JP2020164719A - Method for producing olefin/cyclic olefin copolymer - Google Patents

Abstract

To provide a method for producing an olefin/cyclic olefin copolymer using a catalyst for olefin polymerization containing a novel transition metal compound.SOLUTION: There is provided a production method for copolymerizing an olefin and a cyclic olefin compound in the presence of a catalyst for olefin polymerization including: a transition metal compound represented by a formula [A-1]; and at least one kind of compounds (B) selected from (B-1) an organometallic compound, (B-2) an organic aluminum oxy compound, and (B-3) a compound which reacts with a transition metal compound (A) to form an ion pair, in which M represents Ti, Zr, a Hf atom, m is an integer of 1 to 3, X represents H, a hydrocarbon group, a halogen-containing group, and the like, A and B are S, O, CR3 (where, R3 is H, an alkyl group, and the like), R1 to R2 are H, a C1 to C20 hydrocarbon group, a halogen-containing group, and the like, and L contains C and H as essential components and further contains atom selected from Group 15 element and group 16 element.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an olefin / cyclic olefin copolymer using a catalyst for olefin polymerization containing a transition metal compound.

As a catalyst for producing an olefin polymer such as an ethylene / α-olefin copolymer, a catalyst composed of a metallocene compound and a co-catalyst such as an organoaluminum oxy compound is known.

As such catalysts, transition metal compounds such as various types of metallocene compounds have been actively developed. For example, in Patent Document 1, the transition metal compound (A) represented by the following general formula:

（式中、ＭはＴｉ等の周期律表４族の遷移金属を表し、Ｌは周期律表１５族の元素が配位原子となる１価のアニオン性配位子を表し、Ｘはハロゲン等を表し、ｍは１〜３の整数を表し、Ｒ¹〜Ｒ⁵は、水素、ハロゲン又は炭素原子数１〜２０のアルキル基等を表す。）
ならびに有機アルミニウムオキシ化合物および有機ホウ素化合物から選ばれる１種以上の活性化剤（Ｂ）からなる重合触媒の存在下、エチレンおよび／または炭素原子数３〜２０のα−オレフィンと少なくとも１種類の環状オレフィン化合物との共重合を行う環状オレフィン系共重合体の製造方法が記載され、遷移金属化合物（Ａ）の具体例としては、ＣｐＴｉ（ｔ−Ｂｕ₂Ｃ＝Ｎ）Ｃｌ₂、比較例としてＣｐ^*Ｔｉ（２，６−ⁱＰｒ₂ＰｈＯ）Ｃｌ₂が挙げられている。（Ｃｐはシクロペンタジエニル基を、Ｃｐ^*はη⁵−ペンタメチルシクロペンタジエニル基を表す。）。

(In the formula, M represents a transition metal of Group 4 of the periodic table such as Ti, L represents a monovalent anionic ligand in which an element of Group 15 of the periodic table serves as a coordination atom, and X represents a halogen or the like. , M represents an integer of 1 to 3, and R ^{1 to} R ⁵ represent hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, and the like.)
In the presence of a polymerization catalyst consisting of one or more activators (B) selected from organoaluminum oxy compounds and organoboron compounds, ethylene and / or α-olefins having 3 to 20 carbon atoms and at least one cyclic A method for producing a cyclic olefin-based copolymer that is copolymerized with an olefin compound is described. As a specific example of the transition metal compound (A), CpTi (t-Bu ₂ C = N) Cl _{2 is described} , and as a comparative example, Cp. ^* Ti (2,6- ⁱ Pr ₂ PhO) Cl ₂ is mentioned. (Cp represents a cyclopentadienyl group and Cp ^* represents a η ⁵ -pentamethylcyclopentadienyl group).

On the other hand, a thiophene-condensed half-metallocene is known as a metallocene compound in which a group containing a hetero atom is bonded to a cyclopentadienyl skeleton. This compound also has a structure of ketimid, phosphineimide, and allyloxy type as a substituent (ligand) different from the cyclopentadienyl skeleton (Non-Patent Document 1).

Japanese Unexamined Patent Publication No. 2007-63409

Journal of Organometallic chemistry_2011_2451.

However, when the transition metal compound described in Patent Document 1 as a metallocene compound is used as a catalyst for polymerization of ethylene or α-olefin, further improvements are made in terms of catalytic activity, copolymerizability, and high molecular weight of the polymer. It turned out that there was room.
An object of the present invention is to provide a method for producing an olefin / cyclic olefin copolymer using a catalyst for olefin polymerization containing a novel transition metal compound.

The present invention comprises a transition metal compound represented by the following general formula [A-1] and
(B) (B-1) Organic metal compound,
At least one compound (B) selected from the group consisting of (B-2) organoaluminum oxy compounds and (B-3) compounds that react with transition metal compounds (A) to form ion pairs.
The present invention relates to a method for producing an olefin / cyclic olefin copolymer, which comprises copolymerizing an olefin and a cyclic olefin compound in the presence of a catalyst for olefin polymerization including.

〔式［Ａ−１］において、
Ｍはチタン原子、ジルコニウム原子、またはハフニウム原子であり、
ｍは１〜３の整数であり、
Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、またはジエン系二価誘導体基であり、
ＡおよびＢは、硫黄（Ｓ）、酸素（Ｏ）またはＣＲ³（Ｒ³は、水素、アルキル基等である。）、ＡがＳ又はＯであるならばＢはＣＲ³であるか、又はＢがＳ又はＯであるならばＡはＣＲ³であり、ＡとＢを含む環は可能な位置で二重結合を有する）であり；
Ｒ¹〜Ｒ²はそれぞれ独立に水素原子、炭素原子数１〜２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基であり、
Ｌは炭素、水素を必須とし、さらに１５族元素、および１６族元素から選ばれる原子を含む構造を有する。

[In the formula [A-1]
M is a titanium atom, a zirconium atom, or a hafnium atom,
m is an integer from 1 to 3
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene type. It is a divalent derivative group and
A and B are sulfur (S), oxygen (O) or CR ³ (R ³ is hydrogen, alkyl group, etc.), if A is S or O then B is CR ³ or If B is S or O, then A is CR ³ and the ring containing A and B has a double bond where possible);
R ^{1 to} R ² are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups. And
L requires carbon and hydrogen, and has a structure containing atoms selected from Group 15 elements and Group 16 elements.

By using the catalyst for olefin polymerization of the present invention, it is possible to produce a highly active, high molecular weight olefin / cyclic olefin copolymer.

The olefin polymerization catalyst used in the method for producing an olefin / cyclic olefin copolymer of the present invention includes transition metal compounds (A), (B) (B-1) organometallic compounds, and (B-2) organoaluminum oxy compounds. And (B-3) include at least one compound (B) selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair.

[Transition metal compound (A)]
The transition metal compound (A) that forms the catalyst for olefin polymerization according to the present invention is specified by satisfying the requirements of the following structural formula.

〔式［Ａ−１］において、
Ｍはチタン原子、ジルコニウム原子、またはハフニウム原子であり、
ｍは１〜３の整数であり、
Ｘはそれぞれ独立に水素原子、ハロゲン原子、炭化水素基、ハロゲン含有基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基、リン含有基、ホウ素含有基、アルミニウム含有基、またはジエン系二価誘導体基であり、
ＡおよびＢは、硫黄（Ｓ）、酸素（Ｏ）またはＣＲ³（Ｒ³は、水素、アルキル基等である。）であり、ＡがＳ又はＯであるならばＢはＣＲ³であるか、又はＢがＳ又はＯであるならばＡはＣＲ³であり、ＡとＢを含む環は可能な位置で二重結合を有し；
Ｒ¹およびＲ²はそれぞれ独立に水素原子、炭素原子数１〜２０の炭化水素基、ハロゲン原子、ハロゲン含有基、ケイ素含有基、酸素含有基、窒素含有基、イオウ含有基、またはリン含有基であり、
Ｌは炭素、水素を必須とし、さらに１５族、１６族元素から選ばれる原子を含む構造を有する。〕

[In the formula [A-1]
M is a titanium atom, a zirconium atom, or a hafnium atom,
m is an integer from 1 to 3
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene type. It is a divalent derivative group and
A and B are sulfur (S), oxygen (O) or CR ³ (R ³ is hydrogen, alkyl group, etc.), and if A is S or O, is B CR ³ ? , Or if B is S or O, then A is CR ³ , and the ring containing A and B has a double bond where possible;
R ¹ and R ² are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups. And
L requires carbon and hydrogen, and has a structure containing atoms selected from Group 15 and Group 16 elements. ]

The above-mentioned M is a representative element of the Group 4 element of the so-called periodic table, and is an element having high anionic polymerizable property. Among these, titanium and zirconium are preferable, and titanium is more preferable.
It is preferable that X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.
When m is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

Specific examples of the halogen atom (X) include fluorine, chlorine, bromine, and iodine, but chlorine or bromine is preferable.
A and B are a sulfur atom, an oxygen atom and a CR ³ , and when A is a sulfur atom and an oxygen atom, B is a CR ³ and when B is a sulfur atom and an oxygen atom, A is a CR ³ A preferred embodiment is a mode in which A or B is a sulfur atom and the other is CH. The ring containing A and B has a double bond at a position where a double bond can be formed.

R ^{1 to} R ² are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, respectively. An atom or substituent selected from the group consisting of.
Hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms, and 3 carbon atoms. 20 to 20 cyclic unsaturated hydrocarbon groups are exemplified.

The alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl which are linear saturated hydrocarbon groups. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc., which are branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl. Group, neopentyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1- Examples thereof include a dimethyl-2-methylpropyl group, a 1-methyl-1-isopropyl-2-methylpropyl group, and a cyclopropylmethyl group. The alkyl group preferably has 1 to 6 carbon atoms.

Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornenyl group, 1-adamantyl group, which are cyclic saturated hydrocarbon groups. 3-Methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4 which is a group in which the hydrogen atom of the cyclic saturated hydrocarbon group such as 2-adamantyl group is replaced with a hydrocarbon group having 1 to 17 carbon atoms. -Cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like are exemplified. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.

Chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as etenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). Examples thereof include an ethynyl group, a 1-propynyl group, and a 2-propynyl group (propargyl group), which are alkynyl groups. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopentadienyl group, a norbornyl group, a phenyl group, a naphthyl group, an indenyl group, an azulenyl group, a phenanthryl group and an anthrasenyl group, which are cyclic unsaturated hydrocarbon groups. , 3-Methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which the hydrogen atom of the cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms. , 4-Ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A benzyl group, which is a group in which the hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced with a cyclic saturated hydrocarbon group having 3 to 19 carbon atoms or a cyclic unsaturated hydrocarbon group, such as a mesityl group. Examples include a Kumil group. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a dimethylmethylene group (isopropyridene group), an ethylmethylene group, a 1-methylethylene group, a 2-methylethylene group, and a 1,1-dimethylethylene group. Examples include 1,2-dimethylethylene group and n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.

Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

As the aryl group, although it partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, it is a substituent derived from an aromatic compound, such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Examples thereof include a group, anthrasenyl group, phenanthrenyl group, tetrasenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

Examples of the aromatic compound include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysen, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene. Will be done.

The substituted aryl group partially overlaps with the above-mentioned example of a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but the aryl group has one or more hydrogen atoms having 1 to 20 carbon atoms. Examples thereof include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and specifically, a 3-methylphenyl group (m-tolyl group). ), 4-Methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4- (trimethylsilyl) Phenyl group, 4-aminophenyl group, 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3- (trifluoromethyl) phenyl group, Examples include 4- (trifluoromethyl) phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2- (6-methyl) pyridyl group and the like. Will be done. Further, as the substituted aryl group, "electron donating group-containing substituted aryl group" described later can also be mentioned.

As the silicon-containing group, among hydrocarbon groups having 1 to 20 carbon atoms, alkyl such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group and triisopropylsilyl group in which carbon atom is replaced with silicon atom. Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and t-butyldiphenylsilyl group, pentamethyldisilanyl group and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

As the nitrogen-containing group, an amino group, a nitro group, an N-morpholinyl group, a above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group, = CH-a group in which the structural unit is replaced with a nitrogen atom,- CH ₂ -Structural unit is a group replaced with a nitrogen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, or -CH ₃ Structural unit is a nitrogen atom or nitrile group to which a hydrocarbon group having 1 to 20 carbon atoms is bonded. Examples thereof include a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group and the like which are the groups replaced with. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

The oxygen-containing group includes a hydroxyl group, a above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which the -CH ₂ -structural unit is replaced with an oxygen atom or a carbonyl group, or-. A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, a hydroxymethyl group in which the CH ₃ structural unit is replaced with an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded. Group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl Group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl Examples thereof include a group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an etocarboxymethyl group, a carbamoylmethyl group, a furanyl group and a pyranyl group. As the oxygen-containing group, a methoxy group is preferable.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.
Examples of the halogen-containing group include a trifluoromethyl group and a tribromo, which are groups in which a hydrogen atom is substituted with a halogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group. Examples thereof include a methyl group, a pentafluoroethyl group and a pentafluorophenyl group.

The substituent containing oxygen, sulfur, and nitrogen in the periodic table may contain a ketimide group, a phosphineimide group, and an amidimide group, which will be described later, but preferably have different structures.
In the above formula [A-1]

で表される構造の例としては、以下の構造が挙げられる。

Examples of the structure represented by are the following structures.

は炭素、水素を必須とし、さらに１５族、１６族元素から選ばれる原子を含む構造を有する。Ｌは置換基、配位子のどちらであってもよい。

Requires carbon and hydrogen, and has a structure containing atoms selected from Group 15 and Group 16 elements. L may be either a substituent or a ligand.

Among the above elements, nitrogen, phosphorus and oxygen are preferable, and nitrogen and phosphorus are particularly preferable.
Specific structures of the above L include a ketimide structure (L-1), a phosphineimide structure (L-2), an amidide structure (L-3), and an aryloxy structure (L-4). More specifically, it can be expressed by the following structural formula.

The ketimid ligand is represented by the following general formula L-1 and is defined as follows.
(A) Bonded to a Group 4 metal via a metal-nitrogen atom bond;
(B) The nitrogen atom has a single substituent (where the single substituent is a carbon atom that is double bonded to the N atom); and (c) the carbon atom. Means a ligand having Sub1 and Sub2 as described below with two substituents attached to

〔式（Ｌ−１）において、Sub１、Sub２は各々独立して互いに同一でも異なっていても良く、Sub１、Sub２は水素、炭素数１〜２０のアルキル基、アルコキシ基、アミド基、アリール基、アラルキル基、シリル基、アルキルシリル基、アリールアミド基、シリルアミド基、ホスフィノアミド基、およびホスフィド基を表す。また各々が互いに結合して環を形成してもよい。〕
このような置換基、配位子として、具体的には、上記Sub１、Sub２が結合したＬ−１は、下記の様な構造を例示することが出来る。

[In the formula (L-1), Sub1 and Sub2 may be independently the same or different from each other, and Sub1 and Sub2 are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an amide group, an aryl group, and the like. Represents an aralkyl group, a silyl group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphido group. In addition, each may be bonded to each other to form a ring. ]
As such a substituent and a ligand, specifically, L-1 to which Sub1 and Sub2 are bonded can exemplify the following structure.

本前記のホスフィンイミド配位子は下記一般式Ｌ−２で表され、次のように定義される。
（ａ）第4族金属に金属-窒素原子結合を介して結合される；
（ｂ）上記窒素原子に単一の置換基を有する（ここで、その単一の置換基はそのN原子に二重結合で結合されているP原子である）；および
（Ｃ）上記Ｐ原子に結合されている３個の置換基（以下において説明されるSub３、Sub４およびSub５を有する配位子を意味する

The above-mentioned phosphine-imide ligand is represented by the following general formula L-2 and is defined as follows.
(A) Bonded to Group 4 metals via metal-nitrogen atom bonds;
(B) The nitrogen atom has a single substituent (where the single substituent is a P atom bonded to the N atom in a double bond); and (C) the P atom. Means a ligand having three substituents (Sub3, Sub4 and Sub5 described below) attached to

〔式（Ｌ−２）において、Sub３、Sub４およびSub５は各々独立して互いに同一でも異なっていても良く、Sub３、Sub４およびSub５は水素、炭素数1〜20のアルキル基、アルコキシ基、アミド基、アリール基、アラルキル基、シリル基、アルキルシリル基、アリールアミド基、シリルアミド基、ホスフィノアミド基、およびホスフィド基を表す。また各々が互いに結合して環を形成してもよい。〕
このような置換基、配位子として、具体的には、上記Sub３、Sub４およびSub５が結合したＬ−２は、下記の様な構造を例示することが出来る。

[In the formula (L-2), Sub3, Sub4 and Sub5 may be independently the same or different from each other, and Sub3, Sub4 and Sub5 are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group and an amide group. , Aryl group, aralkyl group, silyl group, alkylsilyl group, arylamide group, silylamide group, phosphinoamide group, and phosphido group. In addition, each may be bonded to each other to form a ring. ]
As such a substituent and a ligand, specifically, L-2 to which the above-mentioned Sub3, Sub4 and Sub5 are bonded can exemplify the following structure.

本発明のアミジミド配位子は下記一般式Ｌ−３で表され、次のように定義される。
（ａ）第4族金属に金属-窒素原子結合を介して結合される；
（ｂ）Sub６は第１４族原子を含む置換基であり、第１４族原子を介してSub６がイミン炭素原子に結合される。
（ｃ）Sub７は第１５〜１６族のヘテロ原子を含む置換基であり、該ヘテロ原子を介してSub７がイミン炭素原子に結合される。

The amidimid ligand of the present invention is represented by the following general formula L-3 and is defined as follows.
(A) Bonded to Group 4 metals via metal-nitrogen atom bonds;
(B) Sub6 is a substituent containing a Group 14 atom, and Sub6 is bonded to an imine carbon atom via a Group 14 atom.
(C) Sub7 is a substituent containing a heteroatom of groups 15 to 16, and Sub7 is bonded to an imine carbon atom via the heteroatom.

〔式（Ｌ−３）において、Sub６は第１４族原子を含む置換基であり、第１４族原子を介してSub６がイミン炭素原子に結合される。

[In the formula (L-3), Sub6 is a substituent containing a Group 14 atom, and Sub6 is bonded to an imine carbon atom via a Group 14 atom.

Sub7 is a substituent containing a heteroatom of groups 15 to 16, and Sub7 is bonded to an imine carbon atom via the heteroatom. ]
Specifically, as such a substituent and a ligand, L-3 to which the above Sub6 and Sub7 are bonded can exemplify the following structure.

本発明のアリルオキシ配位子は下記一般式Ｌ−４で表され、次のように定義される。
（ａ）第４族金属に金属-酸素原子結合を介して結合される；

The allyloxy ligand of the present invention is represented by the following general formula L-4 and is defined as follows.
(A) Bonded to Group 4 metal via metal-oxygen atom bond;

〔式（Ｌ−４）において、Ｒ₁〜Ｒ₅は各々独立して互いに同一でも異なっていても良い。Ｒ₁〜Ｒ₅は水素、炭素数１〜２０のアルキル基、アルコキシ基、アミド基、アリール基、アラルキル基、シリル基、アルキルシリル基、アリールアミド基、シリルアミド基、ホスフィノアミド基、およびホスフィド基を表す。また各々が互いに結合して環を形成してもよい。〕
このような置換基、配位子として、具体的には、下記の様な構造を例示することが出来る。

[In the formula (L-4), R _{1 to} R ₅ may be independently the same or different from each other. R _{1 to} R ₅ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphide group. Represent. In addition, each may be bonded to each other to form a ring. ]
Specific examples of such substituents and ligands include the following structures.

[Compound (B)]
The compound (B) forming the olefin polymerization catalyst according to the present invention reacts with (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound (A). It is at least one compound selected from the group consisting of compounds forming an ion pair.

((B-1) Organometallic compound)
As the organometallic compound (B-1) used in the present invention, specifically, the periodic table groups 1, 2, 12, and 13 represented by the following general formulas (B-1a) to (B-1c). Compounds containing at least one atom of:
R ^a _p Al (ОR ^b ) _q H _r Y _s・ ・ ・ (B-1a)
(In the general formula (B-1a), ^Ra and ^Rb may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen atom. , P is 0 <p ≦ 3, q is 0 ≦ q <3, r is 0 ≦ r <3, s is 0 ≦ s <3, and m + n + p + q = 3). Organic aluminum compound;
M ³ AlR ^c ₄ ... (B-1b)
(In the general formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) Complex alkylated product of alkali metal and aluminum of Group 1 of the Ritsudai;
R ^d R ^e M ⁴ ... (B-1c)
(In the general formula (B-1c), R ^d and R ^e may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ⁴ is Mg. , Zn or Cd.) A dialkyl compound with an alkaline earth metal of Group 2 or a metal of Group 12 of the periodic table.

Examples of the organoaluminum compound belonging to the general formula (B-1a) include the following compounds.
R ^a _p Al (ОR ^b ) _3-p ... (B-1a-1)
(In the formula (B-1a-1), ^Ra and ^Rb may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferable. Is a number of 1.5 ≦ p ≦ 3).
R ^a _p AlY _3-p ... (B-1a-2)
(In the formula (B-1a-2), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p preferably 0 <p <3. The organic aluminum compound represented by),
R ^a _p AlH _3-p ... (B-1a-3)
(In the formula (B-1a-3), Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p <3). Represented organic aluminum compound,
R ^a _p Al (ОR ^b ) _q Y _s・ ・ ・ (B-1a-4)
(In the formula (B-1a-4), ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and Y is a halogen. An organic aluminum compound representing an atom, where p is 0 <p ≦ 3, q is 0 ≦ q <3, s is a number of 0 ≦ s <3, and p + q + s = 3).

More specifically, as the organic aluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum. Tri-n-alkylaluminum such as;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4 -Tri-branched alkylaluminum such as methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexylaluminum, tri2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritrylaluminum;
Dialkylaluminum hydride such as diisobutylaluminum hydride;
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkoxides such as isobutylaluminum methoxydo, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxyde, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxydo and butyl aluminum sesquibutoxide;
Partially alkoxylated alkylaluminum with an average composition represented by R ^a _2.5 Al (ОR ^b ) _0.5 (in the formula, R ^a and R ^b may be the same or different from each other and have a number of carbon atoms. Shows 1-15, preferably 1-4 hydrocarbon groups);
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromid;
Partially halogenated alkylaluminum such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromid;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminum such as ethylaluminum dihydride, alkylaluminum dihydride such as propylaluminum dihydride;
Examples thereof include partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butokicyclolide, ethylaluminum ethoxybromid and the like.

A compound similar to (B-1a) can also be used in the present invention, and examples of such a compound include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4, and the} like.
Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, and di-n-. Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, and diethyl cadmium.

In addition, as the organometallic compound (B-1), methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium Chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

Further, a compound such that the organoaluminum compound is formed in the polymerization system, for example, a combination of aluminum halide and alkyllithium, a combination of aluminum halide and alkylmagnesium, and the like can be used as the organometallic compound (B-1). Can also be used as.

Among the organometallic compounds (B-1), organoaluminum compounds are preferable from the viewpoint of catalytic activity.
The above-mentioned organometallic compound (B-1) is used alone or in combination of two or more.

((B-2) Organoaluminium oxy compound)
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or is a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. You may.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.

(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered solution of aluminoxane by distillation, the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing alminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Examples of the solvent used for preparing alminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and simen, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum distillates such as gasoline, kerosene, light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially chlorine Examples thereof include hydrocarbon solvents such as isomers and bromines. Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable. These solvents can be used alone or in combination.

The organoaluminum oxy compound (B-2) according to the present invention is represented by an aluminoxane having a structure represented by the following general formula (B-2a) or (B-2b) and a following general formula (B-2c). Examples thereof include aluminoxane selected from at least one aluminoxane having a repeating unit and a repeating unit represented by the following general formula (B-2d) as a structure.

（一般式中、Ｒ^cは、それぞれ独立に、炭素原子数１〜１０、好ましくは１〜４の炭化水素基であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、イソプロペニル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、シクロヘキシル基、シクロオクチル基、フェニル基、トリル基、エチルフェニル基などの炭化水素基を例示することができる。これら例示したもののうちで、メチル基、エチル基、イソブチル基が好ましく、特にメチル基が好ましく、前記一般式（Ｂ−２ａ）、（Ｂ−２ｂ）および（Ｂ−２ｃ）中、Ｒ^cの一部が塩素、臭素などのハロゲン原子で置換され、かつハロゲン含有率が４０重量％以下であってもよい。

(In the general formula, R ^c is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropenyl. Group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, A hydrocarbon group such as a cyclooctyl group, a phenyl group, a tolyl group, or an ethylphenyl group can be exemplified. Among these exemplified groups, a methyl group, an ethyl group, and an isobutyl group are preferable, and a methyl group is particularly preferable. formula (B-2a), (B -2b) and in (B-2c), chlorine portion of R ^c, are substituted with a halogen atom such as bromine, and halogen content is not more than 40 wt% May be good.

In the general formulas (B-2a) and (B-2b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, particularly preferably 10 to 100.
In the general formulas (B-2c) and (B-2d), s and t represent integers of 1 or more, respectively.

Aluminoxane having a repeating unit represented by the general formula (B-2c) and a repeating unit represented by the general formula (B-2d) has a molecular weight in the range of 200 to 2000 as measured by the freezing point depression method of benzene. It is preferably inside.

Further, the benzene-insoluble organic aluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. That is, it is preferably insoluble or sparingly soluble in benzene. )

As the organoaluminum oxy compound (B-2) used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula (B-2e) can also be mentioned.

（一般式（Ｂ−２ｅ）中、Ｒ¹⁵は炭素原子数が１〜１０の炭化水素基を示し、４つのＲ¹⁶は、互いに同一でも異なっていてもよく、それぞれ独立に、水素原子、ハロゲン原子または炭素原子数が１〜１０の炭化水素基を示す。）

(In the general formula (B-2e), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ^16s may be the same or different from each other, and each of them independently has a hydrogen atom and a halogen. Indicates a hydrocarbon group having 1 to 10 atoms or carbon atoms.)

The organoaluminum oxy compound containing boron represented by the general formula (B-2e) contains an alkylboronic acid represented by the following general formula (B-2f) and an organoaluminum compound in an inert gas atmosphere. It can be produced by reacting with an inert solvent at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ^15- B (ОH) ₂ ... (B-2f)
(In the general formula (B-2f), R ¹⁵ represents the same group as R ¹⁵ in the general formula (B-2e).)

Specific examples of the alkylboronic acid represented by the general formula (B-2f) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-. Examples thereof include hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the general formula (B-1a).

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

When an organoaluminum oxy compound (B-2) such as methylaluminoxane as a cocatalytic component is used in combination with the transition metal compound (A), it exhibits extremely high polymerization activity with respect to the olefin compound.
The above-mentioned organoaluminum oxy compound (B-2) is used alone or in combination of two or more.

((B-3) A compound that reacts with the transition metal compound (A) to form an ion pair)
As the compound (B-3) (hereinafter, referred to as “ionized ionic compound”) used in the present invention that reacts with the transition metal compound (A) to form an ion pair, Japanese Patent Application Laid-Open No. 1-501950 Lewis described in JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-5321106, etc. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. In addition, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group) is used. For example, trifluoroborone, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, etc. Tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include compounds represented by the following general formula (B-3a).

（一般式［Ｂ−３ａ］中、Ｒ¹⁷はＨ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンであり、Ｒ¹⁸〜Ｒ²¹は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）。

(In the general formula [B-3a], R ¹⁷ is a ferrosenium cation having H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptilylyleneyl cation or a transition metal, and R ¹⁸ to R ²¹ may be the same or different from each other and is an organic group, preferably an aryl group or a substituted aryl group).

Specific examples of the carbocation cation include trisubstituted carbocation cations such as triphenyl carbocation cation, tri (methylphenyl) carbocation cation, and tri (dimethylphenyl) carbocation cation.

Specifically, the ammonium cations include trialkylammonary cations such as trimethylammonium cation, triethylammonary cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-dialkylanilinium cations such as N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as di (isopropyl) ammonium cations, dicyclohexylammonium cations And so on.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ¹⁷ , carbonium cations and ammonium cations are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations, and N, N-diethylanilinium cations are particularly preferable.

Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri ( Examples thereof include n-butyl) ammonium tetra (o-tolyl) boron.

Specifically, as the N, N-dialkylanilinium salt, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4. Examples thereof include 6-pentamethylanilinium tetra (phenyl) boron.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula (B-3b) or (B-3c) and the like can also be mentioned.

（式（Ｂ−３ｂ）中、Ｅｔはエチル基を示す。）

(In formula (B-3b), Et represents an ethyl group.)

（式（Ｂ−３ｃ）中、Ｅｔはエチル基を示す。）
イオン化イオン性化合物（化合物（Ｂ−３））の例であるボラン化合物として具体的には、例えば、デカボラン；
ビス〔トリ（ｎ−ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ウンデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカクロロデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩；
トリ（ｎ−ブチル）アンモニウムビス（ドデカハイドライドドデカボレート）コバルト酸塩（ＩＩＩ）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（ＩＩＩ）などの金属ボランアニオンの塩などが挙げられる。

(In formula (B-3c), Et represents an ethyl group.)
Specifically, as a borane compound which is an example of an ionized ionic compound (compound (B-3)), for example, decaborane;
Bis [tri (n-butyl) ammonium] nonabolate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anionic salts such as bis [tri (n-butyl) ammonium] decachlorodecabolate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;
Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Examples include salt.

Specific examples of the carborane compound, which is an example of an ionized ionic compound, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecabolane, and dodecahydride-1-phenyl-1,3-. Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbanonaborane, 2, , 7-Dicarbaundecabolan, Undecahydride-7,8-dimethyl-7,8-dicarbaundecabolan, Dodecahydride-11-methyl-2,7-dicarbundecabolan, Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecabolate, Tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecabolate, tri (n-butyl) ammonium 6-carbadecabolate, tri (n-butyl) ammonium 7- Carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl -7,9-dicarbaundecabolate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7 , 9-Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8 -Dicarbundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbundecaborate and other anion salts;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Telate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Cobalate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7) , 8-dicarbundecaborate) Niklate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-dicarbundecaborate) Copper Acidate (III), Tri (n-butyl) Ammonium Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Hydrochloride (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarba Undecaborate) Tetrate (III), Tri (n-Butyl) Ammonium Bis (Nona Hydride-7,8-Dimethyl-7,8-Dicarbundecaborate) Chromate (III), Tri (n-Butyl) Ammonium Bis (N-butyl) Tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III) , Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Manganate (IV), Bis [Tri (n-Butyl) Ammonium] Bis (Undeca Hydride-7-Cal) Bound decaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbundecaborate) nickelate (IV) and other metal carborane anion salts. Be done.

Heteropoly compounds, which are examples of ionized ionic compounds, include atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. It is a compound. Specifically, limbanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, tungstic acid, germanomolybdic acid, arsenic molybdic acid, tungstic acid, phosphorus. Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdate vanadic acid, phosphombdate vanadic acid, germanotangstvanadic acid, phosphomolybdate tongue tungstic acid, germanomolybdate tongue tungstic acid, phosphomolybdate tungstic acid , Phospholybdoniobic acid, and salts of these acids, but not limited to. Further, the salt includes the acid, for example, an alkali metal of Group 1 of the periodic table or an alkaline earth metal of Group 2, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium. , Salts with cesium, barium and the like, and organic salts such as triphenylethyl salt and the like.

An isopoly compound, which is an example of an ionized ionic compound, is a compound composed of a metal ion of one atom selected from vanadium, niobium, molybdenum and tungsten, and is regarded as a molecular ion species of a metal oxide. Can be done. Specific examples include, but are not limited to, vanadate, niobate, molybdic acid, tungstic acid, and salts of these acids. Examples of the salt include metals of Group 1 or Group 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like. Salts, organic salts such as triphenylethyl salt and the like.

The above-mentioned ionized ionic compound (compound (B-3) that reacts with the transition metal compound (A) to form an ion pair) is used alone or in combination of two or more.
Further, the catalyst for olefin polymerization according to the present invention includes the above transition metal compound (A) (hereinafter, may be abbreviated as "component (A)"), the organic metal compound (B-1), and the organic aluminum oxy. Necessary together with at least one compound [B] (hereinafter, may be abbreviated as "component [B]) selected from the group consisting of the compound (B-2) and the ionized ionic compound (B-3). The following carrier (C) may be contained depending on the above.

[(C) Carrier]
The carrier (C) used in the present invention is an inorganic or organic compound and is a solid in the form of granules or fine particles. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer having good morphology can be obtained.

As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.
Specific examples of the porous oxide include SiО ₂ , Al ₂ О ₃ , Mg О, Zr О, Ti О ₂ , B ₂ О ₃ , Ca О, Zn О, Ba О, Th О _{2 and the} like, or a composite or mixture containing these. In addition, natural or synthetic zeolites such as SiО _2- MgО, SiО ₂ −Al ₂ О ₃ , SiО _{2 −} TiО ₂ , SiО ₂ −V ₂ О ₅ , SiО _{2 −} Cr ₂ О ₃ , SiО _2- TiО _2- MgО etc. can be used. Of these, as the porous oxide, those containing SiO ₂ and / or Al ₂ О ₃ as main components are preferable.

The above-mentioned porous oxides are a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , Ca CO ₃ , Mg CO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO _3). ) ₂ , Al (NO ₃ ) ₃ , Na ₂ О, K ₂ О, Li ₂ О and other carbonates, sulfates, nitrates and oxide components may be contained.

The properties of such a porous oxide differ depending on the type and production method, but the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and has a specific surface area. It is desirable that the pore volume is in the range of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a porous oxide is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Examples of the solid aluminoxane compound include aluminoxane selected from at least one of the aluminoxanes shown in (B-2a) to (B-2d).
Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane used in the present invention does not contain inorganic solid components such as silica and alumina and organic polymer components such as polyethylene and polystyrene, and mainly contains alkylaluminum compounds. The solidified product is shown as. The meaning of "solid state" used in the present invention is to maintain a substantially solid state in a reaction environment in which the aluminoxane component (B-2) is used. More specifically, for example, when the component (A) and the component [B] are brought into contact with each other to prepare a solid catalyst component for olefin polymerization as described later, an inert hydrocarbon solvent such as hexane or toluene used in the reaction is used. Medium, it indicates that the component [B] is in a solid state under a specific temperature / pressure environment. Further, for example, when suspension polymerization is carried out using a solid catalyst component for olefin polymerization prepared by using the component [B] as described later, a specific temperature and pressure are used in a hydrocarbon solvent such as hexane, heptane, and toluene. It is also a necessary requirement that the component [B] contained in the catalyst component in the environment is in a solid state. The same applies to bulk polymerization in which polymerization is carried out in a liquefied monomer instead of a solvent, and vapor phase polymerization in which polymerization is carried out in a monomer gas.

Whether or not the component [B] is in a solid state under the above environment is the easiest method to visually confirm, but it is often difficult to visually confirm, for example, during polymerization. In that case, it is possible to judge from, for example, the properties of the polymer powder obtained after the polymerization and the state of adhesion to the reactor. On the contrary, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the component [B] is eluted in the polymerization environment, the gist of the present invention is not deviated. Examples of the index for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the abundance of amorphous polymer, but the polymer bulk density is preferable from the viewpoint of quantification. The bulk density in the present invention is usually 0.01 to 0.9, preferably in the range of 0.05 to 0.6, more preferably 0.1 to 0.5.

The solid aluminoxane used in the present invention has a dissolution ratio of usually 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol% in n-hexane maintained at a temperature of 25 ° C. Satisfy the% range.

The dissolution ratio of the solid aluminoxane used in the present invention to n-hexane was determined by adding 2 g of the solid aluminoxane carrier to 50 ml of n-hexane maintained at 25 ° C., stirring for 2 hours, and then G-4 glass. The solution part was separated using a filter made by the manufacturer, and the concentration of aluminum in the filtrate was measured. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

As the solid aluminoxane according to the present invention, known solid aluminoxane can be used endlessly. As known manufacturing methods, for example, JP-A-7-42301, JP-A-6-220126, JP-A-6-220128, JP-A-11-140113, JP-A-11-310607, JP-A-2000. Examples thereof include Japanese Patent Application Laid-Open No. -38410, Japanese Patent Application Laid-Open No. 2000-95810, and Japanese Patent Application Laid-Open No. 20001055652.

The average particle size of the solid aluminoxane according to the present invention is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1000 μm, and particularly preferably 1 to 200 μm.
The average particle size of solid aluminoxane is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and averaging the weight. For the particle size of solid aluminoxane, the maximum length of the Pythagoras method was measured from a particle image. That is, the length of the particle image sandwiched between two parallel lines is measured in each of the horizontal direction and the vertical direction, and the calculation is performed using the following formula.
Grain size = ((horizontal length) ² + (vertical length) ² ) ^0.5
The weight average particle size of the solid aluminoxane is calculated by the following formula using the particle size obtained above.
Average particle size = Σnd ⁴ / Σnd ³ (where n; number of particles, d; particle size)

The solid aluminoxane preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, and a pore volume of 0.1 to 2.5 cm ³ / g. desirable.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. It is also possible to use an inorganic halide dissolved in a solvent such as alcohol and then precipitated in the form of fine particles with a precipitant.

The clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, an ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type and CdI ₂ type can be exemplified.

Furthermore, as clays and clay minerals, kaolin, bentonite, wood knot clay, gailome clay, allophane, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, deckite Halloy site etc.
The ion-exchange layered _{compounds, α-Zr (HAsО 4)} 2 · H 2 О, α-Zr (HPО 4) 2, α-Zr (KPО 4) 2 · 3H 2 О, α-Ti (HPО 4) ₂ , α-Ti (HAsО ₄ ) ₂ · H ₂ О, α-Sn (HPО ₄ ) ₂ · H ₂ О, γ-Zr (HPО ₄ ) ₂ , γ-Ti (HPО ₄ ) ₂ , γ-Ti ( Examples thereof include crystalline acidic salts of multivalent metals such as NH ₄ PO ₄ ) ₂ and H ₂ О.

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more, preferably 0.3 to 5 cc / g, as measured by a mercury intrusion method and having a radius of 20 Å or more. Is particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.

When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat the clay and clay mineral used in the present invention. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state in which the layers are expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. .. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl _4, and metal alkoxides such as Ti (ОR) ₄ , Zr (ОR) ₄ , PO (ОR) ₃ and B (ОR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ О ₄ (ОH) ₂₄ ] ⁷⁺ , [Zr ₄ (ОH) ₁₄ ] ²⁺ , [Fe ₃ О (ОCОCH ₃ ) ₆ ] ^+, etc. And so on. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides such as Si (ОR) ₄ , Al (ОR) ₃ , and Ge (ОR) ₄ (R indicates a hydrocarbon group or the like) are hydrolyzed. The obtained polymer, a colloidal inorganic compound such as SiО ₂ and the like can coexist. Further, examples of the pillar include an oxide produced by intercalating the metal hydroxide ions between layers and then heat-dehydrating the pillars.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Of these, preferred are clays or clay minerals, with particularly preferred being montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
As described above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or vinylcyclohexane and styrene. Examples of (co) polymers produced with the above as a main component and variants thereof.

The catalyst for olefin polymerization according to the present invention contains the above-mentioned transition metal compound (A), the above-mentioned compound [B], and if necessary, the carrier (C), and if necessary, the following specific organic compound component (D). It can also be included.

[(D) Organic compound component]
In the present invention, the organic compound component (D) improves the polymerization performance of the catalyst for olefin polymerization of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer), if necessary (in the case of molecular weight, the molecular weight is increased). It is used for the purpose of making it. Examples of such an organic compound include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds and sulfonates.

As the alcohols and the phenolic compound, those represented by R ²² −OH are usually used, where R ²² is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, a carbon atom). The number is 6 to 50) or the number of carbon atoms is 1 to 50 (in the case of phenols, the number of carbon atoms is 6 to 50).

As the alcohols, those having R ²² having a halogenated hydrocarbon group are preferable. Further, as the phenolic compound, those in which the α and α'-positions of the hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms are preferable.

As the carboxylic acid, one represented by R ^23- COOH is usually used. R ²³ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acids having a P—O—H bond, phosphate having a P—ОR, P = О bond, and a phosphine oxide compound are preferably used.
Examples of the sulfonate include those represented by the following general formula (DA).

（一般式（Ｄ−ａ）中、Ｍ⁵は周期律表第１〜１４族の原子であり、Ｒ²⁴は水素、炭素原子数１〜２０の炭化水素基または炭素原子数１〜２０のハロゲン化炭化水素基であり、Ｚは水素原子、ハロゲン原子、炭素原子数が１〜２０の炭化水素基または炭素原子数が１〜２０のハロゲン化炭化水素基であり、ｔは１〜７の整数であり、ｕは１〜７の整数であり、また、ｔ−ｕ≧１である。）

(In the general formula (DA), M ⁵ is an atom of Group 1 to 14 of the periodic table, and R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. It is a hydrocarbon group, Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and t is an integer of 1 to 7. U is an integer of 1 to 7, and tu ≧ 1.)

[Method for producing olefin / cyclic olefin copolymer]
The method for producing an olefin / cyclic olefin copolymer of the present invention is characterized in that the olefin and the cyclic olefin are copolymerized in the presence of the above-mentioned catalyst for olefin polymerization of the present invention.

In the method for producing an olefin / cyclic olefin copolymer of the present invention, a copolymer may be produced by copolymerizing two or more kinds of olefins with a cyclic olefin.
In the polymerization, the usage of each component constituting the olefin polymerization catalyst according to the present invention and the order of addition to the polymerizer are arbitrarily selected, and the following methods are exemplified. Hereinafter, the transition metal complex (A), the compound (B), the carrier (C), and the organic compound component (D) are also referred to as “components (A) to (D)”, respectively. (1) A method of adding the component (A) alone to a polymerizer. (2) A method of adding the component (A) and the component (B) to the polymerizer in an arbitrary order. (3) A method in which a catalyst component in which the component (A) is supported on the component (C) and the component (B) are added to the polymerizer in an arbitrary order. (4) A method in which a catalyst component in which the component (B) is supported on the component (C) and the component (A) are added to the polymerizer in an arbitrary order. (5) A method of adding a catalyst component in which a component (A) and a component (B) are supported on the component (C) to a polymerizer.

In each of the above methods, the component (D) may be added at any stage.
In each of the above methods, at least two of the catalyst components may be previously contacted.
In each of the above methods (4) and (5) in which the component (B) is supported, the non-supported component (B) may be added in any order, if necessary. In this case, the component (B) may be the same or different. Further, the solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are obtained even if the olefin is prepolymerized. Often, the catalyst component may be further supported on the prepolymerized solid catalyst component.

The copolymerization of the olefin and the cyclic olefin can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Aliphatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more.

When polymerizing an olefin using a catalyst for olefin polymerization as described above, the transition metal compound (A) is usually 10 ^-12 to ^10-2 mol, preferably 10 ^-10 to 10 mol, per liter of reaction volume. It is used in an amount such that it becomes ^-3 mol.

The organometallic compound (B-1) usually has a molar ratio [(B-1) / M] of the organometallic compound (B-1) to all the transition metal atoms (M) in the transition metal compound (A). It is used in an amount such that it is 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminum oxy compound (B-2) is the molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) [(B-2). / M] is usually used in an amount such that it is 10 to 5,000, preferably 20 to 2,000.

The ionized ionic compound (B-3) has a molar ratio [(B-3) / M] of the ionized ionic compound (B-3) and the transition metal atom (M) in the transition metal compound (A). , Usually used in an amount such that it is 1 to 10,000, preferably 1 to 5,000.

When the carrier (C) is used, the weight ratio [(A) / (C)] of the transition metal compound (A) to the carrier (C) is preferably 0.0001 to 1, more preferably 0.0005 to 0. It is used in an amount of 5.5, more preferably 0.001 to 0.1.

In the production method of the present invention, the polymerization temperature in the polymerization step is usually −50 to + 200 ° C., preferably 0 to 180 ° C.; the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge. It is pressure. The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, the polymerization can be carried out in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin / cyclic olefin copolymer can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or adjusting the amount of compound (B) used. When hydrogen is added, the amount thereof is appropriately about 0.001 to 5,000 NL per 1 kg of the copolymer to be produced.

Examples of olefins subjected to the polymerization reaction in the method for producing an olefin / cyclic olefin copolymer of the present invention include linear or branched α-olefins.
The present invention is characterized in that a linear or branched olefin is copolymerized with a cyclic olefin in the presence of the catalyst to produce an olefin copolymer. Preferably, the olefin defined by (Z-1) below is copolymerized with the olefin defined by (Z-2) to produce an olefin copolymer.

(Z-1) Linear or branched α-olefin having 2 to 30 carbon atoms The linear or branched α-olefin has a linear or branched carbon atom number of 2 to 30. Examples include α-olefins (Z-1).
The number of carbon atoms of the α-olefin (Z-1) is preferably 2 to 20.
Specific examples of the α-olefin (Z-1) include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 Included are -methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
It is more preferably a linear olefin, and particularly preferably ethylene.

(Z-2) Select from the group consisting of compounds represented by the general formula [ZI], the general formula [Z-II], the general formula [Z-III], the general formula [Z-IV], or the general formula [ZV]. At least one cyclic olefin The cyclic olefin may be represented by the following general formula [ZI], general formula [Z-II], general formula [Z-III], general formula [Z-IV] or general formula [ZV]. Examples thereof include at least one cyclic olefin (Z-2) selected from the group consisting of the represented compounds.

〔式［Z-I］中、ｕは０または１であり、
ｖは０または正の整数であり、
ｗは０または１であり、
Ｒ⁶¹〜Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁷⁵〜Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。〕

[In formula [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1 and
R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and R ^{75 to} R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. .. ]

〔式［Z-II］中、ｘおよびｄは０または１以上の整数であり、
ｙおよびｚは０、１または２であり、
Ｒ⁸¹〜Ｒ⁹⁹は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。〕

[In Equation [Z-II], x and d are integers greater than or equal to 0 or 1.
y and z are 0, 1 or 2,
R ^{81 to} R ⁹⁹ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or R ^91. The carbon atom to which is bonded may be directly bonded or may be bonded via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R. It may be bonded to ⁹⁹ to form a monocyclic or polycyclic aromatic ring. ]

〔式［Z-III］中、Ｒ¹⁰⁰およびＲ¹⁰¹は、それぞれ独立に水素原子または炭素原子数１〜５の炭化水素基であり、ｆは１≦ｆ≦１８である。〕

[In the formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. ]

〔一般式［Z-IV］中、ｘは０または１以上の整数であり、
Ｒ¹¹¹〜Ｒ¹¹⁸は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、
Ｒ¹²¹〜Ｒ¹²⁴は、それぞれ独立に水素原子、ハロゲン原子、および炭化水素基から選ばれ、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。〕

[In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and
R ^{111 to} R ¹¹⁸ are independently selected from hydrogen atom, halogen atom, and hydrocarbon group, respectively.
R ^{121 to} R ¹²⁴ are independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or compound aromatic ring. ]

〔一般式［Z-V］中、ｎおよびｍはそれぞれ独立に０、１または２であり、ｑは１、２または３であり、Ｒ¹⁸〜Ｒ³¹はそれぞれ独立に、水素原子、フッ素原子を除くハロゲン原子、またはフッ素原子を除くハロゲン原子で置換されていてもよい炭素原子数１〜２０の炭化水素基であり、またｑ＝１のときＲ²⁸とＲ²⁹、Ｒ²⁹とＲ³⁰、Ｒ³⁰とＲ³¹は互いに結合して単環または多環を形成していてもよく、またｑ＝２または３のとき、Ｒ²⁸とＲ²⁹、Ｒ²⁹とＲ³⁰、Ｒ³⁰とＲ³¹、Ｒ³¹とＲ³¹は互いに結合して単環または多環を形成していてもよく、前記単環または前記多環が二重結合を有していてもよく、また前記単環または前記多環が芳香族環であってもよい。〕
以下、一般式［Z-I］、一般式［Z-II］、一般式［Z-III］、一般式［Z-IV］、および一般式［Z-V］について詳説する。

[In the general formula [ZV], n and m are independently 0, 1 or 2, q is 1, 2 or 3, and R ^{18 to} R ³¹ are independently excluded from the hydrogen atom and the fluorine atom. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom other than a fluorine atom, and when q = 1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ^30. And R ³¹ may be combined with each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ^31. And R ³¹ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring is aromatic. It may be a tricyclic ring. ]
Hereinafter, the general formula [ZI], the general formula [Z-II], the general formula [Z-III], the general formula [Z-IV], and the general formula [ZV] will be described in detail.

<< General formula [ZI] >>
In equation [ZI], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, this ring is a 5-membered ring.

R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other and are hydrogen atoms, halogen atoms or hydrocarbon groups.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like having 1 to 30 carbon atoms, preferably 1 to 1. 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl; carbon atoms such as ethynyl, propargyl Linear or branched alkynyl groups having a number of 2 to 30, preferably 2 to 20; having 3 to 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbonyl, tetracyclododecyl. 30, preferably 3 to 20 cycloalkyl groups; cyclic unsaturated hydrocarbon groups with 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl And other aryl groups having 6 to 30, preferably 6 to 20 carbon atoms; alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl and the like. ..

The hydrocarbon group may have a hydrogen atom substituted with a halogen, for example, the number of carbon atoms of monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl and the like. Examples thereof include 1 to 30, preferably 1 to 20 alkyl halide groups or aryl halide groups.

Further, the above-mentioned hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as benzyl and cumyl.
Further, the above hydrocarbon group is a heterocyclic compound residue; an oxygen such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group and a carboxylic acid anhydride group. Containing groups: Amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group as ammonium salt Nitrogen-containing groups such as those that have become; boron-containing groups such as bolangyl group, bolantriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid ester group, Sulfur-containing groups such as isothian acid ester group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphide group, phosphoryl group, thiophosphoryl group, phosphat It may have a phosphorus-containing group such as a group, a silicon-containing group; a germanium-containing group; or a tin-containing group.

Examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like having 1 to 30 carbon atoms, preferably 1 Linear or branched alkyl groups of ~ 20; cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbonyl, tetracyclododecyl, etc. with 3-30 carbon atoms, preferably 3-20 cyclos. Alkyl group; aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc .; halogen atom, preferably 1 to 30 carbon atoms in these aryl groups. Substituent aryl groups in which 1 to 20 alkyl groups or alkoxy groups, 6 to 30 carbon atoms, preferably 6 to 20 aryl groups or aryloxy groups are substituted with 1 to 5 substituents are preferable.

Further, in the above general formula [ZI], R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or R ⁷⁶ and R ⁷⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic thus formed is a double bond. May have. Specific examples of the monocyclic or polycyclic ring formed here include the following.

なお、上記例示において、１または２の番号を付した炭素原子は、上記一般式（Ｉ）においてそれぞれＲ⁷⁵（Ｒ⁷⁶）またはＲ⁷⁷（Ｒ⁷⁸）が結合している炭素原子を表す。

In the above example, the carbon atom numbered 1 or 2 represents the carbon atom to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded in the general formula (I), respectively.

Further, an alkylidene group may be formed by R ⁷⁵ and R ⁷⁶ , or by R ⁷⁷ and R ⁷⁸ . Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, isopropylidene and the like.

<< General formula [Z-II] >>
In formula [Z-II], x and d are 0 or positive integers, and y and z are 0, 1 or 2.

Further, R ^{81 to} R ⁹⁹ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, and a hydrocarbon group.
As the halogen atom and the hydrocarbon group, the same halogen atom and the hydrocarbon group in the above formula [ZI] can be exemplified.

Here, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are direct or alkylene groups having 1 to 3 carbon atoms. It may be connected via. That is, when the above two carbon atoms are bonded via an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ cooperate with each other to form a methylene group (-CH _2). -), An alkylene group of either an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ) is formed.

Further, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y = z = 0, the following aromatic rings formed by R ⁹⁵ and R ⁹² can be mentioned.

ここで、ｌは上記一般式［Z-II］におけるｄと同じである。

Here, l is the same as d in the above general formula [Z-II].

<< General formula [Z-III] >>
In the formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. ..
Preferred examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, an alkyl halide group and a cycloalkyl group. These specific examples are the same as the specific examples of R ^{61 to} R ⁷⁸ of the above formula [ZI].

<< General formula [Z-IV] >>
In the general formula [Z-IV], x is 0 or an integer greater than or equal to 1.
R ^{111 to} R ¹¹⁸ and R ^{121 to} R ¹²⁴ are selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, and may be the same or different from each other.

As the halogen atom and the hydrocarbon group, the same halogen atom and the hydrocarbon group in the above formula [ZI] can be exemplified.
In addition, two adjacent groups of R ^{121 to} R ¹²⁴ may be bonded to each other to form a monocyclic or compound aromatic ring. Among these, specific examples of the cyclic olefin in which R ¹²¹ and R ¹²² are bonded to form an aromatic ring include the following structures.

また、Ｒ¹²²とＲ¹²³が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ¹²² and R ¹²³ are bonded to form an aromatic ring include the following structures.

また、Ｒ¹²¹とＲ¹²²、Ｒ¹²³とＲ¹²⁴が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Further, specific examples of the cyclic olefin in which R ¹²¹ and R ¹²² and R ¹²³ and R ¹²⁴ are bonded to form an aromatic ring include the following structures.

これらの芳香族環上にハロゲン原子、アルキル基、およびアリール基から選ばれる置換基が置換された環状オレフィンも例として挙げられる。

Cyclic olefins in which a substituent selected from a halogen atom, an alkyl group, and an aryl group are substituted on these aromatic rings can also be mentioned as an example.

<< General formula [ZV] >>
In the general formula [ZV], m and n are 0, 1 or 2, and R ^{18 to} R ³¹ are independently substituted with a hydrogen atom, a halogen atom excluding a fluorine atom, or a halogen atom excluding a fluorine atom. It is a hydrocarbon group having 1 to 20 carbon atoms, and R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , and R ³⁰ and R ³¹ may be bonded to each other to form a single ring. The ring may have a double bond.

Further, in the general formula [ZV], m is preferably 0 or 1, more preferably 1. n is preferably 0 or 1, more preferably 0. R ^{18 to} R ³¹ are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, and more preferably hydrogen atoms.

Further, examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group and the like, respectively. Be done. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and the cycloalkyl group includes cyclohexyl. Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a trill group, a naphthyl group, a benzyl group and a phenylethyl group, or an aralkyl group. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

Specific examples of the cyclic olefin represented by the above general formula [ZI], [Z-II], [Z-III], [Z-IV] or [ZV] are tetracyclo [4.4.0.1 ^{2]. , 5} . 1 ^7,10 ] -3-Dodecene and the like are examples of the compounds exemplified in [0176] to [0207] of JP-A-2011-122146.

The cyclic olefin (Z-2) represented by these general formulas [ZI], [Z-II], [Z-III], [Z-IV] or [ZV] may be used alone. Two or more types may be used in combination.
In the method for producing an olefin polymer of the present invention, polymerization, other olefins other than the above-mentioned (Z-1) and (Z-2) may be subjected to the reaction. Examples of such olefins include conjugated / non-conjugated polyenes and vinylcyclohexane.

Examples of the conjugated / non-conjugated polyene include cyclic or chain hydrocarbons having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. Specific examples thereof include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, and the like. 1,3-octadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadien, Japanese Patent Application Laid-Open No. 2011-122146 such as 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien butadiene, isoprene, ethylylidene norbornene, vinyl norbornene, dicyclopentadiene, etc. Examples of the compound exemplified in [0211].

In the method for producing an olefin / cyclic olefin copolymer of the present invention, a polymerizable compound other than the olefin may be polymerized together with the above-mentioned olefin, and examples of such a polymerizable compound include a polar group and a polymerizable compound. Examples include compounds having unsaturated bonds, aromatic vinyl compounds, and functional group-containing styrene derivatives.

Specific examples of the compound having a polar group and a polymerizable unsaturated bond include compounds exemplified as unsaturated hydrocarbons having a polar group in [0208] to [0211] of JP2011-122146A.

Specific examples of the aromatic vinyl compound and the functional group-containing styrene derivative include the compounds exemplified in [0211] of JP2011-122146A.
A preferred embodiment of the production method of the present invention is an embodiment in which the α-olefin (Z-1) and the cyclic olefin (Z-2) are copolymerized. In this embodiment, the α-olefin (Z-1) is preferably ethylene, and the cyclic olefin (Z-2) is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene is preferred.

In copolymerizing the α-olefin (Z-1) and the cyclic olefin (Z-2), the pressure of the α-olefin (Z-1) and the concentration of the cyclic olefin (Z-2) are arbitrarily set. It can be done and is not particularly limited. The pressure of the α-olefin (Z-1) is preferably the polymerization pressure, and the concentration of the cyclic olefin (Z-2) is 0.001 to 100 M, preferably 0.01 to 10 M, more preferably 0.1 to 1. It is 1M.

(Cyclic olefin copolymer)
The cyclic olefin copolymer obtained by the method for producing a cyclic olefin copolymer of an olefin of the present invention will be described.

(Molecular weight)
The weight average molecular weight of the cyclic olefin copolymer of the present invention is a value determined by gel permeation chromatography (GPC), 1.0 × 10 ³ or more and 10 × 10 ⁵ or less. The lower limit is more preferably 1.1 × 10 ³ and even more preferably 1.2 × 10 ³ . The upper limit is more preferably 8 × 10 ^5, more preferably 7 × 10 ^5, particularly preferably 6 × 10 ^5. As specific GPC measurement conditions, the conditions described in Examples described later are adopted.
The cyclic olefin copolymer of the present invention has a good balance of moldability, strength, transparency and the like as long as its weight average molecular weight is within the above range, and can be suitably used for various purposes.

<Glass-transition temperature>
As described above, the cyclic olefin copolymer according to the present invention exhibits a high glass transition temperature, for example, 120 ° C. to 250 ° C. The lower limit is preferably 125 ° C, more preferably 130 ° C. On the other hand, the upper limit is more preferably 230 ° C., still more preferably 220 ° C. from the viewpoint of heat resistance stability of the polymer during melt molding.

The value of the glass transition temperature is when measured under the following conditions or equivalent conditions.
Measurement conditions: Using a differential scanning calorimeter (DSC6220, SI Nanotechnology, Inc.), a sample (cyclic olefin copolymer) of about 5.0 mg was sampled from 30 ° C. in a nitrogen atmosphere to 300 ° C. at a heating rate of 10 ° C./min. Heat up to, and hold at that temperature for 5 minutes. (However, in the case of a copolymer that decomposes in the temperature range of 250 ° C. or higher and 320 ° C. or lower, the temperature to be held may be appropriately adjusted to be low as in the conventional method.) Further, the temperature lowering rate is 10 ° C./min and 0 ° C. After cooling to, and holding at that temperature for 5 minutes, the temperature is raised to 300 ° C. at a heating rate of 20 ° C./min. At the time of this second temperature rise, the DSC curve is bent due to the change in the specific heat, and the baseline is sensed as a translation. The temperature at the intersection of the tangent of the baseline, which is lower than this bending, and the tangent of the point where the inclination is maximum at the bending portion is defined as the glass transition temperature (Tg).

(Composition of copolymer)
The cyclic olefin copolymer according to the present invention contains an olefin structural unit derived from "(Z-1)" and an olefin structural unit derived from (Z-2), and has a structure in which these are linked.

Assuming that the total olefin structural unit is 100 mol%, the content of the structural unit derived from (Z-1) is 40 mol% as a preferable lower limit value, more preferably 50 mol%, and further preferably 60 mol%. The preferred upper limit is 90 mol%, more preferably 80 mol%. On the other hand, the preferable lower limit of the content of the structural unit derived from (Z-2) is 10 mol%, preferably 20 mol%. On the other hand, the preferable upper limit value is 60 mol%, more preferably 50 mol%, still more preferably 40 mol%.

The higher the content of the structural unit derived from (Z-2), the higher the glass transition temperature tends to be.
The cyclic olefin copolymer may contain other structural units, if necessary. Examples thereof include conjugated diene compounds such as butadiene and isoprene, non-conjugated diene compounds such as 1,5-hexadiene, 4methyl 1,5 hexadiene and 7 methyl 1,6 octadiene, and aromatic vinyl compounds such as styrene. .. The content of the structural unit derived from such a compound is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less, assuming that the total olefin structural unit is 100 mol% or less. ..

By using the transition metallized product of the present invention, a polymer having a relatively high molecular weight can be produced with high activity. The cause of this is unknown at this time, but one is that oxygen (O) and sulfur (S) (so-called hetero elements), which are groups that bind to the cyclopentadienyl skeleton, preferably suppress the polymerization activity. It is thought that this is the cause. More specifically, it is speculated that the presence of the hetero element suppresses the chain transfer reaction and makes it difficult for the dormant state, which is said to occur during the growth reaction, to occur, so that the polymerization activity tends to increase. Will be done.

In addition, it is considered that the flatness of the group bonded to the cyclopentadienyl skeleton is involved, and while exhibiting an appropriate steric effect of maintaining ion separation with the cocatalyst so that the polymerization reaction can be continued. Since the steric barrier is low for the olefin to be coordinated, it is presumed that the olefin can be polymerized more efficiently.

The above-mentioned cyclic olefin copolymer can be used without limitation in applications of conventional cyclic olefin copolymers, for example, optical products such as plastic lenses, packaging products such as films, and the like.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.
[Measuring method]
[Structure of transition metal compounds]
The structure of the transition metal compound was determined using ^{1 1} H-NMR spectrum (270 MHz, JEOL GSH-270) and FD-MS (JEOL JMS-T100GC).

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of copolymer]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the copolymer were determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by the "Alliance GPC 2000" gel permeation chromatograph (high temperature size exclusion chromatograph) manufactured by Waters, and the operating conditions are as follows:
<Devices and conditions used>
Measuring device: Gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; Chromatography data system Emper (trademark, Waters)
Column; TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2
(Inner diameter 7.5 mm x length 30 cm, Tosoh)
Mobile phase; o-dichlorobenzene [= ОDCB] (Wako Pure Chemical Industries, Ltd. special grade reagent)
Detector; differential refractometer (built-in device)
Column temperature; 140 ° C
Flow velocity; 1.0 mL / min
Injection volume; 400 μL
Sampling time interval; 1 second Sample concentration: 0.15% (w / v)
Molecular Weight Calibration Monodisperse Polystyrene (Tosoh) / Molecular Weight 495 to Molecular Weight 20.6 Million

[Copolymer (TD) content]
The comonomer (cyclic olefin) content of the copolymer was determined by ¹³ C-NMR spectrum according to the description of [0216] to [0219] of JP-A-2011-122146.

[Copolymer Tg]
DSC measurement was performed under the following conditions to determine the Tg of the copolymer.
Equipment: SII Nanotechnology, Inc. DSC6220
Measurement conditions: Tg was determined in the process of rapidly cooling the sample held at 300 ° C. for 5 minutes to 0 ° C. and then raising the temperature to 250 ° C. at a heating rate of 20 ° C./min.

[Manufacturing of titanium compounds]
[Synthesis Example A]
Synthesis of transition metal compound (A) represented by the following formula

（１）配位子Ａの合成

(1) Synthesis of ligand A

窒素雰囲気下、シュレンクフラスコに２，５−ジメチル−７Ｈ−シクロペンタ［１，２−ｂ：４，３−ｂ‘］−ジチオフェン１０３１ｍｇ（５．００ｍｍｏｌ）および脱水ｔ−ブチルメチルエーテル６５ｍＬを添加した。氷浴で冷却しながらｎ−ブチルリチウム（５．２７ｍｍｏｌ）のヘキサン溶液（１．５５Ｍ）３．４０ｍＬを徐々に添加し、室温で１時間攪拌した。ドライアイスメタノール浴で冷却しながら、トリメチルクロロシラン ０．６７ｍＬ（５．３２ｍｍｏｌ）を添加し、室温で２時間攪拌した。飽和塩化アンモニウム水溶液を加えて、有機層を分離し、水層をジクロロメタンで抽出した。先の有機層と合わせて、水、飽和塩化ナトリウム水溶液で洗浄した。硫酸マグネシウムで乾燥後、減圧濃縮した。得られた粗生成物をメタノールで洗浄し、目的物を１２６６ｍｇ（収率９１％）得た。¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）の測定結果により、目的物（以下配位子Ａと記載する。）を同定した。

Under a nitrogen atmosphere, 1031 mg (5.00 mmol) of 2,5-dimethyl-7H-cyclopenta [1,2-b: 4,3-b'] -dithiophene and 65 mL of dehydrated t-butyl methyl ether were added to the Schlenk flask. 3.40 mL of a hexane solution (1.55M) of n-butyllithium (5.27 mmol) was gradually added while cooling in an ice bath, and the mixture was stirred at room temperature for 1 hour. While cooling in a dry ice methanol bath, 0.67 mL (5.32 mmol) of trimethylchlorosilane was added, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous solution of ammonium chloride was added to separate the organic layer, and the aqueous layer was extracted with dichloromethane. It was washed with water and a saturated aqueous sodium chloride solution together with the above organic layer. After drying over magnesium sulfate, the mixture was concentrated under reduced pressure. The obtained crude product was washed with methanol to obtain 1266 mg (yield 91%) of the desired product. ^{1 The} target substance (hereinafter referred to as ligand A) was identified from the measurement results of ¹ H-NMR (CDCl ₃ ).

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 6.81 (2H, d, J = 1.0 Hz), 3.65 (1H, s), 2.54 (6H, s), -0.02 (12H) , S) ppm

(2) Synthesis of transition metal compound (A0)

窒素雰囲気下、シュレンクフラスコに先の反応で得られた配位子Ａを１３９３ｍｇ（５．００ｍｍｏｌ）、ジクロロメタン６５ｍＬを添加した。ドライアイス-メタノール浴で冷却しながら塩化チタン（５．００ｍｍｏｌ）のジクロロメタン溶液（１．０Ｍ）５．００ｍＬを徐々に添加し、室温に戻しながら１８時間攪拌した。反応液の溶媒の半分を減圧留去し、ガラスフィルターを用いてろ過した。得られた固体をジクロロメタンで洗浄し、減圧乾燥して黒色固体を得た。ろ液の溶媒の半分を減圧留去、ろ過した後、ジクロロメタンで洗浄して減圧乾燥することにより黒色固体を得た。得られた黒色固体は合わせて１５７５ｍｇ（収率８８％）で、¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）とＦＤ−ＭＳの測定結果により、目的物（以下「遷移金属化合物（Ａ０）」と記載する。）を同定した。

Under a nitrogen atmosphere, 1393 mg (5.00 mmol) of the ligand A obtained in the previous reaction and 65 mL of dichloromethane were added to the Schlenk flask. While cooling in a dry ice-methanol bath, 5.00 mL of a dichloromethane solution (1.0 M) of titanium chloride (5.00 mmol) was gradually added, and the mixture was stirred for 18 hours while returning to room temperature. Half of the solvent of the reaction solution was distilled off under reduced pressure, and the mixture was filtered using a glass filter. The obtained solid was washed with dichloromethane and dried under reduced pressure to obtain a black solid. Half of the solvent of the filtrate was distilled off under reduced pressure, filtered, washed with dichloromethane and dried under reduced pressure to obtain a black solid. The total amount of the obtained black solid is 1575 mg (yield 88%), and it is described as the target product (hereinafter referred to as “transition metal compound (A0)” based on the measurement results of ¹ H-NMR (CDCl ₃ ) and FD-MS. ) Was identified.

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 7.02-7.01 (2H, m), 6.89 (1H, s), 2.72 (6H, d, J = 1.3Hz) ppm
FD-MS: m / z = 357.9 (M ⁺ )

(3) Synthesis of Transition Metal Compound (A) Under a nitrogen atmosphere, 148 mg (1.05 mmol) of 2,2,4,4-tetramethylpentane-3-imine and 5 mL of toluene were added to the Schlenk flask. This solution was cooled in a dry ice-methanol bath, 0.68 mL of an n-butyllithium solution (hexane solution, 1.55 M, 1.05 mmol) was added, and the mixture was stirred at room temperature for 1 hour.

Under a nitrogen atmosphere, 360 mg (1.00 mmol) of the transition metal compound (A0) and 50 mL of toluene were added to another Schlenk flask. This solution was cooled in a dry ice-methanol bath, and the previously obtained reaction solution was added while washing with 5 mL of toluene. The mixture was stirred at room temperature for 18 hours. The reaction mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The obtained dark purple solid was washed with hexane and dried under reduced pressure. The target product was identified by the measurement results of 286 mg of dark purple solid, 62% yield, ^{1 1} H-NMR (CDCl ₃ ) and FD-MS.

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 6.85 (2H, s), 6.56 (1H, s), 2.56 (6H, d, J = 1.0 Hz) ppm
FD-MS: m / z = 463.1 (M ⁺ )

[Comparative synthesis example a]
Synthesis of transition metal compound (a) represented by the following formula

Journal of American Chemical Society, 2000, 122, 5499-5509.に記載の方法で合成した。

It was synthesized by the method described in Journal of American Chemical Society, 2000, 122, 5499-5509.

[Production of ethylene / tetracyclododecene copolymer]
[Example p1]
Glass reactor thoroughly purged with nitrogen content volume 500 mL, cyclohexane / hexane (9/1) mixed solution 250mL and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene ( Hereinafter, it is also simply referred to as “tetracyclododecene”.) 10 g was charged, and the liquid phase and the gas phase were saturated with 50 liters / hr of ethylene. Then, 0.15 mmol of modified aluminoxane was added in terms of aluminum atom, and 0.0003 mmol of the above transition metal compound (A) was subsequently added to initiate polymerization. Ethylene was continuously supplied at 50 liters / hr, and polymerization was carried out at 50 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of a mixed solvent of acetone / methanol (3/1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130 ° C. for 10 hours to obtain 1.114 g of an ethylene / tetracyclododecene copolymer. The physical property values of the obtained polymers are summarized in Table 1.

[Example p2]
The same procedure as in Example p1 was carried out except that the amount of tetracyclododecene charged was 5 g, and 0.961 g of an ethylene / tetracyclododecene copolymer was obtained. The physical property values of the obtained polymers are summarized in Table 1.

[Comparative example p1]
The same procedure as in Example p1 was carried out except that 0.0015 mmol of the transition metal compound (a) was used instead of the transition metal compound (A), and 0.895 g of an ethylene / tetracyclododecene copolymer was obtained. The physical property values of the obtained polymers are summarized in Table 1.

[Example p3]
250 mL of a mixed solution of cyclohexane / hexane (9/1) and 10 g of tetracyclododecene were charged into a glass reactor having an internal volume of 500 mL sufficiently substituted with nitrogen, and the liquid and gas phases were saturated with 50 liters / hr of ethylene. I let you. Then, 0.06 mmol of triisobutylaluminum was added in terms of aluminum atom, 0.00015 mmol of the transition metal compound (A), and 0.0006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to start polymerization. Ethylene was continuously supplied at 50 liters / hr, and polymerization was carried out at 50 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of a mixed solvent of acetone / methanol (3/1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.340 g of an ethylene / tetracyclododecene copolymer. The physical property values of the obtained polymers are summarized in Table 1.

[Example p4]
The same procedure as in Example p3 was carried out except that the amount of tetracyclododecene charged was 5 g, and 0.327 g of an ethylene / tetracyclododecene copolymer was obtained. The physical property values of the obtained polymers are summarized in Table 1.

[Comparative example p2]
0.0005 mmol of the transition metal compound (a) is used instead of the transition metal compound (A), 0.20 mmol of triisobutylaluminum is used in terms of aluminum atom, and 0.002 mmol of triphenylcarbeniumtetrakis (pentafluorophenyl) borate is used. The same procedure as in Example p3 was carried out except for the above, and 0.546 g of an ethylene / tetracyclododecene copolymer was obtained. The physical property values of the obtained polymers are summarized in Table 1.

表１エチレン・テトラシクロドデセン共重合
助触媒Ｄ：修飾メチルアルミノキサン
助触媒Ｅ：トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート
ＴＤ：テトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン

Table 1 Ethylene / tetracyclododecene copolymer co-catalyst D: modified methylaluminoxane co-catalyst E: triphenylcarbenium tetrakis (pentafluorophenyl) borate TD: tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene

Claims (3)

Transition metal compounds represented by the following general formula [A-1] and
(B) (B-1) Organic metal compound,
At least one compound (B) selected from the group consisting of (B-2) organoaluminum oxy compounds and (B-3) compounds that react with transition metal compounds (A) to form ion pairs.
A method for producing an olefin / cyclic olefin copolymer, which comprises copolymerizing an olefin and a cyclic olefin compound in the presence of a catalyst for olefin polymerization including.

[In the formula [A-1]
M is a titanium atom, a zirconium atom, or a hafnium atom,
m is an integer from 1 to 3
X is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a diene type. It is a divalent derivative group and
A and B are sulfur (S), oxygen (O) or CR ³ (R ³ is hydrogen, alkyl group, etc.), if A is S or O then B is CR ³ or If B is S or O, then A is CR ³ and the ring containing A and B has a double bond where possible);
R ^{1 to} R ³ are independently hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, halogen atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, or phosphorus-containing groups. And
L requires carbon and hydrogen, and has a structure containing atoms selected from Group 15 elements and Group 16 elements. The olefin is
(Z-1) A linear or branched α-olefin having 2 to 30 carbon atoms, and (Z-2) the following general formula [ZI], general formula [Z-II], general formula [Z-III] ], General formula [Z-IV] or general formula [ZV]
The method for producing an olefin polymer according to claim 1, which comprises a cyclic olefin represented by.

[In formula [ZI], u is 0 or 1,
v is 0 or a positive integer,
w is 0 or 1 and
R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and R ^{75 to} R ⁷⁸ are bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. .. ]

[In Equation [Z-II], x and d are integers greater than or equal to 0 or 1.
y and z are 0, 1 or 2,
R ^{81 to} R ⁹⁹ are independently selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, respectively, and a carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and a carbon atom to which R ⁹³ is bonded or R ^91. The carbon atom to which is bonded may be directly bonded or may be bonded via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R. It may be bonded to ⁹⁹ to form a monocyclic or polycyclic aromatic ring. ]

[In the formula [Z-III], R ¹⁰⁰ and R ¹⁰¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18. ]

[In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, and
R ^{111 to} R ¹¹⁸ are independently selected from hydrogen atom, halogen atom, and hydrocarbon group, respectively.
R ^{121 to} R ¹²⁴ are independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or compound aromatic ring. ]

[In the general formula [ZV], n and m are independently 0, 1 or 2, q is 1, 2 or 3, and R ^{18 to} R ³¹ are independently excluded from the hydrogen atom and the fluorine atom. It is a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom other than a fluorine atom, and when q = 1, R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ^30. And R ³¹ may be combined with each other to form a monocyclic or polycyclic ring, and when q = 2 or 3, R ²⁸ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁰ and R ³¹ , R ³¹ and R ³¹ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic ring or the polycyclic ring may have a double bond, and the monocyclic ring or the polycyclic ring may be formed. The polycycle may be an aromatic ring. ] The α-olefin (Z-1) is ethylene, and the cyclic olefin (Z-2) is tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] The method for producing an olefin polymer according to claim 1 or 2, which is -3-dodecene.