JP6858376B2 - Method for Producing Catalyst for Olefin Polymerization and Polar Group-Containing Olefin Polymer - Google Patents

Description

The present invention relates to a catalyst for olefin polymerization and a method for producing an olefin polymer, particularly a polar group-containing monomer polymer such as an allyl compound having a polar group.

Copolymers of olefins such as ethylene and propylene, which are non-polar monomers, and vinyl monomers having a polar group are widely known. For example, an ethylene / vinyl alcohol copolymer (EVOH) is a copolymer composed of an ethylene structural unit and a vinyl alcohol structural unit, and is an ethylene / vinyl acetate copolymer obtained by radical copolymerization of ethylene and vinyl acetate. It is synthesized by saponification. EVOH is used in a wide range of fields such as food packaging by taking advantage of its excellent gas barrier property.

On the other hand, the polymerization of a monomer having an allyl group is more difficult than that of a vinyl monomer, and the polymer thereof is hardly known. The main reason for this is that when a monomer having an allyl group is radically polymerized, the polymer growth reaction is extremely slow due to the degenerative chain transfer reaction to the monomer, and only an oligomer having a low degree of polymerization can be obtained (Chem). . Rev. 58, 808 (1958); Non-Patent Document 1).

Japanese Patent Application Laid-Open No. 2011-68881 (International Publication No. 2011/025053; Patent Document 1), Japanese Patent Application Laid-Open No. 2014-159540 (Patent Document 2), International Publication No. 2013-168626 (Patent Document 3), J. Am Chem. Soc., 133, 1232 (2011) (Non-Patent Document 2) shows coordination copolymerization of ethylene and polar group-containing allyl monomer using a metal complex catalyst of Group 10 of the periodic table. , A polar group-containing allyl monomer copolymer that could not be obtained by the radical polymerization method is being synthesized. However, in the metal complex catalyst described in the above document, the reactivity to the polar group-containing allyl monomer is much lower than the reactivity to ethylene, and the polar group-containing allyl monomer is incorporated in a high content. It was difficult to obtain a polymer.

Japanese Unexamined Patent Publication No. 2011-68881 Japanese Unexamined Patent Publication No. 2014-159540 International Publication No. 2013-168626

Chem. Rev. 58, 808 (1958) J. Am. Chem. Soc., 133, 1232 (2011)

An object of the present invention is to produce an olefin polymer in which a monomer having a polar group is incorporated at a high content, which can be applied in various ways, by using a polymerization catalyst having high reactivity to a monomer having a polar group. To provide a method.

As a result of diligent studies to solve the above problems, the present inventors have a novel cycle in which polar group-containing olefins (including allyl monomers having polar groups) are more reactive than conventional polymerization catalysts. It was found that a copolymer can be obtained with a high content of a polar group-containing olefin by copolymerizing a group 10 metal complex catalyst in Table and a non-polar olefin and a polar group-containing olefin using the catalyst, and the present invention is completed. It came to.

（式中、Ｍは周期表第１０族の元素を表し、Ｘはリン原子（Ｐ）または砒素原子（Ａｓ）を表し、Ｙは、置換または無置換のイミノ基（−ＮＨ−）、置換または無置換のアルキレン基、置換または無置換のアリーレン基、置換または無置換のシクロアルキレン基、オキシ基（−Ｏ−）、及び置換または無置換のシリレン基（−ＳｉＨ₂−）から選ばれる２価の基を表す。Ｒ⁵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す。Ｒ⁶及びＲ⁷はそれぞれ独立して、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、それぞれで結合して環構造を形成してもよい。Ｒ⁸は、水素原子、アルコキシ基、アリールオキシ基、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１〜３０の炭化水素基を表す。Ｚ^-はカチオン性有機金属化合物の対アニオンを表す。Ｌは電子供与性配位子を表し、Ｒ⁵とＬが環形成してもよい。ｑは０、１／２、１または２である。）で示される金属錯体を含むオレフィン重合用触媒。
［２］ 一般式（Ｃ１）

（式中の記号は請求項１の記載と同様の意味を表す。）で示される金属錯体を重合触媒として使用することを特徴とする、ポリエチレン、エチレンと一般式（１）

（式中、Ｒ¹は、水酸基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、炭素原子数２〜１０のアシル基、炭素原子数２〜１０のエステル基（オキシカルボニル基；Ｒ−Ｏ−（Ｃ＝Ｏ）−、Ｒは有機基）、炭素原子数２〜１０のアシロキシ基、アミノ基、炭素原子数１〜１２の置換アミノ基、炭素原子数２〜１２の置換アミド基、炭素原子数５〜１０の置換ピリジル基、炭素原子数４〜１０の置換ピロリジル基、炭素原子数５〜１０の置換ピペリジル基、炭素原子数４〜１０の置換ハイドロフリル基、炭素原子数４〜１０の置換イミダゾリル基、メルカプト基、炭素原子数１〜１０のアルキルチオ基、炭素原子数６〜１０のアリールチオ基、エポキシ基、及びハロゲン原子からなる群より選ばれる置換基を示す。ｎは、０または１〜６より選ばれる任意の整数である。）で示される極性基を有するオレフィンとの共重合体、またはエチレンと前記一般式（１）で示される極性基を有するオレフィンと他のモノマーとの共重合体の製造方法。
［３］ 一般式（１）中のｎが０である前項２に記載の重合体の製造方法。
［４］ 一般式（１）中のｎが１である前項２に記載の重合体の製造方法。
［５］ 一般式（Ｃ１）中のＹが、無置換または置換のイミノ基、無置換または置換のメチレン基または無置換または置換の１，２−フェニレン基である前項２〜４のいずれかに記載の重合体の製造方法。
［６］ 一般式（Ｃ１）中のＹがＮ−メチルイミノ基「−Ｎ（ＣＨ₃）−」である前項２〜４のいずれかに記載の重合体の製造方法。
［７］ 一般式（Ｃ１）中のＲ⁶またはＲ⁷のうち、少なくとも一方がｔ−ブチル基である前項２〜６のいずれかに記載の重合体の製造方法。
［８］ Ｚが、ＳｂＦ₆、ＢＰｈ₄、ＢＡｒＦ₄（ＡｒＦ₄：［３，５−（ＣＦ₃）₂Ｃ₆Ｈ₃］₄）、ＢＦ₄またはＰＦ₆から選択される前項２〜７のいずれかに記載の重合体の製造方法。 That is, the present invention relates to the following [1] to [8].
[1] General formula (C1)

(In the formula, M represents an element of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y represents a substituted or unsubstituted imino group (-NH-), substituted or Divalent selected from an unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, an oxy group (−O−), and a substituted or unsubstituted silylene group (−SiH _2−). R ⁵ represents 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 1 to 10 carbon atoms. A hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, and an amide having 2 to 10 carbon atoms. A group consisting of a hydrocarbon group having 3 to 30 carbon atoms substituted with a group, 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. R ⁶ and R ⁷ each independently represent an alkoxy group, an aryloxy group, a silyl group, an amino group, or one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. It represents a hydrocarbon group having 1 to 120 carbon atoms which may be substituted with, and may be bonded to each of them to form a ring structure. R ⁸ is a hydrogen atom, an alkoxy group, an aryloxy group or an amino group. , Or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from halogen atoms, alkoxy groups and aryloxy groups. Z ^- is the counter anion of the cationic organic metal compound. L represents an electron-donating ligand, and R ⁵ and L may form a ring. Q is 0, 1/2, 1 or 2) olefin polymerization containing a metal complex. For catalyst.
[2] General formula (C1)

(The symbols in the formula represent the same meanings as those described in claim 1.) Polyethylene, ethylene and the general formula (1), which are characterized by using the metal complex represented by the present invention as a polymerization catalyst.

(In the formula, R ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. (Oxycarbonyl group; RO- (C = O)-, R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, and 2 carbon atoms. Substituent amide group of ~ 12, substituted pyridyl group having 5 to 10 carbon atoms, substituted pyrrolidyl group having 4 to 10 carbon atoms, substituted piperidyl group having 5 to 10 carbon atoms, substituted hydrofuryl having 4 to 10 carbon atoms Substituent selected from the group consisting of a substituent, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. N is a copolymer with an olefin having a polar group represented by 0 or an arbitrary integer selected from 1 to 6), or ethylene and a polar group represented by the general formula (1). A method for producing a copolymer of an olefin having an olefin and another monomer.
[3] The method for producing a polymer according to item 2 above, wherein n in the general formula (1) is 0.
[4] The method for producing a polymer according to item 2 above, wherein n in the general formula (1) is 1.
[5] In any of the above items 2 to 4, Y in the general formula (C1) is an unsubstituted or substituted imino group, a unsubstituted or substituted methylene group, or an unsubstituted or substituted 1,2-phenylene group. The method for producing a polymer according to the above.
[6] The method for producing a polymer according to any one of items 2 to 4 above, wherein Y in the general formula (C1) is an N-methylimino group "-N (CH _3)-".
[7] The method for producing a polymer according to any one of the above items 2 to 6, wherein at least one ^{of R 6} or R ^{7 in} the general formula (C1) is a t-butyl group.
[8] Z is selected from SbF ₆ , BPh ₄ , BARF ₄ (ArF ₄ : [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ ), BF ₄ or PF ₆ in the preceding paragraphs 2 to 7. The method for producing a polymer according to any one.

By the method of the present invention in which the metal complex of the present invention is used as a catalyst and an olefin having a polar group containing an allyl monomer having a polar group and a non-polar olefin are copolymerized, the olefin having a polar group, which has been difficult in the past, is high. It becomes possible to produce a copolymer incorporated by the content.

式中、Ｍは周期表第１０族の元素を表し、Ｘはリン原子（Ｐ）または砒素原子（Ａｓ）を表し、Ｙは、置換または無置換のイミノ基（−ＮＨ−）、置換または無置換のアルキレン基、置換または無置換のアリーレン基、置換または無置換のシクロアルキレン基、オキシ基（−Ｏ−）、及び置換または無置換のシリレン基（−ＳｉＨ₂−）から選ばれる２価の基を表す。Ｒ⁵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す。Ｒ⁶及びＲ⁷はそれぞれ独立して、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、それぞれで結合して環構造を形成してもよい。Ｒ⁸は、水素原子、アルコキシ基、アリールオキシ基、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１〜３０の炭化水素基を表す。Ｚ^-はカチオン性有機金属化合物の対アニオンを表す。Ｌは電子供与性配位子を表し、Ｒ⁵とＬが環形成してもよい。ｑは０、１／２、１または２である。
なお、本明細書では、「炭化水素」は飽和、不飽和の脂肪族炭化水素、芳香族炭化水素を含む。 [catalyst]
The catalyst (structure) composed of the metal complex used in the present invention is represented by the general formula (C1).

In the formula, M represents an element of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y represents a substituted or unsubstituted imino group (-NH-), substituted or absent. A divalent selected from a substituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, an oxy group (-O−), and a substituted or unsubstituted silylene group (-SiH _2- ). Represents a group. R ⁵ 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 ⁶ and R ⁷ are independently substituted with 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. It represents a hydrocarbon group having 1 to 120 atoms and may be bonded to each other to form a ring structure. R ⁸ is a carbide having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. Represents a hydrogen group. And Z ^- represents a counter anion of the cationic organometallic compound. L represents an electron donating ligand, and R ⁵ and L may form a ring. q is 0, 1/2, 1 or 2.
In the present specification, "hydrocarbon" includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons.

Hereinafter, the structure of the general formula (C1) will be described.
M represents an element of Group 10 of the periodic table. Examples of the elements of Group 10 of the periodic table include Ni, Pd, and Pt, but Ni and Pd are preferable, and Pd is more preferable, from the viewpoint of catalytic activity and the molecular weight of the obtained polymer.

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 availability and catalyst cost.
Y is a substituted or unsubstituted imino group (-NH-), a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted cycloalkylene group, an oxy group (-O-), and Represents a divalent group selected from substituted or unsubstituted silylene groups (-SiH _2-).

Substituents in the substituted or unsubstituted imino group (-NH-) include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, and 6 to 6 carbon atoms. Examples thereof include an aryl group having an alkyl group or an alkoxy group of 20, and an aralkyl group having 6 to 20 carbon atoms.

Specific examples include an imino group, an N-methylimino group, an N-ethylimino group, an N- (n-propyl) imino group, an N-isopropylimino group, an N- (n-butyl) imino group, and an N- (s-butyl). Imino group, N- (t-butyl) imino group, N-benzylimino group, N-phenylimino group, N-trimethylsilylimino group, N- (2-methoxyphenyl) imino group, N- (3-methoxyphenyl) Imino group, N- (4-methoxyphenyl) imino group, N- (2,6-dimethoxyphenyl) imino group, N- (2,5-dimethoxyphenyl) imino group, N- (2,4-dimethoxyphenyl) Imino group, N- (2,3-dimethoxyphenyl) imino group, N- (3,5-dimethoxyphenyl) imino group, N- (2,4,6-trimethoxyphenyl) imino group, N- (2,2) Examples thereof include a 4,6-trimethylphenyl) imino group, an N- (1-naphthyl) imino group, an N- (2-naphthyl) imino group, and an N- (t-butoxycarbonyl) imino group.
From the viewpoint of ease of catalyst synthesis, Y is preferably an imino group, an N-methylimino group, an N-benzylimino group, or an N- (t-butoxycarbonyl) imino group.

Examples of substituted or unsubstituted alkylene groups are methylene group, 1,2-ethylene group, 1,3-propylene group, dimethylmethylene group, diethylmethylene group, monomethylmethylene group, monoethylmethylene group, diphenylmethylene group, mono. Phenylmethylene group, mono (trimethylsilyl) methylene group, di (trimethylsilyl) methylene group, di (2-methoxyphenyl) methylene group, mono (2-methoxyphenyl) methylene group, di (3-methoxyphenyl) methylene group, mono ( 3-methoxyphenyl) methylene group, di (4-methoxyphenyl) methylene group, mono (4-methoxyphenyl) methylene group, di (2,6-dimethoxyphenyl) methylene group, mono (2,6-dimethoxyphenyl) methylene Group, di (2,5-dimethoxyphenyl) methylene group, mono (2,5-dimethoxyphenyl) methylene group, di (2,4-dimethoxyphenyl) methylene group, mono (2,4-dimethoxyphenyl) methylene group, Di (2,3-dimethoxyphenyl) methylene group, mono (2,3-dimethoxyphenyl) methylene group, di (3,5-dimethoxyphenyl) methylene group, mono (3,5-dimethoxyphenyl) methylene group, di ( 2,4,6-trimethoxyphenyl) methylene group, mono (2,4,6-trimethoxyphenyl) methylene group, di (2,4,6-trimethylphenyl) methylene group, mono (2,4,6- Trimethylphenyl) methylene group, di (2-isopropylphenyl) methylene group, mono (2-isopropylphenyl) methylene group, di (2,6-diisopropylphenyl) methylene group, mono (2,6-diisopropylphenyl) methylene group, Di (1-naphthyl) methylene group, mono (1-naphthyl) methylene group, di (2-naphthyl) methylene group, mono (2-naphthyl) methylene group, dimethoxymethylene group, diethoxymethylene group, dipropoximethylene group, Diisopropoximethylene group, 1,2-ethanedioxymethylene group, 1,3-propanedioxymethylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1- Phenyl-1,2-ethylene group, 1,2-dimethyl-1,2-ethylene group, 1,2-diethyl-1,2-ethylene group, 1,2-diphenyl-1,2-ethylene group, 1, 1-Dimethyl-1,2-ethylene group, 1,1-diethyl-1,2-ethylene group, 1,1-diphenyl-1,2-ethylene group, 1,1,2-tri Methyl-1,2-ethylene group, 1,1,2-triethyl-1,2-ethylene group, 1,1,2-triphenyl-1,2-ethylene group, 1,1,2,2-tetramethyl Examples thereof include -1,2-ethylene group, 1,1,2,2-tetraethyl-1,2-ethylene group, 1,1,2,2-tetraphenyl-1,2-ethylene group and carbonyl group. A methylene group, a monomethylmethylene group, a dimethylmethylene group, a diphenylmethylene group, or a monophenylmethylene group is preferable from the viewpoint of easy availability of raw materials and easy catalyst synthesis.

Examples of unsubstituted arylene groups are 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group, furan-2,3-diyl group, furan-3, Examples thereof include 4-diyl group, thiophene-2,3-diyl group, thiophene-3,4-diyl group, pyridine-2,3-diyl group, pyridine-3,4-diyl group, and the like, and easy availability of raw materials. A 1,2-phenylene group or a 1,2-naphthylene group is preferable because of ease of catalyst synthesis.

One or more substituents may be present in the above-mentioned unsubstituted arylene group. Specific examples of the substituent include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, s-butyl group, t-butyl group, phenyl group, 2-methoxyphenyl group, 3 −methoxyphenyl group, 4-methoxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group , 3,5-Dimethoxyphenyl group, 3,6-dimethoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, methoxy group, ethoxy group, propoxy group , Isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, phenoxy group, amino group, monomethylamino group, monoethylamino group, mono (n-propyl) amino group, mono (isopropyl) amino Group, mono (n-butyl) amino group, mono (isobutyl) amino group, mono (s-butyl) amino group, mono (t-butyl) amino group, dimethylamino group, diethylamino group, di (n-propyl) amino Group, diisopropylamino group, di (n-butyl) amino group, di (isobutyl) amino group, di (s-butyl) amino group, di (t-butyl) amino group, monophenylamino group, monobenzylamino group, Trimethylsilyl group, triethylsilyl group, tri (n-propyl) silyl group, tri (isopropyl) silyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, fluoro group, bromo group, chloro group, iodo group, tri Fluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group and the like can be mentioned. When a plurality of substituents are present, they may be the same or different.

Examples of unsubstituted cycloalkylene groups are cis-cyclobutane-1,2-yl group, trans-cyclobutane-1,2-yl group, cis-cyclopentane-1,2-yl group, and trans-cyclopentane-1. , 2-yl group, cis-cyclohexane-1,2-yl group, trans-cyclohexane-1,2-yl group, cis-cycloheptane-1,2-yl group, trans-cycloheptane-1,2-yl group Groups, cis-cyclooctane-1,2-yl group, trans-cyclooctane-1,2-yl group and the like can be mentioned. Due to the ease of obtaining raw materials and synthesizing catalysts, cis-cyclopentane-1,2-yl group, trans-cyclopentane-1,2-yl group, cis-cyclohexane-1,2-yl group, or trans -Cyclohexane-1,2-yl group is preferred.
One or more substituents may be present in the above-mentioned unsubstituted cycloalkylene group. Specific examples of the substituent are the same as the above-mentioned specific examples of the substituent when the substituent is present in the unsubstituted arylene group. When a plurality of substituents are present, they may be the same or different.

Examples of substituted or unsubstituted silylene groups (-SiH _2- ) include silylene group, dimethylsilylene group, diethylsilylene group, monomethylsilylene group, monoethylsilylene group, diphenylsilylene group, monophenylsilylene group, mono (trimethylsilyl). Silylen group, di (trimethylsilyl) silylene group, di (2-methoxyphenyl) silylene group, mono (2-methoxyphenyl) silylene group, di (3-methoxyphenyl) silylene group, mono (3-methoxyphenyl) silylene group, Di (4-methoxyphenyl) silylene group, mono (4-methoxyphenyl) silylene group, di (2,6-dimethoxyphenyl) silylene group, mono (2,6-dimethoxyphenyl) silylene group, di (2,5-dimethoxyphenyl) silylene group Dimethoxyphenyl) silylene group, mono (2,5-dimethoxyphenyl) silylene group, di (2,4-dimethoxyphenyl) silylene group, mono (2,4-dimethoxyphenyl) silylene group, di (2,3-dimethoxyphenyl) ) Silylen group, mono (2,3-dimethoxyphenyl) silylene group, di (3,5-dimethoxyphenyl) silylene group, mono (3,5-dimethoxyphenyl) silylene group, di (2,4,6-trimethoxy) Phenyl) silylene group, mono (2,4,6-trimethoxyphenyl) silylene group, di (2,4,6-trimethylphenyl) silylene group, mono (2,4,6-trimethylphenyl) silylene group, di ( 2-isopropylphenyl) silylene group, mono (2-isopropylphenyl) silylene group, di (2,6-diisopropylphenyl) silylene group, mono (2,6-diisopropylphenyl) silylene group, di (1-naphthyl) silylene group , Mono (1-naphthyl) silylene group, di (2-naphthyl) silylene group, mono (2-naphthyl) silylene group, dimethoxycilylene group, diethoxycilylene group, dipropoxycilylene group, diisopropoxycilylene group, 1, Examples thereof include a 2-ethanedioxysilylene group and a 1,3-propanedioxysilylene group. From the viewpoint of ease of catalyst synthesis, a silylene group, a monomethylsilylene group, a dimethylsilylene group, a diphenylsilylene group, or a monomethylsilylene group is preferable.

R ⁵ 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.
Preferred specific examples of the halogen atom represented by R ^{5 are fluorine, chlorine and bromine.} Of these, a more preferred substituent is chlorine.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ⁵ is preferably a hydrocarbon group having 1 to 13 carbon atoms, and is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl 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. 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 , Menthyl group, neomentyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xsilyl group, benzyl group, 4-ethylphenyl group and the like.
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 ⁵ is preferably a substituent in which the above-mentioned hydrocarbon group having 1 to 30 carbon atoms is substituted with fluorine, chlorine, or bromine. Specific preferred examples thereof include a trifluoromethyl group or a pentafluorophenyl group.

The hydrocarbon group having 2 to 10 carbon atoms substituted with the alkoxy group represented by R ⁵ preferably contains the above-mentioned hydrocarbon group having 1 to 30 carbon atoms as a methoxy group, an ethoxy group, an isopropoxy group, or 1-propoxy. A substituent substituted with a 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, and 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 ^{5 is preferably 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-G t-butylphenoxy group substituted substituent. A hydrocarbon group having 1 to 6 carbon atoms substituted with a phenoxy group or a 2,6-dimethylphenoxy group is more preferable, and a 1- (phenoxymethyl) ethyl group or 1- (2,6) is particularly preferable. -Dimethylphenoxy group Methyl) Ethyl group.

A hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms represented by R ^{5 (R- (C = O) NH-, R is an organic group) is preferably used.} , The above-mentioned hydrocarbon group having 1 to 30 carbon atoms is replaced with an acetamido group, a propionylamino group, a butyrylamino group, an isobutylylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, or a benzoylamino group. It is a substituent. More preferably, it is a 2-acetamidophenyl group, 2-propionylaminophenyl group, 2-valerylaminophenyl group, 2-benzoylaminophenyl group, and particularly preferably a 2-acetamidophenyl group.

When R ⁵ is a hydrocarbon group substituted with an amide group, the carbonyl oxygen of the amide group can coordinate with M to form a ring without using an electron-donating ligand L separately. it can. That is, R ⁵ can also serve as L. In this case, ^{it is said that R 5} and L form a ring. Specifically, it corresponds to the case of 2-acetamidophenyl group, 2-propionylaminophenyl group, 2-valerylaminophenyl group, and 2-benzoylaminophenyl group. The case of 2-acetamide phenyl group is shown in the following chemical formula.

The alkoxy group having 1 to 30 carbon atoms represented by R ⁵ is preferably an alkoxy group having 1 to 6 carbon atoms, and preferred specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a 1-propoxy group. 1-butoxy group, t-butoxy group and the like. 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 5} is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples thereof include a phenoxy group, a 4-methylphenoxy group, and a 4-methoxyphenoxy group. Groups include 2,6-dimethylphenoxy groups, and 2,6-di-t-butylphenoxy groups. 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 ⁵ is preferably an asyloxy group having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetyloxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy. Examples thereof include a group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group and a benzoyloxy group.
Among these, more preferable groups are acetyloxy group, propionyloxy group and benzoyloxy group, and particularly preferably acetyloxy group and propionyloxy group.

Among these ^{preferable groups as R 5} , 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, and an alkoxy having 1 to 20 carbon atoms. It is a group. As the hydrocarbon group having 1 to 20 carbon atoms, an alkyl group, an aryl group and an aryloxy group are preferable. Particularly preferable specific examples include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group and an acetyloxy group.

R ⁶ and R ⁷ are independently substituted with 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. Represents a hydrocarbon group having 1 to 120 atoms.

The ^{alkoxy group represented by R 6} and R ⁷ preferably has 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 6} and R ⁷ is preferably one having 6 to 24 carbon atoms, and examples thereof include a phenoxy group.

Examples of the silyl group represented by R ⁶ and R ⁷ include a trimethylsilyl group, and examples of the amino group include 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 the halogen atom, alkoxy group and aryloxy group represented by R ⁶ and R ^{7 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 ⁶ and R ⁷ may be the same or different. Further, R ⁶ and R ⁷ may be combined to form a ring structure.
A hydrocarbon group having 1 to 120 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group and an aryloxy group represented by R ⁶ and R ^{7 has an unsubstituted carbon atom number of 1.} A hydrocarbon group of about 20 is preferable, and an alkyl group having 1 to 20 carbon atoms is more preferable. More specifically, 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 particularly preferable.

R ⁸ is a carbide having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a hydrogen atom, an alkoxy group, an aryloxy group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group. Represents a hydrogen group.
A hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, an amino group, or a halogen atom, an alkoxy group and an aryloxy group represented by R ^8. Examples are the same as those of R ⁶ and R ⁷ described above. From the viewpoint of availability of raw materials, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkyl halide group having 1 to 10 carbon atoms are more preferable. Specifically, a methyl group, a trifluoromethyl group, or a phenyl group is particularly preferable.

And Z ^- represents a counter anion of the cationic organometallic complex. Z ^- counter anion represented by may be any one as long a monovalent anion. If further the central metal (M) charges per atom through so that monovalent, Z ^- may be a polyvalent anion. Z ^- Examples of sulfate ion (SO ₄ ^2-), nitrate ion (NO ₃ ^-), carbonate ions (CO ₃ ^2-), perchlorate ion (ClO ₄ ^-), chloride ion (Cl ^- ), bromide ion (Br ^-), iodide ion (I ^-), such as a halide ion, tetrafluoroborate (BF ₄ ^-), bromo trifluoroborate (BBrF ₃ ^-), chloro trifluoroborate (BCLF ₃ ^-) , trifluoromethoxy borate ^{_{(BF 3 (OCH 3) -}} ), trifluoroethoxy borate _{(BF 3 (OC 2 H 5} ) -), trifluoroacetic Ali Loki Chevrolet preparative _{(BF 3 (OC 3 H 5} ) -), tetraphenylborate _{(B (C 6 H 5)} 4 -), tetrakis (3,5-bis (trifluoromethyl) phenyl) borate _{(B (3,5- (CF 3)} 2 C 6 H 3) 4 - = BArF 4 - ), bromo triphenyl borate _{(BBr (C 6 H 5)} 3 -), chlorotrifluoroethylene tetraphenylborate _{(BCl (C 6 H 5)} 3 -), methoxy triphenyl borate _{(B (OCH 3) (C} 6 H 5) ₃ ^-), ethoxy triphenyl borate _{(B (OC 2 H 5)} (C 6 H 5) 3 -), allyloxy triphenyl borate _{(B (OC 3 H 5)} (C 6 H 5) 3 -), tetrakis (pentafluorophenyl) borate _{(B (C 6 F 5)} 4 -), bromotris (pentafluorophenyl) borate _{(BBr (C 6 F 5)} 3 -), chlorotris (pentafluorophenyl) borate (BCl (C ₆ F _{5) 3} ^-), methoxy tris (pentafluorophenyl) borate (B (OCH ₃₎ (C ₆ F _{5) 3} ^-), ethoxy tris (pentafluorophenyl) borate _{(B (OC 2 H 5)} (C 6 F _{5) 3} ^-), Arirokishitorisu (pentafluorophenyl) borate _{(B (OC 3 H 5)} (C 6 F 5) 3 -) borate ion, methanesulfonate etc. (CH ₃ SO ₃ ^-), trifluoromethanesulfonate (CF ₃ SO ₃ ^-), nonafluorobutanesulfonate ^{_{(C 4 F 9 SO 3 -}} ), benzenesulfonic Sulfonates ^{_{(C 6 H 5 SO 3 -}} ), p- toluenesulfonate _{(p-CH 3 -C 6 H} 4 SO 3 -) sulfonate ion, acetate ion such as (CH ₃ CO ₂ ^-), trifluoroacetate (CF ₃ CO ₂ ^-), trichloroacetate ion (CCl ₃ CO ₂ ^-), propionate ion ^{_{(C 2 H 5 CO 2 -}} ), benzoate ^{_{(C 6 H 5 CO 2 -}} ) , such as a carboxylate ion, a hexafluoro phosphate (PF ₆ ^-), etc. phosphate ion, hexafluoroarsenate ion (AsF ₆ ^-) Arce sulfonate ions such as, hexafluoroantimonate (SbF ₆ ^-) antimonate ion, hexafluorosilicate such (SiF ₆ ^-) Such as silicate anion and the like.
Among these counter ions, in the present invention, from the viewpoint of raw material availability and catalytic activity, Z ^- is _{^{SbF 6 -, BPh 4 -,}} BArF 4 -, BF 4 - is preferably ^- or PF ₆ ..

The metal complex that is the catalyst represented by the general formula (C1) can be synthesized by the same method as that described in known literature (for example, J. Am. Chem. Soc. 2012, 134, 8802). .. That is, zero-valent or after reaction with divalent M source and the general formula (C1) ligands in the further counter anion Z ^- to introduce, monovalent metal salts are reacted by combining the metal complex To do.

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 (acetritale) 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 is a nickel source that contains (allyl) nickel chloride, (allyl) nickel bromide, nickel chloride, nickel acetate, bis (acetylacetonato) nickel (II): Ni (acac) ₂ , Examples thereof include (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 also be subjected to in situ polymerization. ^{In particular, when R 5} in the general formula (C1) is a hydrogen atom, it is preferable to react the metal source containing 0-valent M with the ligand and then directly carry out the polymerization without isolating the complex.

The ratio ((C1 ligand) / M) of the M source (M) to the ligand (C1 ligand) in the general formula (C1) is in the range of 0.5 to 2.0, and further 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.

The metal complex represented by the general formula (C1) can also be supported on a carrier and used for polymerization. The carrier in this case is not particularly limited, and examples thereof include inorganic carriers such as silica gel and alumina, and organic carriers such as polystyrene, polyethylene and polypropylene. Examples of the method for supporting the metal complex include a physical adsorption method in which a carrier is impregnated with a solution of the metal complex and dried, and a method in which the metal complex and the carrier are chemically bonded and supported.

で示される。 [monomer]
In the method for producing a polymer of the present invention, not only ethylene can be homopolymerized, but ethylene and an olefin having a polar group can be copolymerized. The olefin having a polar group, which is the second monomer used for copolymerization in the present invention, has the general formula (1).

Indicated by.

In the formula, R ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms ( Oxycarbonyl group; RO- (C = O)-, R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms. Substituent amide group of 12, substituted pyridyl group having 5 to 10 carbon atoms, substituted pyrrolidyl group having 4 to 10 carbon atoms, substituted piperidyl group having 5 to 10 carbon atoms, substituted hydrofuryl group having 4 to 10 carbon atoms Represents a substituent selected from the group consisting of a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. .. n is an integer chosen from 0 or 1-6.

^{R 1} , which is an alkoxy group having 1 to 10 carbon atoms, is preferably an alkoxy group having 1 to 4 carbon atoms, and preferred specific examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a 1-propoxy group. It may be a 1-butoxy group, a t-butoxy group, or the like.
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.

^{R 1} , which is an aryloxy group having 6 to 20 carbon atoms, is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples thereof include a phenoxy group, a 4-methylphenoxy group, and a 4-methoxy group. Examples thereof include a phenoxy group, a 2,6-dimethylphenoxy group, a 3,5-di-t-butylphenoxy group, or a 2,6-di-t-butylphenoxy group.

Among these, more preferable substituents are phenoxy group, 3,5-di-t-butylphenoxy group, or 2,6-dimethylphenoxy group, and particularly preferably, phenoxy group, 3,5-di-. It is a t-butylphenoxy group.

^{R 1} , which is an acyl group having 2 to 10 carbon atoms, is preferably an acyl group having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. , Isovaleryl group, pivaloyl group, benzoyl group and the like.
Among these, more preferable substituents are an acetyl group, a pivaloyl group, and a benzoyl group, and a benzoyl group is particularly preferable.

^{R 1} , which is an ester group (oxycarbonyl group) having 2 to 10 carbon atoms, is preferably an ester group having 2 to 8 carbon atoms, and preferred specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and n. Examples thereof include a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, a (4-glycidylbutoxy) carbonyl group, and a phenoxycarbonyl group.
Among these, more preferable substituents include a methoxycarbonyl group, an ethoxycarbonyl group, and a (4-hydroxybutoxy) carbonyl group, and a methoxycarbonyl group is particularly preferable.

^{R 1} , which is an asyloxy group having 2 to 10 carbon atoms, is preferably an asyloxy group having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetyloxy group, a propionyloxy group, a butyryloxy group, and isobutylyl. Examples thereof include an oxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group and a benzoyloxy group.
Among these, more preferable substituents are acetyloxy group, propionyloxy group and benzoyloxy group, and particularly preferably acetyloxy and propionyloxy group.

^{Preferred specific examples of R 1} which is a substituted amino group having 1 to 12 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. , Diphenylamino group, bis (trimethylsilyl) amino group, morpholinyl group and the like.
Among these, more preferable substituents are a dimethylamino group and a diphenylamino group.

^{Preferred specific examples of R 1} , which is a substituted amide group having 1 to 12 carbon atoms (R- (C = O) NH-, R is an organic group), are an acetamide group, a propionylamino group, a butyrylamino group, and isobutylyl. Examples thereof include an amino group, a valeryl amino group, an isovaleryl amino group, a pivaloyl amino group and a benzoyl amino group.
Among these, a more preferable substituent is an acetamide group, a propionylamino group, and a benzoylamino group, and a particularly preferable one is an acetamide group.

^{Preferred specific examples of R 1} , which is a substituted pyridyl group having 5 to 10 carbon atoms, are 2-pyridyl group, 3-pyridyl group, 2- (3-methyl) pyridyl group, and 2- (4-methyl) pyridyl group. , 3- (2-Methyl) pyridyl group, 3- (4-methyl) pyridyl group, 2- (4-chloromethyl) pyridyl group, 3- (4-chloromethyl) pyridyl group.
Among these, more preferable substituents include 2-pyridyl group, 3-pyridyl group and 2- (4-methyl) pyridyl group, and particularly preferably 2-pyridyl group.

^{Preferred specific examples of R 1} , which is a substituted pyrrolidyl group having 4 to 10 carbon atoms, include a 2-pyrrolidyl group, a 3-pyrrolidyl group, a 2- (1-methyl) pyrrolidyl group, and a 2- (1-butyl) pyrrolidyl group. , 2- (1-Cyclopentenyl) pyrrolidyl group, 2- (4-methoxycarbonyl) pyrrolidyl group, 2- (5-methoxycarbonyl) pyrrolidyl group, 2- (6-methoxycarbonyl) pyrrolidyl group.
Among these, more preferable substituents include 2-pyrrolidyl group, 3-pyrrolidyl group, 2- (1-methyl) pyrrolidyl group and 2- (6-methoxycarbonyl) pyrrolidyl group, and particularly preferably. It is a 2-pyrrolidyl group.

^{Preferred specific examples of R 1} , which is a substituted piperidyl group having 5 to 10 carbon atoms, include 2-piperidyl group, 3-piperidyl group, 2- (1,2,3,6-tetrahydro) piperidyl group, 2- ( Examples thereof include 1-methyl) piperidyl group, 2- (1-ethyl) piperidyl group, 2- (4-methyl) piperidyl group, 2- (5-methyl) piperidyl group and 2- (6-methyl) piperidyl group.
Among these, more preferable substituents include 2-piperidyl group, 3-piperidyl group, 2- (1,2,3,6-tetrahydro) piperidyl group and 2- (6-methyl) piperidyl group. , Particularly preferred are 2-piperidyl groups and 2- (1,2,3,6-tetrahydro) piperidyl groups.

^{Preferred specific examples of R 1} , which is a substituted hydrofuryl group having 4 to 10 carbon atoms, are 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, 2-. (5-Isopropyl) tetrahydrofuryl group, 2- (5-ethyl) tetrahydrofuryl group, 2- (5-methoxy) tetrahydrofuryl group, 2- (5-acetyl) tetrahydrofuryl group, 2- (4) , 5-Benzo) Tetrahydrofuryl group is mentioned.
Among these, more preferable substituents include 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, 2- (5-isopropyl) tetrahydrofuryl group, and the like. Examples thereof include 2- (4,5-benzo) tetrahydrofuryl group, and particularly preferably 2-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, 2- (5-isopropyl) tetrahydrofuryl group. It is a group.

^{Preferred specific examples of R 1} , which is a substituted imidazolyl group having 4 to 10 carbon atoms, include 2-imidazolyl group, 2- (1-methyl) imidazolyl group, 2- (1-benzyl) imidazolyl group, and 2- (1). Examples thereof include a −acetyl) imidazolyl group, a 2- (4,5-benzo) imidazolyl group, and a 2- (1-methyl-4,5-benzo) imidazolyl group.
Among these, more preferable substituents include 2-imidazolyl group, 2- (1-methyl) imidazolyl group, 2- (4,5-benzo) imidazolyl group, and particularly preferably 2- (1). -Methyl) imidazolyl group, 2- (4,5-benzo) imidazolyl group.

^{Preferred specific examples of R 1} which is an alkylthio group having 1 to 10 carbon atoms are a methylthio group, an ethylthio group, a propylthio group and a t-butylthio group, and R ¹ which is an arylthio group having 6 to 10 carbon atoms is preferable. A specific example is a phenylthio group.
Among these, more preferable substituents include a methylthio group, a t-butylthio group and a phenylthio group, and particularly preferably a methylthio group and a phenylthio group.

Preferred specific examples of the halogen atom R ¹ are fluorine, chlorine and bromine. Of these, a more preferred substituent is chlorine.

Of these ^{preferred groups as R 1} , an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, and an acrylate group having 2 to 10 carbon atoms are more preferable, and the general formula (1) is used. Specific examples of the particularly preferable polar comonomer represented by)) include methyl acrylate, ethyl acrylate, allyl acetate, and allyl methyl ether.

In the method for producing a (co) polymer of the present invention, two or more kinds of olefins having a polar group represented by the general formula (1) to be copolymerized with ethylene may be polymerized in combination.

Further, in the method for producing a (co) polymer of the present invention, a third monomer may be used in addition to ethylene and an olefin having a polar group represented by the general formula (1). As the third monomer, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene. Can be mentioned. Of these, propylene, 1-butene, or 1-hexene is preferred. Further, these may be polymerized by combining two or more kinds. However, when the α-olefin is copolymerized as the third monomer, the ratio of the α-olefin to the total of the α-olefin and ethylene contained in the obtained polymer is less than 40 mol%.

[Polymerization method]
The method of polymerizing ethylene alone or ethylene and the monomer represented by the general formula (1) using the metal complex of the present invention as a catalyst is not particularly limited, and can be polymerized by a generally used method. .. That is, process methods such as a solution polymerization method, a suspension polymerization method, and a gas phase polymerization method are possible, but a solution polymerization method and a suspension polymerization method are particularly preferable. Further, the polymerization mode can be a batch format or a continuous format. Further, it can be carried out by either one-step polymerization or multi-step polymerization.

Two or more kinds of metal complex catalysts represented by the general formula (C1) may be mixed and used in the polymerization reaction. By mixing and using the polymer, it is possible to control the molecular weight, the molecular weight distribution, and the content of the monomer unit derived from the monomer of the general formula (1), and obtain a polymer suitable for a desired application. Can be done. The molar ratio of the total amount of the metal complex catalyst to the total amount of the monomer is the monomer / metal complex ratio in the range of 1 to 10,000,000, preferably in the range of 10 to 1,000,000, more preferably 100 to 100, A range of 000 is used.

The polymerization temperature is not particularly limited, but is usually carried out in the range of -30 to 400 ° C, preferably 0 to 200 ° C, and more preferably 30 to 150 ° C.

The polymerization pressure in which the ethylene pressure occupies most of the internal pressure is carried out in the range of normal pressure to 100 MPa, preferably in the range of normal pressure to 20 MPa, and more preferably in the range of normal pressure to 10 MPa.

The polymerization time can be appropriately adjusted depending on the process mode, the polymerization activity of the catalyst, and the like, and a short time of several tens of seconds to several minutes or a long reaction time of several thousand hours is possible.

In order to prevent a decrease in the activity of the catalyst, the atmosphere in the polymerization system is preferably filled with an inert gas such as nitrogen gas or argon so that air, oxygen, water and the like other than the monomer are not mixed. In the case of solution polymerization, an inert solvent can be used in addition to the monomer. The inert solvent is not particularly limited, but is limited to an aliphatic hydrocarbon such as isobutane, pentane, hexane, heptane, and cyclohexane, an aromatic hydrocarbon such as benzene, toluene, and xylene, chloroform, methylene chloride, carbon tetrachloride, dichloroethane, and tetra. Aliphatic hydrocarbons such as chloroethane, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, aliphatic esters such as methyl acetate and ethyl acetate, aromatic esters such as methyl benzoate and ethyl benzoate, etc. Can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.

[Method for analyzing polymer structure]
The number average molecular weight and weight average molecular weight of the (co) polymer obtained in the examples were determined by a high temperature GPC apparatus manufactured by Toso Co., Ltd., HLC-8121 GPC equipped with an AT-806MS column (two in series) manufactured by Showa Denko KK. It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) using polystyrene as a standard substance of molecular weight using / HT.

The content of the monomer unit derived from the olefin having a polar group represented by the general formula (1) is 1,1,2,2-tetrachloroethane- as a solvent using JNM-ECS400 manufactured by JEOL Ltd. ^{It was determined by 1 1} H-NMR at 120 ° C. using d2.

（ａ）化合物１ａ（Ｎ−（ジ−ｔ−ブチルホスフィノ）−Ｎ−メチルアセトアミド）の合成
塩化アセチル（２．４ｇ，３０．０ｍｍｏｌ，１．５ｅｑ）とトリエチルアミン（４．０ｇ，３９．９ｍｍｏｌ，２ｅｑ）のジクロロメタン溶液（５０ｍＬ）に、Ｎ−（ジ−ｔ−ブチルホスフィノ）−Ｎ−メチルアミン（３．５ｇ，２０．０ｍｍｏｌ）を０℃にてゆっくりと加え、室温で１６時間撹拌した。この溶液を減圧下にて乾燥し、黄色固体を得た。この黄色固体に、ヘキサン（５０ｍＬ）とジクロロメタン（２ｍＬ）を加えてろ過し、ろ液を減圧下にて乾燥することにより、黄色オイル状の化合物１ａを得た。収量３．７ｇ（収率８１％）。
¹Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ₃）：δ 3.07 (s, 3 H), 2.36 (d, J = 5.2 Hz, 3 H), 1.23 (d, J = 14.0 Hz, 18 H). ³¹Ｐ−ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ₃）：δ 92.4． [Synthesis of metal complex 1 and metal complex 2]
Synthesis Example 1: Metal Complex 1 ([Methylpalladium (N- (di-t-butylphosphino) -N-methylacetamide) (2,6-lutidine)] [Tetrakis (3,5-bis (trifluoromethyl)) Phenylborate]) synthesis

(A) Synthesis of compound 1a (N- (di-t-butylphosphino) -N-methylacetamide) Acetyl chloride (2.4 g, 30.0 mmol, 1.5 eq) and triethylamine (4.0 g, 39.9 mmol) , 2eq) in dichloromethane (50 mL), slowly add N- (di-t-butylphosphino) -N-methylamine (3.5 g, 20.0 mmol) at 0 ° C. and stir at room temperature for 16 hours. did. The solution was dried under reduced pressure to give a yellow solid. Hexane (50 mL) and dichloromethane (2 mL) were added to the yellow solid, and the mixture was filtered, and the filtrate was dried under reduced pressure to give compound 1a in the form of a yellow oil. Yield 3.7 g (yield 81%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 3.07 (s, 3 H), 2.36 (d, J = 5.2 Hz, 3 H), 1.23 (d, J = 14.0 Hz, 18 H). ^{31 1} P-NMR (162 MHz, CDCl ₃ ): δ 92.4.

(B) Metal complex 1 ([Methylpalladium (N- (di-t-butylphosphino) -N-methylacetamide) (2,6-lutidin)] [Tetrakis (3,5-bis (trifluoromethyl) phenyl) Borate]) synthesis Compound 1a (0.40 g, 1.8 mmol) in dichloromethane solution (5 mL) (cod) PdMeCl (cod = 1,5-cyclooctadiene, 0.49 g, 1.8 mmol, 1.0 eq) Dichloromethane solution (5 mL) was added and stirred at room temperature for 20 minutes. This solution was concentrated to about 1/3 volume under reduced pressure, 30 mL of hexane was added and stirred, and then the resulting precipitate was precipitated to settle the supernatant. The residue was washed twice with 10 mL of hexane and then dried under reduced pressure to obtain 0.6 g of white-brown powder. 2,6 in a dichloromethane solution (20 mL) of this white-brown powder. -Lutidine (0.38 mL, 3.2 mmol, 2.0 eq), sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (1.4 g, 1.6 mmol, 1.0 eq) in dichloromethane (10 mL) ) Was added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered through Celite (dried diatomaceous earth) and sodium sulfate, and then dried under reduced pressure. By washing with hexane (15 mL × 3 times). Metal complex 1 was obtained. Yield 1.7 g (yield 81%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.69 (br, 8 H), 7.65 (t, J = 7.8 Hz, 1 H), 7.51 (br, 4 H), 7.17 (d, J = 7.8 Hz, 2 H), 3.20 (d, J = 3.6 Hz, 3 H), 2.87 (s, 6 H), 2.10 (s, 3 H), 1.46 (d, J = 16.0 Hz, 18 H), 0.56 (d, J = 1.4Hz, 3 H). ^{31 1} P-NMR (162MHz, CDCl ₃ ): δ 142.0

Synthesis Example 2: Metal Complex 2 ([Methylpalladium (N- (di-t-butylphosphino) -N-methylbenzamide) (2,6-lutidine)] [Tetrakis (3,5-bis (trifluoromethyl)) Phenylborate]) synthesis

(A) Synthesis of compound 2a (N- (di-t-butylphosphino) -N-methylbenzamide) HATU (O- (7-azabenzotriazole-1-yl) -N, N, N', N' -Tetramethyluronium hexafluorophosphate)) (6.5 g, 17.2 mmol, 1.0 eq) in an acetonitrile solution (50 mL) with benzoic acid (2.1 g, 17.2 mmol) and triethylamine (4.4 g). , 43.0 mmol, 2.5 eq) was added slowly at 0 ° C., and the mixture was stirred at 0 ° C. for 0.5 hours. N- (di-t-butylphosphino) -N-methylamine (3.0 g, 17.2 mmol) was added to this reaction solution, and the mixture was stirred at 20 ° C. for 16 hours to obtain a pale yellow solution. After distilling off the solvent, the mixture was purified by silica gel chromatography (pentane / ethyl acetate = 10/1) to obtain a white solid. This white solid was washed twice with hexane (10 mL) at −30 ° C. and then filtered under an argon (Ar) atmosphere to obtain compound 2a as a white powder. Yield 1.7 g (yield 32%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.35-7.28 (m, 5 H), 3.29 (s, 3 H), 1.22 (d, J = 12.0 Hz, 18 H). ³¹ P-NMR (162 MHz, CDCl ₃ ): δ 92.5.

(B) Metal complex 2 ([Methylpalladium (N- (di-t-butylphosphino) -N-methylbenzamide) (2,6-lutidin)] [Tetrakis (3,5-bis (trifluoromethyl) phenyl) Borate]) synthesis Compound 2a (0.5 g, 1.8 mmol) in dichloromethane solution (5 mL) (cod) PdMeCl (cod = 1,5-cyclooctadiene, 0.5 g, 1.8 mmol, 1.0 eq) Dichloromethane solution (5 mL) was added and stirred at room temperature for 20 minutes. This solution was concentrated to about half the amount under reduced pressure, 20 mL of hexane was added and stirred, and then the resulting precipitate was precipitated to remove the supernatant. The residue was washed twice with 10 mL of hexane and then dried under reduced pressure to give 0.7 g of white powder. 2,6-Lutidine (0.37 mL) was added to a dichloromethane solution (20 mL) of this white powder. , 3.2 mmol, 2.0 eq), sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (1.4 g, 1.6 mmol, 1.0 eq) in dichloromethane (10 mL), and brought to room temperature. The reaction solution was filtered through Celite (dried diatomaceous earth) and sodium sulfate, and then dried under reduced pressure. The reaction solution was washed with hexane (15 mL × 3 times) to obtain a metal complex 2. . Yield 2.0 g (83% yield).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.70 (br, 8 H), 7.62 (t, J = 7.8 Hz, 1 H), 7.49-7.47 (m, 5 H), 7.41 (t, J = 7.7) Hz, 2 H), 7.23-7.21 (m, 2 H), 7.15 (d, J = 7.8 Hz, 2 H), 3.21 (d, J = 3.6 Hz, 3 H), 2.91 (s, 6 H), 1.57 (d, J = 16.4 Hz, 18 H), 0.65 (d, J = 1.8 Hz, 3 H). ^{31 1} P-NMR (162 MHz, CDCl ₃ ): δ 142.8.

比較金属錯体１は、特開２０１１−６８８８１号公報に従って合成した。 [Synthesis of Comparative Metal Complexes 1-3]
Subsequently, the comparative metal complexes 1 to 3 were synthesized as follows.
(I) Synthesis of Comparative Metal Complex 1

The comparative metal complex 1 was synthesized according to Japanese Patent Application Laid-Open No. 2011-68881.

比較金属錯体２は、特開２０１４−１５９５４０号公報に従って合成した。 (J) Synthesis of Comparative Metal Complex 2

The comparative metal complex 2 was synthesized according to Japanese Patent Application Laid-Open No. 2014-159540.

比較金属錯体３は、国際公開第２０１３／１６８６２６号公報に従って合成した。 (K) Synthesis of Comparative Metal Complex 3

The comparative metal complex 3 was synthesized according to International Publication No. 2013/168626.

[Synthesis of polymer]
(Co) polymerization of olefins was carried out using the metal complexes 1 and 2 and the comparative metal complexes 1 and 3 synthesized by the above method. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively.
The catalyst concentration, catalytic activity, and copolymerization ratio were calculated by the following formulas.

Example 1: Copolymerization of allyl acetate and ethylene using metal complex 1 (preparation of polymer 1)
Allyl acetate (11.6 mL, 107.5 mmol) was added to a 120 mL autoclave containing metal complex 1 (6.5 mg, 0.005 mmol) under a nitrogen atmosphere. After filling with ethylene (4.0 MPa, 256.0 mmol, monomer charging ratio = 107.5 mmol / 256.0 mmol = 0.42), the autoclave was stirred at 80 ° C. for 1 hour. After cooling to room temperature, the reaction solution in the autoclave was added to methanol (300 mL) to precipitate a copolymer. The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 1. The yield was 0.14 g. The catalytic activity was calculated to be 28 g / (mmol · h). The molecular weight of the polymer 1 was determined by size exclusion chromatography and calculated to have a number average molecular weight of 33,000 and a weight average molecular weight of 76,000, and Mw / Mn was 2.3. The content of allyl acetate and ethylene in the copolymer was ^{measured by 1} H-NMR measurement, and the molar ratio of ethylene: allyl acetate was 100: 2.60 (allyl acetate molar ratio = 2.53%, ethylene molar fraction = 97. 47%, monomer uptake ratio = 2.53% / 97.47% = 0.026), and the copolymerization ratio was calculated to be 6.2%.

Example 2: Copolymerization of allyl acetate and ethylene using metal complex 2 (preparation of polymer 2)
A metal complex 2 was used instead of the metal complex 1, and copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 1 except that the polymer 2 was obtained.

Comparative Examples 1 to 3: Copolymerization of allyl acetate and ethylene using comparative metal complexes 1 to 3 (preparation of comparative polymers 1 to 3)
Comparative metal complexes 1 to 3 were used instead of the metal complex catalyst 1, and allyl acetate and ethylene were copolymerized in the same manner as in Example 1 except that the polymerization conditions shown in Table 1 were set, and the comparative polymer 1 was subjected to copolymerization. I got ~ 3.

As shown in Tables 1 and 2, the metal complex 1 and the metal complex 2 of the present invention have a higher copolymerization ratio than the conventional catalysts (comparative metal complexes 1 to 3), that is, the polarity with respect to the reactivity of ethylene. It was found that the reactivity of the group-containing olefin (allyl acetate) was high. This makes it possible to efficiently synthesize a polymer having a high content of polar group-containing olefins.

Claims (11)

General formula (C1)

(In the formula, M represents an element of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y represents an imino group substituted with an alkyl group having 1 to 5 carbon atoms. Alternatively, it represents an unsubstituted imino group (-NH- ^{). R 5} is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen atom. A group, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms. , A hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a carbon atom number. Represents a substituent selected from the group consisting of 2 to 10 asyloxy groups. R ⁶ and R ⁷ independently represent 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 which may be substituted with one or more groups selected from the groups, and may be bonded to each other to form a ring structure. R ⁸ is a hydrogen atom. alkoxy group, .Z to an aryloxy group, an amino group or a halogen atom, an alkoxy group and one or more hydrocarbon group which may having 1 to 30 carbon atoms optionally substituted by a group selected from an aryloxy group, ^- the .L representing a counter anion of the cationic organometallic compound represents an electron donating ligand, R ⁵ and L are mAY ring formed .q is 0 / 2,1 or 2.) A catalyst for olefin polymerization containing a metal complex represented by. General formula (C1)

(In the formula , M represents an element of Group 10 of the periodic table, X represents a phosphorus atom (P) or an arsenic atom (As), and Y represents an imino group substituted with an alkyl group having 1 to 5 carbon atoms. Alternatively, it represents an unsubstituted imino group (-NH-). R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon having 1 to 30 carbon atoms substituted with a halogen atom. A group, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms. , A hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and a carbon atom number. Represents a substituent selected from the group consisting of 2 to 10 asyloxy groups. R ⁶ and R ⁷ independently represent 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 which may be substituted with one or more groups selected from the groups, and may be bonded to each other to form a ring structure. R ⁸ is a hydrogen atom. alkoxy group, .Z to an aryloxy group, an amino group or a halogen atom, an alkoxy group and one or more hydrocarbon group which may having 1 to 30 carbon atoms optionally substituted by a group selected from an aryloxy group, ^- the .L representing a counter anion of the cationic organometallic compound represents an electron donating ligand, R ⁵ and L are mAY ring formed .q is 0 / 2,1 or 2.) Polyethylene, ethylene and the general formula (1), characterized in that the metal complex represented by is used as a polymerization catalyst.

(In the formula, R ¹ is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. (Oxycarbonyl group; RO- (C = O)-, R is an organic group), an acyloxy group having 2 to 10 carbon atoms, an amino group, a substituted amino group having 1 to 12 carbon atoms, and 2 carbon atoms. Substituent amide group of ~ 12, substituted pyridyl group having 5 to 10 carbon atoms, substituted pyrrolidyl group having 4 to 10 carbon atoms, substituted piperidyl group having 5 to 10 carbon atoms, substituted hydrofuryl having 4 to 10 carbon atoms Substituent selected from the group consisting of a substituent, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. N is a copolymer with an olefin having a polar group represented by 0 or an arbitrary integer selected from 1 to 6), or ethylene and a polar group represented by the general formula (1). A method for producing a copolymer of an olefin having an olefin and another monomer. The method for producing a polymer according to claim 2, wherein n in the general formula (1) is 0. The method for producing a polymer according to claim 2, wherein n in the general formula (1) is 1. The method for producing a polymer according to any one of claims 2 to 4, wherein Y in the general formula (C1) is an N-methylimino group "-N (CH _3)-". The method for producing a polymer according to any one of claims 2 to 5 ^{, wherein at least one of R 6} or R ^{7 in} the general formula (C1) is a t-butyl group. One of claims 2 to 6 in which Z is selected from SbF ₆ , BPh ₄ , BARF ₄ (ArF ₄ : [3,5- (CF ₃ ) ₂ C ₆ H ₃ ] ₄ ), BF ₄ or PF _6. The method for producing a polymer according to one item. The catalyst for olefin polymerization according to claim 1, wherein X in the general formula (C1) is a phosphorus atom (P). The catalyst for olefin polymerization according to any one of claims 1 or 8, wherein M in the general formula (C1) is Pd. The method for producing a polymer according to any one of claims 2 to 7, wherein X in the general formula (C1) is a phosphorus atom (P). The method for producing a polymer according to any one of claims 2 to 7 and 10, wherein M in the general formula (C1) is Pd.