JP2021188009A - Process for producing polar group-containing allyl monomer copolymer - Google Patents

Abstract

To provide, when producing a copolymer of ethylene and an allyl monomer having a polar group using a group 10 metal complex in the periodic table as a catalyst, a process for producing the copolymer with higher catalytic activity.SOLUTION: Provided is a production process in which, using a metal complex represented by the general formula (C1) as a catalyst, ethylene, an allyl monomer having a polar group, and a 2,5-norbornadiene-like compound are copolymerized by having the ratio of the number of charged moles of allyl monomer having a polar group to the sum of the number of charged moles of ethylene and allyl monomer having a polar group 70 mole% or more.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an allyl monomer copolymer containing a polar group.

Copolymers of non-polar monomers such as ethylene and propylene with olefins and vinyl monomers having polar groups have functionality and properties not found in non-polar polyethylene and polypropylene, and are used in a wide range of fields. ing. For example, an ethylene / vinyl alcohol copolymer (EVOH) is a copolymer composed of an ethylene monomer structural unit and a vinyl alcohol monomer structural unit, and is an ethylene / vinyl acetate copolymer obtained by radical copolymerization of ethylene and vinyl acetate. Manufactured by copolymerizing. 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 an allyl monomer having a polar group such as allyl acetate or allyl alcohol is more difficult than that of a normal vinyl monomer, and the polymer thereof is hardly known. The main reason for this is that when an allyl monomer is radically polymerized, the polymer growth reaction is extremely slow and the degree of polymerization is low due to the degenerative chain transfer reaction to the monomer by extracting the hydrogen atom present on the allyl-position carbon. This is because it can only be obtained (Chem. Rev. 58, 808 (1958); Non-Patent Document 1).

Japanese Patent Laying-Open No. 2011-68881 (Patent Document 1), International Publication No. 2013/168626 (Patent Document 2) and J. Am. Chem. Soc., 133, 1232 (2011) (Non-Patent Document 2) Coordination copolymerization of ethylene and polar group-containing allyl monomer using a metal complex catalyst of Group 10 of the periodic table has been shown, and successful synthesis of a polar group-containing allyl monomer copolymer that could not be obtained by the radical polymerization method was successfully performed. is doing.

In Japanese Patent Application Laid-Open No. 2013-07934 (Patent Document 3), a metal complex catalyst of Group 10 of the periodic table is used to copolymerize a diene compound as a third monomer other than ethylene and a polar group-containing allyl monomer. An example is shown. Compared to the polymer obtained by the copolymerization of ethylene and the polar group-containing allyl monomer, a polymer having a higher molecular weight can be obtained, while the cross-linking reaction with the diene compound is also proceeding, and the gelation component insoluble in the solvent is obtained. Was generated. Therefore, a step of separating the soluble polymer and the insoluble polymer by Soxhlet extraction using 1,2-dichlorobenzene as a solvent was required.

Further, in Japanese Patent Application Laid-Open No. 2014-159540 (Patent Document 4) and International Publication No. 2016/0677776 (Patent Document 5), various molded products can be formed by further improving the catalyst described in the above documents. It is disclosed that it has become possible to produce a polymer having a molecular weight of a level. However, from the viewpoint of catalyst cost, the catalytic activity and the polymer productivity per unit catalyst are not sufficient, and there are still problems for industrialization.

Japanese Unexamined Patent Publication No. 2011-68881 International Publication No. 2013/168626 Japanese Unexamined Patent Publication No. 2013-07934 Japanese Unexamined Patent Publication No. 2014-159540 International Publication No. 2016/0677776

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

An object of the present invention is to provide a method for producing a copolymer of ethylene and an allyl monomer having a polar group with higher catalytic activity when using a metal complex of Group 10 of the periodic table as a catalyst.

As a result of diligent studies to solve the above problems, the present inventors have used a Group 10 metal complex in the periodic table as a catalyst, and in addition to ethylene and an allyl monomer having a polar group, 2,5-norbornadiene. We have found that by copolymerizing similar compounds, it is possible to produce an allyl monomer copolymer having a polar group capable of various applications with high catalytic activity, and have completed the present invention.

（式中、Ｍは周期表第１０族の元素を表し、Ｘはリン原子（Ｐ）又は砒素原子（Ａｓ）を表し、Ｙは、炭素原子数６〜３０の置換若しくは無置換のアリーレン基、炭素原子数１〜２０の置換若しくは無置換のアルキレン基、炭素原子数３〜３０の置換若しくは無置換のシクロアルキレン基、置換若しくは無置換のイミノ基（−ＮＨ−）、オキシ基（−Ｏ−）、又は置換若しくは無置換のシリレン基（−ＳｉＨ_２−）から選ばれる２価の基を表す。Ｒ^５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。Ｒ^６及びＲ^７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、又はハロゲン原子、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^６とＲ^７は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、Ｒ^５とＬが環形成してもよい。ｑは０、１／２、１又は２である。）で示される金属錯体を触媒として使用し、エチレン、
一般式（１）

（式中、Ｒ^１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の置換又は無置換のアミド基、炭素原子数５〜１０の置換又は無置換のピリジル基、炭素原子数４〜１０の置換又は無置換のピロリジル基、炭素原子数５〜１０の置換又は無置換のピペリジル基、炭素原子数４〜１０の置換又は無置換のヒドロフリル基、炭素原子数４〜１０の置換又は無置換のイミダゾリル基、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表す。）で示される極性基を有するアリルモノマー、
及び一般式（２）

（式中、Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立して、水素原子又は炭素原子数１〜３のアルキル基を表し、それぞれ同じであっても、異なっていてもよい。）で示される２，５−ノルボルナジエン類似化合物を、
エチレンと一般式（１）で示される極性基を有するアリルモノマーの仕込みのモル数の和に対する一般式（１）で示される極性基を有するアリルモノマーの仕込みのモル数の割合を７０モル％以上として共重合することを特徴とする極性基含有アリルモノマー共重合体の製造方法。
［２］
得られる共重合体がゲル化していないことを特徴とする［１］に記載の共重合体の製造方法。
［３］
一般式（Ｃ１）中のＹが、置換若しくは無置換の１，２−フェニレン基又は置換若しくは無置換のメチレン基である［１］又は［２］のいずれかに記載の共重合体の製造方法。
［４］
一般式（Ｃ１）中のＲ^６及びＲ^７が、いずれも炭素原子数３〜２０のアルキル基又は炭素原子数５〜２０のシクロアルキル基である［１］〜［３］のいずれかに記載の共重合体の製造方法。
［５］
一般式（Ｃ１）中のＲ^６及びＲ^７が、イソプロピル基、ｔ−ブチル基、２−メチル−２−ペンチル基、２，３，３−トリメチル−２−ブチル基、又はメンチル基から選択される［１］〜［４］のいずれかに記載の共重合体の製造方法。
［６］
一般式（２）で示される２，５−ノルボルナジエン類似化合物が、無置換の２，５−ノルボルナジエン（一般式（２）中のＲ^２、Ｒ^３、及びＲ^４がいずれも水素原子）である［１］〜［５］のいずれかに記載の共重合体の製造方法。
［７］
一般式（１）で示される極性基を有するアリルモノマーが酢酸アリル（一般式（１）中のＲ^１がアセトキシ基（ＣＨ_３Ｃ（＝Ｏ）−Ｏ−））である［１］〜［６］のいずれかに記載の共重合体の製造方法。 That is, the present invention relates to the following methods for producing the copolymers [1] to [7].
[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 arylene group having 6 to 30 carbon atoms. Substituent or unsubstituted alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, substituted or unsubstituted imino group (-NH-), oxy group (-O-). ), or a substituted or unsubstituted silylene group (-SiH ₂ - is .R ⁵ representing a divalent group selected from) a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a halogen atom Substituted with a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A hydrocarbon group having 7 to 30 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, and a carbon atom number Represents a substituent selected from the group consisting of an aryloxy group of 6 to 30 and an acyloxy group having 2 to 10 carbon atoms. R ⁶ and R ⁷ independently represent an alkoxy group, an aryloxy group, a silyl group, and the like. It represents an amino group or 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, and R ⁶ and R ⁷ are bonded to each other. may also form a ring .L represents an electron-donating ligand, represented by R ⁵ and L are mAY ring formed .q is 0 / 2,1 or 2.) Using a metal complex as a catalyst, ethylene,
General formula (1)

(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. ~ 12 substituted or unsubstituted amide group, substituted or unsubstituted pyridyl group having 5 to 10 carbon atoms, substituted or unsubstituted pyrrolidyl group having 4 to 10 carbon atoms, substitution or substitution of 5 to 10 carbon atoms Unsubstituted piperidyl group, substituted or unsubstituted hydrofuryl group having 4 to 10 carbon atoms, substituted or unsubstituted imidazolyl group having 4 to 10 carbon atoms, mercapto group, alkylthio group having 1 to 10 carbon atoms, carbon An allyl monomer having a polar group represented by (representing a substituent selected from the group consisting of an arylthio group having 6 to 10 atoms, an epoxy group, and a halogen atom).
And general formula (2)

(In the formula, R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other.) The 2,5-norbornadiene-like compound shown,
The ratio of the number of moles of the allyl monomer having a polar group represented by the general formula (1) to the sum of the number of moles of ethylene and the allyl monomer having a polar group represented by the general formula (1) is 70 mol% or more. A method for producing a polar group-containing allyl monomer copolymer, which comprises copolymerizing as a copolymer.
[2]
The method for producing a copolymer according to [1], wherein the obtained copolymer is not gelled.
[3]
The method for producing a copolymer according to any one of [1] or [2], wherein Y in the general formula (C1) is a substituted or unsubstituted 1,2-phenylene group or a substituted or unsubstituted methylene group. ..
[4]
^{Described in any one of [1] to [3], wherein R 6} and R ⁷ in the general formula (C1) are both alkyl groups having 3 to 20 carbon atoms or cycloalkyl groups having 5 to 20 carbon atoms. Method for producing a copolymer of.
[5]
^{R 6} and R ⁷ in the general formula (C1) are selected from an isopropyl group, a t-butyl group, a 2-methyl-2-pentyl group, a 2,3,3-trimethyl-2-butyl group, or a menthyl group. The method for producing a copolymer according to any one of [1] to [4].
[6]
2,5-norbornadiene analogous compound represented by the general formula (2) is, is unsubstituted 2,5-norbornadiene (general formula ^(R 2 in 2), ^{R 3,} and ^{R 4} both are hydrogen atom) The method for producing a copolymer according to any one of [1] to [5].
[7]
Allyl monomers allyl acetate having a polar group represented by the general formula (1) ^{(R 1} in the formula (1) is an acetoxy group _{(CH 3 C (= O)} -O-)) [1] ~ [ 6] The method for producing a copolymer according to any one of.

An allyl monomer copolymer having a polar group can be produced with high catalytic activity, and a low production cost can be realized.

[catalyst]
(Structure of metal complex)
The structure of the catalyst composed of the Group 10 metal complex of the periodic table used in one embodiment 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 arylene group having 6 to 30 carbon atoms and carbon. Substituent or unsubstituted alkylene group having 1 to 20 atoms, substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, substituted or unsubstituted imino group (-NH-), oxy group (-O-) , Or a divalent group selected from substituted or unsubstituted silylene groups (-SiH _2-). R ⁵ is a hydrogen atom, a halogen atom, substituted with a hydrocarbon group, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with a halogen atom, an alkoxy group having 1 to 10 carbon atoms having 1 to 30 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 acyloxy group having 2 to 10 carbon atoms. Represents. Each of R ⁶ and R ⁷ may be 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 R ⁶ and R ⁷ may be bonded to form a ring structure. L represents an electron donor ligand, R ⁵ and L may be ring formation. 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 arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, or a substituent. Alternatively, it represents a divalent group selected from an unsubstituted imino group (-NH-), an oxy group (-O-), or a substituted or unsubstituted silylene group (-SiH _2-).

Examples of the unsubstituted arylene group having 6 to 30 carbon atoms include 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 1,8-naphthylene group and the like, and raw materials are obtained. 1,2-Phenylene group and 1,2-naphthylene group are preferable because of the ease of the above and the ease of catalyst synthesis.

One or more substituents may be present in the above-mentioned unsubstituted arylene group. Substituents include an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxyphenyl group having 7 to 10 carbon atoms, a naphthyl group, an anthracenyl group, and 1 to 1 carbon atoms. A alkoxy group, an aryloxy group, a substituted or unsubstituted amino group, a silyl group, a halogen atom, and a fluoroalkyl group of 4 are preferable. Specific examples of the substituent include methyl group, ethyl group, 1-propyl group, isopropyl group, 1-butyl group, isobutyl group, sec-butyl group, t-butyl group; phenyl group, 1-naphthyl group, 2-. Naftyl group, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl 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; methoxy group, ethoxy group, propoxy group , Isopropoxy group, butoxy group, isobutoxy group, sec-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 (sec-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 (sec-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, iodine 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.

As the unsubstituted alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms is preferable. Specific examples of the unsubstituted alkylene group having 1 to 20 carbon atoms include a methylene group, a 1,2-ethylene group, a dimethylmethylene group, a diethylmethylene group, a monomethylmethylene group, a monoethylmethylene group, and 1-methyl-1. , 2-ethylene group, 1-ethyl-1,2-ethylene group, 1,2-dimethyl-1,2-ethylene group, 1,2-diethyl-1,2-ethylene group, 1,1-dimethyl-1 , 2-ethylene group, 1,1-diethyl-1,2-ethylene group, 1,1,2-trimethyl-1,2-ethylene group, 1,1,2-triethyl-1,2-ethylene group, 1 , 1,2,2-tetramethyl-1,2-ethylene group, 1,1,2,2-tetraethyl-1,2-ethylene group and the like. A methylene group and an ethylene group are preferable from the viewpoint of easy availability of raw materials and easy catalyst synthesis.

One or more substituents may be present in the above-mentioned unsubstituted alkylene group. Examples of the substituent include an aryl group, an alkoxy group, an alkoxyphenyl group, an aryloxy group, a silyl group, an oxo group (= O) and the like.

Specific examples of the alkylene group having a substituent and having 1 to 20 carbon atoms include a diphenylmethylene group, a monophenylmethylene group, a mono (trimethylsilyl) methylene group, a di (trimethylsilyl) methylene group, and a 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, monophenoximethylene group, diphenoxymethylene group, 1,2-ethanedioxymethylene group, 1,3-Propanedioxymethylene group, 1-phenyl-1,2-ethylene group, 1,2-diphenyl-1,2-ethylene group, 1,1,2-triphenyl-1,2-ethylene group, Examples thereof include 1,1,2,2-tetraphenyl-1,2-ethylene group and carbonyl group (-C (= O)-).

Substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms include methylene groups, monomethylmethylene groups, dimethylmethylene groups, monophenylmethylene groups, and diphenylmethylene groups because of the ease of obtaining raw materials and synthesizing catalysts. Is preferable.

Examples of unsubstituted cycloalkylene groups having 3 to 30 carbon atoms are cis-cyclopropane-1,2-yl group, trans-cyclopropane-1,2-yl group, and cis-cyclobutane-1,2-yl group. Group, trans-cyclobutane-1,2-yl group, cis-cyclopentane-1,2-yl group, 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, cis-cyclooctane-1,2-yl group, trans-cyclooctane- Examples include 1,2-yl groups. 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, and trans -Cyclohexane-1,2-yl group is preferred.

One or more substituents may be present in the above-mentioned unsubstituted cycloalkylene group. The specific example of the substituent is the same as the above-mentioned specific example 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 from each other.

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

Specific examples of the substituted or unsubstituted imino group (-NH-) include an imino group, an N-methylimino group, an N-ethylimino group, an N- (n-propyl) imino group, an N-isopropylimino group, and an N- (n). -Butyl) imino group, N- (sec-butyl) imino group, N- (t-butyl) imino group, N-benzylimino group, N-phenylimino group, N-trimethylsilylimino group, N- (2-methoxy) Phenyl) 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- (2,4,6-trimethylphenyl) imino group, N- (1-naphthyl) imino group, N- (2-naphthyl) imino group, N- (t-butoxycarbonyl) ) Examples include imino groups.

From the viewpoint of ease of catalyst synthesis, an imino group, an N-methylimino group, an N-benzylimino group, and an N- (t-butoxycarbonyl) imino group are preferable.

As an example of a substituted or unsubstituted silylene group (-SiH _2- ), a silylene group, a dimethylsilylene group, a diethylsilylene group, a monomethylcyrylene group, a monoethylsilylene group, a diphenylcyrylene group, a monophenyltylylene group, a 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, 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 monophenylcilylene group, and a diphenylcilylene group are preferable.

Among these groups preferred as Y, a substituted or unsubstituted 1,2-phenylene group or a substituted or unsubstituted methylene group is particularly preferable.

R ⁵ is a hydrogen atom, a halogen atom, substituted with a hydrocarbon group, a hydrocarbon group having 1 to 30 carbon atoms which is substituted with a halogen atom, an alkoxy group having 1 to 10 carbon atoms having 1 to 30 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 acyloxy 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, chlorine is preferred.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ⁵ is preferably a hydrocarbon group having 1 to 20 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. , T-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group, isopropyl group, 1,1-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, Cyclo Propyl 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 Examples thereof include a group, a mentyl group, a neomentyl group, a neopentyl group, a 5-decyl group, a phenyl group, a naphthyl group, an anthrasenyl group, a fluorenyl group, a trill group, a xylyl group, a benzyl group and a 4-ethylphenyl group. Among these, a methyl group or a benzyl group is more preferable, and a methyl group is particularly preferable.

Hydrocarbon group having 1 to 30 carbon atoms which is substituted by halogen atoms contained in R ⁵ represents is preferably a substituted hydrocarbon group described above having 1 to 30 carbon atoms fluorine, chlorine or bromine radical, preferably Specific examples include a trifluoromethyl group and a pentafluorophenyl group.

Hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms which R ⁵ represents preferably above methoxy groups a hydrocarbon group having 1 to 30 carbon atoms, an ethoxy group, A group substituted with an isopropoxy group, a 1-propoxy group, a 1-butoxy group, or a t-butoxy group. More preferably, it is a hydrocarbon group having 2 to 6 carbon atoms substituted with a methoxy group or an ethoxy group. Specifically, 1- (methoxymethyl) ethyl group, 1- (ethoxymethyl) ethyl group, 1- (methoxyethyl) ethyl group, 1- (ethoxyethyl) ethyl group, di (methoxymethyl) methyl group, and Di (ethoxymethyl) methyl group is mentioned. Particularly preferred is a 1- (methoxymethyl) ethyl group or a 1- (ethoxymethyl) ethyl group.

Hydrocarbon group having 7 to 30 carbon atoms which is substituted with an aryloxy group having 6 to 20 carbon atoms contained in R ⁵ represents preferably a phenoxy group and a hydrocarbon group having 1 to 30 carbon atoms described above, 4 -A group substituted with a methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, or a 2,6-di-t-butylphenoxy group. A hydrocarbon group having 7 to 12 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. -Dimethylphenoxymethyl) 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-, where R is an organic group) is preferably described above.} It is a substituent in which a hydrocarbon group having 1 to 30 carbon atoms is substituted with an acetamide group, a propionylamino group, a butyrylamino group, an isobutylylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, or a benzoylamino group. .. A 2-acetamidophenyl group, a 2-propionylaminophenyl group, a 2-valerylaminophenyl group, or a 2-benzoylaminophenyl group is more preferable, and a 2-acetamidophenyl group is particularly preferable.

When R ⁵ is a hydrocarbon group substituted with an amide group, the carbonyl oxygen of the amide group coordinates with M to form a ring structure without using an electron-donating ligand L separately. Can be done. That is, R ⁵ can also serve as L. The case that R ⁵ and L are ring formation. 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 are a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group and 1 -Butoxy group and t-butoxy group. Among these, a methoxy group, an ethoxy group, or an isopropoxy group is more preferable, and a methoxy group is particularly preferable.

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 are a phenoxy group, a 4-methylphenoxy group, and a 4-methoxyphenoxy group. , 2,6-Dimethylphenoxy group, and 2,6-di-t-butylphenoxy group. Among these, a phenoxy group or a 2,6-dimethylphenoxy group is more preferable, and a phenoxy group is particularly preferable.

The acyloxy group having 2 to 10 carbon atoms represented by R ⁵ is preferably an acyloxy group having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy group. , Valeryloxy group, isovaleryloxy group, pivaloyloxy group, and benzoyloxy group. Among these, an acetoxy group, a propionyloxy group, or a benzoyloxy group is more preferable, and an acetoxy group or a propionyloxy group is particularly preferable.

Among the preferred groups as these R ^5, more preferably, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a carbon atom substituted with an amide group having 2 to 10 carbon atoms It is a hydrocarbon group having a number of 3 to 30 or an acyloxy group having 2 to 10 carbon atoms, and is particularly preferably a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group, or an acetoxy group.

Each of R ⁶ and R ⁷ may be 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 is preferably one having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

As the ^{aryloxy group represented by R 6} and R ⁷ , those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group.

Examples of the silyl group represented by R ⁶ and R ⁷ include a trimethyl silyl group, a triethyl silyl group, a tri (n-propyl) silyl group, a tri (isopropyl) silyl group and the like, and examples of the amino group include an amino group, a monomethyl amino group and a dimethyl group. Examples thereof include an amino group, a monoethylamino group and a diethylamino group.

The hydrocarbon group in 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 is an alkyl group.} Examples thereof include (including a chain alkyl group, a cycloalkyl group, and a bridging cycloalkyl group) and an aryl group (phenyl group, naphthyl group, etc.), and an alkyl group having 3 to 20 carbon atoms is preferable. A fluorine atom is preferable as the halogen atom as a substituent. The alkoxy group and the aryloxy group as the substituent are preferably the same as the alkoxy group and the aryloxy group represented by ^{R 6} and R ^{7, respectively.}

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, n-heptyl 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, 2-methyl-2-butyl group, 2-methyl-2-pentyl group, 2-methyl-3-pentyl group, 2,3,3-trimethyl-2-butyl group , Cyclopropyl group, Cyclobutyl group, Cyclopentyl group, Cyclohexyl group, Cycloheptyl group, Cyclooctyl group, 1-adamantyl group, 2-adamantyl group, Mentyl group (mentyl group, neomentyl group, isomentyl group, neoisomentyl group is menthyl) Groups are collectively referred to as groups.), Trifluoromethyl group, benzyl group, 2'-methoxybenzyl group, 3'-methoxybenzyl group, 4'-methoxybenzyl group, 4'-trifluoromethylbenzyl group, 9-fluorenyl group. , 2,7-dimethyl-9-fluorenyl group, 2,7-diethyl-9-fluorenyl group, 2,7-di-n-propyl-9-fluorenyl group, 2,7-diisopropyl-9-fluorenyl group, 2, , 7-di-n-butyl-9-fluorenyl group, 2,7-diisobutyl-9-fluorenyl group, 2,7-di-sec-butyl-9-fluorenyl group, 2,7-di-t-butyl- 9-Fluorenyl 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 -Trimethoxyfe Nyl group, 4-fluorophenyl group, pentafluorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis (trifluoromethyl) phenyl group, 1-naphthyl group, 2-naphthyl group, 2-furyl group, Examples thereof include 2-biphenyl group, 2', 6'-dimethoxy-2-biphenyl group, 2'-methyl-2-biphenyl group, 2', 4', 6'-triisopropyl-2-biphenyl group and the like.

From the viewpoint of catalytic activity and the molecular weight of the obtained copolymer, ^{both R 6} and R ⁷ are preferably an alkyl group having 3 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, preferably an isopropyl group. , T-Butyl group, 4-Heptyl group, 2,6-dimethyl-4-Heptyl group, 2-Methyl-2-butyl group, 2-Methyl-2-pentyl group, 2,3,3-trimethyl-2- Butyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group or menthyl group are more preferable, and isopropyl group, t-butyl group, 2-methyl-2-pentyl group, 2,3,3-trimethyl- It is particularly preferable that it is a 2-butyl group or a menthyl group. R ⁶ and R ⁷ may be the same or different. R ⁶ and R ⁷ may be combined to form a ring structure.

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. As described above, when R ⁵ is a hydrocarbon group substituted with amide groups can be carbonyl oxygen of the amide group to form a ring structure coordinated to M. That is, R ⁵ also serves as L, and L forms a ring with ^{R 5.}

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, 2,6-dimethylpyridine (2,6-lutidine), Aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N, N, N', N'-tetramethylethylenediamine (TMEDA), 4- (N, N-dimethylamino) pyridine (DMAP), acetonitrile, Examples thereof include benzonitrile, quinoline and 2-methylquinoline. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and the like. From the standpoint of stability and catalytic activity of the metal complex, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (2,6-lutidine), and N, N, N', N'-tetramethylethylenediamine (TMEDA). ) Is preferred, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (2,6-lutidine) are more preferred.

q is 0, 1/2, 1 or 2.

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.

[Manufacturing method of metal complex]
The metal complex 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, a 0-valent or divalent M source is reacted with the ligand in the general formula (C1).

As for the 0-valent M source, tris (dibenzylideneacetone) dipalladium can be mentioned as a palladium source, and tetracarbonyl nickel (0): Ni (CO) ₄ and bis (1,5-cycloocta) can be mentioned as nickel sources. Dien) Nickel is mentioned.

For the divalent M source, as the palladium source, (1,5-cyclooctadiene) (methyl) palladium chloride, palladium chloride, palladium acetate, bis (nitrile) 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), and palladium trifluoromethanesulfonate (II). ): Pd (OSO ₂ CF ₃ ) _{2 and} examples of the nickel source include (allyl) nickel chloride, (allyl) brominated nickel, nickel chloride, nickel acetate, bis (acetylacetonato) nickel (II): Ni ( Acac) ₂ , (1,2-dimethoxyethane) dichloronickel (II): NiCl ₂ (DME), and 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 that the metal source containing 0-valent M is reacted with the ligand and then subjected to the polymerization as it is without isolating the complex.

The ratio ((C1 ligand) / M) of the M source (M) and the ligand (C1 ligand) in the general formula (C1) is in the range of 0.5 to 2.0 on a molar basis. It is preferable to select it, and it is more preferable to select it in the range of 1.0 to 1.5.

The metal complex represented by the general formula (C1) can also be supported on a carrier and used for polymerization. The carrier is not particularly limited, and examples thereof include an inorganic carrier such as silica gel and alumina, and an organic carrier 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 copolymer of one embodiment, the allyl monomer having a polar group to be copolymerized with ethylene is a 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. Asyloxy group with 2 to 10 carbon atoms, amino group, substituted amino group with 1 to 12 carbon atoms, substituted or unsubstituted amide group with 2 to 12 carbon atoms, substituted or unsubstituted group with 5 to 10 carbon atoms Pyridyl group, substituted or unsubstituted pyrrolidyl group having 4 to 10 carbon atoms, substituted or unsubstituted piperidyl group having 5 to 10 carbon atoms, substituted or unsubstituted hydrofuryl group having 4 to 10 carbon atoms, carbon Substitution selected from the group consisting of a substituted or unsubstituted imidazolyl group having 4 to 10 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. Represents a group.

^{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. , 1-butoxy group, and t-butoxy group. Among these, a methoxy group, an ethoxy group, or an isopropoxy group is more preferable, and a methoxy group is particularly preferable.

^{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 4-methoxy. Examples thereof include a phenoxy group, a 2,6-dimethylphenoxy group, a 3,5-di-t-butylphenoxy group, and a 2,6-di-t-butylphenoxy group. Among these, a phenoxy group, a 3,5-di-t-butylphenoxy group, or a 2,6-dimethylphenoxy group is more preferable, and a phenoxy group or a 3,5-di-t is particularly preferable. -Butyl phenoxy 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, and benzoyl group. Among these, an acetyl group, a pivaloyl group, or a benzoyl group is more preferable, and a benzoyl group is particularly preferable.

^{R 1} , which is an ester group having 2 to 10 carbon atoms (oxycarbonyl group; RO- (C = O)-, R is an organic group), is preferably an ester group having 2 to 8 carbon atoms. Preferred specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, a (4-hydroxybutoxy) carbonyl group, and (4-hydroxybutoxy). A glycidyl butoxy) carbonyl group and a phenoxycarbonyl group can be mentioned. Among these, a methoxycarbonyl group, an ethoxycarbonyl group, or a (4-hydroxybutoxy) carbonyl group is more preferable, and a methoxycarbonyl group is particularly preferable.

^{R 1} , which is an acyloxy group having 2 to 10 carbon atoms, is preferably an acyloxy group having 2 to 8 carbon atoms, and preferred specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, and an isobutyryloxy. Examples include a group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, a benzoyloxy group, and a trifluoroacetoxy group. Among these, an acetoxy group, a propionyloxy group, a benzoyloxy group, or a trifluoroacetoxy group is more preferable, and an acetoxy group or a propionyloxy group is particularly preferable.

^{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, and morpholinyl group. Among these, a dimethylamino group or a diphenylamino group is more preferable.

^{Preferred specific examples of R 1} , which is a substituted or unsubstituted amide group having 2 to 12 carbon atoms (R- (C = O) NH-, R is an organic group), are an acetamide group, a propionylamino group, and a butyrylamino group. , Isobutyrylamino group, Valerylamino group, Isovalerylamino group, Pivaloylamino group, and Benzoylamino group. Among these, an acetamide group, a propionylamino group, or a benzoylamino group is more preferable, and an acetamide group is particularly preferable.

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

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

^{Preferred specific examples of R 1} , which is a substituted or unsubstituted piperidyl group having 5 to 10 carbon atoms, are 2-piperidyl group, 3-piperidyl group, and 2- (1,2,3,6-tetrahydro) pyridyl group. , 2- (1-Methyl) piperidyl group, 2- (1-ethyl) piperidyl group, 2- (4-methyl) piperidyl group, 2- (5-methyl) piperidyl group, and 2- (6-methyl) piperidyl The group is mentioned. Among these, a 2-piperidyl group, a 3-piperidyl group, a 2- (1,2,3,6-tetrahydro) pyridyl group, or a 2- (6-methyl) piperidyl group is more preferable, and a 2- (6-methyl) piperidyl group is particularly preferable. Is a 2-piperidyl group or a 2- (1,2,3,6-tetrahydro) pyridyl group. The "piperidyl group" of the present disclosure also includes those having a non-aromatic unsaturated bond, for example, a 2- (1,2,3,6-tetrahydro) pyridyl group.

^{Preferred specific examples of R 1} , which is a substituted or unsubstituted 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, and 2- (4,5-) Benzo) Tetrahydrofuryl group is mentioned. Among these, more preferably, a 2-tetrahydrofuryl group, a 3-tetrahydrofuryl group, a 2- (5-methyl) tetrahydrofuryl group, a 2- (5-isopropyl) tetrahydrofuryl group, or a 2- (4,5) group. -Benzo) tetrahydrofuryl group, particularly preferably 2-tetrahydrofuryl group, 2- (5-methyl) tetrahydrofuryl group, or 2- (5-isopropyl) tetrahydrofuryl group.

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

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

^{Preferred specific examples of R 1} which is a halogen atom include fluorine, chlorine, and bromine. Of these, chlorine or bromine is more preferred.

Among these ^{preferable groups as R 1} , a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, or a halogen atom are more preferable. Yes, more preferably an acyloxy group having 2 to 10 carbon atoms. Specific examples of the allyl monomer having a preferable polar group represented by the general formula (1) include allyl acetate, allyl tolfluoroacetate, allyl benzoate, allyl alcohol, allyl methyl ether, allyl bromide, allyl chloride and the like. ^{, Allyl acetate (R 1} in the general formula (1) is an acetoxy group (CH ₃ C (= O) -O-)) is particularly preferable.

In the method for producing a copolymer of one embodiment, two or more kinds of allyl monomers having a polar group represented by the general formula (1) to be copolymerized with ethylene may be polymerized in combination.

（式中、Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立して、水素原子又は炭素原子数１〜３のアルキル基を表し、それぞれ同じであっても、異なっていてもよい。）
で示される２，５−ノルボルナジエン類似化合物を共重合させることを特徴とする。 In the method for producing a copolymer of one embodiment, in addition to ethylene and an allyl monomer having a polar group represented by the general formula (1), the general formula (2) is used.

(In the formula, R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other.)
It is characterized by copolymerizing a 2,5-norbornadiene analog compound represented by.

Examples of the alkyl group having 1 to 3 carbon atoms of R ² , R ³ and R ⁴ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is preferable. R ² , R ³ and R ⁴ are more preferably hydrogen atoms or methyl groups, and even more preferably all hydrogen atoms.

Preferred specific examples of the 2,5-norbornadiene-like compound represented by the general formula (2) include 2,5-norbornadiene, 7-methyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, and the like. 1-Methylnorbornadiene and 1,4-dimethylnorbornadiene are mentioned, and 2,5-norbornadiene is particularly preferable.

The above 2,5-norbornadiene analogs may be used alone or in combination of two or more.

In olefin polymerization of ethylene or the like using a metal complex (C1) as a catalyst, the polymer grows due to repeated coordination and insertion of the monomer into the metal, and the polymer dissociates from the catalyst by a chain transfer reaction. It is generally known that the chain transfer reaction in the polymerization using the Group 10 metal complex of the periodic table proceeds by the mechanism represented by the following formula (in the formula, R'represents the polymer chain of the metal M. The ligand is omitted.). In the following formula, a polymerization example using ethylene as a monomer is described, but the same applies to other olefin monomers. In the complex species produced by inserting ethylene into the MR'complex species, β-hydride desorption proceeds, and at the same time _{, the polymer (CH 2 = CH-R'in the formula) dissociates from the catalyst.} , Hydride complex species (MH in the formula) are generated and the growth reaction is stopped. Since this hydride complex species has extremely high reactivity, the coordination / insertion reaction of the monomer proceeds immediately and the repolymerization starts.

On the other hand, in the polymerization of an allyl monomer having a polar group represented by allyl acetate, the polymer growth reaction proceeds by repeating the coordination and insertion of the monomer to the metal as in the above formula, but the chain transfer reaction It has become clear that the mechanism is different. The mechanism of the polymer growth reaction and the chain transfer reaction in the polymerization of the allyl monomer having a polar group is shown in the following formula (in the formula, R'represents the polymer chain and Ac represents the CH ₃ C (= O) -group. .). In the following formula, an example of polymerization in which allyl acetate is used as a monomer and 2,5-norbornadiene coexists is described, but other allyl monomers having a polar group represented by the general formula (1) and The same applies to the 2,5-norbornadiene-like compound represented by the general formula (2).

When allyl acetate is incorporated into the polymer, the coordination of allyl acetate to the metal M and the insertion reaction into the M-R'bond occur, as in ethylene. Then, the polymer grows by coordinating and inserting a monomer such as ethylene or allyl acetate to the produced complex species. On the other hand, β-acetoxy desorption proceeds with a certain probability in competition with the coordination / insertion of the next monomer for the complex species produced by inserting allyl acetate into the MR'complex species. As a result, the polymer (CH ₂ = CH-CH ₂ -R'in the formula) is dissociated from the catalyst, and an acetoxy complex species (M-OAc in the formula) is produced. Since this acetoxy complex species has much lower reactivity than the hydride complex species, the rate-determining initiation of repolymerization by the coordination / insertion reaction of the monomer to the acetoxy complex species is the rate-determining factor. Since this acetoxy complex species is a dormant species in the reaction system, the catalyst exhibiting the catalytic activity is substantially a part of the charged amount, and the polymer productivity per catalyst is lowered.

In the method for producing a copolymer of one embodiment, a 2,5-norbornadiene-like compound is allowed to coexist in a polymerization system, so that an acetoxy complex species, which is a dormant species, is reacted with a 2,5-norbornadiene-like compound to make an alkyl. It is rapidly converted to a complex species (MR "in the formula). Since this alkyl complex species has the same reactivity with the monomer as the above-mentioned MR'complex species, the coordination / insertion reaction of the monomer This allows the polymer productivity per catalyst to be significantly improved, leading to a reduction in the cost of the catalyst.

In the copolymerization, the total charge amount of the 2,5-norbornadiene analog compound represented by the general formula (2) is 1.0 to 1 mol with respect to the total charge amount of 1 mol of the allyl monomer having a polar group represented by the general formula (1). It is preferably 25.0 mmol.

In the method for producing a copolymer of one embodiment, in addition to ethylene, an allyl monomer having a polar group represented by the general formula (1), and a 2,5-norbornadiene analog represented by the general formula (2), a fourth. You may use the monomer of. As the fourth monomer, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-norbornene, 1-decene and styrene. Cyclic olefins such as norbornene, cyclopentene and cyclohexene; olefins having polar groups such as acrylic acid ester, methacrylic acid ester, vinyl acetate, vinyl ether, acrylonitrile and achlorine can be mentioned. These may be polymerized by combining two or more kinds. However, when the α-olefin is copolymerized as the fourth monomer, the ratio of the α-olefin to the total amount of the α-olefin and ethylene contained in the obtained polymer is less than 40 mol%. The content of the fourth monomer contained in the copolymer is preferably less than 5 mol%.

[Polymerization method]
Using the metal complex represented by the general formula (C1) as a catalyst, ethylene, an allyl monomer having a polar group represented by the general formula (1), and a 2,5-norbornadiene-like compound represented by the general formula (2). The method for copolymerizing the above is not particularly limited, and the copolymer 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, and a solution polymerization method and a suspension polymerization method are particularly preferable. The polymerization mode can be either a batch mode or a continuous mode. The copolymerization can be carried out by either one-stage polymerization or multi-stage 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, it is possible to control the molecular weight, molecular weight distribution, or the content of the monomer unit derived from the monomer of the general formula (1), and a polymer suitable for a desired application can be obtained. be able to. The molar ratio of the total amount of the metal complex catalyst to the total amount of the monomer is in the range of 1 to 10,000,000, preferably in the range of 10 to 1,000,000, more preferably 100 to 100, in terms of the monomer / metal complex ratio. A range of 000 is used.

In the method for producing a copolymer of one embodiment, as described above, for the catalytic dormant species produced after the allyl monomer having a polar group represented by the general formula (1) is incorporated into the MR'complex species. , The 2,5-norbornadiene-like compound represented by the general formula (2) reacts to reactivate the catalyst, thereby improving the catalytic activity. This effect of improving the catalytic activity is a polymerization condition in which the allyl monomer having a polar group represented by the general formula (1) is incorporated into the MR'complex species to some extent, that is, the allyl monomer having a polar group represented by the general formula (1). It can be said that the larger the amount of the charged material, the more prominent the polymerization conditions.

Here, the ratio of the number of moles of the allyl monomer having a polar group represented by the general formula (1) to the sum of the number of moles of ethylene and the allyl monomer having a polar group represented by the general formula (1) is ". When referred to as "allyl monomer charging ratio", the "allyl monomer charging ratio" can be expressed by the following formula.
Allyl monomer charging ratio (mol%) = {number of moles of allyl monomer charged having a polar group represented by the general formula (1) × 100} / {number of moles of ethylene charging + polarity represented by the general formula (1) Number of moles of allyl monomer having a group}

From the viewpoint of the effect of improving the catalytic activity, the preferable range of the allyl monomer charging ratio is 70 mol% or more and less than 100 mol%, the more preferable range is 75 mol% or more and 98 mol% or less, and the particularly preferable range is 80 mol%. More than 95 mol% or less.

The allyl monomer charging ratio is calculated based on the total charging amount when the polymerization reaction is a batch type or a piston flow type continuous type, and is calculated based on the average concentration in the polymerization tank when the polymerization reaction is a continuous tank type.

The polymerization temperature is not particularly limited, but is usually 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 in the range of 100 MPa from the normal pressure, preferably in the range of 20 MPa from the normal pressure, and more preferably in the range of 10 MPa from the normal pressure.

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

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, in order to prevent the activity of the catalyst from decreasing. In the case of solution polymerization, it is possible to use an inert solvent other than the monomer. The inert solvent is not particularly limited, but is an aliphatic hydrocarbon such as isobutane, pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; chloroform, methylene chloride, carbon tetrachloride, dichloroethane, and the like. Halogened aliphatic hydrocarbons such as tetrachloroethane; Halogenized aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene; Aromatic esters such as methyl acetate and ethyl acetate; Fragrant esters such as methyl benzoate and ethyl benzoate And so on.

The 2,5-norbornadiene analog compound to be coexistent may be incorporated as a monomer into the obtained copolymer, or may be a cross-linking point for linking the polymers. The content of the 2,5-norbornadiene analog compound contained in the copolymer is preferably less than 3 mol%. When the 2,5-norbornadiene analog compound links the copolymer as a cross-linking point, it is preferable that the obtained copolymer is not gelled. The presence or absence of gelation is determined by whether the copolymer is completely dissolved or the insoluble component remains when the copolymer is mixed with a good solvent. Specifically, the method described in the examples is used. The molecular weight of the copolymer is particularly preferably 1,000,000 or less in terms of weight average molecular weight Mw.

In the method for producing the copolymer of one embodiment, there is no particular limitation on the method for adding the 2,5-norbornadiene analog represented by the general formula (2), and even if it is dissolved in the reaction solvent before the reaction, it may be dissolved. It may be added after the reaction is started. Examples of the method for adding the 2,5-norbornadiene analog include a method of adding all at once at the start of the reaction, an intermittent feed method in which the compound is added over a predetermined reaction time after the start of the reaction, and a continuous feed method in which the compounds are continuously added. Be done. From the viewpoint of improving catalytic activity, productivity and suppressing gelation, 2,5-norbornadiene analogs are added in small portions or continuously during the reaction time rather than being added all at once at the start of the reaction. Is preferable.

The amount of the 2,5-norbornadiene analog compound used is not particularly limited, and the optimum amount is determined by the reactivity of the catalyst used and the 2,5-norbornadiene analog compound. The molar ratio of the amount of the metal complex catalyst to the total amount of the 2,5-norbornadiene-like compound added is the molar ratio of the 2,5-norbornadiene-like compound / metal complex, preferably in the range of 1 to 2000, more preferably 50 to 1000. , More preferably in the range of 100 to 500. Specifically, when 2,5-norbornadiene analogs are collectively added to the reaction system at the initial stage of polymerization, the molar ratio of the amount of the metal complex catalyst to the total amount of the 2,5-norbornadiene analogs added is 2. The ratio of the 5-norbornadiene analog / metal complex is preferably in the range of 10 to 1500, more preferably in the range of 30 to 1000, and more preferably in the range of 50 to 300. In the case of the intermittent feed method or the continuous feed method, the molar ratio of the amount of the metal complex catalyst to the total amount of the 2,5-norbornadiene-like compound added is the ratio of the 2,5-norbornadiene-like compound / metal complex, preferably 1. It is in the range of ~ 2000, more preferably in the range of 50 to 1000, and particularly preferably in the range of 100 to 500.

When the 2,5-norbornadiene analog compound is added to the reaction system, the 2,5-norbornadiene analog compound may be added alone or dissolved in an organic solvent. When the solvent is dissolved in an organic solvent and added, the solvent used in the polymerization reaction is preferable as the organic solvent to be dissolved. When the allyl monomer having a polar group to be copolymerized with ethylene is liquid at room temperature, a 2,5-norbornadiene-like compound may be added by dissolving it in the allyl monomer.

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

The average molecular weight and the monomer unit content of the polymer were measured, analyzed and calculated by the following methods.
[Average molecular weight]
The number average molecular weight and weight average molecular weight of the copolymers obtained in Examples and Comparative Examples were obtained by HLC-, a high-temperature GPC apparatus manufactured by Tosoh Corporation equipped with an AT-806MS column (two in series) manufactured by Showa Denko Corporation. It was calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C.) using polystyrene as a standard substance of molecular weight using 8121 GPC / HT.

[Monomer unit content]
The content of the monomer unit derived from the olefin having a polar group represented by the general formula (1) and the 2,5-norbornadiene-like compound is 1,1 as a solvent using JNM-ECS400 manufactured by JEOL Ltd. , 2,2-Tetrachloroethane-d2 ^{was determined by 1} H-NMR at 120 ° C.

[Presence / absence of gelation of copolymer]
The presence or absence of gelation of the obtained copolymer was confirmed by the following method. Toluene (5 mL) and a copolymer (0.2 g) were added to an eggplant flask containing a stirrer, and the mixture was stirred at 25 ° C. and then heated to 50 ° C. in an oil bath and stirred. When the copolymer was completely dissolved, it was regarded as no gelation, and when there was an undissolved residue, it was considered as gelation.

Synthesis Example 1: Synthesis of Metal Complex 1 The metal complex 1 was synthesized according to the following reaction scheme using the method described in JP-A-2014-159540.

(A) Synthesis of Mentil Chloride (Compound 1a) Mentil Chloride (Compound 1a) was synthesized by the method described in the literature (J. Org. Chem., 17, 1116. (1952)). Specifically, (-)-menthol (27 g, 0.17 mol) was added to a 37 mass% hydrochloric acid (52 mL, 0.63 mol) solution of zinc chloride (77 g, 0.56 mol), and the mixture was heated to 35 ° C. The mixture was stirred for 5 hours. After cooling to room temperature, hexane (50 mL) was added to the reaction solution, and the organic layer and the aqueous layer were separated using a separating funnel. The organic layer was washed with water (30 mL × 1 time) and then with concentrated sulfuric acid (10 mL × 5 times) and water (30 mL × 5 times). The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure to give mentyl chloride (Compound 1a) as a colorless oily substance. The yield was 27 g (yield 91%).

(B) Synthesis of Dimentylphosphine Chloride (Compound 1c) Dimentylphosphine chloride (Compound 1c) was synthesized by the method described in the literature (Journal fur Praktische Chemie, 322, 485 (1980)). Specifically, in an atmosphere of argon gas, menthyl chloride (Compound 1a; 2.6 g, 15 mmol) and magnesium (0.63 g, 26 mmol) are reacted in tetrahydrofuran (THF) (30 mL) while heating at 70 ° C. The resulting solution of menthyl magnesium chloride (Compound 1b) was added to a solution of phosphorus trichloride (0.63 mL, 7.2 mmol) in THF (30 mL) at −78 ° C. After raising the temperature to room temperature, the mixture was stirred for 2 hours while heating at 70 ° C. After distilling off the solvent under reduced pressure, distillation purification was carried out to obtain dimentylphosphine chloride (Compound 1c). The yield was 0.62 g (yield 25%).

³¹ P-NMR (162 MHz, THF): δ 123.9.

(C) Synthesis of 2- (dimentylphosphonio) benzenesulfonate (Compound 1d) n-Butyllithium (1.6M hexane solution) in THF solution (10mL) of benzenesulfonic acid (0.18g, 1.2 mmol) , 1.4 mL, 2.3 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 1 hour. After cooling the reaction vessel to −78 ° C., dimentylphosphine chloride (Compound 1c; 0.36 g, 1.1 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 15 hours. After stopping the reaction by adding trifluoroacetic acid (0.97 mL, 1.3 mmol), the solvent was distilled off under reduced pressure. The residue was dissolved in dichloromethane and washed with saturated aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give 2- (dimentylphosphonio) benzenesulfonate (Compound 1d) as a white powder. The yield was 0.31 g (yield 63%).

^{1 1} H-NMR (500 MHz, CDCl ₃ ): δ 8.27 (br s, 1H), 7.77 (t, J = 7.3 Hz, 1H), 7.59-7.52 (m, 2H), 3.54 (br s, 1H), 2.76 (br s, 1H), 2.16 (br s, 1H), 1.86-1.38 (m, 12H), 1.22-0.84 (m, 22H), 0.27 (br s, 1H);
³¹ P { ¹ H} -NMR (162 MHz, CDCl ₃ ): δ 45.1 (br), -4.2 (br).

(D) Synthesis of metal complex 1 Under an argon atmosphere, 2- (dimentylphosphonio) benzenesulfonate (Compound 1d; 0.14 g, 0.30 mmol) and N, N-diisopropylethylamine (0.26 mL, 1.5 mmol) ) In a methylene chloride solution (10 mL) according to (cod) PdMeCl (literature (Inorg. Chem., 1993, 32, 5769-5778), cod = 1,5-cyclooctadien, 0.079 g, 0.30 mmol). ) Was added, and the mixture was stirred at room temperature for 1 hour. After concentrating the solution, the residue was dissolved in methylene chloride (10 mL) and the solution was mixed with potassium carbonate (0.42 g, 3.0 mmol) and 2,6-lutidine (0.35 mL, 3.0 mmol) methylene chloride. It was added to the suspension (2 mL) and stirred at room temperature for 1 hour. This reaction solution was filtered through cerite (dried diatomaceous earth) and fluorosyl (magnesium silicate), the solvent was concentrated, and the mixture was dried under reduced pressure to obtain a metal complex 1. The yield was 0.17 g (yield 80%).

¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.26 (ddd, J = 7.8, 3.9, 1.4 Hz, 1H), 7.81 (t, J = 7.9 Hz, 1H), 7.56 (t, J = 7.7 Hz, 1H) ), 7.49 (t, J = 7.6 Hz, 1H), 7.43 (t, J = 7.4 Hz, 1H), 7.13 (d, J = 7.8 Hz, 1H), 7.08 (d, J = 7.6 Hz, 1H), 3.75 (s, 1H), 3.24 (s, 3H), 3.17 (s, 3H), 2.59 (s, 1H), 2.49-2.39 (m, 2H), 2.29-2.27 (m, 1H), 2.05-1.96 ( m, 1H), 1.89-1.37 (m, 12H), 1.21-1.11 (m, 2H), 0.98 (d, J = 6.6 Hz, 3H), 0.95 (d, J = 6.2 Hz, 3H), 0.84 (d) , J = 6.6 Hz, 3H), 0.78 (d, J = 6.6 Hz, 3H), 0.58 (d, J = 6.6 Hz, 3H), 0.41 (d, J = 2.3 Hz, 3H), 0.08 (d, J) = 6.6 Hz, 3H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 16.6.

Synthesis Example 2: Synthesis of Metal Complex 2 The metal complex 2 was synthesized according to the following reaction scheme using the method described in JP-A-2011-68881.

(A) Synthesis of 2- (diisopropylphosphonio) benzenesulfonate (Compound 2a) n-Butyllithium (1.6M hexane solution, 174mL, 174mL) was added to a THF solution (400mL) of benzenesulfonic acid (21.7g, 137 mmol). 274 mmol) was added at 0 ° C. and the mixture was stirred at room temperature for 3 hours. After cooling the reaction vessel to −78 ° C., diisopropylphosphine chloride (19.0 g, 125 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 15 hours. The reaction was stopped by adding trifluoroacetic acid (15.6 g, 137 mmol), and then the solvent was distilled off under reduced pressure. The residue was dissolved in dichloromethane and washed with saturated aqueous ammonium chloride solution. The organic layer was dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give 2- (diisopropylphosphonio) benzenesulfonate (Compound 2a) as a white powder. The yield was 26.8 g (yield 78%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 1.25 (dd, J = 21.6, 7.0 Hz, 6H), 1.53 (dd, J = 21.8, 7.2 Hz, 6H), 3.45 (m, 2H), 5.42 (br d, ¹ J _PH = 380 Hz), 7.58 (tdd, J = 7.6, 2.8, 1.1 Hz, 1H), 7.69 (ddd, J = 15.1, 7.7, 0.7 Hz, 1H), 7.83 (dd, J = 7.6, 7.6 Hz, 1H), 8.27 (dd, J = 7.5, 4.4 Hz, 1H);
¹³ C-NMR (101 _{MHz, CDCl 3} ): δ 19.4 (s), 24.5-27.7 (m), 114.4 (br d, J = 93 Hz), 129.1 (d, J = 8.6 Hz), 130.3 (d, J) = 12.5 Hz), 134.7-137.1 (m), 150.7 (br s);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 62.5 (d, ¹ J _PH = 380 Hz) (83%), 31.0 (d, ¹ J _PH = 460 Hz) (17%).

(B) Synthesis of Metal Complex 2 A methylene chloride solution of 2- (diisopropylphosphonio) benzenesulfonate (Compound 2a; 16.3 g, 59 mmol) and N, N-diisopropylethylamine (38.3 g, 296 mmol) under an argon atmosphere. To (500 mL), add (cod) PdMeCl (synthesized according to the literature (Inorg. Chem., 1993, 32, 5769-5778), cod = 1,5-cyclooctadien, 16.3 g, 62 mmol) and add 2 at room temperature. . Stirred for 5 hours. After concentrating the solution, the residue was dissolved in methylene chloride (200 mL) and the solution was mixed with a suspension of potassium carbonate (80.8 g, 585 mmol) and 2,6-lutidine (62.7 g, 585 mmol) in methylene chloride (62.7 g, 585 mmol). It was added to 500 mL) and stirred at room temperature for 1 hour. This reaction solution was filtered through cerite (dried diatomaceous earth) and floridil (magnesium silicate), the solvent was concentrated, and the mixture was dried under reduced pressure. Further, recrystallization purification from methylene chloride / hexane was performed to obtain the metal complex 2 as white crystals. The yield was 18.9 g (yield 61%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 0.34 (d, J = 2.3 Hz, 3H), 1.32 (ddd, J = 49.9, 16.0, 7.0 Hz, 12H), 2.58 (dt, J = 22.3, 7.2 Hz) , 2H), 3.18 (s, 6H), 7.12 (d, J = 7.8 Hz, 2H), 7.46 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.58 (t) , J = 7.7 Hz, 2H), 8.29-8.32 (m, 1H);
¹³ C-NMR (101 _{MHz, CDCl 3} ): δ -10.10 (d, J = 4.8 Hz), 18.44 (s), 19.29 (d, J = 4.8 Hz), 25.91 (d, J = 25.9 Hz), 26.20 ( s), 122.72 (d, J = 3.8 Hz), 124.56 (d, J = 35.5 Hz), 129.19 (t, J = 6.7 Hz), 131.03 (d, J = 1.9 Hz), 132.39 (s), 138.30 (s) s), 151.13 (d, J = 10.5 Hz), 159.17 (s);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 34.4 (s).

Synthesis Example 3: Synthesis of metal complex 3 The metal complex 3 was synthesized according to the following reaction scheme.

(A) Synthesis of isopropyl methanesulfonate (Compound 3b) 2-propanol (10.5 g, 174.6 mmol, 1) in a dichloromethane solution (50 mL) of methanesulfonic acid chloride (Compound 3a; 20.0 g, 174.6 mmol). A dichloromethane solution (50 mL) of .0 eq) and triethylamine (44.2 g, 436.5 mmol, 2.5 eq) was slowly added at 0 ° C. and stirred at 25 ° C. for 16 hours. The reaction mixture was filtered, and the recovered filtrate was concentrated, then dissolved again in dichloromethane (50 mL), and washed with 1 M hydrochloric acid (20 mL), saturated aqueous sodium hydrogen carbonate solution (20 mL), and saturated brine (20 mL). The target product (Compound 3b) was obtained as a yellow oil by dehydrating with anhydrous sodium sulfate, filtering, and then concentrating. The yield was 20.2 g (yield 84%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 4.91 (m, 1H), 3.04 (s, 3H), 1.39 (s, 3H), 1.38 (s, 3H).

(B) Synthesis of isopropyl dit-butylphosphanylmethanesulfonate (Compound 3c) n-butyllithium (2.) In a tetrahydrofuran solution (100 mL) of isopropyl methanesulfonate (Compound 3b; 6.0 g, 43.4 mmol). 5M hexane solution, 45.6 mmol, 1.1eq) was added at 0 ° C. and stirred at 0 ° C. for 1 hour. After cooling the reaction vessel to −78 ° C., dit-butylphosphine chloride (7.8 g, 43.4 mmol, 1.0 eq) was added at −78 ° C., and the mixture was stirred at room temperature for 16 hours. After distilling off the solvent under reduced pressure, the residue was purified by silica gel chromatography (pentane / ethyl acetate = 20/1) and washed with pentane (5 mL × 2 times) to obtain the desired product (compound 3c) as a white powder. .. The yield was 3.6 g (yield 29%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 5.00 (m, 1H), 3.26 (br, 2H), 1.41 (d, J = 6.4 Hz, 6H), 1.19 (d, J = 12.0 Hz, 18H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 18.4.

(C) Synthesis of isopropyl dit-butyl (thio) phosphinomethanesulfonate (Compound 3d) A solution of isopropyl dit-butylphosphanylmethanesulfonate (Compound 3c; 3.58 g, 12.68 mmol) in THF (tetrachloride). To (40 mL), sulfur (2.5 M hexane solution, 2.03 g, 63.39 mmol, 5 eq) was added at −78 ° C., stirred at 25 ° C. for 16 hours, and further stirred at 60 ° C. for 2 hours. The reaction mixture was filtered, the filtration residue was washed with ethyl acetate (20 mL), all the solutions were recovered, and the solvent was distilled off under reduced pressure. Pentane (10 mL) was added, the mixture was filtered, and the mixture was dried under reduced pressure to obtain the desired product (Compound 3d) as a white powder. The yield was 3.5 g (yield 88%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 5.16 (m, 1H), 3.80 (br, 2H), 1.46 (d, J = 6.4 Hz, 6H), 1.43 (d, J = 12.0 Hz, 18H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 74.5.

(D) Synthesis of dit-butyl (thio) phosphinomethanesulfonic acid (Compound 3e) Methanol (40 mL) of dit-butyl (thio) isopropyl phosphinomethanesulfonic acid (Compound 1d; 5.5 g, 16.62 mmol) ), THF (20 mL) and water (5 mL) were added with sodium hydroxide (2.66 g, 66.47 mmol, 4 eq) and stirred at 66 ° C. for 16 hours. After distilling off the solvent from this reaction solution and concentrating it, it was washed with ethyl acetate (20 mL), and the obtained white powder was suspended in a mixed solution of ethanol (100 mL) and dichloromethane (50 mL) to make HCl / ethyl acetate. It was neutralized to pH = 5. The neutralized solution was filtered, the filtrate was concentrated and then dissolved in dichloromethane, the insoluble material was removed by filtration, and the solvent was distilled off under reduced pressure to obtain the target product (Compound 3e) as a pale yellow powder. The yield was 4.2 g (yield 93%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 6.28 (br, 1H), 3.75 (d, J = 6.4 Hz, 2H), 1.41 (d, J = 16.8 Hz, 18H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 72.2.

(E) Synthesis of dit-butylphosphanylmethanesulfonic acid (Compound 3f) dit-butyl in a THF solution (100 mL) of RANEY®-Ni (4.5 g, 52.5 mmol, 6.8 eq). (Thio) A THF solution (40 mL) of phosphinomethanesulfonic acid (Compound 3e; 2.1 g, 7.71 mmol, 1 eq) was slowly added using a syringe and stirred at room temperature for 16 hours. Dichloromethane (80 mL) was added to this reaction solution, the mixture was filtered, and the solvent was distilled off under reduced pressure. The reaction product was suspended in dichloromethane (200 mL), the insoluble material was removed by filtration, and the solvent was distilled off under reduced pressure to obtain the desired product (Compound 3f) as a pink powder. The yield was 0.8 g (yield 44%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 4.88 (br, 1H), 3.06 (d, J = 3.2 Hz, 2H), 1.17 (d, J = 11.2 Hz, 18H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 19.1.

(F) Synthesis of Metal Complex 3 Under a nitrogen atmosphere, dit-butylphosphanylmethanesulfonic acid (Compound 3f; 0.95 g, 3.96 mmol) and N, N-diisopropylethylamine (3.5 mL, 19.8 mmol) (Cod) PdMeCl (cod = 1,5-cyclooctadiene, 1.05 g, 3.96 mmol) was added to a methylene chloride solution (30 mL), and the mixture was stirred at room temperature for 1 hour. After concentrating the solution, the residue is dissolved in dichloromethane (15 mL) and the solution is suspended in dichloromethane with potassium carbonate (5.47 g, 39.6 mmol) and 2,6-lutidine (4.61 mL, 39.8 mmol). The mixture was added to the solution (10 mL) and stirred at room temperature for 1 hour. This reaction solution was filtered through cerite (dried diatomaceous earth) and floridil (magnesium silicate), the solvent was concentrated, and the mixture was dried under reduced pressure. The metal complex 3 was obtained by washing with hexane (15 mL × 3 times). The yield was 1.2 g (yield 63%).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.57 (t, J = 7.8 Hz, 1H), 7.11 (d, J = 7.8 Hz, 2H), 3.44 (d, J = 8.2 Hz, 2H), 3.06 ( s, 6H), 1.49 (d, J = 14.6 Hz, 18H), 0.54 (d, J = 1.9 Hz, 3H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 46.5.

金属錯体３合成用中間体３ｃの原料である塩化ジｔ−ブチルホスフィンを塩化ジ（２−メチル−２−ペンチル）ホスフィン（同モル数）に変えた以外は、金属錯体３の合成スキームの（ａ）〜（ｆ）と同様の方法で、金属錯体４を合成した。 Synthesis Example 4: Synthesis of metal complex 4

Except for changing dit-butylphosphine chloride, which is the raw material of the intermediate 3c for synthesizing the metal complex 3, to di (2-methyl-2-pentyl) phosphine chloride (same number of moles), the (same number of moles) of the synthesis scheme of the metal complex 3 The metal complex 4 was synthesized by the same method as in a) to (f).

^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.57 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 8.0 Hz, 2H), 3.48 (d, J = 7.6 Hz, 2H), 3.07 ( s, 6H), 1.95-1.85 (m, 4H), 1.55-1.45 (m, 16H), 0.98 (t, J = 7.2 Hz, 6H), 0.53 (d, J = 2.0 Hz, 3H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 50.9.

金属錯体３合成用中間体３ｃの原料である塩化ジｔ−ブチルホスフィンを塩化ｔ−ブチル（２，３，３−トリメチル−２−ブチル）ホスフィン（同モル数）に変えた以外は、金属錯体３の合成スキームの（ａ）〜（ｆ）と同様の方法で、金属錯体５を合成した。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ 7.57 (t, J = 7.7 Hz, 1H), 7.12 (d, J = 7.7 Hz, 2H), 3.66 (dd, J = 15.2, 8.0 Hz, 1H), 3.38 (dd, J = 15.2, 9.2 Hz, 1H), 3.14(s, 3H), 3.03(s, 3H), 1.59 (d, J = 14.0 Hz, 9H), 1.55-1.30(m, 6H) , 1.40 (s, 9H) , 0.58(s, 3H)；
^３１Ｐ−ＮＭＲ（１６２ＭＨｚ，ＣＤＣｌ_３）：δ 34.4。 Synthesis Example 5: Synthesis of metal complex 5

Metal complex 3 Metal complex except that di-t-butylphosphine chloride, which is the raw material of intermediate 3c for synthesis, was changed to t-butyl chloride (2,3,3-trimethyl-2-butyl) phosphine (same number of moles). The metal complex 5 was synthesized by the same method as in (a) to (f) of the synthesis scheme of 3.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ 7.57 (t, J = 7.7 Hz, 1H), 7.12 (d, J = 7.7 Hz, 2H), 3.66 (dd, J = 15.2, 8.0 Hz, 1H), 3.38 (dd, J = 15.2, 9.2 Hz, 1H), 3.14 (s, 3H), 3.03 (s, 3H), 1.59 (d, J = 14.0 Hz, 9H), 1.55-1.30 (m, 6H), 1.40 (s, 9H), 0.58 (s, 3H);
³¹ P-NMR (162 MHz, CDCl ₃ ): δ 34.4.

[Synthesis of polymer]
A copolymerization reaction of allyl acetate and ethylene was carried out using each metal complex produced in the synthetic example. Productivity and catalytic activity were calculated by the following formulas.

Example 1: Copolymerization of allyl acetate and ethylene in the coexistence of 2,5-norbornadiene using metal complex 1 (preparation of polymer 1)
Under a nitrogen gas atmosphere, allyl acetate (150 mL, 1,390 mmol) as the monomer represented by the general formula (1) and 2,5-norbornadiene (184. A 500 mL autoclave containing 3 mg, 2.0 mmol) was filled with ethylene (0.51 MPa) with stirring at 65 ° C. An allyl acetate solution (30 mL) of metal complex 1 (13.9 mg, 0.020 mmol) was added to the autoclave by pressure feeding, and the mixture was stirred for 24 hours. The allyl monomer charging ratio at this time is calculated to be 95 mol%. After cooling to room temperature and depressurizing ethylene, the reaction solution in the autoclave was added to methanol (500 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 1.32 g. The productivity was calculated to be 66 g / mmol and the catalytic activity was calculated to be 2.8 g / (mmol · h). The number average molecular weight of the polymer 1 was 31,000, the weight average molecular weight was 65,000, and Mw / Mn was 2.1. Regarding the content of allyl acetate and 2,5-norbornadiene in the copolymer, the molar ratio of ethylene: allyl acetate: 2,5-norbornadiene is 100: 24.7: 0.11 (mole fraction of allyl acetate = 19.8). %, 2,5-Norbornadiene mole fraction = 0.09%). Polymer 1 was completely dissolved in toluene and did not gel.

Comparative Example 1: Copolymerization of Allyl Acetate and Ethylene Using Metal Complex 1 (Preparation of Comparative Polymer 1)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 1 except that 2,5-norbornadiene was not added.

Comparative Example 2: Copolymerization of Allyl Acetate and Ethylene in the Coexistence of 2-Norbornene Using Metal Complex 1 (Preparation of Comparative Polymer 2)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 1 except that 2-norbornene (188.3 mg, 2.0 mmol) was added instead of 2,5-norbornadiene.

The polymerization conditions and results of Examples 1 and Comparative Examples 1 and 2 are shown in Tables 1 and 2, respectively.

From Example 1 and Comparative Example 1, it was found that the coexistence of 2,5-norbornadiene improved the catalytic activity. Further, in Comparative Example 2, although an attempt was made to add 2-norbornene having a skeleton similar to 2,5-norbornadiene, no improvement in catalytic activity was observed. At this time, no incorporation of 2-norbornene into the polymer was also observed.

Example 2: Copolymerization of allyl acetate and ethylene in the coexistence of 2,5-norbornadiene using the metal complex 2 (preparation of polymer 2)
Under a nitrogen gas atmosphere, allyl acetate (120 mL, 1,112 mmol) as the monomer represented by the general formula (1) and 2,5-norbornadiene (110. Norbornadiene) as the 2,5-norbornadiene-like compound represented by the general formula (2). A 500 mL autoclave containing 6 mg, 1.2 mmol) was filled with ethylene (0.79 MPa) with stirring at 65 ° C. A solution of allyl acetate (allyl acetate: 30 mL) of metal complex 2 (10.0 mg, 0.020 mmol) was added to the autoclave by pumping, and the mixture was stirred for 24 hours. The allyl monomer charging ratio at this time is calculated to be 92.5 mol%. During this 24 hour, a feed pump was used to additionally feed 2,5-norbornadiene into the reaction at a rate of 0.25 mmol / h (23.2 mg / h). After cooling to room temperature and depressurizing ethylene, the reaction solution in the autoclave was added to methanol (500 mL) to precipitate a copolymer. The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain polymer 2. The yield was 3.86 g. The productivity was calculated to be 193 g / mmol and the catalytic activity was calculated to be 8.0 g / (mmol · h). The number average molecular weight of the polymer 2 was 6100, the weight average molecular weight was 33000, and Mw / Mn was 5.5. Regarding the content of allyl acetate and 2,5-norbornadiene in the copolymer, the molar ratio of ethylene: allyl acetate: 2,5-norbornadiene is 100: 19.9: 6.3 (mole fraction of allyl acetate = 15.8). %, 2,5-Norbornadiene mole fraction = 5.00%). Polymer 2 was completely dissolved in toluene and did not gel.

Comparative Example 3: Copolymerization of Allyl Acetate and Ethylene Using Metal Complex 2 (Preparation of Comparative Polymer 3)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 2 except that 2,5-norbornadiene was not added.

Comparative Example 4: Copolymerization of Allyl Acetate and Ethylene in the Coexistence of 2,5-Norbornadiene Using Metal Complex 2 (Preparation of Comparative Polymer 4)
Copolymerization of allyl acetate and ethylene was carried out using the metal complex 2 in the presence of 2,5-norbornadiene under the condition that the allyl monomer charging ratio was low. Metal complex 2 (25.1 mg, 0.050 mmol), allyl acetate (75 mL, 700 mmol), and 2,5-norbornadiene (25.1 mg, 0.050 mmol), and 2,5-norbornadiene (25.1 mg, 0.050 mmol), and 2,5-norbornadiene (25.1 mg, 0.050 mmol), and 2,5-norbornadiene (75 mL, 700 mmol) under a nitrogen gas atmosphere, according to the polymerization conditions described in Examples of JP2013-079347A. A 120 mL autoclave containing 46.1 mg, 0.50 mmol) was filled with ethylene (4.0 MPa) with stirring at 80 ° C. Then, stirring was performed for 5 hours while maintaining 80 ° C. The allyl monomer charging ratio at this time is calculated to be 67.0 mol%. After cooling to room temperature and depressurizing ethylene, the reaction solution in the autoclave was added to methanol (500 mL) to precipitate a copolymer. The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain a comparative polymer 4. The yield was 5.10 g. The productivity was calculated to be 102 g / mmol and the catalytic activity was calculated to be 20.0 g / (mmol · h). The number average molecular weight of the polymer 2 was 11,000, the weight average molecular weight was 37,000, and Mw / Mn was 3.4. Regarding the content of allyl acetate and 2,5-norbornadiene in the copolymer, the molar ratio of ethylene: allyl acetate: 2,5-norbornadiene is 100: 4.3: 0.28 (mole fraction of allyl acetate = 4.1). %, 2,5-Norbornadiene mole fraction = 0.27%). The comparative polymer 4 was not completely dissolved in toluene, and it was determined that there was gelation.

Comparative Example 5: Copolymerization of Allyl Acetate and Ethylene Using Metal Complex 2 (Preparation of Comparative Polymer 5)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Comparative Example 4 except that 2,5-norbornadiene was not added.

The polymerization conditions and results of Example 2 and Comparative Examples 3 to 5 are shown in Tables 3 and 4, respectively.

From Example 2 and Comparative Example 3, even when the metal complex 2 was used as a catalyst, the effect of improving the catalytic activity by coexistence of 2,5-norbornadiene was observed. Further, from Comparative Examples 4 and 5, it was found that under the condition that the allyl monomer charging ratio was low, the effect of improving the catalytic activity by the coexistence of 2,5-norbornadiene was hardly observed, and the polymer gelled.

Examples 3-5: Copolymerization of allyl acetate and ethylene in the presence of 2,5-norbornadiene using metal complexes 3-5 (preparation of polymers 3-5)
Allyl acetate and ethylene were used in the same manner as in Example 2 except that the ethylene pressure, the allyl monomer charging ratio, the amount of 2,5-norbornadiene added, and the reaction temperature were changed using the metal complexes 3 to 5. Was copolymerized.

Comparative Examples 6 to 8: Copolymerization of allyl acetate and ethylene using metal complexes 3 to 5 (preparation of comparative polymers 6 to 8)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Examples 3 to 5 except that 2,5-norbornadiene was not added.

The polymerization conditions and results of Examples 3 to 5 and Comparative Examples 6 to 8 are shown in Tables 5 and 6, respectively.

From the comparison of Example 3 and Comparative Example 6, Example 4 and Comparative Example 7, and Example 5 and Comparative Example 8, even when the metal complexes 3 to 5 are used as catalysts, the catalytic activity is improved by the coexistence of 2,5-norbornadiene. The effect of was seen. Furthermore, it was found that when the metal complex 3 or the metal complex 4 was used, the molecular weight of the obtained polymer increased. Moreover, the solubility of the obtained polymer in toluene was good, and gelation was not observed.

Examples 6-7: Copolymerization of allyl acetate and ethylene in the coexistence of 2,5-norbornadiene using the metal complex 3 (preparation of polymers 6-7)
Described in Example 2 except that the metal complex 3 was used and the amount of the metal complex 3 used (only in Example 7), the ethylene pressure, the allyl monomer charging ratio, the amount of 2,5-norbornadiene added, and the reaction temperature were changed. The copolymerization of allyl acetate and ethylene was carried out in the same manner as in the above method.

Comparative Example 9: Copolymerization of Allyl Acetate and Ethylene Using Metal Complex 3 (Preparation of Comparative Polymer 9)
Copolymerization of allyl acetate and ethylene was carried out in the same manner as in Examples 6 to 7 except that 2,5-norbornadiene was not added.

The polymerization conditions and results of Examples 6 to 7 and Comparative Example 9 are shown in Tables 7 and 8, respectively.

From the comparison between Examples 6 to 7 and Comparative Example 9, it was found that the effect of improving the catalytic activity can be seen even when the reaction temperature is raised.

From the results of the above Examples and Comparative Examples, in the method for producing a copolymer of ethylene and an allyl monomer having a polar group, a catalyst is produced by allowing a diene compound, a 2,5-norbornadiene-like compound, to coexist in the reaction system. Succeeded in accelerating the copolymerization of ethylene and improving productivity and catalytic activity. This makes it possible to reduce the production cost of the polymer, and it can be said that the present invention is industrially useful.

Claims (7)

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 arylene group having 6 to 30 carbon atoms. Substituent or unsubstituted alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 30 carbon atoms, substituted or unsubstituted imino group (-NH-), oxy group (-O-). ), or a substituted or unsubstituted silylene group (-SiH ₂ - is .R ⁵ representing a divalent group selected from) a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a halogen atom Substituted with a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. A hydrocarbon group having 7 to 30 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, and a carbon atom number Represents a substituent selected from the group consisting of an aryloxy group of 6 to 30 and an acyloxy group having 2 to 10 carbon atoms. R ⁶ and R ⁷ independently represent an alkoxy group, an aryloxy group, a silyl group, and the like. It represents an amino group or 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, and R ⁶ and R ⁷ are bonded to each other. may also form a ring .L represents an electron-donating ligand, represented by R ⁵ and L are mAY ring formed .q is 0 / 2,1 or 2.) Using a metal complex as a catalyst, ethylene,
General formula (1)

(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. ~ 12 substituted or unsubstituted amide group, substituted or unsubstituted pyridyl group having 5 to 10 carbon atoms, substituted or unsubstituted pyrrolidyl group having 4 to 10 carbon atoms, substitution or substitution of 5 to 10 carbon atoms Unsubstituted piperidyl group, substituted or unsubstituted hydrofuryl group having 4 to 10 carbon atoms, substituted or unsubstituted imidazolyl group having 4 to 10 carbon atoms, mercapto group, alkylthio group having 1 to 10 carbon atoms, carbon An allyl monomer having a polar group represented by (representing a substituent selected from the group consisting of an arylthio group having 6 to 10 atoms, an epoxy group, and a halogen atom).
And general formula (2)

(In the formula, R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other.) The 2,5-norbornadiene-like compound shown,
The ratio of the number of moles of the allyl monomer having a polar group represented by the general formula (1) to the sum of the number of moles of ethylene and the allyl monomer having a polar group represented by the general formula (1) is 70 mol% or more. A method for producing a polar group-containing allyl monomer copolymer, which comprises copolymerizing as a copolymer. The method for producing a copolymer according to claim 1, wherein the obtained copolymer is not gelled. The method for producing a copolymer according to claim 1 or 2, wherein Y in the general formula (C1) is a substituted or unsubstituted 1,2-phenylene group or a substituted or unsubstituted methylene group. ^{The invention according to any one of claims 1 to 3, wherein R 6} and R ⁷ in the general formula (C1) are both an alkyl group having 3 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. Method for producing a copolymer of. ^{R 6} and R ⁷ in the general formula (C1) are selected from an isopropyl group, a t-butyl group, a 2-methyl-2-pentyl group, a 2,3,3-trimethyl-2-butyl group, or a menthyl group. The method for producing a copolymer according to any one of claims 1 to 4. 2,5-norbornadiene analogous compound represented by the general formula (2) is, is unsubstituted 2,5-norbornadiene (general formula ^(R 2 in 2), ^{R 3,} and ^{R 4} both are hydrogen atom) The method for producing a copolymer according to any one of claims 1 to 5. Claims 1 to 6 in which the allyl monomer having a polar group represented by the general formula (1) is allyl acetate (R ¹ in the general formula (1) is an acetoxy group (CH ₃ C (= O) -O-)). The method for producing a copolymer according to any one of the above.