ethylene:comonomer, and the incorp. (%) is shown in Table 1. incorp. (%) means comonomer content (mol%).
[1-2] Amount of methyl branching 200 mg of a sample was placed in an inner The solution was placed in an NMR sample tube of 10 mmφ, purged with nitrogen, sealed, dissolved by heating, and subjected to NMR measurement as a homogeneous solution. For NMR measurement, an NMR apparatus AVANCE III 400 (Bruker Biospin Co., Ltd.) equipped with a 10 mmφ cryoprobe was used.
The amount of methyl branching is normalized to 1,000 for the sum of the integrated intensities of the signals in the range of 10 to 180 ppm in the ¹³ C-NMR spectrum. It was determined as the number of methyl branches per 000C.

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

In the following synthesis examples, unless otherwise specified, operations were performed under a purified argon atmosphere, and dehydrated and deoxygenated solvents were used. Metal complex 1 and metal complex 2 used as catalysts are described in Non-Patent Document 3; Nozaki et al. , J. Am. Chem. Soc. , 2015, 137, 10934-10937, Non-Patent Document 11; synthesized according to JP-A-2014-219220. In addition, as a comonomer, methyl methacrylate (MMA; Kanto Chemical), α-methylstyrene (α-methylstyrene (α-MS); TCI), β-methallyl chloride (MACl); TCI ), methyl butenyl acetate (MBAc); Aldrich), and methyl phenyl ether (MAPE); Alfa Aesar). All these comonomers were distilled and used. Among these comonomers, the structural formulas of methyl methacrylate (MMA), methylbutenyl acetate (MBAc), α-methylstyrene (α-MS), and methallylphenyl ether (MAPE) are shown below.

[3] Synthesis of polar group-containing olefin copolymers of Experimental Examples 1, 2, 4, 5, 6, 8, 9, 10, 11, and 12 Under an argon atmosphere, a predetermined amount of the following catalyst (metal complex 1) was In a 50 mL autoclave manufactured by Pressure Glass Industry Co., Ltd. containing (amount shown in Table 1), a predetermined amount (amount shown in Table 1) of toluene and a prescribed amount (amount shown in Table 1) of each comonomer (table 1) was added. After charging a predetermined amount of ethylene (the amount shown in Table 1), 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 Experimental Examples 3 and 7 Under an argon atmosphere, in a 50 mL autoclave manufactured by Pressure Glass Industry Co., Ltd. containing a predetermined amount (amount shown in Table 1) of metal complex 1, A predetermined amount (the amount listed in Table 1) of toluene and a predetermined amount (the amount listed in Table 1) of each comonomer (listed in Table 1) were added. After charging a predetermined amount of ethylene (the amount shown in Table 1), 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 Experimental Example 13 Under an argon atmosphere, a 50 mL autoclave manufactured by Pressure Glass Industry Co., Ltd. containing a predetermined amount (amount shown in Table 1) of the following catalyst (metal complex 2) A predetermined amount (the amount shown in Table 1) of toluene and a predetermined amount (the amount shown in Table 1) of each comonomer (shown in Table 1) were added therein. After charging a predetermined amount of ethylene (the amount shown in Table 1), 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 was obtained in each of the experimental examples. According to this experimental example, a novel polar group-containing olefin copolymer is provided that exhibits physical properties such as adhesiveness, printability, or compatibility with fillers and the like. Moreover, according to this experimental example, a polar group-containing olefin copolymer is efficiently produced.
It was confirmed that the olefin copolymer was a linear random copolymer with a degree of methyl branching of 20 or less per 1,000 carbons of the copolymer as calculated by ¹³ C-NMR analysis.

The present invention is not limited to the embodiments detailed above, and various modifications and changes are possible within the scope of the claims of the present invention.

According to the present invention, there is provided a novel polar group-containing olefin copolymer that exhibits good adhesiveness and printability or exhibits good compatibility with fillers and the like. Being 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 requiring physical properties such as adhesiveness with other materials, printability, or compatibility with fillers and the like.

Claims (3)

a structural unit derived from ethylene and/or an α-olefin having 3 to 10 carbon atoms;
A polar group-containing olefin consisting of 20 to 0.001 mol% of a structural unit 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) is a copolymer,
And,
A polar group-containing olefin copolymer characterized by being a linear random copolymer having a degree of methyl branching of 20 or less per 1,000 carbon atoms of the copolymer as calculated by ¹³ C-NMR analysis.

[In formula (1), FG is a substituted amino group having a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. , a cyano group, or an acyloxy group having a hydrocarbon group of 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. a substituted amino group having a hydrocarbon group of 1 to 20, a cyano group, a carboxyl 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 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 may form a cyclic structure with FG. good. ] In formula (1), FG is a halogen atom, a substituted amino group having a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, or an acyloxy group having a hydrocarbon group having 1 to 20 carbon atoms,
In formulas (2) and (3), FG is a substituted amino group having a halogen atom, an aryl group having 6 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, and 1 carbon atom. 2. The polar group-containing olefin copolymer according to claim 1, which is an ester group having a hydrocarbon group of up to 20 or an acyloxy group having a hydrocarbon group of 1 to 20 carbon atoms. In formula (1), FG is a halogen atom or an acyloxy group having a hydrocarbon group with 1 to 20 carbon atoms,
In formulas (2) and (3), 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 a 3. The polar group-containing olefin copolymer according to claim 2, which is an acyloxy group having a hydrocarbon group.