JP7329720B1 - Method for producing cyclic olefin copolymer and catalyst composition - Google Patents

Abstract

A method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, comprising at least charging a norbornene monomer and ethylene as monomers into a polymerization vessel; A method for producing a cyclic olefin copolymer comprising a step of polymerizing a monomer in a container in the presence of a catalyst having a phosphineimide group, wherein the catalyst having a phosphineimide group comprises a compound having a specific structure.

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin copolymer and a catalyst composition.

Cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used in various applications including the field of optical materials such as optical disk substrates, optical films, and optical fibers. Copolymers of cyclic olefins and ethylene, which are widely used as transparent resins, are known as representative cyclic olefin copolymers. The copolymer of cyclic olefin and ethylene can change its glass transition temperature (Tg) according to the composition of the copolymer of cyclic olefin and ethylene. Coalescing can be produced (see, for example, Non-Patent Document 1).

Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, 250, p. 212-241

However, depending on the method described in Non-Patent Document 1, there is a problem that a copolymer of cyclic olefin and ethylene cannot be produced in a high yield. As a countermeasure against this problem, it is conceivable to carry out polymerization using a highly active catalyst. However, when polymerization is performed using a highly active catalyst, polyethylene-like impurities are likely to be generated in some cases. If the cyclic olefin copolymer contains polyethylene-like impurities, turbidity occurs when the cyclic olefin copolymer is dissolved in a solvent. Therefore, we are anxious about the fall of the transparency of a cyclic olefin copolymer. Furthermore, when polyethylene-like impurities are produced, a process for filtering and removing insoluble polyethylene-like impurities is required in a general production process for producing a cyclic olefin copolymer, which leads to an increase in production cost.

The present invention has been made in view of the above-mentioned conventional problems, and its object is to obtain a cyclic olefin copolymer in a high yield and to produce a cyclic olefin copolymer with less polyethylene-like impurities. An object of the present invention is to provide a method for producing a polymer.
Another object of the present invention is to provide a catalyst composition that is highly active in the copolymerization of cyclic olefins and ethylene and that can suppress the formation of polyethylene-like impurities. .

The present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by using a catalyst having a specific structure having a phosphineimide group in a copolymer of a cyclic olefin and ethylene. The inventors have found that and completed the present invention.

One aspect of the present invention for solving the above problems is as follows.
(1) A method for producing a cyclic olefin copolymer containing structural units derived from norbornene monomers and structural units derived from ethylene,
charging at least a norbornene monomer and ethylene as monomers into a polymerization vessel;
and polymerizing the monomer in the polymerization vessel in the presence of a catalyst having a phosphine imide group,
The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following A method for producing a cyclic olefin copolymer having a substituent satisfying condition A.
Condition A: In the compound (C ₆ H ₅ —(CH ₂ ) _n R) in which the substituent represented by —(CH ₂ ) _n R is bonded to the benzene ring, the —(CH ₂ ) _n R The charge of the carbon atom directly bonded to the benzene ring in the substituent is -0.46 or less.

［一般式（Ａ）中、Ｍは周期律表第４族遷移金属を示し、Ｘはヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又はハロゲン原子を示し、Ｒ^ａ１～Ｒ^ａ３は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又は無機置換基を示し、Ｒは水素原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、及びアルキルシリル基、及びアリールシリル基から選択される１種以上を示し、ｎは１～５の整数を示す。］

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group; n is an integer of 1 to 5; ]

(2) The method for producing a cyclic olefin copolymer according to (1) above, wherein the catalyst has an insertion activation energy of ethylene with respect to titanium-ethylene-ethylene of 7 kcal/mol or less.

(3) The method for producing a cyclic olefin copolymer according to (1) or (2) above, wherein the catalyst has an insertion activation energy of norbornene with respect to titanium-norbornene-ethylene of 31 kcal/mol or less.

⁽ 4) The ^above ( A method for producing a cyclic olefin copolymer according to any one of 1) to (3).

(5) The method for producing a cyclic olefin copolymer according to any one of (1) to (4) above, wherein R in the general formula (A) is a perfluorophenyl group.

(6) A catalyst composition containing a catalyst having a phosphine imide group for copolymerization of a norbornene monomer and ethylene,
The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following A catalyst composition that is a substituent that satisfies condition A.
Condition A: In the compound (C ₆ H ₅ —(CH ₂ ) _n R) in which the substituent represented by —(CH ₂ ) _n R is bonded to the benzene ring, the —(CH ₂ ) _n R The charge of the carbon atom directly bonded to the benzene ring in the substituent is -0.46 or less.

［一般式（Ａ）中、Ｍは周期律表第４族遷移金属を示し、Ｘはヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又はハロゲン原子を示し、Ｒ^ａ１～Ｒ^ａ３は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又は無機置換基を示し、Ｒは水素原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、及びアルキルシリル基、及びアリールシリル基から選択される１種以上を示し、ｎは１～５の整数を示す。］

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group; n is an integer of 1 to 5; ]

⁽ 7) The ^above ( The catalyst composition according to 6).

(8) The catalyst composition according to (6) or (7) above, wherein R in formula (A) is a perfluorophenyl group.

ADVANTAGE OF THE INVENTION According to this invention, the cyclic olefin copolymer can be obtained with a high yield, and the manufacturing method of the cyclic olefin copolymer with few production|generation of polyethylene-like impurities can be provided.
In addition, according to the present invention, it is possible to provide a catalyst composition that is highly active in the copolymerization of cyclic olefins and ethylene and that can suppress the formation of polyethylene-like impurities.

<Method for producing cyclic olefin copolymer>
The method for producing a cyclic olefin copolymer of the present embodiment is a method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, and comprises at least a norbornene monomer and A step of charging ethylene as a monomer into a polymerization vessel (hereinafter also referred to as a "charging step"), and a step of polymerizing the monomer in the polymerization vessel in the presence of a catalyst having a phosphineimide group (hereinafter, "polymerization ), including The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following is a substituent that satisfies the condition A of
Condition A: Substitution represented by -(CH ₂ ) _n R in a compound (C ₆ H ₅ -(CH ₂ ) _n R) in which a substituent represented by -(CH ₂ ) _n R is bonded to a benzene ring The charge of the carbon atom directly attached to the benzene ring in the group is -0.46 or less.

［一般式（Ａ）中、Ｍは周期律表第４族遷移金属を示し、Ｘはヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又はハロゲン原子を示し、Ｒ^ａ１～Ｒ^ａ３は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又は無機置換基を示し、Ｒは水素原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、及びアルキルシリル基、及びアリールシリル基から選択される１種以上を示し、ｎは１～５の整数を示す。］

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group; n is an integer of 1 to 5; ]

The method for producing a cyclic olefin copolymer of the present embodiment is characterized by the catalyst used for the copolymerization of norbornene and ethylene. Since the catalyst has high catalytic activity, a large amount of cyclic olefin copolymer can be obtained with a smaller amount. In addition, although the catalyst has high activity, polyethylene-like impurities are less likely to form, and a cyclic olefin copolymer having excellent transparency can be obtained.
Each step will be described in detail below.

[Preparation process]
In the charging step, at least the norbornene monomer and ethylene are charged into the polymerization vessel as monomers. The polymerization vessel may be charged with monomers other than the norbornene monomer and ethylene as long as they do not adversely affect the production method of the present embodiment. In the cyclic olefin copolymer, the sum of the ratio of structural units derived from norbornene monomer and the ratio of structural units derived from ethylene is typically 80% by mass or more with respect to all structural units. It is preferably 95% by mass or more, more preferably 98% by mass or more.

The method of charging ethylene into the polymerization solution is not particularly limited as long as the desired amount of ethylene can be charged into the polymerization vessel. Typically, ethylene is charged to the polymerization vessel such that the charging pressure of ethylene in the polymerization vessel is 0.5 MPa or higher. The charging pressure of ethylene is preferably 0.55 MPa or higher, more preferably 0.6 MPa or higher. When the ethylene feed pressure is increased, the amount of catalyst used per product polymer can be reduced. Regarding the upper limit, the charging pressure of ethylene is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 3 MPa or less.

A solvent may be charged into the polymerization vessel along with the norbornene monomer and ethylene. The solvent is not particularly limited as long as it does not inhibit the polymerization reaction. Examples of solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, chloroform, methylene chloride. , dichloromethane, dichloroethane, and halogenated hydrocarbon solvents such as chlorobenzene.

When the norbornene monomer is added to the solvent, the lower limit of the concentration of the norbornene monomer is, for example, preferably 0.5% by mass or more, more preferably 10% by mass or more. The upper limit is, for example, preferably 50% by mass or less, more preferably 35% by mass or less.

The norbornene monomer will be described in detail below.

[Norbornene monomer]
Norbornene monomers include, for example, norbornene and substituted norbornenes, with norbornene being preferred. A norbornene monomer can be used individually by 1 type or in combination of 2 or more types.

The above-mentioned substituted norbornene is not particularly limited, and examples of substituents possessed by this substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of substituted norbornenes include compounds represented by the following general formula (I).

［一般式（Ｉ）中、Ｒ^１～Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、
Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、
Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、
ｎが２以上の場合には、Ｒ^５～Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。
ただし、ｎ＝０の場合、Ｒ^１～Ｒ^４及びＲ^９～Ｒ^１２の少なくとも１個は、水素原子ではない。］

[In general formula (I), R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group,
R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may combine to form a divalent hydrocarbon group,
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring together.
Also, n represents 0 or a positive integer,
When n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.
However, when n=0, at least one of R ¹ to R ⁴ and R ⁹ to R ¹² is not a hydrogen atom. ]

The substituted norbornene represented by general formula (I) will be described. R ¹ to R ¹² in general formula (I) may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups.

Specific examples of R ¹ to R ⁸ include hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 to 20 carbon atoms; , may be partially different, or all may be the same.

Specific examples of R ⁹ to R ¹² include hydrogen atom; halogen atom such as fluorine, chlorine and bromine; alkyl group having 1 to 20 carbon atoms; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups, and anthryl groups; benzyl groups, phenethyl groups, and other aralkyl groups in which alkyl groups are substituted with aryl groups; These may be different, partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are combined to form a divalent hydrocarbon group include alkylidene groups such as ethylidene group, propylidene group and isopropylidene group. can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring together, the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a ring having a double bond, or a ring consisting of a combination of these rings. Moreover, these rings may have a substituent such as a methyl group.

Specific examples of substituted norbornenes represented by general formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta- 2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2. 1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[ 2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5- bicyclic cyclic olefins such as propenyl-bicyclo[2.2.1]hept-2-ene;
tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]dec-3-ene; tricyclo[ 4.4.0.1 ^2,5 ]undeca-3,7-diene or tricyclo[4.4.0.1 ^2,5 ]undeca-3,8-diene or partially hydrogenated products thereof (or cyclopentadiene and cyclohexene) which are tricyclo[4.4.0.1 ^2,5 ]undec-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo 3 such as [2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene cyclic olefins of the ring;
Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene (also referred to simply as tetracyclododecene), 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-methylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 4-ring cyclic olefins such as 1 ^7,10 ]dodeca-3-ene;
8-Cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene; tetracyclo[7.4.1 ^3,6 . 0 ^{1, 9} . 0 ^2,7 ]tetradeca-4,9,11,13-tetraene (also called 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 ^4,7 . 0 ^{1, 10} . 0 ^3,8 ]pentadeca-5,10,12,14-tetraene (also called 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclo[6.6.1. 1 ^{3, 6} . 0 ^{2, 7} . 0 ^9,14 ]-4-hexadecene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 ^2,7 . 1 ^{3, 6} . 1 ^10,13 ]-4-pentadecene; heptacyclo[8.7.0.1 ^2,9 . 1 ^{4, 7} . 1 ^{11, 17} . 0 ^{3, 8} . 0 ^12,16 ]-5-eicosene, heptacyclo[8.7.0.1 ^2,9 . 0 ^{3, 8} . 1 ^{4, 7} . 0 ^{12, 17} . 1 ^13,16 ]-14-eicosene; and polycyclic cyclic olefins such as tetramer of cyclopentadiene.

Among these are alkyl-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), alkylidene-substituted norbornenes (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups). [2.2.1]hept-2-ene) is preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) ) is particularly preferred.

The norbornene monomer and monomers other than ethylene are not particularly limited as long as they are copolymerizable with the norbornene monomer and ethylene. Typical examples of such other monomers include α-olefins. The α-olefin may be substituted with at least one substituent such as a halogen atom.

As the α-olefin, C3 to C12 α-olefins are preferred. The C3 to C12 α-olefins are not particularly limited, but examples include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1 -pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Among them, 1-hexene, 1-octene and 1-decene are preferred.

[Polymerization step]
In the polymerization step, the monomers in the polymerization vessel are polymerized in the presence of a specific catalyst having a phosphine imide group.
The temperature during polymerization is not particularly limited. The temperature during polymerization is preferably 20° C. or higher, more preferably 30° C. or higher, still more preferably 50° C. or higher, and even more preferably 60° C. or higher, because the yield of the cyclic olefin copolymer is good. 70° C. or higher is particularly preferred. The temperature during polymerization may be 80° C. or higher, or may be 85° C. or higher.
The upper limit of the temperature during polymerization is not particularly limited. The upper limit of the temperature during polymerization may be, for example, 200° C. or lower, 140° C. or lower, or 120° C. or lower.

(Catalyst having a phosphine imide group)
A catalyst having a phosphine imide group (hereinafter also referred to as "catalyst A") used in the production method of the present embodiment is represented by the following general formula (A). The substituent represented by —(CH ₂ ) _n R in the following general formula (A) is a substituent satisfying condition A below.
Condition A: Substitution represented by -(CH ₂ ) _n R in a compound (C ₆ H ₅ -(CH ₂ ) _n R) in which a substituent represented by -(CH ₂ ) _n R is bonded to a benzene ring The charge of the carbon atom directly attached to the benzene ring in the group is -0.46 or less.

［一般式（Ａ）中、Ｍは周期律表第４族遷移金属を示し、Ｘはヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又はハロゲン原子を示し、Ｒ^ａ１～Ｒ^ａ３は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又は無機置換基を示し、Ｒは水素原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、及びアルキルシリル基、及びアリールシリル基から選択される１種以上を示し、ｎは１～５の整数を示す。］

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group; n is an integer of 1 to 5; ]

In general formula (A), M represents a Group 4 transition metal in the periodic table, specifically Ti, Zr, or Hf. Ti is preferable as M.

In general formula (A), X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.
Regarding the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, when the organic substituent contains a heteroatom, the type of the heteroatom is not particularly limited. Specific examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, and halogen atoms.

The organic substituent is not particularly limited as long as it does not inhibit the production reaction of the compound represented by the general formula (A). For example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, α- naphthylcarbonyl group, β-naphthylcarbonyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, trialkylsilyl group having 3 to 20 carbon atoms, 3 to 3 carbon atoms 20 triarylsilyl groups, monosubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms, and disubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms.

Among these organic substituents, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and aliphatic acyl groups having 2 to 6 carbon atoms. benzoyl, phenyl, benzyl, phenethyl, trialkylsilyl groups having 3 to 10 carbon atoms and triarylsilyl groups having 3 to 10 carbon atoms are preferred.

Among organic substituents, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methoxy group, ethoxy group, n-propyloxy group , isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, phenyl group, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group , a triphenylsilyl group, and a trispentafluorophenylsilyl group.

X is preferably a halogen atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

In general formula (A), R ^a1 to R ^a3 may each independently be the same or different, and may be a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic is a substituent. In addition, two groups selected from R ^a1 to R ^a3 may bond together to form a ring.
Regarding the organic substituents having 1 to 20 carbon atoms which may contain a hetero atom as R ^a1 to R ^a3 , when the organic substituent contains a hetero atom, the type of the hetero atom is not particularly limited. Specific examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, and halogen atoms.

The organic substituent is not particularly limited as long as it does not inhibit the production reaction of the compound represented by the general formula (A). For example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aliphatic acyl group having 2 to 20 carbon atoms, a benzoyl group, α- naphthylcarbonyl group, β-naphthylcarbonyl group, aromatic hydrocarbon group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, trialkylsilyl group having 3 to 20 carbon atoms, 3 to 3 carbon atoms 20 triarylsilyl groups, monosubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms, and disubstituted amino groups substituted with hydrocarbon groups having 1 to 20 carbon atoms.

Among these organic substituents, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and aliphatic acyl groups having 2 to 6 carbon atoms. benzoyl, phenyl, benzyl, phenethyl, trialkylsilyl groups having 3 to 10 carbon atoms and triarylsilyl groups having 3 to 10 carbon atoms are preferred.

Among organic substituents, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, adamantyl, methoxy, ethoxy, n- propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, acetyl group, propionyl group, butanoyl group, phenyl group, o-tolyl group, trimethylsilyl group, triethylsilyl group , a tert-butyldimethylsilyl group, a triphenylsilyl group, and a trispentafluorophenylsilyl group are more preferred.

In addition, the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R ^a1 to R ^a3 is a group represented by the following general formula (a), wherein R ^a1 to Groups in which each R ^a3 is independently a hydrocarbon group having 1 to 20 carbon atoms are also preferred.

Preferred examples of the case where the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R ^a1 to R ^a3 are groups represented by general formula (a) include -N= P(Me) ₃ , -N=P(Et) ₃ , -N=P(n-Pr) ₃ , -N=P(iso-Pr) ₃ , -N=P(n-Bu) ₃ , -N =P(iso-Bu) ₃ , -N=P(sec-Bu) ₃ , -N=P(tert-Bu) ₃ , -N=P(-N=P(tert-Bu)3)Ph ₂ , and -N=P(Ph) ₃ . Among these, -N=P(tert-Bu) ₃ and -N=P(iso-Pr) ₃ are preferred, and -N=P(tert-Bu) ₃ is more preferred. Incidentally, Me is a methyl group, Et is an ethyl group, n-Pr is an n-propyl group, iso-Pr is an iso-propyl group, n-Bu is an n-butyl group, iso -Bu is an isobutyl group, sec-Bu is a sec-butyl group, tert-Bu is a tert-butyl group and Ph is a phenyl group.

The inorganic substituents for R ^a1 to R ^a3 are not particularly limited as long as they do not inhibit the production reaction of the compound represented by the general formula (A).
Specific examples of inorganic substituents include halogen atoms, nitro groups, unsubstituted amino groups, cyano groups, and the like.

R ^a1 to R ^a3 in general formula (A) are preferably cyclic or non-cyclic tertiary alkyl groups, or aromatic ring groups having at least one alkyl group at the ortho position. Cyclic tertiary alkyl groups include adamantyl groups and the like, and non-cyclic tertiary alkyl groups include tert-butyl groups and the like. Examples of the aromatic ring group having at least one or more alkyl groups at the ortho position include o-tolyl group and mesityl group. When R ^a1 to R ^a3 are cyclic or non-cyclic tertiary alkyl groups, all may be different tertiary alkyl groups, and any two of the three may be the same tertiary alkyl group. preferably, and more preferably the same tertiary alkyl group.

In general formula (A), R represents one or more selected from a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group. .

The alkyl group for R includes an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group for R include methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, etc. Among them, tert-butyl group is preferred.
The cycloalkyl group as R includes a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 10 carbon atoms, and more preferably a cycloalkyl group having 5 to 8 carbon atoms. Specific examples of the cycloalkyl group for R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. Among them, a cyclohexyl group is preferred.
The halogenated alkyl group as R is an alkyl group having at least one halogen element as a substituent and includes an alkyl group having 1 to 7 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms. , more preferably a halogenated alkyl group having 1 to 3 carbon atoms. As the halogen element in the halogenated alkyl group as R, fluorine and chlorine are preferred. Specific examples of halogenated alkyl groups for R include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl groups and the like, and among them, a trifluoromethyl group is preferable.
The aryl group as R includes an aryl group having 6 to 20 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, and more preferably an aryl group having 7 to 8 carbon atoms.
Specific examples of the aryl group for R include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, an aralkyl group, a biphenyl group, etc. Among them, a phenyl group is preferred.
Examples of the halogenated aryl group as R include an aryl group having at least one halogen element as a substituent for the above aryl group as R and having 6 to 20 carbon atoms. An aryl group having 6 to 10 numbers is preferred, and an aryl group having 7 to 8 carbon atoms is more preferred. As the halogen element in the halogenated aryl group as R, fluorine and chlorine are preferable. Specific examples of halogenated aryl groups as R include 4-fluorophenyl group, 2,4-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,6-trifluorophenyl group, per A fluorophenyl group (--C ₆ F ₅ ), a perfluorobiphenyl group, a perchlorophenyl group (--C ₆ Cl ₅ ) and the like can be mentioned, and among them, a perfluorophenyl group (--C ₆ F ₅ ) is preferred.
Examples of the alkylsilyl group for R include trialkylsilyl groups such as a trimethylsilyl group and a triethylsilyl group. Among them, a trimethylsilyl group is preferred.
Examples of the arylsilyl group for R include triarylsilyl groups such as a triphenylsilyl group and a trispentafluorophenylsilyl group, among which the triphenylsilyl group is preferred.
Among these R, hydrogen atoms, those having a large number of carbon atoms in an alkyl group (the number of carbon atoms: 3 to 12), or those containing a fluorine atom are preferred. For example, a _hydrogen atom, a tert-butyl group, a phenyl group, a perfluorophenyl group ( _-C6F5 ), and a trimethylsilyl group are particularly preferred.

In general formula (A), n represents an integer of 1 to 5, preferably 1 to 3.

Specific examples of the compound represented by formula (A) are shown below, but the present embodiment is not limited to the following compounds.

On the other hand, in the general formula (A) of the catalyst A, the substituent represented by —(CH ₂ ) _n R satisfies the following condition A.
Condition A: A compound (C ₆ H ₅ —(CH ₂ ) _n R) in which a substituent represented by —(CH ₂ ) _n R is bonded to a benzene ring is represented by —(CH ₂ ) _n R. The charge of the carbon atom directly bonded to the benzene ring in the substituent is -0.46 or less. When the charge of the carbon atom exceeds -0.46, the activity as a catalyst decreases. The charge is preferably −0.47 or less, more preferably −0.48 or less, further preferably −0.49 or less, even more preferably −0.50 or less, and particularly preferably −0.60 or less. Also, the lower limit of the charge of the carbon atom is preferably −0.70.
The charge of the carbon atom can be calculated as follows. That is, the quantum chemical calculation for C ₆ H ₅ —(CH ₂ ) _n R, which is a compound in which the substituent represented by —(CH ₂ ) _n R is bonded to the benzene ring, is performed by DFT called M11 as natural bond orbital analysis. It is implemented using theory and basis functions called cc-pvdz. A natural bond orbital analysis is performed on the obtained molecular orbital to calculate the atomic charge (elementary charge (e)) of the carbon atom (C) bonded to the benzene ring.

In the compound (C ₆ H ₅ —(CH ₂ ) _n R) in _which the substituent represented by —(CH 2 ) n R in general _{formula (A) is bonded to the benzene ring, —(CH 2 ) n} R The charge on the carbon atom directly bonded to the benzene ring in the substituents, ie, the charge on the carbon atom according to condition A, is shown below.
_-CH2 - _{C6F5 :} -0.49
_-CH2CH2 - _{C6F5 : -0.46
-CH2CH2} - _{C6H5 : -0.46
-CH2CH2 -} C( _CH3 ) ₃ : -0.47
—CH ₂ CH ₂ —Si(CH ₃ ) ₃ : −0.47
_-CH2 - _{C6H5 :} -0.48
—CH ₃ : —0.68
However, in the above, —C ₆ F ₅ is a perfluorophenyl group.

From the viewpoint of improving activity, the catalyst A preferably has an insertion activation energy of ethylene with respect to titanium-ethylene-ethylene of 7 kcal/mol or less, more preferably 0.8 to 6.9 kcal/mol. Similarly, catalyst A preferably has an insertion activation energy of norbornene with respect to titanium-norbornene-ethylene of 31 kcal/mol or less, more preferably 17 to 30 kcal/mol.
For the above activation energy, the quantum chemical calculation Gaussian uses a DFT theory called M11 and a basis function called cc-pvdz to analyze the reactivity and calculate the activation enthalpy in the polymerization reaction. obtained by

Catalyst A (compound represented by general formula (A)) may produce a viscous substance when in an unactivated state and in contact with norbornene. It is speculated that the formation of the viscous substance is caused by the decomposition of the catalyst A with water to produce HCl, which promotes the cationic polymerization of norbornene. The formation of such a viscous substance can be suppressed by including at least one fluorine in R in the general formula (A). That is, the larger the number of fluorine atoms in R in formula (A), the higher the water repellency, the more suppressed the production of HCl, and the more suppressed the production of viscous substances. Therefore, it is preferable that R in general formula (A) contains one or more fluorine atoms. Specifically, the fluorine in R in general formula (A) is bonded to sp ² carbon (for example, -(CH ₂ ) _n -C ₆ F ₅ ), or three fluorines are attached to the same carbon A bond (eg, —(CH ₂ ) _n —CF ₃ ) is preferred. Among them, bonding to sp ² carbon (for example, —(CH ₂ ) _n —C ₆ F ₅ ) is particularly preferable from the viewpoint of ease of synthesis. However, if the amount of fluorine is too large, the electron-withdrawing property may increase and the catalyst A may become unstable. The sp ² carbon is a carbon atom forming an sp ² hybrid orbital.

The compound represented by the general formula (A), which is the catalyst A, is described by Douglas W. et al. Stephan et al. Organometallics 1999, 18, 1116-1118. can be manufactured with reference to

Polymerization of the monomers is preferably carried out in the presence of catalyst A and a co-catalyst. As the co-catalyst, compounds generally used as co-catalysts in the polymerization of olefins can be used without particular limitation. Suitable examples of co-catalysts include aluminoxanes and ionic compounds. The polymerization of the monomers is preferably carried out using at least one of an aluminoxane and a borate compound as an ionic compound as a cocatalyst because the polymerization reaction tends to proceed well. Details of the co-catalyst will be described later.

In the present embodiment, in the polymerization step, a norbornene monomer and ethylene are copolymerized using the above catalyst A (and, if necessary, a cocatalyst to be described later). It will be described together with the catalyst composition to be described.

<Catalyst composition>
The catalyst composition of the present embodiment is a catalyst composition containing a catalyst having a phosphineimide group, which is used for copolymerization of a norbornene monomer and ethylene. The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following is a substituent that satisfies the condition A of
Condition A: Substitution represented by -(CH ₂ ) _n R in a compound (C ₆ H ₅ -(CH ₂ ) _n R) in which a substituent represented by -(CH ₂ ) _n R is bonded to a benzene ring The charge of the carbon atom directly attached to the benzene ring in the group is -0.46 or less.

［一般式（Ａ）中、Ｍは周期律表第４族遷移金属を示し、Ｘはヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又はハロゲン原子を示し、Ｒ^ａ１～Ｒ^ａ３は、それぞれ独立に、同一でも異なっていてもよく、水素原子、ヘテロ原子を含んでいてもよい炭素原子数１～２０の有機置換基又は無機置換基を示し、Ｒは水素原子、アルキル基、シクロアルキル基、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、アルキルシリル基、及びアリールシリル基から選択される１種以上を示し、ｎは１～５の整数を示す。］

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, cycloalkyl group, halogenated alkyl group, aryl group, halogenated aryl group, alkylsilyl group, and arylsilyl group, and n is an integer of 1-5. ]

The catalyst in the catalyst composition of this embodiment is the same as the catalyst A described in the manufacturing method of this embodiment. That is, the catalyst composition of this embodiment contains the catalyst A. Therefore, the explanation of the catalyst in the catalyst composition of the present embodiment is the same as the explanation of the catalyst A, so the explanation is omitted here, and the components other than the catalyst will be mainly explained below.

The catalyst composition of the present embodiment preferably contains a co-catalyst in addition to the catalyst A. As a co-catalyst, it is preferable to use an aluminoxane and/or an ionic compound.
Here, the ionic compound is a compound that produces a cationic transition metal compound by reaction with a metal-containing catalyst.

The catalyst composition of this embodiment is preferably prepared using a solution of catalyst A. The solvent contained in the solution of catalyst A is not particularly limited. Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), mineral oil, benzene, toluene, and xylene, chloroform, Halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene are included.

The amount of solvent used is not particularly limited as long as a catalyst composition with desired performance can be produced. Typically, the concentrations of catalyst A, aluminoxane, and ionic compound are preferably 0.00000001 to 100 mol/L, more preferably 0.00000005 to 50 mol/L, and particularly preferably 0.0000001 to 20 mol/L. amount of solvent is used.

When mixing the liquid containing the raw materials of the catalyst composition, the number of moles of the transition metal M in the catalyst A is M _a , the number of moles of aluminum in the aluminoxane is M _b1 , and the number of moles of the ionic compound is M _b2 . In the case, the value of (M _b1 +M _b2 )/M _a is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000. preferably.

The temperature at which the liquid containing the raw materials of the catalyst composition is mixed is not particularly limited, but -100 to 100°C is preferable, and -50 to 50°C is more preferable.

Mixing of the solution of catalyst A, the aluminoxane, and/or the ionic compound for preparing the catalyst composition may be performed in a device separate from the polymerization vessel before polymerization. It may be done before or during the polymerization.

The materials used for preparing the catalyst composition and the conditions for preparing the catalyst composition are described below.

[Aluminoxane]
As the aluminoxane, various aluminoxanes conventionally used as co-catalysts in the polymerization of various olefins can be used without particular limitation. Typically the aluminoxane is an organic aluminoxane.
In the production of the catalyst composition, the aluminoxanes may be used singly or in combination of two or more.

As the aluminoxane, an alkylaluminoxane is preferably used. Examples of alkylaluminoxanes include compounds represented by the following formula (b1-1) or (b1-2). An alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting trialkylaluminum with water.

［式（ｂ１－１）及び式（ｂ１－２）中、Ｒは炭素原子数１～４のアルキル基、ｎは０～４０、好ましくは２～３０の整数を示す。］

[In formulas (b1-1) and (b1-2), R represents an alkyl group having 1 to 4 carbon atoms; n represents an integer of 0 to 40, preferably 2 to 30; ]

Examples of alkylaluminoxanes include methylaluminoxane and modified methylaluminoxane obtained by substituting a portion of the methyl groups of methylaluminoxane with other alkyl groups. As the modified methylaluminoxane, for example, modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group as an alkyl group after substitution is preferable, and in particular, Modified methylaluminoxane in which part of the methyl groups are substituted with isobutyl groups is more preferred. Specific examples of alkylaluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferred.

Alkyl aluminoxanes can be prepared by known methods. Moreover, you may use a commercial item as an alkylaluminoxane. Examples of commercially available alkylaluminoxanes include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), and methylaluminoxane solution (manufactured by Albemarle). . It is more preferable to use an alkylaluminoxane other than solid MAO from the viewpoint of easily suppressing the generation of polyethylene-like impurities.

[Ionic compound]
An ionic compound is a compound that reacts with catalyst A to form a cationic transition metal compound.
Such ionic compounds include the anion of tetrakis(pentafluorophenyl)borate, amine cations with active protons such as the dimethylphenylammonium cation ((CH ₃ ) ₂ N(C ₆ H ₅ )H ⁺ ), (C ₆ H ₅ ) Ionic compounds containing ions such as trisubstituted carbonium cations such as _3C ⁺ , carborane cations, metal carborane cations, ferrocenium cations with transition metals can be used.

Suitable examples of ionic compounds include borates. Preferred specific examples of borates include tetrakis(pentafluorophenyl)tritylborate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and N-methyldi-normaldecyl Examples include N-methyldialkylammonium tetrakis(pentafluorophenyl)borate such as ammonium tetrakis(pentafluorophenyl)borate.

Next, the step of copolymerizing a norbornene monomer and ethylene using the catalyst A or the catalyst composition of the present embodiment in the production method of the present embodiment will be described.
Aluminoxanes and alkylaluminum compounds are selected from aluminoxanes and alkylaluminum compounds before adding the metal-containing catalyst or the catalyst composition containing the metal-containing catalyst to the polymerization vessel, since the cyclic olefin copolymer can be easily produced in a good yield. It is preferred to have one or more present.

Aluminoxanes are as described above.
As the alkylaluminum compound, compounds conventionally used for polymerization of olefins can be used without particular limitation. Examples of alkylaluminum compounds include compounds represented by the following general formula (II).
(R ¹⁰ ) _z AlX _3-z (II)
(In general formula (II), R ¹⁰ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3. )

Examples of alkyl groups having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and n-octyl group.

Specific examples of alkylaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as aluminum chloride and diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.

When the aluminoxane is added to the polymerization vessel before adding the catalyst A or the catalyst composition containing the catalyst A, the amount used is preferably 1 to 1,000,000 mol as the number of moles of aluminum in the aluminoxane per 1 mol of the transition metal compound, 10 to 100,000 moles is more preferred.
When the alkylaluminum compound is added to the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A, the amount used is preferably 1 to 500,000 mol, preferably 10, as the number of moles of aluminum per 1 mol of the transition metal compound. ~50000 moles is more preferred.

Polymerization conditions are not particularly limited as long as a cyclic olefin copolymer having desired physical properties can be obtained, and known conditions can be used.
The amount of catalyst A used is derived from the amount of transition metal compound used in its preparation. The amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, relative to 1 mol of the norbornene monomer, as the mass of the transition metal compound used for its preparation. more preferred.

The polymerization time is not particularly limited, and the polymerization is carried out until the desired yield is reached or the molecular weight of the polymer is increased to the desired extent.
The polymerization time varies depending on the temperature, the composition of the catalyst composition, and the monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and 0.2 hours. hours to 10 hours is more preferred.

At least a portion, preferably all, of Catalyst A or the catalyst composition is preferably added continuously to the polymerization vessel.
By continuously adding the catalyst A or the catalyst composition, continuous production of the cyclic olefin copolymer becomes possible, and the production cost of the cyclic olefin copolymer can be reduced.

According to the method described above, a cyclic olefin copolymer can be efficiently produced by copolymerizing a norbornene monomer and a monomer containing ethylene, while suppressing the production of polyethylene-like impurities.
The glass transition temperature of the obtained cyclic olefin copolymer is not particularly limited, but from the viewpoint of processability, for example, it is preferably 185° C. or lower, more preferably 160° C. or lower, even more preferably 130° C. or lower, and even more preferably 120° C. or lower. 100° C. or lower is particularly preferred.
In addition, a sample of the cyclic olefin copolymer produced by the above method was measured by a differential scanning calorimeter (DSC) under a nitrogen atmosphere at a heating rate of 20°C/min according to the method described in JIS K7121. In that case, it is preferred that the DSC curve obtained does not have a melting point (melting enthalpy) peak derived from polyethylene-like impurities. This means that there are no or very few polyethylene-like impurities in the cyclic olefin copolymer. When polyethylene-like impurities are contained in the cyclic olefin copolymer, the melting point peak derived from the polyethylene-like impurities on the DSC curve is generally detected within the range of 100°C to 140°C. be.

EXAMPLES The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to the following examples.

[Examples 1-5, Comparative Examples 1-2]
Decahydronaphthalene (Decalin) and the amount (75-185 mmol) of 2-norbornene described in Table 1 were added to a well-dried 150 mL stainless steel autoclave containing a stir bar.
After adding 250 μmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.), the autoclave was heated to 90°C. A catalyst solution of the catalyst species listed in Table 1 prepared using toluene was added so that the catalyst amount was 0.5 μmol, and then N-methyldialkylammonium tetrakis(pentafluorophenyl)borate prepared using decalin. A solution of (alkyl: C14 to C18 (average: C17.5) (manufactured by Tosoh Finechem Co., Ltd.) was added so that the amount of N-methyldialkylammonium tetrakis(pentafluorophenyl)borate was 1.5 μmol. Then, after applying an ethylene pressure of 0.9 MPa gauge pressure, 30 seconds later was taken as the polymerization initiation point.
The total amount of the monomer solution immediately before applying ethylene pressure was 80 mL.
After 15 minutes from the initiation of polymerization, the supply of ethylene was stopped and the pressure was carefully returned to normal pressure, and then isopropyl alcohol was added to the reaction solution to terminate the reaction. After that, the polymerization solution was added to a mixed solvent of 300 mL of acetone, 200 mL of methanol or isopropyl alcohol, and 5 mL of hydrochloric acid to precipitate the copolymer. The copolymer was recovered by suction filtration, washed with acetone and methanol, and vacuum-dried at 110° C. for 12 hours to obtain a copolymer of norbornene and ethylene.
In Table 1, Exemplified Compounds 1 to 5 correspond to Exemplified Compounds 1 to 5 shown as specific examples of the compound represented by the above general formula (A). The structures of Comparative Compounds 1 and 2 are shown below. Furthermore, the “charge of carbon atom” is calculated for a compound (C ₆ H ₅ —(CH ₂ ) _n R) in which the substituent represented by —(CH ₂ ) _n R of the catalyst is attached to the benzene ring. , indicates the charge of the carbon atom directly attached to the benzene ring. However, for Comparative Compound 1 and Comparative Compound 2, which do not contain a substituent represented by —(CH ₂ ) _n R, C ₆ For H ₅ —C(CH ₃ ) ₃ or C ₆ H ₅ —Si(CH ₃ ) ₃ , it was calculated as the charge of the carbon or silicon atom directly attached to the benzene ring. In Table 1, the Ti-E-E activation energy indicates the insertion activation energy of ethylene to titanium-ethylene-ethylene, and the Ti-NE activation energy indicates the insertion activation energy of norbornene to titanium-norbornene-ethylene. Show energy.

[evaluation]
(1) Yield of Cyclic Olefin Copolymer In each of the examples and comparative examples, the copolymer yield (kg) per 1 g of catalyst was calculated from the amount of catalyst used and the yield of copolymer. Table 1 shows the calculation results.
(2) Measurement of glass transition temperature (Tg) The glass transition temperature of the cyclic olefin copolymer obtained in each example and comparative example was measured by the DSC method (method described in JIS K7121) using a differential scanning calorimeter (TA Measurement was performed using a differential scanning calorimeter (DSC-Q1000, manufactured by Instrument Co.) in a nitrogen atmosphere at a heating rate of 20°C/min. Table 1 shows the measurement results.
(3) Impurity thermal analysis In the DSC curve obtained by measuring the glass transition temperature, the calorific value (mJ/mg) is calculated from the peak area of the melting point derived from polyethylene-like impurities observed in the range of 100 to 140 ° C. Calculated. The higher the calculated calorific value, the higher the content of polyethylene-like impurities.
Not detected in Table 1 indicates that no melting point peak derived from polyethylene-like impurities is detected on the DSC curve.
(4) Turbidity test After dissolving 0.1 g of the cyclic olefin copolymer obtained in each example and comparative example in 10 g of toluene, the presence or absence of turbidity in the solution was observed. A case where no turbidity was observed was evaluated as "good", and a case where turbidity was observed was evaluated as "poor". Table 1 shows the evaluation results.
(5) Formation of viscous substance 3 mL of norbornene decalin solution (concentration: 35% by mass) is added to 1 μmol of the catalyst used in each example and comparative example to form a gel-like substance (viscous substance). It was visually observed whether or not When no gel-like substance was generated, it was evaluated as "absent", and when it was generated, it was evaluated as "yes". Table 1 shows the evaluation results.

From Table 1, it can be seen that in Examples 1 to 5, compared to Comparative Examples 1 and 2, the yield was large and the activity of the catalyst was high. In addition, in Examples 1 to 5, no impurities were detected by impurity thermal analysis, and the polymer solution did not show turbidity in the turbidity test, indicating that the formation of polyethylene-like impurities was suppressed.
On the other hand, when a solution of norbornene in decalin was added to the catalyst used in each example, Examples 1, 2 and 5 did not produce a viscous substance, whereas Examples 3 and 4 produced a viscous substance. A thick material resulted. From these comparisons, it can be seen that the formation of viscous substances is suppressed when R in general formula (A) has fluorine.

Claims (8)

A method for producing a cyclic olefin copolymer containing structural units derived from norbornene monomers and structural units derived from ethylene,
charging at least a norbornene monomer and ethylene as monomers into a polymerization vessel;
and polymerizing the monomer in the polymerization vessel in the presence of a catalyst having a phosphine imide group,
The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following A method for producing a cyclic olefin copolymer having a substituent satisfying condition A.
Condition A: In the compound (C ₆ H ₅ —(CH ₂ ) _n R) in which the substituent represented by —(CH ₂ ) _n R is bonded to the benzene ring, the —(CH ₂ ) _n R The charge of the carbon atom directly bonded to the benzene ring in the substituent is -0.46 or less.

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, cycloalkyl group, halogenated alkyl group, aryl group, halogenated aryl group, alkylsilyl group, and arylsilyl group, and n is an integer of 1-5. ] 2. The method for producing a cyclic olefin copolymer according to claim 1, wherein the catalyst has an insertion activation energy of ethylene with respect to titanium-ethylene-ethylene of 7 kcal/mol or less. 3. The method for producing a cyclic olefin copolymer according to claim 1, wherein the catalyst has an insertion activation energy of norbornene with respect to titanium-norbornene-ethylene of 31 kcal/mol or less. Claim 1 or 2 , wherein R ^a1 to R ^a3 in the general formula (A) are a cyclic or non-cyclic tertiary alkyl group, or an aromatic ring group having at least one alkyl group at the ortho position. The method for producing the cyclic olefin copolymer according to 1. The method for producing a cyclic olefin copolymer according to claim 1 or 2 , wherein R in the general formula (A) is a perfluorophenyl group. A catalyst composition containing a catalyst having a phosphine imide group for copolymerization of a norbornene monomer and ethylene,
The catalyst having a phosphineimide group is a compound represented by the following general formula (A), and the substituent represented by —(CH ₂ ) _n R in the following general formula (A) is the following A catalyst composition that is a substituent that satisfies condition A.
Condition A: In the compound (C ₆ H ₅ —(CH ₂ ) _n R) in which the substituent represented by —(CH ₂ ) _n R is bonded to the benzene ring, the —(CH ₂ ) _n R The charge of the carbon atom directly bonded to the benzene ring in the substituent is -0.46 or less.

[In the general formula (A), M represents a Group 4 transition metal of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom or a halogen atom, and R ^a1 to R ^a3 each independently, which may be the same or different, represents a hydrogen atom, an organic substituent or an inorganic substituent having 1 to 20 carbon atoms which may contain a hetero atom, R is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group, and an arylsilyl group; n is an integer of 1 to 5; ] 7. The group according to claim 6, wherein R ^a1 to R ^a3 in the general formula (A) are a cyclic or non-cyclic tertiary alkyl group, or an aromatic ring group having at least one alkyl group at the ortho position. catalyst composition. 8. The catalyst composition according to claim 6, wherein R in said general formula (A) is a perfluorophenyl group.