JP2008120733A - Rare earth metal complex, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rare earth metal complex useful as a polymerization catalyst. <P>SOLUTION: This rare earth metal complex is expressed by formula (1) [wherein, Ln is a group 3 metal atom or lanthanoid metal atom (provided that samarium and ytterbium are excluded); R<SP>1</SP>to R<SP>8</SP>are each the same or different and H, a halogen atom, a 1-20C alkyl or the like; each of adjacent groups to the R<SP>1</SP>to R<SP>8</SP>may form a ring by optionally bonding with each other; the (m) pieces of Xs are each the same or different and a mono anion ligand; the (n) pieces of Ys are each the same or different and a neutral ligand; (m) is 0 to 3 integer; and (n) is 0 to 3 integer]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a rare earth metal complex, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

Group 4 metal complexes having a ligand in which two molecules of phenol are cross-linked with a sulfur atom (hereinafter referred to as bisphenol ligand) are compounds used as various olefin polymerization catalyst components (for example, patent documents). 1 and 2). However, there is no known example of a complex in which the central metal is a Group 3 metal or a lanthanoid metal (hereinafter, the Group 3 metal and the lanthanoid metal are collectively referred to as a rare earth metal) as a catalyst for olefin polymerization.
As such a metal complex having a bisphenol ligand, a samarium complex is known as a selective acylation reaction catalyst of 1,2-diol (for example, see Non-Patent Document 1). In addition, as a study of luminescent materials, samarium complexes, yttrium complexes, europium complexes, and ytterbium complexes are known, and it is known that bisphenol ligands form complexes in which two or more molecules are bonded to rare earth metals. (For example, see Non-Patent Document 2), it was not easy to obtain a rare earth metal complex formed of a rare earth metal and a bisphenol ligand in a one-to-one relationship.
Japanese Patent Laid-Open No. 6-1336048 Japanese Patent Laid-Open No. 6-136049 J. et al. Organomet. Chem. 2002, 205, 215. Dalton Trans. 2004, 3748.

The present invention intends to provide a novel rare earth metal complex, an olefin polymerization catalyst and a method for producing an olefin polymer which can be used as a catalyst component for olefin polymerization.

（式中、Ｌｎは第３族金属原子又はランタノイド金属原子（ただし、サマリウム、イッテルビウムを除く）を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は同一又は相異なり、水素原子、ハロゲン原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基、炭素原子数１〜２０の炭化水素を有するシリル基、炭素原子数１〜２０のアルコキシ基、炭素原子数６〜２０のアリールオキシ基、炭素原子数７〜２０のアラルキルオキシ基又は炭素原子数１〜２０の炭化水素を有するアミノ基を表し、
ここで、Ｒ^１〜Ｒ^８において、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基及び炭化水素は、ハロゲン原子で置換されていてもよい、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８の隣接する基はそれぞれ任意に結合して環を形成していてもよく、ｍ個のＸは同一又は相異なり、モノアニオン配位子を表し、ｎ個のＹは同一又は相異なり中性配位子を表し、ｍは０〜３までの整数を表し、ｎは０〜３までの整数を表す。）
で示される希土類金属錯体；
［２］：式（２）

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、前記と同じ意味を表す。）
で示される置換もしくは無置換のビスフェノール配位子と式（３）

（式中、Ｌｎ、Ｘ、Ｙ、ｍ及びｎは前記と同じ意味を表し、Ｒ^９及びＲ^１０は炭素原子数１〜２０の炭化水素を有するシリル基で置換されていてもよいアルキル基又は、炭素原子数１〜２０の炭化水素を有するアミノ基で置換されていてもよいアラルキル基を表す。）
で示される希土類金属化合物とを反応させることを特徴とする請求項１に記載の式（１）で示される希土類金属錯体の製造方法；
［３］：式（１）で示される希土類金属錯体からなるオレフィン重合用触媒成分；
［４］：該オレフィン重合用触媒成分と、下記化合物（Ａ）及び／又は下記化合物（Ｂ）とを接触させて得られるオレフィン重合用触媒。
化合物（Ａ）：下記（Ａ１）〜（Ａ３）からなる群から選ばれる１種以上のアルミニウム化合物
（Ａ１）：式（Ｅ^１）_ａＡｌＺ_{（３−ａ）}で表される有機アルミニウム化合物；
（Ａ２）：式｛−Ａｌ（Ｅ^２）−Ｏ−｝_ｂで表される構造を有する環状のアルミノキサン；
（Ａ３）：式Ｅ^３｛−Ａｌ（Ｅ^３）−Ｏ−｝_ｃＡｌ（Ｅ^３）_２で表される構造を有する線状のアルミノキサン
（式中、ａは０＜ａ≦３を満足する数を表し、ｂは２以上の整数を表し、ｃは１以上の整数を表す。Ｅ^１、Ｅ^２及びＥ^３はそれぞれ炭素原子数１〜２０の炭化水素基を表し、複数のＥ^１、複数のＥ^２及び複数のＥ^３はそれぞれ同じであっても異なっていてもよい。Ｚは水素原子又はハロゲン原子を表し、複数のＺは互いに同じであっても異なっていてもよい。）
化合物（Ｂ）：下記（Ｂ１）〜（Ｂ３）からなる群から選ばれる１種以上のホウ素化合物
（Ｂ１）：式 ＢＱ^１Ｑ^２Ｑ^３で表されるホウ素化合物；
（Ｂ２）：式 Ｇ^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で表されるホウ素化合物；
（Ｂ３）：式 （Ｌ^１−Ｈ）^＋（ＢＱ^１Ｑ^２Ｑ^３Ｑ^４）⁻で表されるホウ素化合物
（式中、Ｂは３価の原子価状態のホウ素原子を表し、Ｑ^１、Ｑ^２、Ｑ^３及びＱ^４はそれぞれ独立にハロゲン原子、炭化水素基、ハロゲン化炭化水素基、置換シリル基、アルコキシ基又は２置換アミノ基を表し、Ｇ^＋は無機又は有機のカチオンを表し、Ｌ^１は中性ルイス塩基を表す。）；
及び、
［５］：該オレフィン重合用触媒の存在下、オレフィンを重合させるオレフィン重合体の製造方法
を提供するものである。 As a result of intensive studies in order to solve the above problems, the present inventors have found a rare earth metal complex useful as a catalyst component capable of polymerizing olefins, and have reached the present invention.
That is, the present invention
[1]: Formula (1)

(Wherein, Ln represents a Group 3 metal atom or a lanthanoid metal atom (excluding samarium, ^{ytterbium), R 1, R 2,} R 3, R 4, R 5, R 6, R 7 and ^{R 8} Are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, carbonization having 1 to 20 carbon atoms Amino having a silyl group having hydrogen, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms Represents a group,
Here, in R ^{1 to} R ⁸ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group and hydrocarbon may be substituted with a halogen atom.
The adjacent groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring, and m Xs are the same or Differently, it represents a monoanionic ligand, n Y's are the same or different and represent a neutral ligand, m represents an integer from 0 to 3, and n represents an integer from 0 to 3. )
A rare earth metal complex represented by:
[2]: Formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above.)
A substituted or unsubstituted bisphenol ligand represented by the formula (3)

(In the formula, Ln, X, Y, m and n represent the same meaning as described above, and R ⁹ and R ¹⁰ are an alkyl group which may be substituted with a silyl group having a hydrocarbon having 1 to 20 carbon atoms, or And represents an aralkyl group optionally substituted with an amino group having a hydrocarbon having 1 to 20 carbon atoms.)
A method for producing a rare earth metal complex represented by the formula (1) according to claim 1, wherein the rare earth metal compound represented by formula (1) is reacted:
[3]: Olefin polymerization catalyst component comprising a rare earth metal complex represented by the formula (1);
[4] An olefin polymerization catalyst obtained by contacting the olefin polymerization catalyst component with the following compound (A) and / or the following compound (B).
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3) (A1): an organoaluminum compound represented by the formula (E ¹ ) _a AlZ _(3-a) ;
(A2): a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b ;
(A3): a linear aluminoxane having a structure represented by the formula E ³ {-Al (E ³ ) —O—} _c Al (E ³ ) ₂ (wherein a satisfies 0 <a ≦ 3) B represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ each represent a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of E ¹ , The plurality of E ² and the plurality of E ³ may be the same or different from each other, Z represents a hydrogen atom or a halogen atom, and the plurality of Z may be the same or different from each other.
Compound (B): One or more boron compounds selected from the group consisting of the following (B1) to (B3) (B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ ;
(B2): a boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ ;
(B3): a boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— (wherein B represents a boron atom in a trivalent valence state, Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, L ¹ represents a neutral Lewis base);
as well as,
[5]: Provided is a method for producing an olefin polymer in which an olefin is polymerized in the presence of the olefin polymerization catalyst.

The novel rare earth metal complex obtained by the present invention is useful, for example, as a catalyst for olefin polymerization reaction.

Hereinafter, the present invention will be described in detail.

Examples of the group 3 metal atom or lanthanoid metal atom represented by Ln in the rare earth metal complex represented by the formula (1) (hereinafter abbreviated as rare earth metal complex (1)) include scandium, yttrium, and lanthanoid. Preferably, scandium and yttrium are used. Here, the lanthanoid represents 15 elements from lanthanum having atomic number 57 to lutetium having atomic number 71 in the periodic table of elements.

In the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , examples of the halogen atom include a fluorine atom, chlorine atom, bromine atom, iodine atom, etc. A chlorine atom is mentioned.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, tetradecyl group, Examples include a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an n-eicosyl group, and preferred examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and an amyl group.
Specific examples of the halogen-substituted alkyl group having 1 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include those alkyl groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. What was done is illustrated.

Specific examples of the aryl group having 6 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2 , 4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5- Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3 , 4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec- Butyl Enyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group , A naphthyl group, an anthracenyl group and the like, and a phenyl group is preferable.
As specific examples of the halogen-substituted aryl group having 6 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ , these aryl groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. What was done is illustrated.

Specific examples of the aralkyl group having 7 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, and (4-methylphenyl). ) Methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3 , 4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3 , 6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group , (2,3,4 6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, Examples include (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. Preferably a benzyl group is mentioned.
In the substituents R ^{1 to} R ⁸ , as specific examples of the halogen-substituted aralkyl group having 7 to 20 carbon atoms, these aralkyl groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Are illustrated.

In the substituents R ^{1 to} R ⁸ , examples of the silyl group hydrocarbon having a hydrocarbon include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, alkyl group having 1 to 10 carbon atoms such as n-decyl group, phenyl An aryl group such as a group is exemplified. Specific examples of the silyl group substituted with a hydrocarbon having 1 to 20 carbon atoms include monosubstituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, and diethyl. Disubstituted silyl group having 1 to 20 carbon atoms such as silyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group , Tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, Three having a C1-C20 hydrocarbon such as a triphenylsilyl group It is like the illustration conversion silyl group, preferably a trimethylsilyl group, tert- butyldimethylsilyl group, and triphenylsilyl group.
Examples of the hydrocarbon group constituting these substituted silyl groups include hydrocarbon groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom in addition to the hydrocarbon group as described above. .

In the substituents R ^{1 to} R ⁸ , specific examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert -Butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-dodecyloxy group, n-undecyloxy group, Examples include n-dodecyloxy group, tridecyloxy group, tetradecyloxy group, n-pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, n-eicosyloxy group, etc. Preferably, a methoxy group, an ethoxy group, and a tert-butoxy group can be mentioned.
Specific examples of the halogen-substituted alkoxy group having 1 to 20 carbon atoms include those in which these alkoxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Specific examples of the aryloxy group having 6 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4- Trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,4,5- Trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-te Lamethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n- Examples thereof include aryloxy groups having 6 to 20 carbon atoms such as octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group and anthracenoxy group. As specific examples of the halogen-substituted aryloxy group having 6 to 20 carbon atoms, the aryloxy group having 6 to 20 carbon atoms is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Are illustrated.

Specific examples of the aralkyloxy group having 7 to 20 carbon atoms in the substituents R ^{1 to} R ⁸ include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4- Methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2 , 3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) ) Methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy Group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group , (Tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, naphthylmethoxy group, anthracenylmethoxy group, etc. A benzyloxy group is preferable.
Specific examples of the halogen-substituted aralkyloxy group having 7 to 20 carbon atoms include those in which these aralkyloxy groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the substituents R ^{1 to} R ⁸ , the amino group having 1 to 20 carbon atoms is an amino group having two hydrocarbons, and examples of the hydrocarbon include a methyl group, ethyl group, and the like. Alkyl having 1 to 20 carbon atoms, such as a group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Group, an aryl group such as a phenyl group, and the like, and these substituents may be bonded to each other to form a ring. Examples of the amino group having a hydrocarbon having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec- Butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino Group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, pyrrolyl group, pyrrolidinyl group, piperidinyl group, carbazolyl group, dihydroindolyl group, dihydroisoindolyl group and the like, preferably dimethylamino group, Diethylamino group, pyrrolidinyl group, piperidinyl Etc. The.
Examples of the hydrocarbon constituting these substituted amino groups include hydrocarbon groups substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom in addition to the above hydrocarbon group.

Two adjacent substituents among the substituents R ^{1 to} R ⁸ may be optionally bonded to form a ring.

Examples of the ring formed by combining two adjacent substituents among the substituents R ^{1 to} R ⁸ include saturated or unsaturated hydrocarbon rings having 1 to 20 carbon atoms. The Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, benzene ring, naphthalene ring, anthracene ring and the like.

Examples of the rare earth metal complex (1) of the present invention include (2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) scandium, (2 , 2′-thiodiphenoxy) (trimethylsilylmethyl) scandium, (2,2′-thio-4,4 ′, 6,6′-tetra-tert-butyldiphenoxy) (trimethylsilylmethyl) scandium, (2,2 '-Thio-4,4', 6,6'-tetramethyldiphenoxy) (trimethylsilylmethyl) scandium, (2,2'-thio-6,6'-di-tert-butyldiphenoxy) (trimethylsilylmethyl) Scandium, (2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (o-N, N-dimethyla Nobenzyl) scandium, (2,2′-thiodiphenoxy) (oN, N-dimethylaminobenzyl) scandium, (2,2′-thio-4,4 ′, 6,6′-tetra-tert-butyl) Diphenoxy) (o-N, N-dimethylaminobenzyl) scandium, (2,2′-thio-4,4 ′, 6,6′-tetramethyldiphenoxy) (o-N, N-dimethylaminobenzyl) Scandium, (2,2′-thio-6,6′-di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) scandium

(2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) yttrium, (2,2′-thiodiphenoxy) (trimethylsilylmethyl) yttrium, (2,2′-thio-4,4 ′, 6,6′-tetra-tert-butyldiphenoxy) (trimethylsilylmethyl) yttrium, (2,2′-thio-4,4 ′, 6,6′- Tetramethyldiphenoxy) (trimethylsilylmethyl) yttrium, (2,2′-thio-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) yttrium, (2,2′-thio-4,4 ′) -Dimethyl-6,6'-di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) yttrium, (2,2'-thiodi Enoxy) (o-N, N-dimethylaminobenzyl) yttrium, (2,2'-thio-4,4 ', 6,6'-tetra-tert-butyldiphenoxy) (o-N, N-dimethylamino) (Benzyl) yttrium, (2,2′-thio-4,4 ′, 6,6′-tetramethyldiphenoxy) (o—N, N-dimethylaminobenzyl) yttrium, (2,2′-thio-6, 6'-di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) yttrium

(2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) lutetium, (2,2′-thiodiphenoxy) (trimethylsilylmethyl) lutetium, (2,2′-thio-4,4 ′, 6,6′-tetra-tert-butyldiphenoxy) (trimethylsilylmethyl) lutetium, (2,2′-thio-4,4 ′, 6,6′- Tetramethyldiphenoxy) (trimethylsilylmethyl) lutetium, (2,2′-thio-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) lutetium, (2,2′-thio-4,4 ′ -Dimethyl-6,6'-di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) lutetium, (2,2'-thiodiphenoxy) o-N, N-dimethylaminobenzyl) lutetium, (2,2′-thio-4,4 ′, 6,6′-tetra-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) lutetium , (2,2'-thio-4,4 ', 6,6'-tetramethyldiphenoxy) (o-N, N-dimethylaminobenzyl) lutetium, (2,2'-thio-6,6'- Di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) lutetium and the like, scandium, lutetium and yttrium are substituted with lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, Examples of holmium, erbium, thulium and ytterbium are also exemplified.

Examples of the rare earth metal complex (1) added with tetrahydrofuran, diethyl ether, N, N-dimethylaniline, trimethylphosphine and the like are also exemplified.

The rare earth metal complex (1) comprises a substituted or unsubstituted bisphenol ligand represented by formula (2) (hereinafter abbreviated as bisphenol ligand (2)) and a rare earth metal compound represented by formula (3) ( Hereinafter, it can be produced by reacting with a rare earth metal compound (3).

Examples of the hydrocarbon group having 1 to 20 carbon atoms in the alkyl group which may be substituted with a silicon atom having a hydrocarbon having 1 to 20 carbon atoms in the substituents R ⁹ and R ¹⁰ include, for example, methyl group, ethyl Group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and n-eicosyl group are exemplified, preferably methyl group , Ethyl group, isopropyl group, tert-butyl group, amyl group and the like.

Examples of the alkyl group which may be substituted with a silicon atom having a hydrocarbon having 1 to 20 carbon atoms in the substituents R ⁹ and R ¹⁰ include a trimethylsilylmethyl group, a triethylsilylmethyl group, a triisopropylsilylmethyl group, A tri-n-butylsilylmethyl group, a t-butyldimethylsilylmethyl group, etc. are mentioned, Preferably a trimethylsilylmethyl group is mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in the aralkyl group substituted with the amino group having 1 to 20 carbon atoms in the substituents R ⁹ and R ¹⁰ include, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, heptyl group, n-octyl group, n-nonyl Group, n-decyl group, n-dodecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and n-eicosyl group, preferably methyl group, ethyl Group, isopropyl group, tert-butyl group, amyl group and the like.

Examples of the aralkyl group substituted with an amino group having a hydrocarbon having 1 to 20 carbon atoms in the substituents R ⁹ and R ¹⁰ include, for example, o-N, N-dimethylaminobenzyl group, o-N, N- A diethylaminobenzyl group etc. are mentioned, Preferably an o-N, N-dimethylaminobenzyl group is mentioned.

A bisphenol ligand (2) can be manufactured according to a well-known technique (for example, refer nonpatent literature 1, for example).

Examples of the bisphenol ligand (2) include 2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′- Thiobis (4,6-dimethyl-butylphenol), 2,2'-thiobis (4-methyl-6-phenylphenol), 2,2'-thiobis (4-methoxy-6-tert-butylphenol), 2,2 ' -Thiobis (4-chloro-6-tert-butylphenol), 2,2'-thiobis (4-phenyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-trimethylsilylphenol), 2 , 2′-thiobisnaphthol and the like, among which 2,2′-thiobis (6-tert-butylphenol), 2, '- thiobis (4-methyl -6-tert-butylphenol), 2,2'-thiobis (4,6-dimethyl - butylphenol) is preferred.

In the rare earth metal complex (1) and the rare earth metal compound (3), examples of the monoanionic ligand represented by the substituent X include a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an n-butyl group, Neopentyl group, phenyl group, neopentylidene group, methoxy group, tert-butoxy group, phenoxy group, benzyl group, amide group, phosphino group, trimethylsilylmethyl group, o-dimethylaminobenzyl group, preferably methyl group, Examples thereof include a trimethylsilylmethyl group and an o-dimethylaminobenzyl group.

When m is 2, two Xs may be bonded to each other or may form a dianionic ligand together.

In the rare earth metal complex (1) and the rare earth metal compound (3), examples of the neutral ligand represented by the substituent Y include olefins, aromatic compounds, ethers, sulfides, amines, nitriles, Examples include phosphines or phosphine oxides, preferably ethers or amines.
Specific examples of the neutral coordination represented by Y include ethylene, propylene, 1-butene, cyclooctadiene, styrene, benzene, toluene, naphthalene, anthracene, diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, and dimethyl. Sulfide, thiophene, tetrahydrothiophene, trimethylamine, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine, pyridine, N, N-dimethylaminopyridine, acetonitrile, trimethylphosphine , Triethylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, trimethylphosphine oxide, triphenylphosphine oxide, etc. The like, preferably tetrahydrofuran, diethyl ether, N, N-dimethylaniline, etc. trimethyl phosphine.

X and Y may combine to form a multidentate ligand.
Specific examples of the multidentate ligand include o-N, N-dimethylaminobenzyl group.

m represents an integer of 0 to 3, preferably 1 to 2, and more preferably 1. n represents an integer of 0 to 3, preferably 1 to 3.

The rare earth metal compound (3) is based on a known method (for example, J. Am. Chem. Soc. 1978, 100, 8068. or J. Chem. Soc., Chem. Comm. 1973, 126.). Can be synthesized.

Examples of the rare earth metal compound (3) include tris (trimethylsilylmethyl) scandium, tris (o-N, N-dimethylaminobenzyl) scandium, and diethyl ether, tetrahydrofuran, trimethylamine of these compounds. , Triethylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine adduct. Further, examples in which scandium is yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium are also included. More preferably, tris (o-N, N-dimethylaminobenzyl) scandium and tris (o-N, N-dimethylaminobenzyl) lutetium are used.

In the method of reacting the bisphenol ligand (2) and the rare earth metal compound (3), it is usually carried out by adding the rare earth metal compound (3) to the solvent and then adding the bisphenol ligand (2). Can do.

The usage-amount of a rare earth metal compound (3) is 0.5-3 mol normally per mol of bisphenol ligand (2), Preferably it is 0.7-1.5 mol.

The reaction temperature is usually from −100 ° C. to the boiling point of the solvent, preferably in the range from −80 ° C. to 60 ° C.

The reaction is usually performed in a solvent inert to the reaction. Examples of such solvents include aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Amide solvents such as hollic amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene Etc. are exemplified. These solvents are used alone or in admixture of two or more, and the amount used is usually 1 to 200 parts by weight, preferably 3 to 50 parts by weight, per 1 part by weight of the bisphenol ligand (2). .

After completion of the reaction, the desired reaction mixture is obtained from the resulting reaction mixture by, for example, a method in which the formed precipitate is separated by filtration, and the filtrate is concentrated to precipitate the rare earth metal complex (1). The rare earth metal complex (1) can be obtained.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization of the present invention is an olefin polymerization catalyst having the rare earth metal complex (1) as a catalyst component for olefin polymerization, and is obtained by bringing the rare earth metal complex (1) into contact with another cocatalyst component. Examples of the olefin polymerization catalyst include olefin polymerization catalysts obtained by bringing the rare earth metal complex (1) into contact with the following compound (A) and / or the following compound (B).
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3) (A1): Organoaluminum compound (A2) represented by the formula E ¹ _a AlZ _(3-a ): Cyclic aluminoxane (A3) having a structure represented by the formula {—Al (E ² ) —O—} _b : Formula E ³ {—Al (E ³ ) —O—} _c Al (E ³ ) ₂ A linear aluminoxane having the structure (wherein a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. E ¹ , E ² And E ³ represents a hydrocarbon group having 1 to 20 carbon atoms, and the plurality of E ¹ , the plurality of E ^2, and the plurality of E ³ may be the same or different, and Z is a hydrogen atom or halogen. Represents an atom, and when there are a plurality of Z, the plurality of Z may be the same or different May be.)
Compound (B): One or more boron compounds (B1) selected from the group consisting of the following (B1) to (B3): Boron compound (B2) represented by formula BQ ¹ Q ² Q ³ : Formula G ⁺ ( Boron compound (B3) represented by BQ ¹ Q ² Q ³ Q ⁴ ) ^- : Boron compound represented by formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- Represents a trivalent boron atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a halogen atom, hydrocarbon group, halogenated hydrocarbon group, substituted silyl group, alkoxy group or disubstituted Represents an amino group, G ⁺ represents an inorganic or organic cation, and L ¹ represents a neutral Lewis base.)

(A1): As the organoaluminum compound represented by the formula E ¹ _a AlZ _(3-a) , for example, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethyl Dialkylaluminum chlorides such as aluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride ; Dimethyl aluminum Examples thereof include dialkylaluminum hydrides such as nium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

(A2): a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b or (A3): a formula E ³ {—Al (E ³ ) —O—} _c Al (E as E ² and E ³ in the linear aluminoxane having a structure represented by ³⁾ _2, for example, a methyl group, an ethyl group, normal propyl group, an isopropyl group, normal butyl group, isobutyl group, normal pentyl group, neopentyl And an alkyl group such as a group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are each independently a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution in which a trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (such as benzene or an aliphatic hydrocarbon) is contacted with water. Moreover, the method etc. which make trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water are mentioned.

(B1): In the boron compound represented by the formula BQ ¹ Q ² Q ³ , B is a boron atom in a trivalent valence state. Q ^{1 to} Q ³ are preferably each independently a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a substituted silyl group having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, more preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a 1 to 20 carbon atom. A halogenated hydrocarbon group;

(B1): Examples of the boron compound represented by the formula BQ ¹ Q ² Q ³ include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2, 3,4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, etc. Preferred is tris (pentafluorophenyl) borane.

(B2): In the boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ is an inorganic or organic cation, and B is a trivalent valence state boron atom. , Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (B1) above.

In the boron compound represented by (B2): G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , G ⁺ which is an inorganic cation includes, for example, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ⁺ whose cation is an organic cation include, for example, a triphenylmethyl cation. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include, for example, tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4, 5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3 , 5-bistrifluoromethylphenyl) borate and the like.

(B2): Boron compounds represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include, for example, ferrocenium tetrakis (pentafluorophenyl) borate and 1,1′-dimethylferrocenium tetrakis (Pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, etc. Is triphenylmethyltetrakis (pentafluorophenyl) borate.

(B3): In the boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L ¹ is a neutral Lewis base, and (L ¹ -H) ⁺ is Brene. It is a Sted acid, B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (B1) above.

(B3): In the boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (L ¹ -H) ⁺ includes, for example, trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like can be mentioned. Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same ones as described above.

(B3): Examples of the boron compound represented by the formula (L ¹ —H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (penta Fluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) Borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Anilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) ) Phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, etc., preferably tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N -Dimethylanilinium tetrakis (pentafluorophenyl) borate.

As the compound (B), usually, (B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ , (B2): a boron represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ Either a compound or a boron compound represented by the formula (B3): Formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ is used.

In the method of contacting each catalyst component in the production of an olefin polymerization catalyst, any two catalyst components may be contacted in advance, and then another catalyst component may be contacted. In addition, each catalyst component may be contacted in the polymerization reactor, each catalyst component may be separately introduced into the polymerization reactor in any order, and any two or more catalyst components are contacted in advance. You may throw in something.

As the usage-amount of each catalyst component, the molar ratio of a compound (A) (aluminum atom conversion) / rare earth metal complex (1) is 0.1-10000 normally, Preferably it is 5-2000. When the (A1) organoaluminum compound is used as the compound (A), the molar ratio of the compound (A) / rare earth metal complex (1) is more preferably 0.3 to 500, still more preferably 0.5 to 100. . The molar ratio of compound (B) / rare earth metal complex (1) is usually 0.01 to 100, preferably 0.5 to 10.

Regarding the concentration when each catalyst component is used in a solution state, the concentration of the rare earth metal complex (1) is usually 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. The concentration of A) is usually 0.01 to 500 mmol / liter, preferably 0.1 to 100 mmol / liter in terms of aluminum atoms, and the concentration of compound (B) is usually 0.0001 to 5 mmol. / Liter, preferably 0.001 to 1 mmol / liter.

[Olefin polymer production method]
The method for producing an olefin polymer of the present invention is a method in which an olefin is polymerized in the presence of an olefin polymerization catalyst using the rare earth metal complex (1) as a catalyst component for olefin polymerization.

As the olefin used for the polymerization, a chain olefin, a cyclic olefin or the like can be used, and homopolymerization may be performed using one type of olefin, or copolymerization may be performed using two or more types of olefins. Good. Usually, an olefin having 2 to 20 carbon atoms is used as the olefin.

Examples of chain olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-pentene, 4-methyl- An α-olefin having 3 to 20 carbon atoms such as 1-pentene, 3,3-dimethyl-1-butene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,5-heptadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,7-nonadiene, 1,8-nonadiene, 1, 8-decadiene, 1,9-decadiene, 1,12-tetradecadiene, 1,13-tetradecadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hex Diene, 7-methyl-1,6-octadiene, 3-methyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3-ethyl-1,4-hexadiene, 3-ethyl-1,5- Non-conjugated dienes such as hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,3-dimethyl-1,5-hexadiene; 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene And conjugated dienes.

Cyclic olefins include alicyclic compounds such as vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, tetracyclo Monoolefins such as dodecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene; 5-ethylidene-2-norbornene, di Cyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 7-methyl-2,5-norbornadiene, 7-ethyl-2,5-norbornadiene, 7 -Propyl- , 5-norbornadiene, 7-butyl-2,5-norbornadiene, 7-pentyl-2,5-norbornadiene, 7-hexyl-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7 -Methylethyl-2,5-norbornadiene, 7-chloro-2,5-norbornadiene, 7-bromo-2,5-norbornadiene, 7-fluoro-2,5-norbornadiene, 7,7-dichloro-2,5- Norbornadiene, 1-methyl-2,5-norbornadiene, 1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5- Norbornadiene, 1-bromo-2,5-norbornadiene, 5,8-endomethylenehexahydronaphtha Down, non-conjugated dienes such as vinylcyclohexene; 1,3-cyclooctadiene, etc. conjugated dienes such as 1,3-cyclohexadiene and the like. As aromatic compounds, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, α-methylstyrene And divinylbenzene.

Examples of the combination of olefins when copolymerizing olefins include, for example, ethylene / propylene, ethylene / 1-butene, ethylene / 1-hexene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, propylene / Combinations of chain olefins / chain olefins such as 1-butene and propylene / 1-hexene; ethylene / vinylcyclohexane, ethylene / norbornene, ethylene / tetracyclododecene, ethylene / 5-ethylidene-2-norbornene, propylene / vinyl Chain olefins / cyclic olefins such as cyclohexane, propylene / norbornene, propylene / tetracyclododecene, propylene / 5-ethylidene-2-norbornene, ethylene / propylene / 5-ethylidene-2-norbornene Or the like can be mentioned a combination of.

The polymerization method is not particularly limited. For example, aliphatic hydrocarbons (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbons (benzene, toluene, etc.) or halogenated hydrocarbons (methylene dichloride). Etc.) as a solvent, solvent polymerization or slurry polymerization, gas phase polymerization in a gaseous monomer, and the like are possible, and either continuous polymerization or batch polymerization is possible.

The polymerization temperature can range from −50 ° C. to 300 ° C., but the range of −20 ° C. to 250 ° C. is particularly preferable. The polymerization pressure is preferably normal pressure to 90 MPa. In general, the polymerization time is appropriately determined depending on the type of the target polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail by an experiment example, this invention is not limited to these experiment examples.

<Production of rare earth metal complexes>
The physical properties were measured by the following method.
(1) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)
Apparatus: EX270 manufactured by JEOL Ltd. or DPX-300 manufactured by Bruker
Sample cell: 5 mmφ tube Measurement solvent: CDCl ₃ or toluene-d ₈
Sample concentration: 10 mg / 0.5 mL (CDCl ₃ or toluene-d ₈ )
Measurement temperature: room temperature (about 25 ° C)
Measurement parameters: 5 mmφ probe, MENU NON, OBNUC ¹ H, integration number 16 times Pulse angle: 45 degrees Repeat time: ACQTM 3 seconds, PD 4 seconds Internal standards: CDCl ₃ (7.26 ppm), toluene-d ₈ (2. 09ppm)

[Experimental Example 1]
“Synthesis of (2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (trimethylsilylmethyl) scandium (hereinafter referred to as scandium complex (1))”

<Synthesis of Tris (trimethylsilylmethyl) scandium (THF) ₂ >
Tris (trimethylsilylmethyl) scandium (THF) ₂ was synthesized according to known literature (J. Chem. Soc., Chem. Comm. 1973, 126.).

<Synthesis of scandium complex (1)>
Under nitrogen, tris (trimethylsilylmethyl) scandium (THF) ₂ (0.50 g, 1.11 mmol) was dissolved in 22 mL of hexane, and 2,2′-dihydroxy-3,3′-di-tert-butyl-5,5 '-Dimethyldiphenyl sulfide (0.40 g, 1.79 mmol) was added at room temperature. Stirring was continued at room temperature for 3 hours. Insoluble matter was filtered, the solvent was concentrated under reduced pressure, and pentane was added to obtain scandium complex (1) (0.19 g, yield 26.5%) to which two molecules of THF were added as a pale yellow solid.
< ¹ > H-NMR (toluene-d < ₈ >, [delta] ppm)): -0.05 (s, 2H), 0.46 (s, 9H), 1.26 (brs, 8H), 1.62 (s, 18H) ), 2.10 (s, 6H), 3.72 (br s, 8H), 7.04 (s, 2H), 7.41 (s, 2H)

[Experiment 2]
“(2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (oN, N-dimethylaminobenzyl) scandium (hereinafter referred to as“ scandium complex (2) ”) ))

<Synthesis of Tris (o-N, N-dimethylaminobenzyl) scandium>
Tris (o-N, N-dimethylaminobenzyl) scandium was synthesized according to known literature (J. Am. Chem. Soc. 1978, 100, 8068.).
¹ H-NMR (toluene-d ₈ , δ ppm)): 1.58 (s, 6H), 2.28 (s, 18H), 6.71-6.78 (m, 6H), 6.85-6 .95 (m, 6H)
Mass spectrum (EI-MS, m / z): 313 (M ⁺ −134), 268, 134, 91, 65

<Synthesis of scandium complex (2)>
Under nitrogen, tris (o-N, N-dimethylaminobenzyl) scandium (0.80 g, 1.79 mmol) was dissolved in 9 mL of THF, and 2,2′-dihydroxy-3,3′-di-tert-butyl-5 was dissolved. , 5′-dimethyldiphenyl sulfide (0.64 g, 1.79 mmol) in 9 mL of tetrahydrofuran was added at room temperature. Stirring was continued at room temperature for 20 hours. The solvent was concentrated under reduced pressure, pentane was added, and the insoluble material was filtered off. The filtrate was concentrated to obtain a scandium complex (2) (0.36 g, yield 33.2%) to which one molecule of THF was added as a white solid.
¹ H-NMR (toluene-d ₈ , δ ppm)): 1.27 (br s, 4H), 1.47 (s, 18H), 1.47 (s, 2H), 2.13 (s, 6H) 2.68 (s, 6H), 3.60 (brs, 4H), 6.74-6.87 (m, 2H), 6.92-7.10 (m, 4H), 7.42 ( s, 2H)

[Experiment 3]
“(2,2′-thio-4,4′-dimethyl-6,6′-di-tert-butyldiphenoxy) (o-N, N-dimethylaminobenzyl) yttrium (hereinafter referred to as yttrium complex (1) and ))

<Synthesis of Tris (o-N, N-dimethylaminobenzyl) yttrium>
Tris (o-N, N-dimethylaminobenzyl) yttrium was synthesized in the same manner as the synthesis of tris (o-N, N-dimethylaminobenzyl) scandium except that yttrium chloride was used.
¹ H-NMR (toluene-d ₈ , δ ppm)): 1.54 (s, 6H), 2.11 (s, 18H), 6.58-6.66 (m, 3H), 6.80-6 .82 (m, 3H), 6.90-7.03 (m, 6H)
Mass spectrum (EI-MS, m / z): 357 (M ⁺ -134), 268, 134, 120, 91, 65

<Synthesis of Yttrium Complex (1)>
Under nitrogen, tris (o-N, N-dimethylaminobenzyl) yttrium (0.80 g, 1.63 mmol) was dissolved in 8 mL of THF and 2,2′-dihydroxy-3,3′-di-tert-butyl-5 was dissolved. , 5′-Dimethyldiphenyl sulfide (0.58 g, 1.79 mmol) in 8 mL of tetrahydrofuran was added at room temperature. Stirring was continued at room temperature for 20 hours. The solvent was concentrated under reduced pressure, and pentane was added to obtain yttrium complex (1) (1.08 g, yield 83.2%) to which 3 molecules of THF were added as a white solid.
¹ H-NMR (toluene-d ₈ , δ ppm)): 1.30 (br s, 12H), 1.48 (s, 18H), 1.66 (s, 2H), 2.15 (s, 6H) 3.01 (s, 6H), 3.63 (brs, 12H), 6.75-7.09 (m, 6H), 7.53 (s, 2H)

<Production of ethylene-α-olefin copolymer>

The physical properties were measured by the following method.

(1) 1-hexene unit content in the copolymer (SCB, unit: 1 / 1000C)
It calculated | required by the infrared spectroscopy using the infrared spectrophotometer (Equinox55 by Bruker). The characteristic absorption of butyl ^branches, using a peak of 1378cm ^-1 ~1303cm -1, 1- hexene unit content was expressed as the ethylene-1-hexene copolymer 1000 number of butyl branches per carbon.

(2) Molecular weight and molecular weight distribution It was measured under the following conditions by gel permeation chromatography (GPC). The molecular weight distribution was evaluated by the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
Apparatus: Liquid feeding apparatus (LC pump) Model 305 (pump head 25.SC) manufactured by Gilson
Column: Polymer Laboratories PLgel Mixed-B 10 μm (7.5 mmφ × 300 mm)
Measurement temperature: 160 ° C
Mobile phase: Orthodichlorobenzene Sample concentration: 1 mg of copolymer / 1 mL of 1,2,4-trichlorobenzene
Flow rate: 2 mL / min Standard substance: (standard PS molecular weight) 5,000, 10,050, 28,500, 65,500, 185,400, 483,000, 1,013,000, 3,390,000

Using scandium complex (1) obtained in Experimental Example 1 as a catalyst component for olefin polymerization, copolymerization of ethylene and 1-hexene was carried out under the following polymerization conditions using Symyx PPR (48 series autoclave).

"Experimental example 4"
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. 100 μmol (Al atom conversion value) of aluminoxane (manufactured by Tosoh Finechem Co., 5.8 wt% Al) and 0.10 μmol of scandium complex (1) were added thereto, and polymerization was performed for 30 minutes. As a result of polymerization, a polymer having a molecular weight (Mw) = 241,000, a molecular weight distribution (Mw / Mn) = 1.6, and a content of 1-hexene unit (SCB) = 1 in the copolymer is 1 hour per 1 mol of the catalyst. 1.1 × 10 ⁶ g was produced per unit.

“Experimental Example 5”
Polymerization was performed in the same manner as in Experimental Example 4 except that 1-hexene was changed to 50 μL and the polymerization temperature was changed to 70 ° C., molecular weight (Mw) = 63,000, molecular weight distribution (Mw / Mn) = 1.5, copolymer The polymer of 1-hexene unit content (SCB) = 32 in the inside was produced at 9.0 × 10 ⁵ g per hour per 1 mol of the catalyst.

"Experimental example 6"
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol, and scandium complex (1) 0.10 μmol were added. Polymerized for minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 31,000 and a molecular weight distribution (Mw / Mn) = 1.9 was produced at 1.8 × 10 ⁶ g per hour per 1 mol of the catalyst.

"Experimental example 7"
Polymerization was conducted in the same manner as in Experimental Example 6 except that 1-hexene was changed to 50 μL and the polymerization temperature was changed to 70 ° C., molecular weight (Mw) = 10,000, molecular weight distribution (Mw / Mn) = 1.5, copolymer 7.7 × 10 ⁶ g of 1-hexene unit content (SCB) = 16 of the polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 8"
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), triphenylmethyltetrakis (pentafluorophenyl) borate 0.30 μmol, and scandium complex (1) 0.10 μmol were added, Polymerized for minutes. As a result of the polymerization, 3.2 × 10 ⁶ g of a polymer having a molecular weight (Mw) = 28,000 and a molecular weight distribution (Mw / Mn) = 1.7 was produced per hour per 1 mol of the catalyst.

"Experimental example 9"
Polymerization was carried out in the same manner as in Experimental Example 8 except that 1-hexene was changed to 50 μL and the polymerization temperature was changed to 70 ° C., molecular weight (Mw) = 5,000, molecular weight distribution (Mw / Mn) = 1.4, copolymer A polymer having a 1-hexene unit content (SCB) of 14 was produced at 4.5 × 10 ⁶ g per hour per 1 mol of the catalyst.

Using scandium complex (2) obtained in Experimental Example 2 as a catalyst component for olefin polymerization, copolymerization of ethylene and 1-hexene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.

"Experimental example 10"
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol, and scandium complex (2) 0.10 μmol were added, Polymerized for minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 11,000 and a molecular weight distribution (Mw / Mn) = 1.7 was produced at a rate of 3.8 × 10 ⁶ g per hour per 1 mol of the catalyst.

"Experimental example 11"
An autoclave was charged with 5.0 mL of toluene and 60 μL of 1-hexene under nitrogen and stabilized at 40 ° C., and then ethylene was pressurized to 0.60 MPa and stabilized. To this, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), triphenylmethyltetrakis (pentafluorophenyl) borate 0.30 μmol, and scandium complex (1) 0.10 μmol were added, Polymerized for minutes. As a result of the polymerization, a polymer having a molecular weight (Mw) = 14,000 and a molecular weight distribution (Mw / Mn) = 2.0 was produced at a rate of 2.0 × 10 ⁶ g per hour per 1 mol of the catalyst.

<Manufacture of ethylene homopolymer>
Using the scandium complex (1) obtained in Experimental Example 1 as a catalyst component for olefin polymerization, homopolymerization of ethylene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.

"Experimental example 12"
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. 100 μmol (Al atom conversion value) of aluminoxane (manufactured by Tosoh Finechem Co., 5.8 wt% Al) and 0.10 μmol of scandium complex (1) were added thereto, and polymerization was performed for 30 minutes. As a result of the polymerization, 1.2 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 13"
Polymerization was conducted in the same manner as in Experimental Example 12 except that 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) and 0.30 μmol of tris (pentafluorophenyl) borane were used instead of methylaluminoxane. It was. As a result of the polymerization, 2.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 14"
Similar to Experimental Example 12, except that 40 μL of TIBA hexane solution (TIBA concentration 1.0 mol / L) and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol were used instead of methylaluminoxane. Polymerization was performed. As a result of the polymerization, 2.7 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental Example 15"
Similar to Experimental Example 12, except that 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) and 0.30 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate were used instead of methylaluminoxane. Polymerization was performed. As a result of the polymerization, 3.6 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

Using the scandium complex (2) obtained in Experimental Example 2 as a catalyst component for olefin polymerization, homopolymerization of ethylene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.

"Experimental example 16"
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. 100 μmol (Al atom conversion value) of aluminoxane (manufactured by Tosoh Finechem Co., 5.8 wt% Al) and 0.10 μmol of scandium complex (1) were added thereto, and polymerization was performed for 30 minutes. As a result of the polymerization, 6.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 17"
Polymerization was conducted in the same manner as in Experimental Example 12 except that 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) and 0.30 μmol of tris (pentafluorophenyl) borane were used instead of methylaluminoxane. It was. As a result of the polymerization, 2.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of the catalyst.

"Experiment 18"
Similar to Experimental Example 12, except that 40 μL of TIBA hexane solution (TIBA concentration 1.0 mol / L) and dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol were used instead of methylaluminoxane. Polymerization was performed. As a result of the polymerization, 4.2 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

"Experimental example 19"
Similar to Experimental Example 12, except that 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L) and 0.30 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate were used instead of methylaluminoxane. Polymerization was performed. As a result of the polymerization, 3.3 × 10 ⁶ g of polymer was produced per hour per 1 mol of the catalyst.

Using the yttrium complex (1) obtained in Experimental Example 3 as a catalyst component for olefin polymerization, homopolymerization of ethylene was carried out under the following polymerization conditions using PPR (48 autoclave) manufactured by Symyx.

"Experimental example 20"
In an autoclave, 5.0 mL of toluene was charged under nitrogen and stabilized at 40 ° C. Then, ethylene was pressurized to 0.60 MPa and stabilized. To this, 40 μL of TIBA hexane solution (manufactured by Kanto Chemical Co., Inc., TIBA concentration 1.0 mol / L), dimethylanilinium tetrakis (pentafluorophenyl) borate 0.30 μmol, yttrium complex (1) 0.10 μmol were added, and 30 minutes Polymerized. As a result of the polymerization, 5.0 × 10 ⁵ g of polymer was produced per hour per 1 mol of the catalyst.

Claims (7)

Formula (1)

(Wherein, Ln represents a Group 3 metal atom or a lanthanoid metal atom (excluding samarium, ^{ytterbium), R 1, R 2,} R 3, R 4, R 5, R 6, R 7 and ^{R 8} Are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, carbonization having 1 to 20 carbon atoms Amino having a silyl group having hydrogen, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a hydrocarbon having 1 to 20 carbon atoms Represents a group,
Here, in R ^{1 to} R ⁸ , the alkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group and hydrocarbon may be substituted with a halogen atom.
The adjacent groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form a ring, and m Xs are the same or Differently, it represents a monoanionic ligand, n Y's are the same or different and represent a neutral ligand, m represents an integer from 0 to 3, and n represents an integer from 0 to 3. )
A rare earth metal complex represented by The rare earth metal complex according to claim 1, wherein Ln is scandium or yttrium. Formula (2)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above.)
A substituted or unsubstituted bisphenol ligand represented by the formula (3)

(In the formula, Ln, X, Y, m and n represent the same meaning as described above, and R ⁹ and R ¹⁰ are each an alkyl group optionally substituted with a silyl group having a hydrocarbon having 1 to 20 carbon atoms. Or, it represents an aralkyl group which may be substituted with an amino group having a hydrocarbon having 1 to 20 carbon atoms.)
The method for producing a rare earth metal complex represented by the formula (1) according to claim 1, wherein the rare earth metal compound represented by formula (1) is reacted. A catalyst component for olefin polymerization comprising a rare earth metal complex represented by the formula (1) according to claim 1. The catalyst for olefin polymerization obtained by making the catalyst component for olefin polymerization of Claim 4 and the following compound (A) and / or the following compound (B) contact.
Compound (A): One or more aluminum compounds selected from the group consisting of the following (A1) to (A3) (A1): an organoaluminum compound represented by the formula (E ¹ ) _a AlZ _(3-a) ;
(A2): a cyclic aluminoxane having a structure represented by the formula {—Al (E ² ) —O—} _b ;
(A3): a linear aluminoxane having a structure represented by the formula E ³ {-Al (E ³ ) —O—} _c Al (E ³ ) ₂ (wherein a satisfies 0 <a ≦ 3) B represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ each represent a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of E ¹ , The plurality of E ² and the plurality of E ³ may be the same or different from each other, Z represents a hydrogen atom or a halogen atom, and the plurality of Z may be the same or different from each other.
Compound (B): One or more boron compounds selected from the group consisting of the following (B1) to (B3) (B1): a boron compound represented by the formula BQ ¹ Q ² Q ³ ;
(B2): a boron compound represented by the formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ ;
(B3): a boron compound represented by the formula (L ¹ -H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— (wherein B represents a boron atom in a trivalent valence state, Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, G ⁺ represents an inorganic or organic cation, L ¹ represents a neutral Lewis base.)   The manufacturing method of the olefin polymer which polymerizes an olefin in presence of the catalyst for olefin polymerization of Claim 5. A process for producing an ethylene-α-olefin copolymer, wherein ethylene and an α-olefin are copolymerized in the presence of the olefin polymerization catalyst according to claim 6.