Olefin Polymerization Catalyst and Method for Producing Olefin Polymer

Abstract

Provided are a catalyst, which enables the production of a high molecular weight olefin polymer having a polar group and being usable for various applications at a high catalytic activity, and a method for producing such an olefin polymer. Use is made of, as a polymerization catalyst for an olefin having a polar group, a metal complex represented by general formula (C1) [wherein: M represents an element in group 10 of the periodic table; X represents a phosphorus atom (P) or arsenic atom (As); R5 to R11 are as described in claims; at least one of R6 and R7 is an aralkyl group represented by general formula (2) (wherein R12 to R21 are as described in claims); L represents an electron-donating ligand; and q is 0, 1 / 2, 1 or 2].

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization, an olefin polymer, and a method for producing a polar group-containing monomer polymer such as an allyl compound having a polar group.

Background Art

[0002] Copolymers of olefins such as ethylene and propylene, which are non-polar monomers, and vinyl monomers having a polar group have functions and properties not found in non-polar polyethylene and polypropylene, and are used in a wide range of fields. In particular, ethylene-vinyl alcohol copolymer (EVOH) is a copolymer composed of ethylene monomer structural units and vinyl alcohol monomer structural units, and is produced by saponifying an ethylene-vinyl acetate copolymer obtained by radical copolymerization of ethylene and vinyl acetate. EVOH is used in a wide range of fields such as food packaging applications, taking advantage of its excellent gas barrier properties.

[0003] On the other hand, the polymerization of monomers having an allyl group is more difficult than that of ordinary vinyl monomers, and the polymers thereof are hardly known. The main reason is that when a monomer having an allyl group is radical polymerized, due to the degenerative chain transfer reaction to the monomer by hydrogen atom abstraction on the allylic carbon, the growth reaction of the polymer is extremely slow, and only oligomers with a low degree of polymerization can be obtained (Chem. Rev. 58, 808 (1958); Non-Patent Document 1).

[0004] JP 2011-68881 A (US Patent No. 8,916,663; Patent Document 1), JP 2014-159540 A (US Patent No. 9,499,644; Patent Document 2), JP 2015-137282 A (Patent Document 3), WO 2019 / 093364 (Patent Document 4), WO 2020 / 175482 (Patent Document 5), and J. Am. Chem. Soc., 133, 1232 (2011) (Non-Patent Document 2) disclose the coordination copolymerization of ethylene and allyl monomers containing polar groups using a Group 10 metal complex catalyst, and have succeeded in synthesizing allyl monomer copolymers containing polar groups that could not be obtained by radical polymerization methods. Regarding the resulting copolymers, it is desirable that the weight average molecular weight (Mw) be tens of thousands or more from the viewpoints of film formability, transparency, etc., and that the polar group content in the polymer be high. However, in conventional production methods, the catalytic activity is insufficient under the conditions for producing a polymer having the above weight average molecular weight and high polar group content, and problems remain for industrialization from the viewpoints of catalyst cost and the like.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Documents

[0006]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a catalyst and a method capable of producing a high molecular weight olefin polymer having a polar group applicable to various applications with high catalytic activity.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors used a novel Group 10 metal complex of the periodic table as a catalyst to copolymerize a vinyl monomer (non-polar olefin) such as ethylene or propylene alone or the non-polar olefin and an olefin containing a polar group (including an allyl monomer having a polar group), and found that a high molecular weight olefin polymer having a polar group applicable to various applications can be produced with high catalytic activity, thus completing the present invention.

[0009] That is, the present invention relates to an olefin polymerization catalyst of the following [1] to [6] and a method for producing a (co)polymer of ethylene of [7] to

[13] . [1] General formula (C1)

Chemical formula

[10] R in the general formula (2) 12 and R 13 and R 14 and R15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 wherein each of R, R, R, R, R, R, and R is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, according to any one of [7] to [9].

[11] R in general formula (2) 13 , R 14 , R 15 , R 18 , R 19 and R 20 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R, R, R, and R are hydrogen atoms, according to any one of [7] to

[10] . 12 , R 16 , R 17 and R 21 are hydrogen atoms, according to any one of [7] to

[10] .

[12] The aralkyl group represented by general formula (2) is a diphenylmethyl group, a bis(3,5-dimethylphenyl)methyl group, or a bis(3,5-dimethoxyphenyl)methyl group, according to any one of [7] to

[11] .

[13] R in general formula (C1) 8 , R 9 , R 10 and R 11 are all hydrogen atoms, according to any one of [7] to

[12] . [Advantages of the Invention]

[0010] According to the present invention, there are provided a catalyst and a method capable of producing a high molecular weight olefin polymer having a polar group applicable to various applications with high catalytic activity. For example, by copolymerizing a nonpolar olefin (ethylene) with an olefin having a polar group such as an allyl monomer having a polar group using the olefin polymerization catalyst of the present invention, a high molecular weight olefin polymer having a polar group applicable to various applications can be produced at low cost. [Brief Description of the Drawings]

[0011]

Figure 1

Mode for Carrying Out the Invention

[0012] [Catalyst] The catalyst comprising a Group 10 metal complex of the periodic table used in the present invention is represented by the general formula (C1).

Chemical formula

[0013] In the formula, M represents an element of Group 10 of the periodic table, and X represents a phosphorus atom (P) or an arsenic atom (As). R 5 represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amido group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R 6 and R 7 each independently represent a hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from an alkoxy group, an aryloxy group, a silyl group, an amino group, or a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group, and at least one of R 6 and R 7 is represented by the general formula (2)

Chemical formula

[0014] In this specification, "hydrocarbon" includes saturated and unsaturated aliphatic hydrocarbons and aromatic hydrocarbons.

[0015] Hereinafter, the structure of the general formula (C1) will be described.

[0016] M represents an element of Group 10 of the periodic table. Examples of the element of Group 10 of the periodic table include Ni, Pd, and Pt. From the viewpoints of catalytic activity and the molecular weight of the resulting polymer, Ni and Pd are preferred, and Pd is more preferred.

[0017] X is a phosphorus atom (P) or an arsenic atom (As) and is coordinated to the central metal M with two electrons. From the viewpoints of availability and catalyst cost, a phosphorus atom (P) is preferred as X.

[0018] R 5 represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms.

[0019] R 5 Preferred specific examples of the halogen atom represented by

[0020] R 5The hydrocarbon group having 1 to 30 carbon atoms represented by is preferably a hydrocarbon group having 1 to 13 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms. As the hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group are preferable, and an alkyl group and an aralkyl group are more preferable. Preferable specific examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, t-butyl group, tricyclohexylmethyl group, 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, cycloheptyl group, cyclooctyl group, cyclododecyl group, 1-adamantyl group, 2-adamantyl group, exo-norbornyl group, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, nopinyl group, decahydronaphthyl group, menthyl group, neomenthyl group, neopentyl group, 5-decyl group, phenyl group, naphthyl group, anthracenyl group, fluorenyl group, tolyl group, xylyl group, benzyl group, and p-ethylphenyl group. Among these, a methyl group and a benzyl group are more preferable, and a methyl group is particularly preferable.

[0021] R 5 The hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with fluorine, chlorine, or bromine. Preferable specific examples include a trifluoromethyl group and a pentafluorophenyl group.

[0022] R 5The hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with a methoxy group, an ethoxy group, 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. Specific examples include a 1-(methoxymethyl)ethyl group, a 1-(ethoxymethyl)ethyl group, a 1-(phenoxymethyl)ethyl group, a 1-(methoxyethyl)ethyl group, a 1-(ethoxyethyl)ethyl group, a di(methoxymethyl)methyl group, a di(ethoxymethyl)methyl group, and a di(phenoxymethyl)methyl group. Particularly preferred are a 1-(methoxymethyl)ethyl group and a 1-(ethoxymethyl)ethyl group.

[0023] R 5 The hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, or a 2,6-di-t-butylphenoxy group. More preferably, it is a hydrocarbon group having 1 to 6 carbon atoms substituted with a phenoxy group or a 2,6-dimethylphenoxy group, and particularly preferably, it is a 1-(phenoxymethyl)ethyl group and a 1-(2,6-dimethylphenoxymethyl)ethyl group.

[0024] R 5 The hydrocarbon group having 3 to 30 carbon atoms substituted with an amido group (R-(C=O)NH-, R is an organic group) having 2 to 10 carbon atoms represented by is preferably a substituent obtained by substituting the aforementioned hydrocarbon group having 1 to 30 carbon atoms with an acetamido group, a propionylamino group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, or a benzoylamino group. More preferably, they are a 2-acetamidophenyl group, a 2-propionylaminophenyl group, a 2-valerylaminophenyl group, and a 2-benzoylaminophenyl group, and particularly preferably, it is a 2-acetamidophenyl group.

[0025] R 5 The alkoxy group having 1 to 30 carbon atoms represented by R is preferably an alkoxy group having 1 to 6 carbon atoms. Preferred specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a 1-propoxy group, a 1-butoxy group, and a t-butoxy group. Among these, more preferably, a methoxy group, an ethoxy group, and an isopropoxy group, and particularly preferably a methoxy group.

[0026] R 5 The aryloxy group having 6 to 30 carbon atoms represented by R is preferably an aryloxy group having 6 to 12 carbon atoms. Preferred specific examples include a phenoxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethylphenoxy group, and a 2,6-di-t-butylphenoxy group. Among these, more preferably a phenoxy group and a 2,6-dimethylphenoxy group, and particularly preferably a phenoxy group.

[0027] R 5 The acyloxy group having 2 to 10 carbon atoms represented by R is preferably an acyloxy group having 2 to 8 carbon atoms. Preferred specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, and a benzoyloxy group. Among these, more preferably an acetyloxy group, a propionyloxy group, and a benzoyloxy group, and particularly preferably an acetyloxy group and a propionyloxy group.

[0028] These Rs 5Among the preferred groups, more preferably, they are a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms, and most preferably, a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred specific examples include a methyl group, a benzyl group, a methoxy group, a 2-acetamidophenyl group, and an acetyloxy group.

[0029] R 6 and R 7 each independently represents a hydrocarbon group having 1 to 180 carbon atoms which may be 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, and at least one of R 6 and R 7 is an aralkyl group represented by the general formula (2)

[0030]

Chemical formula

[0031] R 6 and R 7 Examples of the alkoxy group represented by R and R include those having 1 to 20 carbon atoms, and preferably include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.

[0032] R 6 and R 7 Examples of the aryloxy group represented by R and R preferably include those having 6 to 24 carbon atoms, and preferably include a phenoxy group.

[0033] R 6 and R 7 Examples of the silyl group represented by R and R include a trimethylsilyl group. Examples of the amino group include an amino group, a methylamino group, and a dimethylamino group.

[0034] R 6 and R 7 The hydrocarbon group having 1 to 180 carbon atoms, which may be substituted with one or more groups selected from a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group represented by R and R, has a halogen atom that is a fluorine atom, a chlorine atom, or a bromine atom, and preferably a fluorine atom. The alkoxy group preferably has 1 to 20 carbon atoms, and preferably includes a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The aryloxy group preferably has 6 to 24 carbon atoms, and preferably includes a phenoxy group. Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a benzoyloxy group. The number of carbon atoms of the substituents is also included in the number of carbon atoms of the hydrocarbon group having 1 to 180 carbon atoms. The hydrocarbon group is not particularly limited, but at least one is a group represented by the following general formula (2).

[0035] Specific examples of the hydrocarbon group having 1 to 180 carbon atoms which may be substituted with one or more groups selected from a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group and an acyloxy group other than the group represented by the general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a neopentyl group, an n-hexyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-methyl-4-heptyl group, a 2,6-dimethyl-4-heptyl group, a 3-methyl-4-heptyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a 1-adamantyl group, a trifluoromethyl group, a benzyl group, a 2'-methoxybenzyl group, a 3'-methoxybenzyl group, a 4'-methoxybenzyl group, a 4'-trifluoromethylbenzyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, a 2,6-diisopropylphenyl group, a 3,5-diisopropylphenyl group, a 2,4,6-triisopropylphenyl group, a 2-t-butylphenyl group, a 2-cyclohexylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,4,6-trimethoxyphenyl group, a 4-fluorophenyl group, a pentafluorophenyl group, a 4-trifluoromethylphenyl group, a 3,5-bis(trifluoromethyl)phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-furyl group, a 2-biphenyl group, a 2',6'-dimethoxy-2-biphenyl group, a 2'-methyl-2-biphenyl group, and a 2',4',6'-triisopropyl-2-biphenyl group.

[0036] R 6 and R 7 may be the same or different.

[0037] R 6 and R 7 At least one of them is an aralkyl group represented by the general formula (2)

Chemical Formula

[0038] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Specific examples of the halogen atom represented by are iodine atom, fluorine atom, bromine atom and chlorine atom, and fluorine atom and chlorine atom are particularly preferred.

[0039] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21The hydrocarbon group having 1 to 10 carbon atoms represented by is preferably an alkyl group or an aryl group. Preferred examples of the hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group, and particularly preferred are a methyl group, an isopropyl group, a t-butyl group, and a phenyl group.

[0040] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Preferred examples of the hydrocarbon group having 1 to 10 carbon atoms substituted with one or more halogen atoms represented by the formula (I) include the above-mentioned hydrocarbon groups having 1 to 10 carbon atoms substituted with one or more halogen atoms, and particularly preferred are a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, and a pentafluorophenyl group.

[0041] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21Preferred examples of the alkoxy group having 1 to 10 carbon atoms in the hydrocarbon group having 2 to 20 carbon atoms (including the number of carbon atoms of the alkoxy group) substituted with an alkoxy group having 1 to 10 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a 1-propoxy group, an isopropoxy group, a 1-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, and a pentyloxy group. Preferred examples of the hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms include the above-mentioned hydrocarbon groups having 1 to 10 carbon atoms substituted with these alkoxy groups, and particularly preferred are a methoxymethyl group, a 2-methoxyethyl group, an isopropoxymethyl group, a 2-isopropoxyethyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, and a 4-methoxyphenyl group.

[0042] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Among the hydrocarbon groups having 7 to 20 carbon atoms (including the number of carbon atoms of the aryloxy group) substituted with an aryloxy group having 6 to 10 carbon atoms represented by the formula (I), preferred examples of the aryloxy group having 6 to 10 carbon atoms include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group. Preferred examples of the hydrocarbon groups having 7 to 20 carbon atoms substituted with an aryloxy group having 6 to 10 carbon atoms include the above-mentioned hydrocarbon groups having 1 to 10 carbon atoms substituted with these aryloxy groups, and particularly preferred are a phenoxymethyl group, a 2-phenoxyethyl group, a 2-phenoxyphenyl group, a 3-phenoxyphenyl group, and a 4-phenoxyphenyl group.

[0043] R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R20 and R 21 Preferable examples of the alkoxy group having 1 to 10 carbon atoms represented by R include a methoxy group, an ethoxy group, a 1-propoxy group, an isopropoxy group, a 1-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, and a pentyloxy group, with a methoxy group and an isopropoxy group being particularly preferable.

[0044] R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 and R 21 Preferable examples of the aryloxy group having 6 to 10 carbon atoms represented by R include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group, with a phenoxy group being particularly preferable.

[0045] R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 and R 21 Preferable examples of the acyloxy group having 2 to 10 carbon atoms represented by R include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, and a benzoyloxy group, with an acetyloxy group, a propionyloxy group, and a benzoyloxy group being particularly preferable.

[0046] R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 and R 21is preferably, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. R 13 、R 14 、R 15 、R 18 、R 19 and R 20 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R 12 、R 16 、R 17 and R 21 are more preferably hydrogen atoms. The hydrocarbon group having 1 to 10 carbon atoms or the alkoxy group having 1 to 10 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and most preferably a methyl group, a t-butyl group, or a methoxy group.

[0047] In one embodiment, the aralkyl group represented by the general formula (2) has no bond between R 12 and R 17 、R 12 and R 21 、R 16 and R 17 、and R 16 and R 21 .

[0048] R 6 or R 7 When R 6 or R 7Specific examples thereof include a diphenylmethyl group, 2-methyldiphenylmethyl group, 3-methyldiphenylmethyl group, 4-methyldiphenylmethyl group, 2-ethyldiphenylmethyl group, 3-ethyldiphenylmethyl group, 4-ethyldiphenylmethyl group, 2-n-propyldiphenylmethyl group, 3-n-propyldiphenylmethyl group, 4-n-propyldiphenylmethyl group, 2-isopropyldiphenylmethyl group, 3-isopropyldiphenylmethyl group, 4-isopropyldiphenylmethyl group, 2-n-butyldiphenylmethyl group, 3-n-butyldiphenylmethyl group, 4-n-butyldiphenylmethyl group, 2-isobutyldiphenylmethyl group, 3-isobutyldiphenylmethyl group, 4-isobutyldiphenylmethyl group, 2-sec-butyldiphenylmethyl group, 3-sec-butyldiphenylmethyl group, 4-sec-butyldiphenylmethyl group, 2-t-butyldiphenylmethyl group, 3-t-butyldiphenylmethyl group, 4-t-butyldiphenylmethyl group, 2-methoxydiphenylmethyl group, 3-methoxydiphenylmethyl group, 4-methoxydiphenylmethyl group, 2-ethoxydiphenylmethyl group, 3-ethoxydiphenylmethyl group, 4-ethoxydiphenylmethyl group, 2-hydroxydiphenylmethyl group, 3-hydroxydiphenylmethyl group, 4-hydroxydiphenylmethyl group, 2-trifluoromethyldiphenylmethyl group, 3-trifluoromethyldiphenylmethyl group, 4-trifluoromethyldiphenylmethyl group, 2-fluorodiphenylmethyl group, 3-fluorodiphenylmethyl group, 4-fluorodiphenylmethyl group, 2-chlorodiphenylmethyl group, 3-chlorodiphenylmethyl group, 4-chlorodiphenylmethyl group, 2,3-dimethyldiphenylmethyl group, 2,4-dimethyldiphenylmethyl group, 2,5-dimethyldiphenylmethyl group, 2,3'-dimethyldiphenylmethyl group, 2,4'-dimethyldiphenylmethyl group, bis(2-methylphenyl)methyl group, 3,4-dimethyldiphenylmethyl group, 3,5-dimethyldiphenylmethyl group, bis(3-methylphenyl)methyl group, 3,4'-dimethyldiphenylmethyl group, bis(4-methylphenyl)methyl group, 2,3-diethyldiphenylmethyl group, 2,4-diethyldiphenylmethyl group, 2,5-diethyldiphenylmethyl group, 2,3'-diethyldiphenylmethyl group, 2,4'-diethyldiphenylmethyl group, bis(2-ethylphenyl)methyl group, 3,4-diethyldiphenylmethyl group, 3,5-diethyldiphenylmethyl group, bis(3-ethylphenyl)methyl group, 3,4'-diethyldiphenylmethyl group, bis(4-ethylphenyl)methyl group, 2,3-di-n-propyldiphenylmethyl group, 2,4-di-n-propyldiphenylmethyl group, 2,5-di-n-propyldiphenylmethyl group, 2,3'-di-n-propyldiphenylmethyl group, 2,4'-di-n-propyldiphenylmethyl group, bis(2-n-propylphenyl)methyl group, 3,4-di-n-propyldiphenylmethyl group, 3,5-di-n-propyldiphenylmethyl group, bis(3-n-propylphenyl)methyl group, 3,4'-di-n-propyldiphenylmethyl group, bis(4-n-propylphenyl)methyl group, 2,3-diisopropyldiphenylmethyl group, 2,4-diisopropyldiphenylmethyl group, 2,5-diisopropyldiphenylmethyl group, 2,3'-diisopropyldiphenylmethyl group, 2,4'-diisopropyldiphenylmethyl group, bis(2-isopropylphenyl)methyl group, 3,4-diisopropyldiphenylmethyl group, 3,5-diisopropyldiphenylmethyl group, bis(3-isopropylphenyl)methyl group, 3,4'-diisopropyldiphenylmethyl group, bis(4-isopropylphenyl)methyl group, 2,3-di-t-butyldiphenylmethyl group, 2,4-di-t-butyldiphenylmethyl group, 2,5-di-t-butyldiphenylmethyl group, 2,3'-di-t-butyldiphenylmethyl group, 2,4'-di-t-butyldiphenylmethyl group, bis(2-t-butylphenyl)methyl group, 3,4-di-t-butyldiphenylmethyl group, 3,5-di-t-butyldiphenylmethyl group, bis(3-t-butylphenyl)methyl group, 3,4'-di-t-butyldiphenylmethyl group, bis(4-t-butylphenyl)methyl group, 2,3-dimethoxydiphenylmethyl group, 2,4-dimethoxydiphenylmethyl group, 2,5-dimethoxydiphenylmethyl group, 2,3'-dimethoxydiphenylmethyl group, 2,4'-dimethoxydiphenylmethyl group, bis(2-methoxyphenyl)methyl group, 3,4-dimethoxydiphenylmethyl group, 3,5-dimethoxydiphenylmethyl group, bis(3-methoxyphenyl)methyl group, 3,4'-dimethoxydiphenylmethyl group, bis(4-methoxyphenyl)methyl group, 3-methoxy-2-methyldiphenylmethyl group, 4-methoxy-2-methyldiphenylmethyl group, 5-methoxy-2-methyldiphenylmethyl group, 3-methoxy-2'-methyldiphenylmethyl group, 4-methoxy-2'-methyldiphenylmethyl group, 2-methoxy-2'-methyldiphenylmethyl group, 4-methoxy-3-methyldiphenylmethyl group, 5-methoxy-3-methyldiphenylmethyl group, 3-methoxy-3'-methyldiphenylmethyl group, 4-methoxy-3'-methyldiphenylmethyl group, 4-methoxy-4'-methyldiphenylmethyl group, 2-methoxy-3-methyldiphenylmethyl group, 2-methoxy-4-methyldiphenylmethyl group, 2-methoxy-5-methyldiphenylmethyl group, 2-methoxy-3'-methyldiphenylmethyl group, 2-methoxy-4'-methyldiphenylmethyl group, 3-methoxy-4-methyldiphenylmethyl group, 3-methoxy-4'-methyldiphenylmethyl group, bis(2-fluorophenyl)methyl group, bis(2-chlorophenyl)methyl group, bis(3-fluorophenyl)methyl group, bis(3-chlorophenyl)methyl group, bis(4-fluorophenyl)methyl group, bis(4-chlorophenyl)methyl group, bis(2,6-dimethylphenyl)methyl group, bis(3,5-dimethylphenyl)methyl group, bis(2,6-diethylphenyl)methyl group, bis(3,5-diethylphenyl)methyl group, bis(2,6-di-n-propylphenyl)methyl group, bis(3,5-di-n-propylphenyl)methyl group, bis(2,6-diisobutylphenyl)methyl group, bis(3,5-diisobutylphenyl)methyl group, bis(2,6-di-t-butylphenyl)methyl group, bis(3,5-di-t-butylphenyl)methyl group, bis(2,6-dimethoxyphenyl)methyl group, bis(3,5-dimethoxyphenyl)methyl group, bis(2-methoxy-4-methylphenyl)methyl group, bis(2-methoxy-5-methylphenyl)methyl group, bis(2,6-difluorophenyl)methyl group, bis(3,5-difluorophenyl)methyl group, bis(2,6-dichlorophenyl)methyl group, and bis(3,Examples include a (5-dichlorophenyl)methyl group. Among these, preferably, a diphenylmethyl group, a bis(3,5-dimethylphenyl)methyl group, a bis(3,5-diethylphenyl)methyl group, a bis(3,5-diisopropylphenyl)methyl group, and a bis(3,5-di-t-butylphenyl)methyl group, and particularly preferably a diphenylmethyl group, a bis(3,5-dimethylphenyl)methyl group, and a bis(3,5-dimethoxyphenyl)methyl group.,

[0049] Furthermore, R 6 and R 7 are more preferably aralkyl groups represented by the general formula (2) independently from the viewpoints of ease of synthesis and catalytic activity, and most preferably the same aralkyl group represented by the general formula (2).

[0050] R 8 、R 9 、R 10 and R 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silyl group substituted with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom.

[0051] R 8 、R 9 、R 10 and R 11 Preferred specific examples of the halogen atom represented by are a fluorine atom, a chlorine atom, and a bromine atom. Among these, a fluorine atom is preferred.

[0052] R 8 、R 9 、R 10 and R 11The hydrocarbon group having 1 to 20 carbon atoms represented by is preferably a hydrocarbon group having 1 to 13 carbon atoms. Preferred examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specific examples of preferred groups include a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, a 1-nonyl group, a 1-decyl group, a t-butyl group, a tricyclohexylmethyl group, a 1,1-dimethyl-2-phenylethyl group, an isopropyl group, a 1,1-dimethylpropyl group, a 1,1,2-trimethylpropyl group, a 1,1-diethylpropyl group, a 1-phenyl-2-propyl group, an isobutyl group, a 1,1-dimethylbutyl group, a 2-pentyl group, a 3-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-ethylhexyl group, a 2-heptyl group, a 3-heptyl group, a 4-heptyl group, a 2-propyl ... Examples of the alkyl group include propylheptyl, 2-octyl, 3-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, 1-adamantyl, 2-adamantyl, exo-norbornyl, endo-norbornyl, 2-bicyclo[2.2.2]octyl, nopinyl, decahydronaphthyl, menthyl, neomenthyl, neopentyl, 5-decyl, phenyl, naphthyl, anthracenyl, fluorenyl, tolyl, xylyl, benzyl, and p-ethylphenyl. Among these, more preferred are methyl and benzyl, and particularly preferred is methyl.

[0053] R 8 , R 9 , R 10 and R 11 Specific examples of the alkoxy group having 1 to 8 carbon atoms represented by include a methoxy group, an ethoxy group, a 1-propoxy group, an isopropoxy group, a 1-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, and a pentyloxy group. Among these, more preferred are a methoxy group, an ethoxy group, a 1-propoxy group, and an isopropoxy group, and particularly preferred are a methoxy group and an ethoxy group.

[0054] R 8 、R 9 、R 10 and R 11 Specific examples of the aryloxy group having 6 to 20 carbon atoms represented by R

[0055] R 8 、R 9 、R 10 and R 11 Preferred examples of the hydrocarbon group having 1 to 20 carbon atoms in the silyl group substituted with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms represented by R 8 、R 9 、R 10 and R 11 are the same as the preferred examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 8 、R 9 、R 10 and R 11 More preferred examples of the silyl group substituted with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms represented by R

[0056] R 8 、R 9 、R 10 and R 11The hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom represented by is preferably a group obtained by substituting the aforementioned hydrocarbon group having 1 to 20 carbon atoms with a fluorine atom, a chlorine atom, or a bromine atom. Specific preferred examples include a trifluoromethyl group and a pentafluorophenyl group.

[0057] In one embodiment, R 8 , R 9 , R 10 and R 11 are all hydrogen atoms.

[0058] The electron-donating ligand (L) is a compound having an electron-donating group and capable of coordinating to the metal atom M to stabilize the metal complex.

[0059] Examples of the electron-donating ligand (L) having a sulfur atom include dimethyl sulfoxide (DMSO). Examples of the electron-donating ligand (L) having a nitrogen atom include trialkylamines having 1 to 10 carbon atoms in the alkyl group, dialkylamines having 1 to 10 carbon atoms in the alkyl group, pyridine, 2,6-dimethylpyridine (alias: 2,6-lutidine), aniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, N,N,N’,N’-tetramethylethylenediamine (TMEDA), 4-(N,N-dimethylamino)pyridine (DMAP), acetonitrile, benzonitrile, quinoline, and 2-methylquinoline. Examples of the electron-donating ligand (L) having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane. From the viewpoints of the stability and catalytic activity of the metal complex, dimethyl sulfoxide (DMSO), pyridine, 2,6-dimethylpyridine (alias: 2,6-lutidine), and N,N,N’,N’-tetramethylethylenediamine (TMEDA) are preferred, and dimethyl sulfoxide (DMSO) and 2,6-dimethylpyridine (alias: 2,6-lutidine) are more preferred.

[0060] q is 0, 1 / 2, 1 or 2. When q is 1 / 2, it means that one bidentate electron-donating ligand coordinates 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.

[0061] The metal complex represented by the general formula (C1) is preferably a compound represented by the formula (C2), the formula (C3) or the formula (C4).

Chemical formula

Chemical formula

Chemical formula

[0062] The metal complex represented by the general formula (C1) can be synthesized by the method described in known literature (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, a metal complex is synthesized by reacting a zero-valent or divalent M source with the ligand in the general formula (C1).

[0063] Examples of the zero-valent M source include tris(dibenzylideneacetone)dipalladium as a palladium source, and tetracarbonylnickel(0): Ni(CO)4 and bis(1,5-cyclooctadiene)nickel as nickel sources.

[0064] Examples of the divalent M source include, as palladium sources, (1,5-cyclooctadiene)(methyl)palladium chloride, palladium chloride, palladium acetate, bis(acetonitrile)dichloropalladium: PdCl2(CH3CN)2, bis(benzonitrile)dichloropalladium: PdCl2(PhCN)2, (N,N,N’,N’-tetramethylethylenediamine)dichloropalladium(II): PdCl2(TMEDA), (N,N,N’,N’-tetramethylethylenediamine)dimethylpalladium(II): PdMe2(TMEDA), bis(acetylacetonato)palladium(II): Pd(acac)2 (acac = acetylacetonato), and palladium(II) trifluoromethanesulfonate: Pd(OSO2CF3)2. Examples of the nickel source include (allyl)nickel chloride, (allyl)nickel bromide, nickel chloride, nickel acetate, bis(acetylacetonato)nickel(II): Ni(acac)2, (1,2-dimethoxyethane)dichloronickel(II): NiCl2(DME), and nickel(II) trifluoromethanesulfonate: Ni(OSO2CF3)2.

[0065] The metal complex represented by the general formula (C1) can be used in isolated form, or the metal source containing M and the ligand precursor can be brought into contact in the reaction system without isolating the complex and directly used for polymerization in situ. In particular, when R 5 in the general formula (C1) is a hydrogen atom, it is preferable to react the metal source containing zero-valent M with the ligand precursor and then directly use it for polymerization without isolating the complex.

[0066] In this case, the ligand precursor is, in the case of the general formula (C1),

Chemical formula

[0067] The ratio of the M source (M) to the ligand precursor (C1-1) (C1 ligand) in the general formula (C1), ((C1 ligand) / M), is preferably selected from the range of 0.5 to 2.0, more preferably from the range of 1.0 to 1.5.

[0068] When isolating the metal complex of the general formula (C1), it is also possible to use one that has been previously coordinated with an electron-donating ligand (L) for stabilization. In this case, q is 1 / 2, 1, or 2. As described above, q being 1 / 2 means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1 / 2 or 1 in terms of stabilizing the metal complex catalyst. Note that when q is 0, it means there is no ligand.

[0069] The metal complex represented by the general formula (C1) can also be supported on a carrier and used for polymerization. The carrier in this case is not particularly limited, and examples include inorganic carriers such as silica gel and alumina, and organic carriers such as polystyrene, polyethylene, and polypropylene. Examples of the method for supporting the metal complex include a physical adsorption method in which a solution of the metal complex is impregnated into the carrier and dried, and a method in which the metal complex and the carrier are chemically bonded and supported.

[0070] [Monomer] In the method for producing the polymer of the present invention, not only ethylene can be homopolymerized, but also ethylene can be copolymerized with an olefin having a polar group. The olefin having a polar group, which is the second monomer used for copolymerization in the present invention, has the general formula (1) [Chemical formula] as shown.

[0071] In the formula, R 1represents a substituent selected from the group consisting of 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, an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R - O - (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, a substituted amide group having 2 to 12 carbon atoms, a substituted pyridyl group having 5 to 10 carbon atoms, a substituted pyrrolidyl group having 4 to 10 carbon atoms, a substituted piperidyl group having 5 to 10 carbon atoms, a substituted hydrofuryl group having 4 to 10 carbon atoms, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. n is an integer selected from 0 to 6.

[0072] R which is an alkoxy group having 1 to 10 carbon atoms 1 is preferably an alkoxy group having 1 to 4 carbon atoms, and preferred specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a 1 - propoxy group, a 1 - butoxy group, and a t - butoxy group. Among these, more preferably are a methoxy group, an ethoxy group, and an isopropoxy group, and particularly preferably a methoxy group.

[0073] R which is an aryloxy group having 6 to 20 carbon atoms 1 is preferably an aryloxy group having 6 to 12 carbon atoms, and preferred specific examples include a phenoxy group, a 4 - methylphenoxy group, a 4 - methoxyphenoxy group, a 2,6 - dimethylphenoxy group, a 3,5 - di - t - butylphenoxy group, and a 2,6 - di - t - butylphenoxy group. Among these, more preferably are a phenoxy group, a 3,5 - di - t - butylphenoxy group, and a 2,6 - dimethylphenoxy group, and particularly preferably a phenoxy group and a 3,5 - di - t - butylphenoxy group.

[0074] R which is an acyl group having 2 to 10 carbon atoms 1is preferably an acyl group having 2 to 8 carbon atoms, and preferred specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, and a benzoyl group. Among these, an acetyl group, a pivaloyl group, and a benzoyl group are more preferable, and a benzoyl group is particularly preferable.

[0075] In an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R-O-(C=O)-, where R is an organic group), the organic group R is preferably an alkyl group which may have a functional group such as a hydroxyl group or an epoxy group, or an aryl group which may have the said functional group. R 1 is preferably an ester group having 2 to 8 carbon atoms, and preferred specific examples 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, a (4-glycidylbutoxy)carbonyl group, and a phenoxycarbonyl group. Among these, a methoxycarbonyl group, an ethoxycarbonyl group, and a (4-hydroxybutoxy)carbonyl group are more preferable, and a methoxycarbonyl group is particularly preferable.

[0076] R which is an acyloxy group having 2 to 10 carbon atoms 1 is preferably an acyloxy group having 2 to 8 carbon atoms, and preferred specific examples include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, and a benzoyloxy group. Among these, an acetyloxy group, a propionyloxy group, and a benzoyloxy group are more preferable, and an acetyloxy group and a propionyloxy group are particularly preferable.

[0077] R which is a substituted amino group having 1 to 12 carbon atoms 1Preferred specific examples thereof include a monomethylamino group, a dimethylamino group, a monoethylamino group, a diethylamino group, a monoisopropylamino group, a diisopropylamino group, a monophenylamino group, a diphenylamino group, a bis(trimethylsilyl)amino group, and a morpholinyl group. Among these, a dimethylamino group and a diphenylamino group are more preferred.

[0078] In a substituted amide group having 1 to 12 carbon atoms (R-(C=O)NH-, where R is an organic group), the organic group R is preferably an alkyl group which may have a functional group such as a hydroxyl group or an epoxy group, or an aryl group which may have the functional group. R 1 Preferred specific examples thereof include an acetamide group, a propionylamino group, a butyrylamino group, an isobutyrylamino group, a valerylamino group, an isovalerylamino group, a pivaloylamino group, and a benzoylamino group. Among these, an acetamide group, a propionylamino group, and a benzoylamino group are more preferred, and an acetamide group is particularly preferred.

[0079] R which is a substituted pyridyl group having 5 to 10 carbon atoms 1 Preferred specific examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 2-(3-methyl)pyridyl group, a 2-(4-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, and a 2-(4-methyl)pyridyl group are more preferred, and a 2-pyridyl group is particularly preferred.

[0080] R which is a substituted pyrrolidyl group having 4 to 10 carbon atoms 1Preferred specific examples thereof include a 2-pyrrolidyl group, 3-pyrrolidyl group, 2-(1-methyl)pyrrolidyl group, 2-(1-butyl)pyrrolidyl group, 2-(1-cyclopentenyl)pyrrolidyl group, 2-(4-methoxycarbonyl)pyrrolidyl group, 2-(5-methoxycarbonyl)pyrrolidyl group, and 2-(6-methoxycarbonyl)pyrrolidyl group. Among these, more preferred are a 2-pyrrolidyl group, 3-pyrrolidyl group, 2-(1-methyl)pyrrolidyl group, and 2-(6-methoxycarbonyl)pyrrolidyl group, and particularly preferred is a 2-pyrrolidyl group.

[0081] R which is a substituted piperidyl group having 5 to 10 carbon atoms 1 Preferred specific examples thereof include a 2-piperidyl group, 3-piperidyl group, 2-(1,2,3,6-tetrahydro)piperidyl 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 group. Among these, more preferred are a 2-piperidyl group, 3-piperidyl group, 2-(1,2,3,6-tetrahydro)piperidyl group, and 2-(6-methyl)piperidyl group, and particularly preferred are a 2-piperidyl group and 2-(1,2,3,6-tetrahydro)piperidyl group.

[0082] R which is a substituted hydrofuryl group having 4 to 10 carbon atoms 1Preferred specific examples thereof include a 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. Among these, more preferred are a 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2-(5-methyl)tetrahydrofuryl group, 2-(5-isopropyl)tetrahydrofuryl group, and 2-(4,5-benzo)tetrahydrofuryl group, and particularly preferred are a 2-tetrahydrofuryl group, 2-(5-methyl)tetrahydrofuryl group, and 2-(5-isopropyl)tetrahydrofuryl group.

[0083] R which is a substituted imidazolyl group having 4 to 10 carbon atoms 1 Preferred specific examples thereof include a 2-imidazolyl group, 2-(1-methyl)imidazolyl group, 2-(1-benzyl)imidazolyl group, 2-(1-acetyl)imidazolyl group, 2-(4,5-benzo)imidazolyl group, and 2-(1-methyl-4,5-benzo)imidazolyl group. Among these, more preferred are a 2-imidazolyl group, 2-(1-methyl)imidazolyl group, and 2-(4,5-benzo)imidazolyl group, and particularly preferred are a 2-(1-methyl)imidazolyl group and 2-(4,5-benzo)imidazolyl group.

[0084] R which is an alkylthio group having 1 to 10 carbon atoms 1 Preferred specific examples thereof include a methylthio group, ethylthio group, propylthio group, and t-butylthio group. R which is an arylthio group having 6 to 10 carbon atoms 1 Preferred specific examples thereof include a phenylthio group. Among these, more preferred are a methylthio group, t-butylthio group, and phenylthio group, and particularly preferred are a methylthio group and phenylthio group.

[0085] R which is a halogen atom 1Preferable specific examples include a fluorine atom, a chlorine atom, and a bromine atom. Among these, a chlorine atom is more preferable.

[0086] Among these groups preferred for these Rs 1 more preferably, an alkoxy group having 1 to 10 carbon atoms, an ester group having 2 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms.

[0087] In general formula (1), the value of n is preferably 0 or 1, and more preferably 1.

[0088] Specific examples of particularly preferred polar comonomers represented by general formula (1) include methyl acrylate, ethyl acrylate, allyl acetate, and allyl methyl ether.

[0089] In the method for producing the (co)polymer of the present invention, olefins having a polar group represented by general formula (1) copolymerized with ethylene may be polymerized in combination of two or more kinds.

[0090] In the method for producing the (co)polymer of the present invention, in addition to ethylene and an olefin having a polar group represented by general formula (1), another monomer (third monomer) may be used. Examples of the third monomer include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and styrene. Among these, propylene, 1-butene, and 1-hexene are preferable. These third monomers may be polymerized in combination of two or more kinds. However, when an α-olefin is copolymerized as the third monomer, the ratio of the α-olefin to the total of the α-olefin and ethylene contained in the resulting polymer is less than 40 mol%.

[0091] [Polymerization method] The method of polymerizing ethylene alone or ethylene and the monomer represented by the general formula (1) using the metal complex of the present invention as a catalyst is not particularly limited and may be a commonly used polymerization method. That is, process methods such as solution polymerization method, suspension polymerization method, gas phase polymerization method, etc. can be used, and solution polymerization method and suspension polymerization method are particularly preferred. The polymerization mode can be either batch mode or continuous mode. The polymerization can be carried out either by one-stage polymerization or multi-stage polymerization.

[0092] Two or more metal complex catalysts represented by the general formula (C1) may be mixed and used in the polymerization reaction. By using a mixture of metal complex catalysts, it is possible to control the molecular weight, molecular weight distribution of the polymer, and the content of monomer units derived from the monomer of the general formula (1), and thereby obtain a polymer suitable for a desired application. The molar ratio of the total amount of the metal complex catalyst to the total amount of the monomer, which is the monomer / metal complex ratio, is usually in the range of 1 to 10,000,000, preferably in the range of 10 to 1,000,000, more preferably in the range of 100 to 100,000.

[0093] The polymerization temperature is not particularly limited, but is usually in the range of -30 to 400 °C, preferably in the range of 0 to 200 °C, more preferably in the range of 30 to 180 °C.

[0094] Regarding the polymerization pressure where the ethylene pressure occupies most of the internal pressure, it is in the range from normal pressure to 100 MPa, preferably in the range from normal pressure to 20 MPa, more preferably in the range from normal pressure to 10 MPa.

[0095] The polymerization time can be appropriately adjusted according to the process mode, the polymerization activity of the catalyst, etc., and a short reaction time of several tens of seconds to several minutes is possible, as well as a long reaction time of several thousand hours.

[0096] In the polymerization system, the atmosphere is preferably filled with an inert gas such as nitrogen gas or argon so that air, oxygen, moisture, etc. other than the monomer do not mix in order to prevent a decrease in the activity of the catalyst. In the case of solution polymerization, it is possible to use an inert solvent in addition to the monomer. The inert solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, dichloroethane, and tetrachloroethane; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; aliphatic esters such as methyl acetate and ethyl acetate; and aromatic esters such as methyl benzoate and ethyl benzoate.

Examples

[0097] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.

[0098] [Method for analyzing the structure of the polymer] The number average molecular weight and weight average molecular weight of the (co)polymer were calculated by size exclusion chromatography (solvent: 1,2-dichlorobenzene, temperature: 145 ° C, detector: RI) using a high temperature GPC apparatus HLC-8121GPC / HT manufactured by Tosoh Corporation equipped with two AT-806MS columns (connected in series) manufactured by Showa Denko KK, with polystyrene as the molecular weight standard substance.

[0099] The content of the monomer unit derived from the olefin having a polar group represented by the general formula (1) was determined by 1H-NMR at 120 ° C using JNM-ECS400 manufactured by JEOL Ltd. and using 1,1,2,2-tetrachloroethane-d2 as the solvent. 1

[0100] [Synthesis of Metal Complex 1] Metal complex 1 was synthesized according to the following reaction formula.

Chemical formula

[0101] (a) Synthesis of bis(diphenylmethyl)phosphinobenzenesulfonic acid To a eggplant flask, diphenylmethane (5.70 g, 33.9 mmol) and dehydrated tetrahydrofuran (150 mL) were added under nitrogen gas, and the mixture was stirred in an ice bath. Normal butyllithium (1.6 M hexane solution, 17.7 mL, 28.3 mmol, 2.5 equivalents) was added dropwise thereto (the solution changed to orange), and stirring was continued for 1.5 hours in the ice bath. The eggplant flask was cooled to -78 °C in a dry ice / ethanol bath, and a dehydrated tetrahydrofuran solution (30 mL) of lithium 2-dichlorophosphinobenzenesulfonate (3.0 g, 11.3 mmol, 1 equivalent) was added. Stirring was continued for 15 hours while gradually raising the temperature to room temperature. After quenching with trifluoroacetic acid (3.2 g, 28.3 mmol, 2.5 equivalents), liquid separation was performed using methylene chloride and distilled water under the atmosphere. After extraction with methylene chloride, the organic layer was washed with a saturated aqueous sodium chloride solution, dried by adding magnesium sulfate, and then filtered. The solvent was distilled off using a rotary evaporator to obtain 7.1 g of a yellow viscous liquid. When the obtained liquid was dissolved in methylene chloride and hexane was added, it separated into two layers, so the hexane layer was removed by decantation. It was dissolved in methylene chloride again, and the same decantation operation was performed. After the obtained residue was distilled off under reduced pressure, reprecipitation was performed with methylene chloride, diethyl ether, and hexane to obtain 2.79 g of bis(diphenylmethyl)phosphinobenzenesulfonic acid as a solid. (Yield 35%). 31 P-NMR (162 MHz, CDCl3): δ 42.7.

[0102] (b) Synthesis of metal complex 1 In a round-bottom flask, bis(diphenylmethyl)phosphinobenzenesulfonic acid (591 mg, 1.13 mmol), N,N-diisopropylethylamine (DIPEA, 1.46 g, 11.3 mmol, 10 equivalents), and methylene chloride (15 mL) were added under nitrogen gas and stirred. To this, Pd(cod)MeCl (cod = 1,5-cyclooctadiene, 300 mg, 1.13 mmol, 1 equivalent) was added and stirred at room temperature for 1 hour. After concentrating the solution, the residue was dissolved in methylene chloride (10 mL), and potassium carbonate (1.56 g, 11.3 mmol, 10 equivalents) and 2,6-lutidine (1.21 g, 11.3 mmol, 10 equivalents) were added to this solution and stirred at room temperature for 1 hour. The reaction solution was filtered through Celite (dried diatomaceous earth) and Florisil (magnesium silicate), and then the solvent was concentrated. The obtained residue was separated and purified by simple column chromatography using a 30 mL disposable syringe filled with 15 mL of Florisil, changing the eluent in the order of (1) hexane / methylene chloride (3 / 1) → methylene chloride, (2) methylene chloride / diethyl ether (2 / 1), (3) tetrahydrofuran. After combining and concentrating fractions (1) and (2), recrystallization was performed using methylene chloride, diethyl ether, and hexane to obtain metal complex 1 (yield 13%). 1 1H-NMR (400 MHz, CDCl3): δ 8.18 (dd, J = 7.8, 3.8 Hz, 1H), 7.82 (d, J = 7.2 Hz, 4H), 7.50 (t, J = 7.4 Hz, 1H), 7.42 (d, J = 7.2 Hz, 4H), 7.35 (t, J = 7.6 Hz, 4H), 7.24 (d, J = 7.6 Hz, 2H), 7.24 - 7.15 (m, 1H), 7.17 (t, J = 7.4 Hz, 4H), 7.11 (d, J = 6.8 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 6.55 (t, J = 7.6 Hz, 1H), 5.90 (t, J = 7.4 Hz, 1H), 4.96 (d, J = 11.6 Hz, 2H), 2.87 (s, 6H), -0.76 (d, J = 2.0 Hz, 3H). 31 31P-NMR (162 MHz, CDCl3): δ 36.1.

[0103] [Synthesis of Metal Complex 2] Metal complex 2 was synthesized according to the following reaction formula. [Chemical Formula]

[0104] (c) Synthesis of bis(3,5-dimethylphenyl)methanol 3,5-Dimethylbromobenzene (13.9 g, 75 mmol, 2 equivalents) and dehydrated tetrahydrofuran (150 mL) were added to a three-necked reaction vessel under nitrogen gas and cooled to -78°C. Normal butyllithium (1.6 M hexane solution, 50 mL, 80 mmol, 2.1 equivalents) was added dropwise thereto, and the mixture was stirred for 1 hour (the solution changed from transparent to semi-transparent white cream color). Further, ethyl formate (2.81 g, 38 mmol) was added, and the mixture was stirred overnight while gradually warming from -78°C to room temperature. After quenching the reaction solution with a saturated aqueous ammonium chloride solution, the tetrahydrofuran solvent was distilled off. The remaining oily liquid was separated and extracted with methylene chloride and water. The organic layer was dried over sodium sulfate and then the solvent was distilled off using an evaporator. The remaining oily liquid was reprecipitated with hexane to obtain 7.39 g of a white needle-like solid (yield 81%). 1 H-NMR (400 MHz, CDCl3): δ 7.0 (s, 4H), 6.9 (s, 2H), 5.7 (d, J = 3.2 Hz, 1H), 2.3 (s, 12H), 2.1 (d, J = 3.4 Hz, 1H).

[0105] (d) Synthesis of chlorobis(3,5-dimethylphenyl)methane Bis(3,5-dimethylphenyl)methanol (4.6 g, 19 mmol) and methylene chloride (70 mL) were added to a two-necked eggplant flask under nitrogen gas and stirred in an ice bath. Thionyl chloride (4.75 g, 40 mmol, 2 equivalents) was added thereto, and the mixture was stirred for 2 hours (the solution changed from transparent to light yellow). After quenching the reaction solution with an aqueous sodium hydrogen carbonate solution, the methylene chloride was distilled off using an evaporator, and the mixture was separated and extracted with hexane and water. The organic layer was dried over sodium sulfate and then the solvent was distilled off using an evaporator to obtain 5.00 g of a white solid (yield 95%). 1H-NMR (400 MHz, CDCl3): δ 7.0 (s, 4H), 6.9 (s, 2H), 6.0 (s, 1H), 2.3 (s, 12H).

[0106] (e) Synthesis of bis(bis(3,5-dimethylphenyl)methyl)phosphinobenzene sulfonic acid In a two-neck reaction vessel, magnesium (1.17 g, 48.3 mmol, 16 equivalents), lithium chloride (0.5 M tetrahydrofuran solution) (48 mL, 24.2 mmol, 8.0 equivalents), and zinc chloride (1.0 M tetrahydrofuran solution) (21 mL, 21.2 mmol, 7.0 equivalents) were added under nitrogen gas and stirred in an ice bath. Chlorobis(3,5-dimethylphenyl)methane (5.00 g, 19.3 mmol, 6.4 equivalents) was added dropwise thereto, and the mixture was stirred at 45 °C for 5 hours while gradually warming from room temperature (the solution changed from grayish white to greenish black).

[0107] In another three-neck flask, lithium 2-dichlorophosphinobenzenesulfonate (0.80 g, 3 mmol), CuCl (0.03 g, 0.3 mmol, 0.1 equivalent), and tetrahydrofuran (20 mL) were added under nitrogen gas and stirred at room temperature for several minutes. The solution prepared in the previous two-neck reaction vessel was added dropwise thereto, and the mixture was further stirred at room temperature overnight. After quenching with trifluoroacetic acid (4 mL, 17 equivalents), liquid separation was performed under the atmosphere using methylene chloride and distilled water. After extraction with methylene chloride, the organic layer was washed with a saturated aqueous sodium chloride solution and dried over sodium sulfate. The solvent was distilled off from the obtained liquid phase using a rotary evaporator to obtain a yellow viscous liquid. The obtained liquid was dissolved in methylene chloride and then reprecipitated with hexane to obtain 0.3 g of a white solid (yield 16%). 31 P-NMR (162 MHz, CDCl3): δ 42.9.

[0108] (f) Synthesis of metal complex 2 In a round-bottom flask, bis(bis(3,5-dimethylphenyl)methyl)phosphinobenzene sulfonic acid (300 mg, 0.47 mmol), N,N-diisopropylethylamine (DIPEA, 0.32 mL, 1.9 mmol, 4 equivalents), and methylene chloride (6 mL) were added under nitrogen gas and stirred. To this, Pd(cod)MeCl (cod = 1,5-cyclooctadiene, 127 mg, 0.48 mmol, 1 equivalent) was added, and the mixture was stirred at room temperature for 1 hour. After concentrating the solution, the residue was dissolved in methylene chloride (8 mL), and potassium carbonate (0.26 g, 1.9 mmol, 4 equivalents) and 2,6-lutidine (0.22 mL, 1.9 mmol, 4 equivalents) were added to this solution, followed by stirring at room temperature for 1 hour. The reaction solution was filtered through Celite (dried diatomaceous earth) and then subjected to liquid-liquid extraction with methylene chloride and water. The organic layer was dried over sodium sulfate and then the solvent was evaporated using an evaporator. The obtained residue was separated and purified by simple column chromatography using a 30 mL disposable syringe filled with 15 mL of Florisil, changing the eluent in the order of (1) hexane / methylene chloride (3 / 1), (2) ethyl acetate, and (3) tetrahydrofuran. After combining and concentrating fraction (2), recrystallization was performed using methylene chloride and hexane to obtain 35 mg of a white solid (yield 10%). 1 1H-NMR (400 MHz, CDCl3): δ 8.19 - 8.15 (m, 1H), 7.49 (t, J = 7.6 Hz, 1H), 7.34 (s, 4H), 7.22 (t, J = 7.6 Hz, 1H), 7.03 - 7.02 (m, 6H), 6.85 (s, 2H), 6.71 (s, 2H), 6.68 (t, J = 7.2 Hz, 1H), 6.09 (t, J = 8.0 Hz, 1H), 4.64 (d, J = 12.4 Hz, 2H), 2.91 (s, 6H), 2.31 (s, 12H), 2.16 (s, 12H), -0.52 (s, 3H). 31 31P-NMR (162 MHz, CDCl3): δ 32.0.

[0109] [Synthesis of Metal Complex 3] Metal complex 3 was synthesized according to the following reaction formula. [Chemical Formula]

[0110] (g) Synthesis of bis(3,5-dimethoxyphenyl)methanol To a three-necked reaction vessel, 3,5-dimethoxybromobenzene (6.51 g, 30 mmol, 2 equivalents) and dehydrated tetrahydrofuran (60 mL) were added under nitrogen gas, and the mixture was cooled to -78 °C. Normal butyllithium (1.6 M hexane solution, 20.6 mL, 33 mmol, 2.2 equivalents) was added dropwise thereto, and the mixture was stirred for 2 hours (the solution changed from transparent to translucent pale yellow). Further, ethyl formate (1.1 g, 15 mmol) was added, and the mixture was stirred overnight while gradually warming from -78 °C to room temperature. The reaction solution was quenched with a saturated aqueous ammonium chloride solution, and then the solvent tetrahydrofuran was distilled off. The remaining oily liquid was separated and extracted with diethyl ether and water, washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then the solvent was distilled off using an evaporator. Hexane was added to the remaining oily liquid and refrigerated overnight to precipitate a solid, which was collected by suction filtration to obtain 3.85 g of a white solid (yield: 95% or more). 1 H-NMR (400 MHz, CDCl3): δ 6.5 (d, J = 1.6 Hz, 4H), 6.3 (t, J = 2.4 Hz, 2H), 5.6 (d, J = 3.2 Hz, 1H), 3.8 (s, 12H), 2.1 (d, J = 3.6 Hz, 1H).

[0111] (h) Synthesis of chlorobis(3,5-dimethoxyphenyl)methane To a three-necked reaction vessel, bis(3,5-dimethoxyphenyl)methanol (3.85 g, 12.7 mmol), tetrahydrofuran (50 mL), and pyridine (3.5 g, 45 mmol, 3.5 equivalents) were added under nitrogen gas, and the mixture was stirred in an ice bath. Thionyl chloride (2.7 g, 22.4 mmol, 1.8 equivalents) was added thereto, and the mixture was stirred for 1 hour (the solution changed from transparent to pale yellow). The reaction solution was quenched with dilute hydrochloric acid and immediately extracted with methylene chloride. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over sodium sulfate, and then the solvent was distilled off using an evaporator to obtain 4.2 g of an orange oily liquid (yield: 95% or more). 1H-NMR (400 MHz, CDCl3): δ 6.5 (d, J = 2.0 Hz, 4H), 6.3 (t, J = 2.2 Hz, 2H), 5.9 (s, 1H), 3.8 (s, 12H).

[0112] (i) Synthesis of bis(bis(3,5-dimethoxyphenyl)methyl)phosphinobenzenesulfonic acid In a two-neck reaction vessel, magnesium (0.37 g, 15 mmol, 11.5 equivalents), lithium chloride (1 M tetrahydrofuran solution) (8 mL, 8 mmol, 6.2 equivalents), and zinc chloride (0.5 M tetrahydrofuran solution) (14 mL, 7 mmol, 5.4 equivalents) were added under nitrogen gas, and the mixture was stirred in an ice bath. Chlorobis(3,5-dimethoxyphenyl)methane (1.72 g, 5.3 mmol, 4.0 equivalents) was added thereto, and the mixture was stirred at room temperature for 8 hours while gradually warming from 0 °C (the solution changed from grayish white to greenish black).

[0113] In another three-neck flask, lithium 2-dichlorophosphinobenzenesulfonate (0.34 g, 1.3 mmol), CuCl (0.013 g, 0.13 mmol, 0.1 equivalent), and tetrahydrofuran (6 mL) were added under nitrogen gas, and the mixture was stirred at room temperature for several minutes. The solution prepared in the previous two-neck reaction vessel was added dropwise thereto, and the mixture was further stirred at room temperature overnight. Trifluoroacetic acid was added until the solution reached pH < 3, and liquid separation was performed using methylene chloride and distilled water under air. The organic layer was dried over sodium sulfate, and then the solvent was distilled off using a rotary evaporator to obtain a yellow viscous liquid. The obtained liquid was dissolved in methylene chloride and then reprecipitated with hexane to obtain 0.1 g of a white solid (yield 10%). 31 P-NMR (162 MHz, CDCl3): δ 42.2.

[0114] (j) Synthesis of metal complex 3 In a round-bottom flask, bis(bis(3,5-dimethoxyphenyl)methyl)phosphinobenzenesulfonic acid (0.1 g, 0.13 mmol), N,N-diisopropylethylamine (DIPEA, 0.052 g, 0.4 mmol, 3 equivalents), and methylene chloride (3 mL) were added under nitrogen gas and stirred. To this, Pd(cod)MeCl (cod = 1,5-cyclooctadiene, 0.04 g, 0.15 mmol, 1.2 equivalents) was added, and the mixture was stirred at 0 °C for 3 hours. After concentrating the solution, the residue was dissolved in methylene chloride (3 mL). To this solution, potassium carbonate (0.055 g, 0.4 mmol, 3 equivalents) and 2,6-lutidine (0.043 g, 0.4 mmol, 3 equivalents) were added, and the mixture was stirred at room temperature overnight. The reaction solution was filtered through Celite (dried diatomaceous earth), and then the solvent was distilled off. The obtained residue was reprecipitated with methylene chloride and hexane. The obtained brown solid was separated and purified by simple column chromatography using a 30 mL disposable syringe filled with 15 mL of Florisil, changing the eluent in the order of (1) methylene chloride, (2) ethyl acetate, and (3) tetrahydrofuran. After collecting and concentrating fraction (2), recrystallization was performed using methylene chloride and hexane to obtain 0.033 g of a white solid (yield 25%). 1 1H-NMR (400 MHz, CDCl3): δ 8.14 (dq, J = 4.7, 1.2 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.01 (d, J = 7.6 Hz, 2H), 6.89 (s, 4H), 6.71 (t, J = 7.6 Hz, 1H), 6.53 (d, J = 1.2 Hz, 4H), 6.31 (s, 3H), 6.21 - 6.17 (m, 3H), 4.85 (d, J = 12.4 Hz, 2H), 3.77 (s, 12H), 3.60 (s, 12H), 2.88 (s, 6H), -0.53 (d, J = 2, 4 Hz, 3H). 31 31P-NMR (162 MHz, CDCl3): δ 33.6.

[0115] [Synthesis of Comparative Metal Complexes 1 - 3] (k) Synthesis of Comparative Metal Complex 1 According to the method described in JP-A-2011-68881, the following formula [Chemical Formula] The comparative metal complex 1 shown below was synthesized.

[0116] (l) Synthesis of comparative metal complex 2 According to the method described in JP-A-2014-159540, the following formula

Chemical formula

[0117] (m) Synthesis of comparative metal complex 3 According to the method described in WO 2020 / 175482, the following formula

Chemical formula

[0118] [Synthesis of polymer] Using the metal complexes 1 to 3 and the comparative metal complexes 1 to 3 synthesized by the above methods, (co)polymerization of olefins was carried out. The polymerization conditions and polymerization results are shown in Tables 1 and 2, respectively. The catalyst concentration, productivity, and catalyst activity were calculated by the following formulas. (a) When the polar group-containing monomer is not included or the polar group-containing monomer is a gas at room temperature

[0119]

Mathematical formula

Mathematical formula

Mathematical formula

Mathematical formula

[0120] (Example 1): Homopolymerization of ethylene using metal complex 1 (Preparation of polymer 1) In a nitrogen gas atmosphere, toluene (50 mL) was added to a 120 mL autoclave containing metal complex 1 (0.075 mg, 0.00010 mmol). After filling with ethylene (3.0 MPa), the autoclave was stirred at 80 °C for 1 hour. After cooling to room temperature, the reaction solution in the autoclave was added to methanol (300 mL) to precipitate the polymer. The resulting polymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain Polymer 1. The yield was 1.57 g. The productivity was calculated to be 15700 g / mmol, and the catalytic activity was calculated to be 15700 g / (mmol·h). The molecular weight of Polymer 1 was measured by size exclusion chromatography, and the number average molecular weight Mn was 138,700, the weight average molecular weight Mw was 274,100, and Mw / Mn was 1.98.

[0121] (Example 2): Homopolymerization of ethylene using metal complex 2 (Preparation of Polymer 2) Ethylene homopolymerization was carried out in the same manner as in Example 1, except that the metal complex used was changed to metal complex 2 and the number of moles of the metal complex used was changed as shown in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0122] (Example 3): Homopolymerization of ethylene using metal complex 3 (Preparation of Polymer 3) Ethylene homopolymerization was carried out in the same manner as in Example 1, except that the metal complex used was changed to metal complex 3 and the number of moles of the metal complex used was changed as shown in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0123] (Comparative Examples 1 - 2): Homopolymerization of ethylene using comparative metal complexes 1 - 2 (Preparation of comparative polymers 1 - 2) Ethylene homopolymerization was carried out in the same manner as in Example 1, except that the metal complex used was changed to comparative metal complex 1 or 2 and the number of moles of comparative metal complex 1 or 2 used and the amount of solvent were changed as shown in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0124] (Example 4): Copolymerization of allyl acetate and ethylene using metal complex 1 (Preparation of Polymer 4) Under a nitrogen gas atmosphere, allyl acetate (75 mL, 698 mmol) as the monomer represented by the general formula (1) was added to a 120 mL autoclave containing metal complex 1 (7.5 mg, 0.010 mmol). After filling with ethylene (0.40 MPa), the autoclave was stirred at 65 °C for 24 hours. After cooling to room temperature, the reaction solution in the autoclave was dried under reduced pressure to obtain Polymer 4. The yield was 0.503 g. The productivity was calculated to be 50.3 g / mmol, and the catalytic activity was calculated to be 2.10 g / (mmol·h). The molecular weight of Polymer 4 was measured by size exclusion chromatography, and the number average molecular weight Mn was 40,400, the weight average molecular weight Mw was 92,200, and Mw / Mn was 2.28. The allyl acetate content in the copolymer was 1 determined by 1H-NMR measurement to be 100:24.7 (allyl acetate molar fraction = 19.8%) in terms of the molar ratio of ethylene to allyl acetate. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0125] (Example 5): Copolymerization of allyl acetate and ethylene using metal complex 3 (Preparation of Polymer 5) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 4, except that the metal complex used was changed to metal complex 3 and the ethylene pressure was changed as described in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0126] (Example 6): Copolymerization of allyl acetate and ethylene using metal complex 1 (Preparation of Polymer 6) Copolymerization of allyl acetate and ethylene was carried out in the same manner as the method described in Example 4, except that the reaction temperature and ethylene pressure were changed as described in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0127] (Comparative Examples 3 - 5): Copolymerization of allyl acetate and ethylene using comparative metal complexes 1 - 3 (Preparation of comparative polymers 3 - 5) The copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 4, except that the metal complex used was changed to Comparative Metal Complex 1, 2, or 3, and the number of moles of the comparative metal complex used, the amount of allyl acetate used, and the ethylene pressure were changed as shown in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0128] (Comparative Example 6): Copolymerization of allyl acetate and ethylene using Comparative Metal Complex 3 (Preparation of Comparative Polymer 6) The copolymerization of allyl acetate and ethylene was carried out in the same manner as in Example 6, except that the metal complex used was changed to Comparative Metal Complex 3 and the ethylene pressure was changed as shown in Table 1. The polymerization conditions and polymerization results are shown in Table 1 and Table 2, respectively.

[0129]

Table 1

[0130]

Table 2

[0131] In the homopolymerization of ethylene, when Metal Complexes 1 to 3 were used (Examples 1 to 3), compared with the case where Comparative Metal Complex 1 was used (Comparative Example 1), the productivity, catalytic activity, and weight-average molecular weight Mw were greatly improved. When Comparative Metal Complex 2 was used (Comparative Example 2), although the weight-average molecular weight Mw of the obtained polymer was high, the productivity and catalytic activity were insufficient. In contrast, when Metal Complexes 1 to 3 were used (Examples 1 to 3), a polymer having a weight-average molecular weight Mw of hundreds of thousands, similar to that in Comparative Example 2, could be synthesized with a catalytic activity more than 10 times higher than that of Comparative Example 2.

[0132] Fig. 1 shows a graph plotting productivity (horizontal axis) and weight average molecular weight Mw (vertical axis) in Examples 4 and 5 and Comparative Examples 3 to 5 where the catalyst concentration, reaction temperature (65 °C), and reaction time (24 hours) are equal. When using Metal Complexes 1 and 3 (Examples 4 and 5), it was found that the productivity and catalytic activity were improved compared to when using Comparative Metal Complexes 1 and 2 (Comparative Examples 3 and 4), and particularly for Metal Complex 1 (Example 4), the weight average molecular weight Mw was also increased. When compared with Comparative Example 5 using Comparative Metal Complex 3, it was found that in Example 4, the productivity was equivalent while the weight average molecular weight Mw and allyl acetate unit content were improved, and in Example 5, the productivity and catalytic activity were improved.

[0133] Furthermore, when the copolymerization of allyl acetate and ethylene was carried out at a reaction temperature of 40 °C, further improvements in productivity, catalytic activity, and weight average molecular weight Mw were observed when using Metal Complex 1 (Example 6) compared to when using Comparative Metal Complex 3 (Comparative Example 6).

[0134] From the above Examples and Comparative Examples, it was found that in the polymerization of olefins containing allyl monomers having polar groups, the metal complex catalyst of the present disclosure has higher catalytic activity compared to conventional metal complex catalysts and can obtain polymers having a high weight average molecular weight. That is, the production cost of high molecular weight olefin-based polymers containing allyl monomers having polar groups can be reduced by the metal complex catalyst of the present disclosure.

Claims

1. General formula (C1) 【Chemical 1】 (In the formula, M represents an element of Group 10 of the periodic table, and X represents a phosphorus atom (P) or an arsenic atom (As). R ５ represents a substituent selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 30 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 30 carbon atoms substituted with an aryloxy group having 6 to 20 carbon atoms, a hydrocarbon group having 3 to 30 carbon atoms substituted with an amide group having 2 to 10 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. R ６ and R ７ are represented by the general formula (2) 【Chemical 2】 (In the formula, R １２ , R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ , R ２０ and R ２１ each independently represents a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, a hydrocarbon group having 2 to 20 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, a hydrocarbon group having 7 to 20 carbon atoms substituted with an aryloxy group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. In the general formula (2), the bond between the carbon atom and X in the general formula (C1) is also shown.) is the same aralkyl group represented by. R ８ , R ９ , R １０ and R １１ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a silyl group substituted with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. L represents an electron-donating ligand, and q is 0, 1 / 2, 1, or 2.) A catalyst for olefin polymerization containing a metal complex represented by.

2. R in the general formula (2) １２ R １３ R １４ R １５ R １６ R １７ R １８ R １９ R ２０ and R ２１ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The olefin polymerization catalyst according to claim 1.

3. R in the general formula (2) １３ R １４ R １５ R １８ R １９ R ２０ and R １２ R １６ R １７ R ２１ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R １２ R １６ R １７ R ２１ is a hydrogen atom, the olefin polymerization catalyst according to claim 1 or 2.

4. The olefin polymerization catalyst according to claim 1 or 2, wherein the aralkyl group represented by the general formula (2) is a diphenylmethyl group, a bis(3,5-dimethylphenyl)methyl group, or a bis(3,5-dimethoxyphenyl)methyl group.

5. R in the general formula (C1) ８ R ９ R １０ and R １１ The olefin polymerization catalyst according to claim 1 or 2, wherein all are hydrogen atoms.

6. General formula (C1) 【Chemical Formula 3】 (The symbols in the formula have the same meanings as described in claim 1.) A metal complex represented by the formula is used as a polymerization catalyst, and a homopolymer of ethylene, ethylene and the general formula (1) 【Chemical Formula 4】 (In the formula, R １ represents a substituent selected from the group consisting of 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, an ester group having 2 to 10 carbon atoms (oxycarbonyl group; R—O—(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, a substituted amide group having 2 to 12 carbon atoms, a substituted pyridyl group having 5 to 10 carbon atoms, a substituted pyrrolidyl group having 4 to 10 carbon atoms, a substituted piperidyl group having 5 to 10 carbon atoms, a substituted hydrofuryl group having 4 to 10 carbon atoms, a substituted imidazolyl group having 4 to 10 carbon atoms, a mercapto group, an alkylthio group having 1 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, an epoxy group, and a halogen atom. n is an integer selected from 0 to 6.) A method for producing a copolymer with an olefin having a polar group represented by the formula, or a copolymer of ethylene, an olefin having a polar group represented by the general formula (1), and another monomer.

7. The method according to claim 6, wherein n in the general formula (1) is 0.

8. The method according to claim 6, wherein n in the general formula (1) is 1.

9. R in the general formula (2) １２ , R １３ , R １４ , R １５ , R １６ , R １７ , R １８ , R １９ , R ２０ and R ２１ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, according to any one of claims 6 to 8.

10. R in general formula (2) １３ , R １４ , R １５ , R １８ , R １９ and R ２０ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and R １２ , R １６ , R １７ and R ２１ is a hydrogen atom, the method according to any one of claims 6 to 8.

11. The method according to any one of claims 6 to 8, wherein the aralkyl group represented by the general formula (2) is a diphenylmethyl group, a bis(3,5-dimethylphenyl)methyl group, or a bis(3,5-dimethoxyphenyl)methyl group.

12. R in the general formula (C1) ８ , R ９ , R １０ and R １１ The method according to any one of claims 6 to 8, wherein all are hydrogen atoms.

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