JP2020164790A - Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Abstract

To provide a novel transition metal compound that can be used as a catalyst for olefin polymerization.SOLUTION: There is provided a transition metal compound represented by a formula [A-1], where M represents Ti, Zr, or Hf; m is an integer of 1 to 3; X independently represents H, a halogen atom, a hydrocarbon group, a halogen-containing group, a Si-containing group, an O-containing group, an S-containing group, an N-containing group, a P-containing group, a B-containing group, an Al-containing group, or a diene-based divalent derivative group; A and B are S, O, or CR3 (where, R3 is H, an alkyl group, or the like); if A is S or O, then B is CR3, or if B is S or O, then A is CR3, and a ring containing A and B has a double bond at a possible position; R1 and R2 each independently represents H, a C1 to C20 hydrocarbon group, a halogen atom, a halogen-containing group, a Si-containing group, an O-containing group, an N-containing group, an S-containing group, or a P-containing group; and L contains C and H as essential components and further contains a structure including atom selected from Group 15 element and group 16 element.SELECTED DRAWING: None

Description

The present invention relates to a novel transition metal compound, more specifically, a novel transition metal compound that can be used as a catalyst for olefin polymerization, a catalyst for olefin polymerization containing the compound, and a method for producing an olefin polymer using the catalyst. Regarding.

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.

In view of such prior art, it is an object of the present invention to provide a novel transition metal compound, particularly a novel transition metal compound that can be used as a catalyst for olefin polymerization.

Further, one aspect of the present invention includes a catalyst for olefin polymerization capable of producing a highly active and high molecular weight olefin polymer, a novel transition metal compound that can be used for such a catalyst for olefin polymerization, and the like. It is intended to be provided.

As a result of studies in view of the above-mentioned problems and purposes, the present inventors have found that a compound having a specific half metallocene structure exhibits a preferable effect as a catalyst for olefin polymerization, and completed the present invention. That is, the invention has the following configuration.

[1] A transition metal compound represented by the following general formula [A-1].

〔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 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 groups 15 and 16 elements. ]

[2] The transition metal compound according to item [1], wherein in the general formula [A-1], M is a titanium atom or a zirconium atom.
[3] The transition metal compound according to Item [1], wherein M is a titanium atom in the general formula [A-1].
[4] The transition metal compound according to item [1], wherein A is sulfur in the general formula [A-1].
[5] The transition metal compound according to [1], wherein in the general formula [A-1], L is the following (L-1) having a ketimid structure.
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 attached to the N atom in a double bond); and (c) the carbon atom. Means a ligand with _two substituents (Sub ₁ and Sub ₂ described below) 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。〕

[In the formula (L-1), Sub ₁ and Sub ₂ may be independently the same or different from each other, and Sub ₁ and Sub ₂ 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. ]

[6] The transition metal compound according to claim 1, wherein in the general formula [A-1], L is the following (L-2) having a phosphineimide structure.
The phosphineimide ligand is represented by the following general formula L-2 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 P atom attached to the N atom in a double bond); and (c) the P atom. Means a ligand having _three substituents (Sub ₃ , Sub ₄ and Sub ₅ described below) attached to.

〔式（Ｌ−２）中、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。〕

[In the formula (L-2), Sub ₃ , Sub ₄ and Sub ₅ may be independently the same or different from each other, and Sub ₃ , Sub ₄ and Sub ₅ are hydrogen and alkyl groups having 1 to 20 carbon atoms. , Aalkyl group, amide group, aryl group, aralkyl group, silyl group, alkylsilyl group, arylamide group, silylamide group, phosphinoamide group, and phosphide group. In addition, each may be bonded to each other to form a ring. ]

[7] The transition metal compound according to Item [1], wherein in the general formula [A-1], L has an amidimid structure (L-3).
The amidimid ligand is represented by the following general formula L-3 and is defined as follows.
(A) Bonded to a Group 4 metal via a metal-nitrogen atom bond;
(B) Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.
(C) Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ 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。
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。〕
「８」前記一般式［Ａ−１］において、Ｌが式（Ｌ−４）表されるアリールオキシ構造であることを特徴とする請求項１に記載の遷移金属化合物。

[In formula (L-3), Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.
Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ is bonded to an imine carbon atom via the heteroatom. ]
"8" The transition metal compound according to claim 1, wherein in the general formula [A-1], L has an aryloxy structure represented by the formula (L-4).

〔式（Ｌ−４）において、Ｏは酸素原子、Ｒ¹¹〜Ｒ¹⁵は各々独立して互いに同一でも異なっていても良い。Ｒ¹¹〜Ｒ¹⁵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。〕
［９］（Ａ）項［１］〜［８］のいずれか一項に記載の遷移金属化合物と、
（Ｂ）（Ｂ−１）有機金属化合物、
（Ｂ−２）有機アルミニウムオキシ化合物、および
（Ｂ−３）遷移金属化合物（Ａ）と反応してイオン対を形成する化合物
からなる群から選ばれる少なくとも１種の化合物とを含むオレフィン重合用触媒。
［１０］項［９］に記載のオレフィン重合用触媒の存在下でオレフィンを重合するオレフィン重合体の製造方法。
［１１］前記オレフィンが、炭素原子数２〜３０のオレフィンから選ばれるオレフィンであることを特徴とする請求項１０に記載のオレフィン重合体の製造方法。

[In the formula (L-4), O may be an oxygen atom, and R ^{11 to} R ¹⁵ may be independently the same or different from each other. R ^{11 to} R ¹⁵ contain 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. ]
[9] The transition metal compound according to any one of items [1] to [8] of (A), and
(B) (B-1) Organic metal compound,
A catalyst for olefin polymerization containing (B-2) an organoaluminum oxy compound and (B-3) at least one compound selected from the group consisting of a compound that reacts with a transition metal compound (A) to form an ion pair. ..
[10] A method for producing an olefin polymer that polymerizes an olefin in the presence of the catalyst for olefin polymerization according to item [9].
[11] The method for producing an olefin polymer according to claim 10, wherein the olefin is an olefin selected from olefins having 2 to 30 carbon atoms.

The transition metal compound of the present invention exhibits high activity when used as a catalyst for the polymerization or copolymerization of ethylene or an olefin having 3 or more carbon atoms, and exhibits a characteristic of giving a high molecular weight polymer.

The transition metal compound according to the present invention is specified by the following structure. When the transition metal compound is used in the olefin polymerization reaction, it is preferably used in combination with an organometallic compound containing elements of Group 1, Group 2, and Group 13 of the periodic table such as an organoaluminum compound. Hereinafter, each component will be described.

[Transition metal compound (A)]
The transition metal compound (A) of 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. If it is a divalent derivative group, A and B are sulfur (S), oxygen (O) or CR ³ (R ³ is a hydrogen, alkyl group, etc.) and A is S or O. 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 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.

上記のＲ³の具体的な構造の例は、前記Ｒ¹、Ｒ²のアルキル基の例と同様である。

The above-mentioned example of the specific structure of R ^{3 is} the same as the above-mentioned example of the alkyl group of R ¹ and R ² .

The L of the formula [A-1] requires carbon and hydrogen, and has a structure containing atoms selected from Group 15 and Group 16 elements of the periodic table. L may be either a substituent or a ligand.

Among the Group 15 and Group 16 elements in the above periodic table, nitrogen, phosphorus and oxygen are 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 _two substituents (Sub ₁ and Sub ₂ described below) 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), Sub ₁ and Sub ₂ may be independently the same or different from each other, and Sub ₁ and Sub ₂ 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. ]
Specifically, as such a substituent and a ligand, L-1 to which Sub ₁ and Sub ₂ are bonded can exemplify the following structure.

本発明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 phosphineimide ligand of the present invention 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 that is double bonded to the N atom); and (C) the P atom. Means a ligand having _three substituents (Sub ₃ , Sub ₄ and Sub ₅ 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), Sub ₃ , Sub ₄ and Sub ₅ may be independently the same or different from each other, and Sub ₃ , Sub ₄ and Sub ₅ are hydrogen and alkyl groups having 1 to 20 carbon atoms. , Aalkyl group, amide group, aryl group, aralkyl group, silyl group, alkylsilyl group, arylamide group, silylamide group, phosphinoamide group, and phosphide group. In addition, each may be bonded to each other to form a ring. ]
Specifically, as such a substituent and a ligand, L-2 to which the above Sub ₃ , Sub ₄ and Sub ₅ 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) Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.
(C) Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ 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 formula (L-3), Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.

Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ is bonded to an imine carbon atom via the heteroatom. ]
Specifically, as such a substituent and a ligand, L-3 to which the above-mentioned Sub ₆ and Sub ₇ are bonded can exemplify the following structure.

本発明のＬとして下記一般式Ｌ−４で表されるアリルオキシ配位子も好ましい態様の一つであり、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；

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

〔式（Ｌ−４）において、Ｏは酸素原子、Ｒ¹¹〜Ｒ¹⁵は各々独立して互いに同一でも異なっていても良い。Ｒ¹¹〜Ｒ¹⁵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), O may be an oxygen atom, and R ^{11 to} R ¹⁵ may be independently the same or different from each other. R ^{11 to} R ¹⁵ contain 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.

本発明の遷移金属化合物は、後述する様に、従来のハーフメタロセン型遷移金属化合物に比して、高い重合活性と高い共重合性を示す傾向がある。この為、幅広い範囲の融点や柔軟性、耐衝撃性を有する重合体を製造することが出来る。
上記のような構造の他、アリールアミノ基の様なアミノ基もＬの好ましい態様として例示することが出来る。

As will be described later, the transition metal compound of the present invention tends to exhibit high polymerization activity and high copolymerizability as compared with the conventional half metallocene type transition metal compound. Therefore, a polymer having a wide range of melting points, flexibility, and impact resistance can be produced.
In addition to the above-mentioned structure, an amino group such as an arylamino group can be exemplified as a preferable embodiment of L.

When the L has the formula [L-4] or an arylamino group, it may be easy to obtain a polymer having a wide molecular weight distribution when the olefin described later is polymerized. The cause of this is not clear, but the present inventors speculate as follows.

The above structure has more rotation axes of oxygen atoms and nitrogen atoms than the structures of the formulas [L-1], [L-2], and [L-3], so that it is easy to rotate. it is conceivable that. Therefore, the active sites of the olefin polymerization reaction may have various structures. Due to this difference in structure, various polymer molecules having different molecular weights are generated, and as a result, it is considered that there is a tendency for the polymer to have a wide molecular weight distribution.

As described above, by using the technique of the present invention, by appropriately selecting the structure of the formula [A-1], it is possible to produce various polymers according to the desired productivity and the performance of the polymer. Become.
Next, each component that can be used in combination with the transition metal compound (A) when polymerizing the olefin will be described.

((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
Is. ) Is a dialkyl compound with an alkaline earth metal of Group 2 or a metal of Group 12.

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 can be regarded as a molecular ion species of an oxide. it can. 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.
Examples of the ion-exchangeable layered compound include α-Zr (HAsО ₄ ) ₂ · H ₂ О and α-Zr (HP).
_{О 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 Examples thereof include crystalline acidic salts of multivalent metals such as ₂ О, γ-Zr (HP О ₄ ) ₂ , γ-Ti (HP О ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ · 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.)

<Polyolefin manufacturing method>
In the method for producing a polyolefin according to the present invention, a polyolefin is obtained by including a step of polymerizing or copolymerizing an olefin in the presence of a catalyst for olefin polymerization as described above. As described above, the term olefin in the present specification refers to any compound having a polymerizable double bond.

In the polymerization, the usage of each component constituting the catalyst of the present invention and the order of addition to the polymerizer are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the transition metal compound (A) alone to the polymerizer.
(2) A method of adding the transition metal compound (A) and the compound [B] to the polymerizer in an arbitrary order.
(3) A method of adding a catalyst component in which a transition metal compound (A) is supported on a carrier (C) and a compound [B] to a polymerizer in an arbitrary order.
(4) A method of adding a catalyst component in which compound [B] is supported on a carrier (C) and a transition metal compound (A) to a polymerizer in an arbitrary order.
(5) A method of adding a catalyst component in which a transition metal compound (A) and a compound [B] are supported on a carrier (C) to a polymerizer.
(6) A method of adding a catalyst component in which a transition metal compound (A) and a compound [B] are supported on a carrier (C), and a compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier (C) and the compound [B] added alone may be the same or different.
(7) A method of adding a catalyst component in which compound [B] is supported on a carrier (C) and a transition metal compound (A) to a polymerizer in an arbitrary order.
(8) A method of adding a catalyst component in which compound [B] is supported on a carrier (C), a transition metal compound (A), and compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier (C) and the compound [B] added alone may be the same or different.
(9) A method in which a component in which the transition metal compound (A) is supported on the carrier (C) and a component in which the compound [B] is supported on the carrier (C) are added to the polymerizer in an arbitrary order.
(10) A method of adding a component in which the transition metal compound (A) is supported on a carrier (C), a component in which compound [B] is supported on a carrier (C), and compound [B] to an arbitrary order polymerizer. In this case, the compound [B] supported on the carrier (C) and the compound [B] added alone may be the same or different.
(11) A method of adding the transition metal compound (A), the compound [B], and the organic compound component (D) to the polymerizer in an arbitrary order.
(12) A method of adding a component in which the compound [B] and the organic compound component (D) are previously brought into contact with each other, and the transition metal compound (A) to the polymerizer in an arbitrary order.
(13) A method in which the compound [B], the component in which the organic compound component (D) is supported on the carrier (C), and the transition metal compound (A) are added to the polymerizer in an arbitrary order.
(14) A method of adding a catalyst component in which a transition metal compound (A) and a compound [B] are previously brought into contact with each other, and an organic compound component (D) to a polymerizer in an arbitrary order.
(15) A method of adding a catalyst component in which the transition metal compound (A) and the compound [B] are previously brought into contact with each other, and the compound [B] and the organic compound component (D) in an arbitrary order.
(16) The catalyst component in which the transition metal compound (A) and the compound [B] are previously contacted, and the component in which the compound [B] and the organic compound component (D) are previously contacted are added to the polymerizer in an arbitrary order. Method. In this case, the compound [B] that is brought into contact with the transition metal compound (A) and the compound [B] that is brought into contact with the organic compound component (D) may be the same or different.
(17) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C), a compound [B], and an organic compound component (D) to a polymerizer in an arbitrary order.
(18) A method of adding a component in which the transition metal compound (A) is supported on a carrier (C) and a component in which the compound [B] and the organic compound component (D) are previously brought into contact with each other in an arbitrary order.
(19) A method of adding a catalyst component in which a transition metal compound (A), a compound [B], and an organic compound component (D) are previously brought into contact with each other in an arbitrary order to a polymerizer.
(20) A method of adding a catalyst component in which a transition metal compound (A), a compound [B] and an organic compound component (D) are previously contacted, and a compound [B] to a polymerizer in an arbitrary order. In this case, the compound [B] that is brought into contact with the transition metal compound (A) and the organic compound component (D) and the compound [B] that is added alone may be the same or different.
(21) A method for adding a catalyst in which a transition metal compound (A), a compound [B], and an organic compound component (D) are supported on a carrier (C) to a polymerizer.
(22) A method of adding a catalyst component in which a transition metal compound (A), a compound [B], and an organic compound component (D) are supported on a carrier (C), and a component (B) to a polymerizer in an arbitrary order. In this case, the compound [B] supported on the carrier (C) and the compound [B] added alone may be the same or different.

An olefin is reserved for the solid catalyst component in which the transition metal compound (A) is supported on the carrier (C) and the solid catalyst component in which the transition metal compound (A) and the compound [B] are supported on the carrier (C). It may be polymerized, or the catalyst component may be further supported on the pre-polymerized solid catalyst component.

In the present invention, the (co) polymerization can be carried out by any of a liquid phase polymerization method such as dissolution polymerization and suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method are aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, and the like, and also for (co) polymerization. The provided olefin itself can also be used as a solvent.

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 100,000, preferably 0.05 to 50,000. 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 500,000, preferably 20 to 100,000. The compounds (ionized ionic compounds) (B-3) that react with the transition metal compound (A) to form an ion pair are the ionized ionic compound (B-3) and the transition metal in the transition metal compound (A). It is used in an amount such that the molar ratio to the atom (M) [(B-3) / M] is usually 1 to 10, preferably 1 to 5.

The organic compound component (D) has a molar ratio [(D) / (B-1)] with the organometallic compound (B-1) of usually 0.01 to 10, preferably 0.1 to 5. Used in large amounts. The molar ratio [(D) / (B-2)] of the organic compound component (D) with the organoaluminum oxy compound (B-2) is usually 0.001 to 2, preferably 0.005 to 1. It is used in such an amount. The molar ratio [(D) / (B-3)] of the organic compound component (D) to the ionized ionic compound (B-3) is usually 0.01 to 10, preferably 0.1 to 5. It is used in such an amount.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually under normal pressure to 100 kg / cm ^2- G, preferably normal pressure to 50 kg / cm ^2- G, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Can also be done. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained polyolefin can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound [B] used.

The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited as long as it has a polymerizable double bond, but has a carbon atom number of 2 to 30, preferably 2 to 20, more preferably. Are 2 to 10 linear or branched α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl- 1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins with 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1. , 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

The catalyst for olefin polymerization of the present invention is used for homopolymerization of ethylene or copolymerization of ethylene with an olefin having 3 to 20 carbon atoms, preferably a linear or branched α-olefin having 3 to 10 carbon atoms. Is more preferable. One type of α-olefin may be used alone, or two or more types may be used in combination.

In the case of copolymerization of ethylene with an α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, the α-olefin (hereinafter, also referred to as olefin A) is not particularly limited as long as the effect of the present invention is exhibited. However, for example, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene preferable. These α-olefins may be used alone or in combination of two or more. Among these, at least one selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene is more preferable.

When ethylene is used as the α-olefin and the olefin A is used, the usage amount ratio of ethylene to the olefin A is ethylene: the olefin A (molar ratio), usually 1: 10 to 5000: 1, preferably. It is 1: 5 to 1000: 1.

The catalyst for olefin polymerization of the present invention may (co) polymerize a known chain of unsaturated hydrocarbons having a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.).
Further, the catalyst for olefin polymerization of the present invention may (co) polymerize vinylcyclohexane, diene, polyene and the like.

Examples of the diene or the polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms and having two or more double bonds. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-Octadiene, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, ethilidene norbornene, vinyl norbornene, dicyclopentadiene;
7-Methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatorien;
Further, mono or poly such as aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. Alkylstyrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

The transition metal compound (A) of the present invention has a novel structure in which a specific substituent is introduced at a specific position of the metallocene skeleton as described above, and the olefin polymerization of the present invention containing the compound (A). The catalyst used has a particularly excellent α-olefin copolymerization property and good olefin polymerization activity as compared with a conventional transition metal compound having a metallocene skeleton (without a specific substituent at a specific position). A low-density ethylene-based copolymer having a sufficient molecular weight can be produced.

The effect is remarkable α-olefin due to (i) the effect of introducing a heteroatom-containing electron-donating substituent into a specific site of metallocene in the transition metal compound (A) represented by the general formula [1] or [3]. It is considered that this is due to the effect of improving the copolymerizability and (ii) the effect of inhibiting the activity decrease phenomenon due to the introduction of heteroatoms by the effect of introducing a substituent into the vicinity.

[Olefin polymer]
According to the present invention, from one or more α-olefins having 2 to 30 carbon atoms in the presence of a catalyst for olefin polymerization containing a useful and novel metallocene compound (A) having the above-mentioned specific structure. By polymerizing the olefin of choice; preferably, the olefin polymer is obtained by homopolymerizing ethylene or by copolymerizing ethylene with at least one olefin A selected from olefins having 3 to 20 carbon atoms. It can be manufactured efficiently.

As one aspect of the olefin polymer of the present invention, an ethylene-based weight containing an ethylene-derived structural unit in the range of preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 90 to 100 mol%. Coalescence is mentioned. The ethylene-based polymer preferably contains the structural units derived from the olefin A in the range of 0 to 50 mol% in total, more preferably 0 to 30 mol%, and further preferably 0 to 10 mol%. However, the total of the content of the ethylene-derived structural unit and the content of the olefin A-derived structural unit is 100 mol%. The ethylene-based polymer whose constituent unit derived from olefin A is in the above range is excellent in moldability. Further, other constituent units may be included as long as the gist of the present invention is not deviated. These contents can be measured by nuclear magnetic resonance spectroscopy, infrared spectroscopy when there is a reference substance, or the like.

Among these polymers, ethylene homopolymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / 1-octene polymer, ethylene / 1 -Hexen polymer, ethylene / 4-methyl-1-pentene polymer, ethylene / propylene / 1-octene polymer, ethylene / propylene / 1-hexene polymer, ethylene / propylene / 4-methyl-1-pentene polymer Is particularly preferable. The above-mentioned copolymer is usually a random copolymer, but it is also a so-called block copolymer (impact copolymer) obtained by mixing or continuously producing two or more kinds selected from these polymers. ) May be used.

Among the polymers having the structural units described above, the ethylene-based polymer of the present invention is preferably an α-olefin polymer consisting of only structural units derived from α-olefins having 2 to 20 carbon atoms. By "substantially", it means that the ratio of the constituent units derived from α-olefin having 2 to 20 carbon atoms to all the constituent units is 95% by weight or more.

In the olefin polymer of the present invention, the weight average molecular weight measured by the gel permeation chromatography (GPC) method is not particularly limited, but is preferably 10,000 to 5,000,000, more preferably 10,000. ~ 2,000,000, particularly preferably 20,000-1,000,000. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but the case including a case where the molecular weight distribution is wide is preferably 1 to 15, more preferably. Is 1 to 13, more preferably 1 to 12. In other cases, it is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5.

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 it is one that oxygen (O) and sulfur (S) (so-called hetero elements), which are the 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. ..

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.

In the olefin polymer of the present invention, the density is not particularly limited, it is preferably not more than 875kg / m ³ or more 975 kg / m ^3.
In the olefin polymer of the present invention, the ultimate viscosity [η] in decalin at 135 ° C. is not particularly limited, but is preferably 0.1 to 40 dl / g, more preferably 0.5 to 15 d.
It is l / g, particularly preferably 1 to 10 dl / g.

In the olefin polymer of the present invention, the melt mass flow rate (MFR; unit is g / 10 minutes) measured under the conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89 is not particularly limited, but is preferably 0. It is 001 g / 10 minutes or more and 300 g / 10 minutes or less, more preferably 0.001 g / 10 minutes or more and 200 g / 10 minutes or less.

Further, according to ASTM D1238-89, the value (I10 / I2) obtained by dividing the MFR value measured under the conditions of 190 ° C. and 10 kg load by the MFR value measured under the conditions of 190 ° C. and 2.16 kg load is 5 It is preferably 0.0 or more and less than 300.
The details of the measurement conditions for the above physical property values are as described in the examples.

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 polymer]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the olefin polymer 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

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

[Polymer Tg]
DSC measurement was performed under the following conditions to determine the Tg of the polymer.
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.

[Hexene content of polymer]
The hexene content in the ethylene / 1-hexene copolymer was measured by FT-IR (FT-IR410 type infrared spectrophotometer manufactured by JASCO Corporation). FT-IR heats the polymer obtained in example 135 ° C., used after dissolving stretched by a hot press, the resulting film by room temperature pressurized cooling as a measurement sample, a light source wavelength 5000 cm ^- Measured between ^{1 and} 400 cm- ¹ . The hexene content uses hexene-based C-CH ₂ CH ₂ CH ₂ CH ₃ skeletal vibration (1378 cm ^-1 ) as the key band, and the absorbance of the key band (D1378) and the internal standard band (4321 cm ^-1 : CH expansion and contraction vibration). It was determined by the ratio [D1378 / D4321] to the absorbance (D4321) of methylene and methyl variable vibration vibration.

A calibration curve that specifies the relationship between the hexene content and the above [D1378 / D4321] is used to determine the hexene content. The calibration curve is prepared in advance by FT-IR measurement of ethylene-based copolymers having various compositions whose hexene content is specified by ¹³ C NMR by the above method and the result of the above [D1378 / D4321].

[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

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) In a nitrogen atmosphere, 1393 mg (5.00 mmol) of ligand A obtained in the previous reaction and 65 mL of dichloromethane were added to a 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 ⁺ )

[Synthesis Example B]
Synthesis of transition metal compound (B) represented by the following formula

窒素雰囲気下、シュレンクフラスコに遷移金属化合物（Ａ０）３６０ｍｇ（１．００ｍｍｏｌ）、1,1,1-tri-tert-butyl-N-(trimethylsilyl) -phosphanimine３２５ｍｇ（１．１２ｍｍｏｌ）とトルエン６０ｍＬを添加した。この溶液を１００℃で２０時間撹拌した。溶媒を減圧留去した後、トルエン、ヘキサンで洗浄し、ろ過により赤色粉末を得た。得られた赤色粉末をジクロメタンに溶解し、ヘキサンを加えて−１０℃で再結晶した。析出した赤色結晶を回収し、ヘキサンで洗浄した後、減圧乾燥した。赤色固体３２７ｍｇ、収率６１％、¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）とＦＤ−ＭＳの測定結果により、目的物を同定した。

Under a nitrogen atmosphere, 360 mg (1.00 mmol) of the transition metal compound (A0), 325 mg (1.12 mmol) of 1,1,1-tri-tert-butyl-N- (trimethylsilyl) -phosphanimine and 60 mL of toluene were added to the Schlenk flask. .. The solution was stirred at 100 ° C. for 20 hours. After distilling off the solvent under reduced pressure, the residue was washed with toluene and hexane, and filtered to obtain a red powder. The obtained red powder was dissolved in diclomethane, hexane was added, and the mixture was recrystallized at −10 ° C. The precipitated red crystals were collected, washed with hexane, and dried under reduced pressure. The target product was identified by the measurement results of 327 mg of red solid, 61% yield, ^{1 1} H-NMR (CDCl ₃ ) and FD-MS.

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 6.83 (2H, s), 6.65 (1H, s), 2.57 (6H, d, J = 1.0 Hz), 1.53 (27H, 27H, d, J = 13.8Hz) ppm
FD-MS: m / z = 539.1 (M ⁺ )

[Synthesis Example C]
Synthesis of transition metal compound (C) represented by the following formula

窒素雰囲気下、シュレンクフラスコに遷移金属化合物（Ａ０）３６０ｍｇ（１．００ｍｍｏｌ）、N,N-diisopropyl-2,6-difluorobenzamidine２４１ｍｇ（１．００ｍｍｏｌ）、トリエチルアミン０．２０ｍL（１．４５ｍｍｏｌ）とトルエン６０ｍＬを添加した。

Under a nitrogen atmosphere, 360 mg (1.00 mmol) of the transition metal compound (A0), 241 mg (1.00 mmol) of N, N-diisopropyl-2,6-difluorobenzamidine, 0.20 mL of triethylamine (1.45 mmol) and 60 mL of toluene were placed in a Schlenk flask. Added.

The mixture was stirred at room temperature for 20 hours. After distilling off the solvent under reduced pressure, it was dissolved in diclomethane and reprecipitated in hexane. The resulting precipitate was collected by filtration and dried under reduced pressure. This was extracted with diethyl ether using Celite. The solid obtained by concentration under reduced pressure was dissolved in diclomethane, reprecipitated in hexane, and repeated once more. The resulting precipitate was collected by filtration and dried under reduced pressure. The target product was identified by the measurement results of 149 mg of purple solid, 26% yield, ^{1 1} H-NMR (CDCl ₃ ) and FD-MS.

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 7.43-7.32 (1H, m), 7.07-7.00 (2H, m), 6.79 (2H, s), 6.33 ( 1H, s), 3.74-3.62 (2H, m), 2.48 (6H, d, J = 1.3Hz), 1.60 (6H, d, J = 6.9Hz), 1. 20 (6H, d, J = 6.9Hz)
FD-MS: m / z = 562.1 (M ⁺ )

[Synthesis example F]
Synthesis of transition metal compound (F) represented by the following formula

Under a nitrogen atmosphere, 190 mg (0.542 mmol) of the transition metal compound (A0) and 30 mL of toluene were added to the Schlenk flask. The solution was cooled in a dry ice-methanol bath and 10 mL of lithium 2,6-diisopropylphenolate 100 mg (0.543 mmol) toluene slurry prepared in another Schlenk flask was added. A cleaning solution washed with 10 mL of toluene was also added. The solution was stirred for 16 hours. After distilling off the solvent under reduced pressure, the mixture was extracted with dichloromethane using Celite. The obtained solution was concentrated under reduced pressure and washed with hexane to obtain a black solid. The obtained black body was dissolved in dichloromethane, hexane was added, and the mixture was recrystallized at −10 ° C. The black solid produced was collected by filtration, washed with hexane, and dried under reduced pressure. The target product was identified by the measurement results of 140 mg of black solid, 52% yield, ^{1 1} H-NMR (CDCl ₃ ) and FD-MS.

^{1 1} H-NMR (270 MHz, CDCl ₃ ) δ 7.11-6.99 (3H, m), 6.86 (2H, s), 6.44 (1H, s), 3.13 (2H, sep, J = 6.6Hz) 2.48 (6H, d, J = 1.3Hz), 1.21 (12H, d, J = 6.6Hz) ppm
FD-MS: m / z = 500.1 (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 に記載の方法で遷移金属化合物(a)を合成した。

The transition metal compound (a) was synthesized by the method described in Journal of the American Chemical Society, 2000, 122, 5499-5509.

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

Organometallics 1999, 18, 1116-1118. に記載の方法で遷移金属化合物(ｂ)を合成した。

The transition metal compound (b) was synthesized by the method described in Organometallics 1999, 18, 1116-1118.

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

特許第4904450号に記載の方法で遷移金属化合物(ｃ)を合成した。

The transition metal compound (c) was synthesized by the method described in Japanese Patent No. 4904450.

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

Organometallics, 1998, 17, 2152-2154に記載の方法で合成した遷移金属化合物（ｆ）を用いた。

The transition metal compound (f) synthesized by the method described in Organometallics, 1998, 17, 2152-2154 was used.

[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 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.

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

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

[Production of ethylene polymer, ethylene / 1-hexene copolymer]
[Example p5]
Using a reactor with a stirrer with an internal volume of 270 L under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative 50% particle size of volume distribution by laser light diffraction scattering method: 70 μm, specific surface area: 340 m ² / g, fine Pore volume: 1.3 cm ³ / g, dried at 250 ° C. for 10 hours) 10 kg was suspended in 77 L of toluene and then cooled to 0-5 ° C. 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atom) was added dropwise to this suspension over 30 minutes. At this time, the temperature inside the system was kept at 0 to 5 ° C. Then, these were brought into contact at 0 to 5 ° C. for 30 minutes, the temperature inside the system was raised to 95 ° C. over 1.5 hours, and the contact was continued at 95 ° C. for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the slurry was washed twice with toluene to prepare a carrier slurry having a total volume of 115 L. When a part of the obtained carrier slurry was collected and analyzed, the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L.

Under a nitrogen atmosphere, 30 mL of toluene and 1.63 mL of the carrier slurry (solid content weight 0.2 g) were added to a reactor with a stirrer having an internal volume of 200 mL. Next, 5.0 μmol of the transition metal compound (B) was added as a toluene solution, and these were contacted at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and then twice using hexane. It was washed. As a result, a catalyst slurry having a total volume of 40 mL was prepared.

After adding 500 mL of heptane to a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 0.375 mmol of triisobutylaluminum and 2.5 mg of ADEKA PLRONIC L-71 (manufactured by ADEKA Corporation) were added as a decane solution, and the catalyst slurry was added in an amount of 20.0 mg as a solid content, and then added to ethylene. The temperature was raised and increased to 0.8 MPaG at 80 ° C., and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and dried under reduced pressure at 80 ° C. for 10 hours to obtain 5.26 g of an ethylene polymer.

[Example p6]
After adding 500 mL of heptane to a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 2.5 mg of ADEKA PLRONIC L-71 (manufactured by ADEKA Corporation) were added as a decane solution, and the catalyst slurry of Example p5 was 16.0 mg as a solid content. After adding the above amount, the temperature was raised and increased to 0.8 MPaG with ethylene at 80 ° C., and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and dried under reduced pressure at 80 ° C. for 10 hours to obtain 8.50 g of an ethylene polymer.

[Comparative example p3]
A catalyst slurry was prepared by the same operation as in Example p5 except that the transition metal compound (b) was used instead of the transition metal compound (B).
The same operation as in Example p5 was performed except that the catalyst slurry of Example p5 was changed to the catalyst slurry (20.0 mg as a solid content) using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen. , 30.6 g of ethylene polymer was obtained.

[Comparative example p4]
Same as Example p6 except that the catalyst slurry of Example p5 was changed to the catalyst slurry of Comparative Example p3 (20.0 mg as a solid content) using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen. The operation was carried out to obtain 96.5 g of an ethylene polymer.

[Example p7]
A solid aluminoxane was synthesized according to the method described in the International Publication 2010/0505652 pamphlet (preliminary experiment 1 and Example 5), and this was used as a carrier. However, in consideration of safety such as ignition of trimethylaluminum, the concentration was about 1/6 times the condition disclosed in the document.

Specifically, 100 mL of a toluene solution of trimethylaluminum adjusted to 0.5 mol / L was charged into a glass reactor having a stirrer. The solution was cooled to 15 ° C. and 2.18 g of benzoic acid was slowly added thereto at a rate such that the temperature of the solution was kept below 25 ° C. Then, heat aging was carried out at 50 ° C. for 1 hour. At this time, the molar ratio of oxygen atoms of trimethylaluminum and benzoic acid was 1.40. The reaction mixture was heated at 70 ° C. for 4 hours, then at 60 ° C. for 6 hours, and then once cooled to room temperature. Then, it was heated at 100 ° C. for 8 hours to precipitate a solid component. After cooling the solution to 30 ° C. or lower, 100 mL of hexane was added under stirring for washing. After allowing to stand for 30 minutes, 150 mL of the supernatant was removed, and 150 mL of hexane was further added under stirring. After allowing to stand for 15 minutes, 150 mL of the supernatant was removed, and 150 mL of hexane was further added under stirring. Finally, after allowing to stand for 15 minutes, 180 mL of the supernatant was removed, and hexane was added to a total volume of 14.6 mL to obtain a carrier slurry. When a part of the obtained carrier slurry was collected and analyzed, the solid content concentration was 41.0 g / L and the Al concentration was 0.583 mol / L. When the particles of the obtained carrier were observed with a scanning electron microscope, the average particle size was 6.8 μm and the specific surface area was 18.1 m ² / mmol-Al.

Under a nitrogen atmosphere, 30 mL of toluene and 2.44 mL of the carrier slurry (solid content weight 0.1 g) were added to a reactor with a stirrer having an internal volume of 200 mL. Next, 5.0 μmol of the transition metal compound (B) was added as a toluene solution, and the mixture was contacted at an in-system temperature of 20 to 25 ° C. for 1 hour, the supernatant was removed by decantation, and the mixture was further washed twice with hexane. .. As a result, a catalyst slurry having a total volume of 40 mL was prepared.

After adding 500 mL of heptane to a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 0.25 mmol of triisobutylaluminum and 2.5 mg of ADEKA PLRONIC L-71 (manufactured by ADEKA Corporation) were added as a decane solution, and the catalyst slurry was added in an amount of 60.0 mg as a solid content, and then the hydrogen concentration. Using a 0.10 vol% ethylene / hydrogen mixed gas, the temperature was raised to 0.65 MPaG at 75 ° C., the pressure was increased, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and dried under reduced pressure at 80 ° C. for 10 hours to obtain 27.6 g of an ethylene polymer.

[Example p8]
After adding 500 mL of heptane to a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, ethylene was circulated and the inside of the reactor was saturated with ethylene. Next, 3 mL of 1-hexene, 0.25 mmol of triisobutylaluminum, and 2.5 mg of ADEKA PLRONIC L-71 (manufactured by ADEKA Corporation) were added as a decane solution, and the catalyst slurry of Example p7 was 60.0 mg as a solid content. After adding the above amount, the temperature was raised and increased to 0.65 MPaG at 75 ° C. using an ethylene / hydrogen mixed gas having a hydrogen concentration of 0.10 vol%, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and dried under reduced pressure at 80 ° C. for 10 hours to obtain 40.9 g of an ethylene polymer.

[Comparative Example p5]
A catalyst slurry was prepared by the same operation as in Example p7 except that the transition metal compound (b) was used instead of the transition metal compound (B).
The same operation as in Example p7 was performed except that the catalyst slurry of Example p7 was changed to the catalyst slurry (10.0 mg as a solid content) using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen. , Ethylene polymer 34.8 was obtained.

[Comparative example p6]
Same as Example p8 except that the catalyst slurry of Example p7 was changed to the catalyst slurry of Comparative Example p5 (6.0 mg as a solid content) using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen. The operation was carried out to obtain 20.0 g of an ethylene polymer.
Table 2 shows the physical properties of the ethylene polymers and ethylene / 1-hexene copolymers obtained in Examples p5 to p8 and Comparative Examples p3 to p6.

担体Ｔ１：実施例p5で得られた担体
担体Ｔ２：実施例p7で得られた担体

Carrier T1: Carrier obtained in Example p5 Carrier T2: Carrier obtained in Example p7

[Manufacturing of propylene polymer]
[Example p9]
Under a nitrogen atmosphere, 4.10 mg (7.59 μmol) of the transition metal compound (B) was placed in a Schlenk tube, and 0.78 mL (n) of a suspension of modified methylaluminoxane (manufactured by Tosoh Corporation, 2.29 mmol in terms of Al atom). -Hexane solvent (2.93M) was added, then 6.81 mL of dehydrated heptane was added, and the mixture was stirred at room temperature for 60 minutes or more to prepare a 0.0010M catalyst solution.

0.40 mL (0.05 M) of a heptane solution of triisobutylaluminum (20 μmol) and 2.80 mL of heptane as a polymerization solvent were placed in a fully nitrogen-substituted SUS autoclave with an internal volume of 15 mL, and the mixture was carried out at 600 rpm. Stirring was performed. The solution was heated to 60 ° C. and then pressurized with propylene until the total pressure reached 7 bar.

0.10 mL (0.0010 M, 0.10 μmol) of the catalyst solution and 0.70 mL of dehydrated heptane were added to the autoclave to initiate polymerization. After polymerizing at 60 ° C. for 30 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer solution, it was dried under reduced pressure at 80 ° C. for 12 hours to obtain 287 mg of a propylene polymer.

[Example p10]
1.00 mL (0.05 M) of a heptane solution of triisobutylaluminum (50 μmol) and 2.05 mL of heptane as a polymerization solvent were placed in a fully nitrogen-substituted SUS autoclave having an internal volume of 15 mL, and the mixture was carried at 600 rpm. Stirring was performed. The solution was heated to 60 ° C. and then pressurized with propylene until the total pressure reached 7 bar.

0.25 mL (0.0010 M, 0.25 μmol) of the catalyst solution prepared in Example p9 was added to the autoclave, and then 0.70 mL of dehydrated heptane was added to initiate polymerization. After polymerizing at 60 ° C. for 10 minutes, a small amount of isobutyl alcohol was added to terminate the polymerization. After removing the solvent from the obtained polymer solution, it was dried under reduced pressure at 80 ° C. for 12 hours to obtain 359 mg of a propylene polymer.

[Comparative example p7]
Under a nitrogen atmosphere, 6.50 mg (16.2 μmol) of the transition metal compound (b) was placed in a Schlenk tube, and 1.66 mL (n) of a suspension of modified methylaluminoxane (manufactured by Tosoh Corporation, 4.86 mmol in terms of Al atoms) was added. -Hexane solvent (2.93 M) was added, then 14.58 mL of dehydrated heptane was added, and the mixture was stirred at room temperature for 60 minutes or more to prepare a 0.0010 M catalyst solution.

Using a SUS autoclave having an internal volume of 15 mL and sufficiently nitrogen-substituted, the same operation as in Example p9 was carried out except that the catalyst solution of Example p9 was changed to the above-mentioned catalyst solution to obtain 122 mg of a propylene polymer. ..

[Comparative example p8]
Same as Example p10 except that the catalyst solution of Example p9 was changed to the catalyst solution of Comparative Example p7 and the polymerization time was changed from 10 minutes to 30 minutes using a SUS autoclave having an internal volume of 15 mL sufficiently nitrogen-substituted. To obtain 249 mg of a propylene polymer.
Table 3 shows the physical properties of the propylene polymers obtained in Examples p9 and p10 and Comparative Examples p7 and p8.

[Production of ethylene / 1-octene copolymer]
[Example p11]
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid and gas phases were saturated with 100 liters / hr of ethylene for 10 minutes. Then, 10 mL of 1-octene and a 1.44 mol / L toluene solution of methylarmoxane (manufactured by Nippon Aluminum Alkyls, Inc.) 0.69 mL (1.0 mmol) (another description method: 1.0 mmol of methylarmoxane in terms of aluminum atom) ), And 2.00 mL (2.0 mmol) of a 1.0 mol / L toluene solution of BHT was charged. Polymerization was started by adding 0.40 mL (0.0002 mmol) of a solution prepared by dissolving 2.6 mg of the transition metal compound (C) in 9.2 mL of toluene. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 25 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was added to 1 liter of a mixed solvent of acetone / methanol (2/1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 120 ° C. for 10 hours to obtain 2.151 g of an ethylene / 1-octene copolymer. Table 4 shows the activity and the physical properties of the obtained polymer.

[Comparative Example p9]
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid and gas phases were saturated with 100 liters / hr of ethylene for 10 minutes. Then, 10 mL of 1-octene and a 1.44 mol / L toluene solution of methylarmoxane (manufactured by Nippon Aluminum Alkyls, Inc.) 0.69 mL (1.0 mmol) (another description method: 1.0 mmol of methylarmoxane in terms of aluminum atom) ), And 2.00 mL (2.0 mmol) of a 1.0 mol / L toluene solution of BHT was charged. Polymerization was started by adding 0.50 mL (0.0002 mmol) of a solution prepared by dissolving 2.8 mg of the transition metal compound (c) in 14.2 mL of toluene. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 25 ° C. for 10 minutes under normal pressure, and then polymerization was stopped by adding a small amount of methanol. After completion of the polymerization, the reaction product was added to 1 liter of a mixed solvent of acetone / methanol (2/1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with the same solvent, it was dried under reduced pressure at 120 ° C. for 10 hours to obtain 0.861 g of an ethylene / octene copolymer. Table 4 shows the activity and the physical properties of the obtained polymer.

[Production of ethylene / tetracyclododecene copolymer]
[Example p12]
Glass reactor thoroughly purged with nitrogen content volume 500 mL, toluene 250mL and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter, simply "tetracyclododecene" Also described.) 10 g was charged, and the liquid phase and the gas phase were saturated with 50 liters / hr of ethylene. Then, 0.75 mmol of modified aluminoxane was added in terms of aluminum atom, and 0.0015 mmol of transition metal compound (F) 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 methanol. 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 93 mg of an ethylene / tetracyclododecene copolymer. The physical property values of the obtained polymers are summarized in Table 5.

[Example p13]
250 mL of toluene and 10 g of tetracyclododecene were charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with 50 liters / hr of ethylene. Then, 0.75 mmol of triisobutylaluminum was added in terms of aluminum atom, 0.005 mmol of the transition metal compound (F), and 0.02 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 methanol. 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 417 mg of an ethylene / tetracyclododecene copolymer. The physical property values of the obtained polymers are summarized in Table 5.

[Comparative Example p10]
The same procedure as in Example p13 was carried out except that 0.005 mmol of the transition metal compound (f) was used instead of the transition metal compound (F), and 253 mg of an ethylene / tetracyclododecene copolymer was obtained. The physical property values of the obtained polymers are summarized in Table 5.

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

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

[Production of ethylene polymer, ethylene / 1-hexene copolymer]
[Example p14]
A catalyst slurry was prepared in the same manner as in Example p5 except that the transition metal compound (F) was used instead of the transition metal compound (B).
Using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, the same operation as in Example p5 was performed except that the catalyst slurry of Example p5 was changed to the catalyst slurry (200 mg as a solid content), and ethylene was used. 1.6 g of the polymer was obtained.

[Comparative Example p11]
A catalyst slurry was prepared in the same manner as in Example p5 except that the transition metal compound (f) was used instead of the transition metal compound (B).
Using a SUS autoclave having an internal volume of 1 L sufficiently substituted with nitrogen, the same operation as in Example p5 was performed except that the catalyst slurry of Example p5 was changed to the catalyst slurry (200 mg as a solid content), and ethylene was used. 2.7 g of the polymer was obtained.
Table 6 shows the physical properties and the like of the ethylene / 1-hexene copolymers obtained in Example p14 and Comparative Example p11.

担体Ｔ１：実施例ｐ５で得られた担体

Carrier T1: Carrier obtained in Example p5

[Example p15]
250 mL of toluene was charged into a glass reactor having an internal volume of 500 mL sufficiently nitrogen-substituted, and the liquid phase and the gas phase were saturated with 100 liters / hr of ethylene. Then, 1.25 mmol of triisobutylaluminum was added in terms of aluminum atom, 0.0025 mmol of the transition metal compound (F), and 0.01 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added to start polymerization. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure, and then polymerization was stopped by adding a small amount of methanol. 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 0.424 g of an ethylene polymer. The physical property values of the obtained polymers are summarized in Table 7.

[Comparative Example p12]
The same procedure as in Example p15 was carried out except that 0.0025 mmol of the transition metal compound (f) was used instead of the transition metal compound (F), and 1.591 g of an ethylene polymer was obtained. The physical property values of the obtained polymers are summarized in Table 7.

Claims (11)

A transition metal compound represented by the following general formula [A-1].

[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 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 groups 15 and 16 elements. ] In the general formula [A-1],
The transition metal compound according to claim 1, wherein M is a titanium atom or a zirconium atom. In the general formula [A-1],
The transition metal compound according to claim 1, wherein M is a titanium atom. The transition metal compound according to claim 1, wherein A is sulfur in the general formula [A-1]. The transition metal compound according to claim 1, wherein in the general formula [A-1], L is the following (L-1) having a ketimid structure.
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 attached to the N atom in a double bond); and (c) the carbon atom. Means a ligand having _two substituents (Sub ₁ and Sub ₂ described below) attached to.

[In the formula (L-1), Sub ₁ and Sub ₂ may be independently the same or different from each other, and Sub ₁ and Sub ₂ 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. ] The transition metal compound according to claim 1, wherein in the general formula [A-1], L is the following (L-2) having a phosphineimide structure.
The phosphineimide ligand is represented by the following general formula L-2 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 P atom attached to the N atom in a double bond); and (c) the P atom. Means a ligand having _three substituents (Sub ₃ , Sub ₄ and Sub ₅ described below) attached to.

[In the formula (L-2), Sub ₃ , Sub ₄ and Sub ₅ may be independently the same or different from each other, and Sub ₃ , Sub ⁴ and Sub ₅ are hydrogen and alkyl groups having 1 to 20 carbon atoms. , Aalkyl group, amide group, aryl group, aralkyl group, silyl group, alkylsilyl group, arylamide group, silylamide group, phosphinoamide group, and phosphide group. In addition, each may be bonded to each other to form a ring. ] The transition metal compound amidimid ligand according to claim 1, wherein L has an amidimid structure (L-3) in the general formula [A-1], is represented by the following general formula L-3. Is defined as follows.
(A) Bonded to a Group 4 metal via a metal-nitrogen atom bond;
(B) Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.
(C) Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ is bonded to an imine carbon atom via the heteroatom.

[In formula (L-3), Sub ₆ is a substituent containing a Group 14 atom, and Sub ₆ is bonded to an imine carbon atom via a Group 14 atom.
Sub ₇ is a substituent containing a heteroatom of groups 15 to 16, and Sub ₇ is bonded to an imine carbon atom via the heteroatom. ] The transition metal compound according to claim 1, wherein in the general formula [A-1], L has an aryloxy structure represented by the formula (L-4).

[In the formula (L-4), O may be an oxygen atom, and R ^{11 to} R ¹⁵ may be independently the same or different from each other. R ^{11 to} R ¹⁵ contain 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. ] (A) The transition metal compound according to any one of claims 1 to 8.
(B) (B-1) Organic metal compound,
A catalyst for olefin polymerization containing (B-2) an organoaluminum oxy compound and (B-3) at least one compound selected from the group consisting of a compound that reacts with a transition metal compound (A) to form an ion pair. .. The method for producing an olefin polymer that polymerizes an olefin in the presence of the olefin polymerization catalyst according to claim 9. The method for producing an olefin polymer according to claim 10, wherein the olefin is an olefin selected from olefins having 2 to 30 carbon atoms.