WO1995014024A1

WO1995014024A1 - Transition metal compound, olefin polymerization catalyst, and process for producing olefin polymer by using said catalyst

Info

Publication number: WO1995014024A1
Application number: PCT/JP1994/001939
Authority: WO
Inventors: Mizutomo Takeuchi; Kenji Nakacho; Toshiya Abiko; Toshinori Tazaki; Yasunori Kadoi
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 1993-11-18
Filing date: 1994-11-17
Publication date: 1995-05-26
Also published as: JP3795072B2

Abstract

A transition metal compound useful as a component of an olefin polymerization catalyst, a highly active olefin polymerization catalyst containing the above compound, and an efficient process for producing an olefin polymer with a reduced content of residual metals by using the above catalyst. The transition metal compound is one having as a π-ligand an indenyl group having on the 5-membered ring side thereof at least one substituted other than the one bonded to the transition metal element. The polymerization catalyst contains (A) the above metal compound, (B) at least one member selected from (a) an organoboron compound, (b) aluminoxane and (c) an ionic compound comprising a noncoordinating anion and a cation, and if necessary (C) a Lewis acid. Various olefin polymers can be produced economically and efficiently by homo- or copolymerizing an olefin in the presence of the above catalyst.

Description

Specification

Transition metal compound, catalyst for polymerization of olefin, method for producing olefin polymer using the catalyst

Technical field

The present invention relates to a transition metal compound, a catalyst for polymerization of an olefin containing the transition metal compound, and a method for producing an olefin polymer using the catalyst. More specifically, the present invention relates to a transition metal compound having a specific substituted indenyl group 7 as a ligand, which is useful as a catalyst component for orphan polymerization, and a highly active orphan polymerization containing this transition metal compound. Ordinary homopolymers or copolymers of good quality with little residual metal and low residual metal content using this catalyst, or excellent balance between elasticity and elastic recovery, and improved low-temperature properties An amorphous high molecular weight propylene-based polymer with a narrow molecular weight distribution that is useful as a cyclic olefin copolymer, elastomer, etc. with improved moldability and a vinyl group useful as a macromonomer, etc. The present invention relates to a high-molecular-weight, low-molecular-weight olefin polymer and a method for efficiently producing the same.

Background art

Olefin polymers such as polyethylenes and polypropylenes are widely used as general-purpose resins in many fields. It is known that this olefin polymer is produced by a catalyst system based on Ziegler's Natsuba catalyst, but in recent years it has one "^^ Γ ligand. Attempts have been made to produce an olefin-based polymer using a polymerization catalyst comprising a transition metal compound in which a ligand and a central metal element are bonded via an arbitrary group as a catalyst component.

For example, European Patent Publication No. 420436, International Patent Publication 9 2 — No. 33003, European Patent Nos. 41 8044, 41 6815, 468651, 495 375, 51 4828, 520732, etc. A catalyst for olefin polymerization using a transition metal compound in which the ligand and a central metal element are bonded via an arbitrary group as a catalyst component, and a method for producing an olefin polymer using the catalyst Is disclosed.

However, among these, those in which the 7: ligand is an indenyl group were all unsubstituted, and their activities were not always sufficiently satisfactory.

On the other hand, a cyclic olefin-based copolymer such as a copolymer of a one-year-old olefin and a cyclic olefin, or a copolymer of a polyolefin, a cyclic olefin and a cyclic gen compound is disclosed in Japanese Unexamined Patent Publication No. Because of its excellent optical properties such as transparency, flexibility, elastic recovery, etc., medical, packaging, and food products It can be used as film sheets in various fields such as fields. Also, a cyclic copolymer random copolymer excellent in well-balanced mechanical properties, optical properties, heat resistance, and the like by copolymerizing ethylene and a specific cyclic copolymer is known. (See, for example, Japanese Unexamined Patent Publication No. 60-168708, Japanese Unexamined Patent Application Publication No. 61-87980) _c . There are a wide variety of molding methods for the olefin polymer. Injection molding, extrusion molding, blow molding, inflation molding, compression molding, and vacuum molding are known. In such molding methods, attempts have been made over the years to impart high-speed moldability and reduce the energy of molding processing in order to improve processing characteristics and reduce processing costs. It is important to provide the optimal physical properties according to the It has become a challenge.

In recent years, homogeneous meta-aqueous catalysts have excellent copolymerizability between orifices, have a narrow molecular weight distribution of the resulting polymer, and exhibit extremely high catalytic activity compared to conventional vanadium catalysts. Was revealed. Therefore, development of various application fields is expected by utilizing such features. On the other hand, polyolefins obtained with a meta-mouth catalyst have many drawbacks in their forming properties, and have the disadvantage of being inevitably restricted in blow molding.

In order to improve the moldability of the cyclic olefin copolymer, Japanese Patent Application Laid-Open

In Japanese Patent Application Laid-Open No. 5-27171485, two types of cyclic olefin copolymers having a specific glass transition temperature (T g) having different intrinsic viscosities [7?] Are used. It is disclosed that the formation of a polymer reduces the melt viscosity, hardly causes melt fracture, and provides a cyclic olefin-based copolymer composition having excellent moldability. However, when a composition is formed using two types having different intrinsic viscosities [77], the molecular weight distribution is widened, and the mechanical properties of the film, especially the film strength, and the transparency are reduced. Problems occur.

Therefore, it has been desired to develop a method for efficiently producing a cyclic olefin copolymer having excellent mechanical properties, improved melt fluidity, and good moldability.

On the other hand, high-molecular-weight reactive polypropylene (high-molecular-weight amorphous polypropylene) can be used alone as an elastomer, or as a component of a thermoplastic olefin-based elastomer (TPO). In particular, the utility value of high molecular weight polypropylene with a narrow molecular weight distribution is high. However, with the conventional catalyst system, Atactic polypropylene has a low molecular weight and is obtained only as a by-product of isotactic polypropylene that is currently industrially produced. Also, U.S. Pat.No. 5,026,798 discloses a technique for homopolymerizing propylene using a catalyst system similar to the present invention having an unsubstituted indenyl group as a 7Γ ligand. However, in this case, the polymer produced is crystalline isotactic polypropylene (melting point: 147 ° C, pentad fraction: 74.7 mol), low catalytic activity, and low molecular weight (Weight average molecular weight: 71, 300). Therefore, it has been desired to develop a method for efficiently producing a high molecular weight atactic polypropylene having a narrow molecular weight distribution.

On the other hand, a low molecular weight olefin polymer having a high terminal vinyl group content can be used as a macromonomer. For example, by using as a comonomer of an olefin copolymer, it is possible to easily introduce a long-chain branch without a gelation reaction, and to provide an olefin copolymer having excellent molding characteristics. An olefin copolymer having performance as an elastomer or a compatibilizer can be provided. The low-molecular-weight, olefin-based polymer having a high terminal vinyl group content can be used as a wax or the like by hydrogenation. Furthermore, by treating with various reaction reagents, it can be used as a terminal-modified macromonomer, for example, as a comonomer of condensation-type copolymer, and can be used as an adhesive, a surface modifier, a compatibilizer, a composite material, etc. .

Disclosure of the invention

An object of the present invention is to provide a transition metal compound useful as a catalyst component for off-polymerization, a highly active catalyst for off-polymerization containing this transition metal compound, and a good quality with a small amount of residual metal by using this catalyst. Ordinary ordinary homopolymers and copolymers, or excellent mechanical properties, Amorphin with good molding processability Amorphous cyclic olefin copolymer, amorphous high molecular weight propylene-based polymer with narrow molecular weight distribution useful as elastomer, etc. and vinyl group content useful as macromonomer etc. An object of the present invention is to provide a high-molecular-weight, low-molecular-weight polymer and a method for efficiently producing the same.

Accordingly, the present inventors have conducted intensive studies in order to achieve the above object, and as a result, a transition metal compound having a substituted indenyl group having a specific structure as a ligand is used as a catalyst for an olefin polymerization. A catalyst comprising a combination of the transition metal compound, an organoboron compound, an aluminoxane or a specific ionic compound, and a Lewis acid used in some cases, having high activity. It has been found that the use thereof enables economical and efficient production of good-quality homopolymers and copolymers having low residual metal content and good quality. Further, by appropriately selecting the transition metal compound, an orefin cyclic orefin copolymer, an amorphous high-molecular-weight propylene-based polymer and a low-molecular-weight orifice-based polymer having a high vinyl group content having the preferable properties described above can be obtained. It has been found that coalescence can be obtained economically and efficiently. The present invention has been completed based on such findings.

That is, the present invention

(1) a transition metal compound having, as a ligand, a substituted indenyl group having at least one substituent other than a substituent bonded to a transition metal element on the five-membered ring side;

(2) For olefin polymerization containing a transition metal compound having a substituted indenyl group having at least one substituent as an r ligand in addition to the substituent bonded to the transition metal element on the five-membered ring side Catalyst,

(3) (A) General formula (II)

And the general formula (III)

[Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, A carboxyl group or an alkylsilyl group, wherein at least one of R ¹ and R ³ is a group other than a hydrogen atom, and a plurality of R ¹ , a plurality of R ² , a plurality of R ³ and a plurality of R ⁴ However, each may be the same or different. M ² and M ³ are metal elements of the 3-10 group of the periodic table or Lanthanide series, respectively, X ² and X ³ are each a ligand, L ² and L ³ are Lewis bases, respectively, Q ¹ and Q ² are alicyclic hydrocarbon groups having 1 to 6 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, and silicon groups having 1 to 6 carbon atoms, respectively. 5 silylene group or germanium number 1-5 gels Mi Ren group, J ¹ and J ² are each § Mi de group, full Osufi de group, an oxygen atom, a sulfur atom or alkylidene group, more X ² , A plurality of X ³ , a plurality of L ^2, and a plurality of L ³ may be the same or different. c and e represent the valences of M ² and M ³ , respectively, and d and ί are 0, 1 or 2. ]

At least one selected from the transition metal compounds represented by the following formulas: (B) (a) an organic boron compound, (b) an aluminoxane, and (c) an ionic compound comprising a non-coordinating anion and a cation. A catalyst for polymerization of olefins comprising at least one combination selected from the group consisting of:

(4) (A) at least one selected from the transition metal compounds represented by the general formulas (II) and (III), (B) (a) an organic boron compound, and (b) aluminum A catalyst for polymerization of an olefin comprising a combination of at least one selected from the group consisting of a nonoxane and (c) a zwitterionic compound comprising a non-coordinating anion and a cation, and (C) a Lewis acid;

as well as

(5) In the presence of the above-mentioned catalysts (2) to (4), orefins are polymerized alone, two or more orefins are copolymerized, or the orefins are copolymerized with another polymerizable unsaturated compound. An object of the present invention is to provide a method for producing an olefin-based polymer characterized by polymerization.

Further, the present invention provides

(6) ① The ratio MwZ Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is 6 or less, and ② The cyclic orefine unit content is 0. 1 to 95 mol% , And the and ③ in deca Li down, the relationship between the 1 3 5 ° intrinsic viscosity measured in C [7?] And the melt index measured by a load _{2. 1 6 kg (MI 2.} 16), the formula

[7?] ≤1.3 3 3 -. 0.6 2 0 xlo gM I 2 16

A cyclic olefin copolymer that satisfies

as well as

(7) ① Intrinsic viscosity [] measured at 135 ° C in decalin is greater than 1.0 d / g, ② Weight average molecular weight (Mw) measured by gel permeation-short chromatography method. ) And number average molecular weight

Propylene polymers with a ratio Mw / Mn of less than (Mil) of less than 3 and no ③ melting point (Tm) and a glass transition point (Tg) of less than 10 ° C Is what you do.

Incidentally, a preferred embodiment of the present invention is:

(8) The method according to the above (5), wherein the olefins and the cyclic olefins are copolymerized to produce an olefin / cyclic olefin copolymer.

(9) The orefino cyclic olefin copolymer has the following properties: ① weight average molecular weight measured by gel permeation chromatography

The ratio of (Mw) to the number average molecular weight (Mn) is not more than 6, Mw / Mn is 6 or less, ② The content of cyclic olefin unit is 0.1 to 95 mol%, and ③ In decalin, 135 ° melt index (MI _2. ₁₆₎ was boss measured intrinsic viscosity [] and a load of 2. 1 6 kg as measured by C and the relationship of the formula

[77] ≤ 1.3 3 3-0.6 ₂₀ x 1 o gM I _2. , ₆

The method of (8), which satisfies

(10) In the transition metal compound of the component (A), the polymerization catalyst of the above (3) or (4), wherein M ² and M ³ in the general formulas (II) and (III) are each titanium. (II) In the transition metal compound of the component (A), the general formulas (II) and (II)

The polymerization catalyst according to (3) or (4), wherein M ² and M ³ in (III) are zirconium or hafdium, respectively.

(12) In the presence of the catalyst of the above (10), propylene is homopolymerized, or is polymerized with propylene and another polymer having 2 to 20 carbon atoms and another polymerizable polymer having 2 to 20 carbon atoms. The method according to the above (5), wherein at least one selected from saturated compounds is copolymerized to produce an amorphous high molecular weight propylene polymer,

(13) The amorphous high-molecular-weight propylene polymer has (1) the intrinsic viscosity [?] Measured at 135 in decalin larger than 1.0 deciliter, and (2) gel permeation chromatography. The ratio MwZMn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by one method is less than 3, and ③ has no melting point (Tm), and has a glass transition point.

(T 2) wherein the (T g) is less than 10 ° C.

(14) In the presence of the catalyst of the above (11), homopolymerization of C 2 to C 20 olefins, copolymerization of two or more C 2 to C 20 olefins or C 2 to C 2 The above (5), in which a low molecular weight olefin polymer having a high vinyl group content is produced by copolymerizing 20 olefins and another polymerizable unsaturated compound having 2 to 20 carbon atoms. Method,

(15) A low molecular weight olefin polymer having a high vinyl group content is obtained by mixing an ethylene homopolymer or ethylene with an olefin having 3 to 20 carbon atoms and another polymerization having 2 to 20 carbon atoms. It is a copolymer with at least one selected from unsaturated unsaturated compounds, and has a weight average molecular weight (Mw) in terms of polyethylene of 200 to 10 measured by gel permeation-junction mouth chromatography. , 000, ② density is 0.925 g / cm ³ or more, and ③ 70 moles of vinyl groups in total unsaturated groups % Or more, wherein the vinyl group content measured by infrared spectroscopy is 1.5 or more per 100 carbon atoms, according to the above (14),

It is.

BEST MODE FOR CARRYING OUT THE INVENTION

The transition metal compound of the present invention is a novel transition metal compound having, as a ligand, a substituted indenyl group having at least one substituent other than the substituent bonded to the transition metal element on the five-membered ring side. There are various transition metal compounds. For example, the general formula (I)

RM ¹ X ¹ L ¹ _b (I)

A transition metal compound having one 7Γ ligand represented by the general formula (Π) in which the ligand and the metal are bonded via an arbitrary group.

A compound represented by the general formula (ΠΙ)

1 o And the like.

In the above general formula (I), R is 7: a ligand and represents a substituted indenyl group having at least one substituent other than the substituent bonded to the transition metal element on the five-membered ring side. In the general formulas (II) and (III), R ′, R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms, respectively. Aromatic hydrocarbon group of 1 to 20 carbon atoms, alkoxy group of 1 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms, thioalkoxy group of 1 to 20 carbon atoms, thioaryloxy group of 6 to 20 carbon atoms, amino group, amino de group, exhibit a carboxyl group or Arukirushiri Le group, R 'and R ³ are the least one is other than hydrogen atom group in each. Further, a plurality of R ¹ , a plurality of R ² , a plurality of R ^3, and a plurality of R ⁴ may be the same or different.

Further, in the general formulas (I), (Π) and (III), M ¹ , M ² and M ³ are each a metal element belonging to Group 3 to 10 of the periodic table or a lanthanoid series, specifically, It shows transition metal elements such as titanium, zirconium, hafnium, lanthanide-based metals, niobium, and tantalum. Of these, titanium, zirconium and hafnium are preferred. X ¹ , X ^2, and X ³ each represent a ligand, specifically, a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 6 to 20 carbon atoms. Aromatic hydrocarbon group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, thioaryloxy group having 6 to 20 carbon atoms, amid Groups, amide groups, carboxyl groups, and alkylsilyl groups. A plurality of X ¹ , a plurality of X ^2, and a plurality of X ³ may be the same or different in each case, and may be linked via an arbitrary group. L ¹ , L ² and L ³ each represent a Lewis base, and a plurality of L ¹ , a plurality of L ² and a plurality of L ³ may be the same or different. a, c and e are the valences of M ¹ , M ² and M ³ , respectively, and b, d and f are 0, 1 or 2.

In the general formulas (II) and (III), Q ¹ and Q ² represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a silicon group having 1 to 5 silicon atoms, respectively. It represents a silylene group or a germanylene group having 1 to 5 germanium. J ¹ and J ² are respectively A mi de group, full Osufi de group, an oxygen atom, a sulfur atom or an alkylidene group.

Substituent Lee Ndeniru group [substituent group bonded to the transition metal element (Q ^1, Q ²⁾ does not contain. Specific examples of are: 2-methylindenyl group; 3-methylindenyl group; 3-trimethylsilylindenyl group; 21-t-butylindenyl group; 2,3-dimethylindenyl group; 1,3-dimethylindenyl 2,4,7-trimethylindenyl group; 1,3,4,7-tetramethylindenyl group; 2,3,4,7, -tetramethylindenyl group; 3,4,5,6,7 —Pentamethylindenyl group; 2,4,5,6,7—Pentamethylindenyl group; 2,3,4,5,6,7—Hexamethylindenyl group; 1,3,4,5,6,7— Oxamethylindenyl group; 2,3-dimethyl-4,7-dimethoxyindenyl group; 2,3-dimethyl-4,7-difluoroindenyl group. Specific examples of (X ² , X ³ ) include a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a benzyl group, a phenyl group, a trimethylsilylmethyl group, a methoxy group and an ethoxy group. Phenoxy, thiomethoxy, thiophenoxy, dimethylamino, diisopropylamino, and the like. Preferred examples of the transition metal compound of the present invention include compounds containing any one of the above-exemplified substituted indenyl groups and X ¹ (X ² , X ³ ).

Specific examples of the transition metal compound include (t-butylamido) (2,3-dimethylindenyl) 1-1,2-ethanethaniltitanium dichloride; (t-butylamido) (2, 3-Dimethylindenyl) 1,2-dienyltitanium dimethyl; (t-butylamide)

(2,3-Dimethylindenyl) -dimethylsilyltitanium dichloride; (t-Butylamide) (2,3-Dimethylindenyl) -dimethylsilyltitanium dimethyl; (t-Butylamide) (1,3— Dimethylindenyl) monodimethylsilyl titanium dichloride

(T-butylamide) (di-3-dimethylindenyl) 1-dimethylsilyltitanium dimethyl; (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitaniumdichloromethane (T-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitanium dimethyl;

(t-Butyl amide) (S, 3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitanium dichloride; (T-Butyl amide) (S 3,4,5,6,7 —Hexamethylindenyl) 1-dimethylsilyltitanium dimethyl; (2,3-dimethylindenyl) 111-ethane-2-oxoxatitanium dichloride; (2,3-dimethylindenyl) 1-1-ethane-1 2—o Xacititanium dimethyl; (phenylamide) (2,3-dimethylindenyl) 1,2,1-dienylzirconium dichloride; (t-butylamide)

(2,3-Dimethylindenyl) 1-1,2-ethanediyl zirconium dimethyl; (t-butylamide) (2,3-Dimethylindenyl) -Dimethylsilyl zirconium dichloride; (t-butylamide) (2,3-dimethylindenyl) -dimethylsilylzirconium dimethyl; (t_butylamide) (1,3-dimethylindenyl) —dimethylsilyl Zirconium dichloride; (t-butylamide)

(1,3-dimethylindenyl) -dimethylsilylzirconium dimethyl; (t-butylamide) (2,3,4,5,6,7_hexamethylindenyl) -dimethylsilylzirconium dichloride;

(t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) dimethylsilylzirconium dimethyl; (t-butylamide) (1,3,4,5,6,7-hexamethylid Ndenyl) dimethylsilyl zirconium dichloride; (t-butyl amide) (1,3,4,5,6,7-hexamethylindenyl) -dimethylsilyl zirconium dimethyl; (2,3-dimethylindenyl) — 1 Ethane-12-oxazirconium dichloride; (2,3-dimethylindenyl) -11-ethane-12-oxazirconium dimethyl and the like, and those obtained by substituting titanium or zirconium in these compounds with hafnium. Can be mentioned. Of course, it is not limited to these. Further, it may be a similar compound of a metal element of another group or a lanthanide series.

The catalyst for polymerization of an olefin according to the present invention is a transition metal having a substituted indenyl group having at least one substituent as a 7-ligand in addition to the substituent bonded to the transition metal element on the 5-membered side. (A) at least one selected from the transition metal compounds represented by the general formulas (II) and (III); and (B) (a) an organic boron compound. At least one selected from (b) an aluminoxane and (c) an ionizable compound comprising a non-coordinating anion and a cation. A catalyst comprising a combination with a species; and (A) at least one selected from the transition metal compounds represented by the general formulas (II) and (III); and (B) (a) an organoboron compound; A catalyst comprising a combination of at least one selected from (b) aluminoxane and (c) an ionizable compound comprising a non-coordinating anion and a cation, and (C) a Lewis acid is preferred.

The organoboron compound of the component (a) in the component (B) is represented by the general formula (IV)

R SB L ⁴ · ■ · (IV)

The compound represented by these is mentioned.

In the general formula (IV), R ⁵ is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a substituted aromatic hydrocarbon group, These are alkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, substituted aryloxy groups, aluminoxy groups, poloxy groups, siroquine groups, germinoxy groups, and the like. May also be different. Specific examples of R ⁵ include a phenyl group, a tolyl group, a fluorophenyl group, a trifluoromethylphenyl group, a trimethylsilyltetrafluorophenyl group, a penfluorofluoro group, a fluorine atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. , Dimethylaluminoxy group, diisobutylaluminoxy group and the like. L ⁴ represents represents a Lewis base, specifically Jechirue ether, ether compounds such as Te tiger arsenide Dorofura emissions, etc. Ryomi emission compounds such as pyridinium gin and the like. V is an integer from 0 to 3.

The aluminoxane as the component (b) in the component (B) is obtained by contacting an organic aluminum compound with a condensing agent, and comprises the general formula (V) RR

A 1 o-e-A l o-A 1 (V)

/

RR ⁶ R

[In the formula, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, and p represents a number of 0 to 50, preferably 0 to 30. ]

Aluminoxane represented by the general formula (VI)

A 1—〇 +

(VI)

R ⁶

[Wherein, R ⁶ is the same as above, and q represents a number of 2 to 50, preferably 2 to 30]. ]

And the like.

Examples of the organic aluminum compound used as a raw material of the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. Examples of the condensing agent include water as a typical one, and any other condensing agent capable of subjecting the trialkyl aluminum to a condensation reaction, for example, adsorbed water such as inorganic substances and diol.

On the other hand, the ionic compound comprising the non-coordinating anion and the cation of the component (c) in the component (B) is represented by the general formula (VII): (CL ⁵ -H) '+) _h (CM ⁴ Y ¹ YY ⁿ ) ⁽ⁿ - ^ffi> ")

• · · (VII) or general formula (VIII)

(CL ^6] _{^{'+) h (CM 5 Y}} 1 Y 2 · Y n m)

] ^<N-

[However, L ⁶ is described below ^{^{^{M 6, R 7 R 8 M}}} 7 or R ⁹ ₃ C. ] The compound represented by these is mentioned.

In the above general formulas (VII) and (VIII), L ⁵ represents a Lewis base, and M ⁴ and M ⁵ are elements selected from Groups 5 to ¹⁵ of the periodic table, specifically B, A 1 , P, As, Sb, etc. M ⁶ is an element selected from Groups 8 to 1 2 of the periodic table, elements in particular Ag, shows and C u, M ⁷ is selected from groups 8 to 1 0 of the periodic table, specifically Indicates Fe, Co, Ni, etc. Y ^{1 to} Y ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aryl group, respectively. These include alkylalkyl groups, alkylaryl groups, substituted alkyl groups, organic metalloid groups, and halogen atoms. Specific examples of the ^Υ ¹ ~Υ η, Jimechirua Mi amino group, Jechirua Mi amino group, main butoxy group, e butoxy group, butoxy group, phenoxy group, 2, 6-dimethyl-phenoxyethanol group, a methyl group, Ethyl group, propyl group, butyl group, octyl group, phenyl group, tolyl group, xylyl group, mesityl group, benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) group, 41 Examples include t-butylphenyl group, F, Cl, Br, I, pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, and diphenylboron group.

R ⁷ and R ⁸ are each a cyclopentagenenyl group, a substituted cyclopentenyl group, an indenyl group, a substituted indenyl group, And an olenyl group. Specific examples include a methylcyclopentagenenyl group and a pentamethylcyclopentenyl group. R ⁹ is an alkyl group, an aryl group, or a substituted aryl group, which may be the same or different, and specifically includes a phenyl group, a 4-methoxyphenyl group, and a 4-methylphenyl group. And the like. m is an atomic number of M ⁴ and M ⁵ and is an integer of 1 to 7, n is an integer of 2 to 8, g is [L ⁵ —H],

(L ⁶ ) is an ion valence of 1 to 7; h is an integer of 1 or more; i =

(h X g) / (n-m).

Non-coordinating anions in the ionic compound include, for example, tetra (phenyl) borate; tetra (fluorophenyl) borate

Tetrakis (difluorophenyl) borate; Tetrakis (trifluorophenyl) borate; Tetrakis (tetrafluorophenyl) borate; Tetrakis (pentafluorophenyl) borate; Tetrakis (triflur) (Tetramethylphenyl) borate; tetra (tolyl) borate; tetra (xylyl) borate; (triphenyl, penfluorophenyl) borate; [tris (pentafluorophenyl), [Phenyl] borate; Trideca hydride 1-7,8- dicarpound power borate. On the other hand, as the cation, for example, tri (ethyl) ammonium; tri (butyl) ammonium; N, N-dimethylanilinium; N, N-jetylanilinium; triphenylphosphinium; dimethylform Enilphosphinium; 1,1'-dimethylphenic acid; decamethylpyrocene; silver (I); tri (phenyl) carbene; tri (tolyl) carbene; tri (methoxyphenyl) ) Carbium; [di (tolyl), phenyl] carbem; [di (methoxyphenyl), phenyl] carbem; [methoxyphenyl, di (phenyl) ] Carvenium and the like.

As the ionic compound, those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be preferably used.

In the catalyst of the present invention, as the component (B), one kind of the organic boron compound (a) may be used, or two or more kinds may be used in combination, and the aluminoxane (b) may be used one kind. They may be used, or two or more kinds may be used in combination. In addition, one kind of the ionic compound (c) may be used, or two or more kinds may be used in combination. Further, the component (a), the component (b) and the component (c) may be used in an appropriate combination.

In the catalyst of the present invention, examples of the Lewis acid used as the component (C) used as desired include organoaluminum compounds, magnesium compounds, zinc compounds, and lithium compounds. The organoaluminum compound has a general formula (IX)

R ^{] 0} _r A 1 (OR ¹¹ ) _s H, Z ¹ u ■ The compound represented by (IX) can be used.

In the general formula (IX), R ^ie and R ¹¹ are each an alkyl group of 1-8 carbon atoms, they may be the same with or different from each other. Z ¹ represents a halogen atom, r, s, t, and u are 0 <r ≤ 3.0 <s ≤ 3, 0 ≤ t <3, 0 ≤ u <3, r + s + t + u = 3 This is the number that satisfies the relationship.

Specific examples of the organic aluminum compound represented by the above general formula (IX) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisoaluminum as a compound having t = u = 0 and r = 3. Butyl aluminum, trioctyl aluminum, etc., t = u = 0, 1.5 ≤ r <3, getyl aluminum ethoxide, dibutyl aluminum butoxide, getyl aluminum sesquioxide, dibutyl aluminum sesquibutoxide, and partially alkoxylated Alkyl aluminum, etc., as compounds with s = t = 0, such as getyl aluminum dichloride, dibutyl aluminum dichloride (r = 2), ethyl aluminum sesquichloride, butyl aluminum sesquichloride, etc. (r = 1.5), ethyl aluminum dichloride, butyl aluminum dichloride (r = l), and s = u = 0 as a compound of getyl aluminum hydride, diisobutyl aluminum hydride, etc. (R = 2), ethyl aluminum dihydride, butyl aluminum Umji hydride etc. (r = 1) can be mentioned.

Examples of the magnesium compound include green compounds such as methylmagnesium bromide, ethylmagnesium bromide, phenylmagnesium bromide, and benzylmagnesium bromide, and jettoxymagnesium and ethylbutylmagnesium. Organic magnesium compounds such as magnesium, and inorganic magnesium compounds such as magnesium chloride. Furthermore, examples of the zinc compound and the lithium compound include, for example, an organic zinc compound such as getyl zinc and an organic lithium compound such as methyllithium.

In the catalyst of the present invention, the Lewis acid of the component (C) may be used alone or in combination of two or more.

The catalyst of the present invention comprises the above components (A) and (B), or the components (A), (B) and (C), and may further comprise other catalyst components. It is possible. The mixing ratio of each catalyst component varies depending on various conditions and cannot be determined uniquely, but usually, (B) When the component is an organic boron compound, the molar ratio of the component (A) to the component (B), preferably 1: 0.1 to 1: 1 0 ^3, more preferably 1: 1 to 1: 1 0 ³ When the component (B) is aluminoxane,

The molar ratio of component (A) to component (B) is preferably 1: 1 to 1: 10,000, and when component (B) is an ionic compound,

The molar ratio with the component (B) is preferably selected in the range of 1: 0.1 to 1: 100. When the component (C) is used, the molar ratio between the component (A) and the component (C) is preferably selected in the range of 1: 0.1 to 1: 10,000.

Examples of the method of contacting the component (A), the component (B) and the component (C) optionally used include the following methods: (1) a contact mixture of the component (A) and the component (B); (2) A method of adding a component (A) to a contact mixture of component (B) and component (C) to make a catalyst and contacting with a monomer to be polymerized, ③ A method in which component (B) is added to the contact mixture of component (A) and component (C) to make a catalyst and contact with the monomer to be polymerized. (1) One component of the monomer to be polymerized is (A), (B), ( C) The components are separately contacted, and ⑤ The catalyst prepared in the above ① to ③ is brought into contact with the contact mixture of the monomer component to be polymerized and the component (C).

The above-mentioned contact between the component (A), the component (B) and the component (C) optionally used can be carried out at a polymerization temperature or in a range of 120 to 200 ° C. is there.

In the present invention Orefi emissions polymerization catalyst, in particular the general formulas used as a component (A) (II), is M ² and M ³ in the transition metal compound of formula (III), respectively of titanium, zirconium or hafnium Some are preferred. In the method for producing an orifice-based polymer of the present invention, in the presence of the above-mentioned polymerization catalyst, homopolymer of orefins, copolymerization of two or more orefins, or polymerization of orefins and other polymerizable polymers. A saturated compound is copolymerized to produce an olefin homopolymer or copolymer.

Examples of the olefins include ethylene, propylene, and butene.

-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; decene-1; 4-phenylbutene1-1; 6-phenylhexene1-1; 3-methylbutene1-1; 4 —Methylpentene 1 1; 3 —Methylpentene 1 1; 3 —Methylhexene 1 1; 4 —Methylhexene 1 1; 5 —Methylhexene 1 1; 3,3 —Dimethylpentene 1; 3, 4 — 1,4-dimethylpentene-1; vinylcyclohexane; vinylolefin, olefins such as trimethylsilane, hexafluorobopen pen; tetrafluoroethylene; 2—fluorobopen pen; fluoroethylene; 1,1 Difluoroethylene; 3—Fluoropropene; Trifluoroethylene; 3, 4—Halogen-substituted 1-year-old fins such as dichlorobutene-11 Cyclopentene; cyclohexene; norbornene; 5—methylnorbornene; 5—ethylnorbornene; 5—propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5,6—to Examples include cyclic methyl olefins such as methyl norbornene; 5-phenyl norbornene; and 5-benzyl norbornene. These orientations may be used alone or in combination of two or more. When copolymerizing two or more kinds of orifices, the above-mentioned orifices can be arbitrarily combined.

In the present invention, the above-mentioned olefins and other polymerizable unsaturated The compound may be copolymerized with the compound. Other polymerizable unsaturated compounds used in this case include styrene, p-methylstyrene; 0-methylstyrene; m-methylstyrene; 2,4-dimethylstyrene; 3,5-dimethylstyrene; 3,5-dimethylstyrene; alkylstyrene such as ρ-t-butylstyrene, ρ-chlorostyrene; m-chlorostyrene; 0-chlorostyrene; ρ-bromostyrene; m-bromo Styrene; 0-bromostyrene; ρ-fluorostyrene; m-fluorostyrene; 0—fluorostyrene; 0—halogenated styrene such as methyl-ρ-fluorostyrene; and aromatics such as organosilicon styrene, vinylbenzoate, and divinylbenzene Vinyl compound, butadiene; iso 1,5—Chain gen compounds such as 1,5-hexadiene; norbornadiene; 5-ethylidene norbornene; 5—Vinylnonolebornene; Cyclic gen compounds such as dicyclobenzene, acetylene; Methylacetylene; Acetylenes such as trimethylsilylacetylene; These other monomers may be used alone or in combination of two or more.

Such a method for producing an orefin-based polymer of the present invention is suitable, for example, for producing an orefin Z cyclic orefine copolymer by copolymerizing orefins and cyclic orefins. At this time, as the orifices, only one kind may be selected from those exemplified above, or two or more kinds may be selected and used as a mixture. As the cyclic orifices, one kind may be selected from those exemplified above, or two or more kinds may be mixed and used. According to the method of the present invention, a copolymer having particularly the following properties can be efficiently produced as an orefin / cyclic orefin copolymer. That is, (1) the ratio MwZMn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the gel permeation chromatography (GPC method) is 6 or less, and the molecular weight distribution is (2) Cyclic olefin unit content is in the range of 0.1 to 95 mol% <(3) Intrinsic viscosity [7?] Measured at 135 ° C in decalin , relationship between melt index, measured under a load _{2. 1 6 kg (MI 2.} 16) is the formula

C a ≤ 1.3 3 3 - 0.6 2 0 X 1 og MI 2 .1 6

Satisfies the conditions and exhibits excellent non-Newtonian properties. Furthermore, (4) the molecular weight is large, and the intrinsic viscosity [7?] Measured at 135 ° C in decalin is usually 1.0 deciliter / g or more. Orolefin cyclic copolymers having such properties have excellent balance between elastic modulus and elastic recovery, improve low-temperature physical properties, and have excellent molding properties as described above. Has features.

The olefinic cyclic copolymer having the above properties may be produced by a method other than the present invention, but by using the method of the present invention, it can be produced economically and efficiently.

In addition, the method for producing an olefin-based polymer of the present invention includes, for example, propylene homopolymerization or propylene, and other olefins having 2 to 20 carbon atoms and other polymerizable polymers having 2 to 20 carbon atoms. It is suitable for producing an amorphous high molecular weight propylene-based homopolymer or copolymer by copolymerizing with at least one selected from saturated compounds. In this case, as the catalyst, a catalyst in which the transition metal compound represented by the general formulas (II) and (III) of the component (A) is a titanium compound is used. As the monomer to be copolymerized with propylene, one other than propylene is selected from the above-listed examples of the olefins and the polymerizable unsaturated compounds. And two or more kinds may be selected and used as a mixture. According to the method of the present invention, an amorphous high molecular weight propylene-based polymer having particularly the following properties can be efficiently produced.

That is, (1) deca Li down, 1 3 5 ^e increased intrinsic viscosity [7?] Is from 1.0 Deshiri Tsu torr measured in C, and a high molecular weight, (2) weight average molecular weight measured by GPC (Mw ) And the number average molecular weight (Mn) are less than 3, MwZMn is narrow, the molecular weight distribution is narrow, (3) it has no melting point (Tm), and the glass transition point (Tg) is less than 10 ° C. The amorphous high-molecular-weight propylene-based polymer having such properties can be used as a single α as an elastomer, and also as a component of a thermoplastic olefin-based elastomer (ΤΡ Ο). High value.

The amorphous high molecular weight propylene polymer having the above properties may be produced by a method other than the present invention, but by using the method of the present invention, it can be produced economically and efficiently.

Furthermore, the method for producing an orphan-based polymer of the present invention includes, for example, homopolymerization of an orphane having 2 to 20 carbon atoms, copolymerization of two or more orefins having 2 to 20 carbon atoms, or copolymerization or Suitable for producing low molecular weight olefin polymers having a high vinyl group content by copolymerizing olefins having a molecular weight of up to 20 and other polymerizable unsaturated compounds having 2 to 20 carbon atoms. At this time, as the catalyst, a catalyst in which the transition metal compound represented by the general formulas (II) and (II) of the component (II) is a zirconium or hafnium compound is used. According to the method of the present invention, as a low molecular weight olefin polymer having a high vinyl group content, particularly, an ethylene homopolymer or ethylene having the following properties, an olefin having 3 to 20 carbon atoms and a carbon number A copolymer with at least one selected from 2 to 20 other polymerizable unsaturated compounds can be efficiently produced. That is, (1) the weight average molecular weight (Mw) in terms of polyethylene measured by the GPC method is 200 to 100,000, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is MwZMn Is preferably 5 or less, more preferably 3 or less. (2) The density measured by a density gradient tube method is 0.925 gZcm ³ or more. (3) The ratio of vinyl groups to all unsaturated groups is 70 mol% or more, and the vinyl group content measured by infrared spectroscopy is 1.5 or more per 100 carbon atoms. The unsaturated group, trans-vinylene group is 9 6 3 cm ^-1, terminal vinyl groups 9 ¹ 0 c m- 1, it is known that vinylidene group is 8 8 8 c m- ^1, of Unsaturated groups can be identified and quantified by infrared spectroscopy after preparing a press sheet (thickness (t) of about 0.1 mm) at a temperature of 190 ° C. In calculating the content of the unsaturated group, the following formula can be used. Here, n is the number of unsaturated bonds per 100 carbon atoms.

Transvinylene group n = 0.83 A9663 / (dxt;

. Terminal vinyl group _{n = l 1 4 A 9 1} o / (dxt) vinylidene group _{n = 1. 0 9 A 8 8} 8 / (dxt) [A: absorbance, 0: Density ^{(8 0 111 3), t} : Sample thickness (mm)] In the case of an ethylene-based copolymer, the monomer to be copolymerized with ethylene may be any one of the above-listed olefins and polymerizable unsaturated compounds other than ethylene. They may be selected and used, or two or more selected and mixed.

Such low-molecular-weight, olefin-based polymers having a high content of nyl groups can be used as macromonomers.For example, by using them as comonomer of an olefin-based copolymer, they can be easily extended without a gelation reaction. Introduces chain branching and has excellent molding properties It is possible to provide an olefin copolymer or an olefin copolymer having performance as an elastomer or a compatibilizer. The low molecular weight olefin polymer having a high terminal vinyl group content can be hydrogenated to be used as a wax or the like. Furthermore, by treating with various reaction reagents, it can be used as a terminal-modified macromonomer, for example, as a comonomer of a condensation copolymer, and can be used as an adhesive, a surface modifier, a compatibilizer, and a composite material.

The low molecular weight olefin polymer having the above properties and a high vinyl group content may be produced by a method other than the present invention, but is economically and efficiently produced by using the method of the present invention. be able to. There is no particular limitation on the type of polymerization in the method for producing the olefin polymer of the present invention, and bulk polymerization may be used. In addition, aliphatic hydrocarbons such as pentane, hexane, and heptane; The reaction may be performed in an alicyclic hydrocarbon or an aromatic hydrocarbon solvent such as benzene, toluene, xylene, and ethylbenzene. Also, by supporting the catalyst on a suitable responsible body, good _t polymerization temperature be conducted polymerization in a solvent or in the gas phase is generally 0~ 2 0 0 ^e C, also using gaseous monomers In this case, the partial pressure of the gaseous monomer is generally at most 300 atm, preferably at most 30 atm. In addition, hydrogen and the like can be added for the purpose of controlling the molecular weight and improving the activity.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The reactions in Example 1 and Example 2 were performed under an inert gas or a gas stream unless otherwise specified. The intrinsic viscosity [7?] Of the polymer is a value measured in decalin at 135 ° C. Example 1

(T one butylamine de) (2, 3, 4, 5, 6, 7 - to Kisamechirui Ndeniru) over dimethylsilyl titanium dichloride Li de _{[M e 2 S i (M ee} I nd) (t - B u N) T i C 1 2]

(1) Synthesis of 2,3,4,5,6,7-hexamethyl-1-one 58.7 g (440 millimoles) of aluminum trichloride was dried with carbon disulfide (dry distillation over calcium hydride) ) Suspended in 300 milliliters and kept at ice-cold temperature. 47.4 g (400 millimoles) of tigloyl chloride and 53.7 g (400 millimoles) of tetramethylbenzene are mixed, added dropwise to the above carbon disulfide solution, and stirred at room temperature. Continuing produced a brown to reddish brown solution. After stirring for 2 hours, the solution was further reacted under reflux for 2 hours, and the solution turned orange.

After the reaction mixture was cooled to room temperature, it was poured onto a mixture of 500 g of water and 500 milliliters of concentrated hydrochloric acid, stirred for about 1 hour, and then stirred with 400 milliliters of ether. Extraction and separation were further performed twice with 200 milliliters twice and the ether phases were combined and dried over anhydrous calcium chloride. After the desiccant was filtered off, ether was distilled off, and the obtained brown viscous solid was dissolved in hexane and recrystallized. The saturated solution at room temperature was allowed to stand at 120 ° C, and the operation of filtering the precipitate was repeated. 2,3,4,5,6,7-Hexamethylindane-oneone as a red-yellow solid 75.9 got _c

(2) Synthesis of 1,2,4,5,6,7-hexamethylindene

Lithium aluminum hydride (LAH) 3.09 g (81 mimol) was suspended in dry ether (distilled from sodium metal) _c. Synthesized by (1) above 2, 3, 4 , 5,6,7—Hexamethylindane 31.8 g (180 millimoles) in 200 milliliters Was dissolved in dry ether, and added dropwise to the LAH suspension at such a rate as to cause gentle reflux. After the dripping was completed in 1.5 hours, stirring was continued for 2.5 hours under reflux with heating. Under ice-cooling, quench with 200 milliliters of water and then with 200 milliliters of IN aqueous ammonium chloride solution. Separate the organic phase, and then use 100 milliliters of ether. An extraction separation operation was performed twice, and the organic phases were combined, washed with a saturated sodium chloride aqueous solution, and then dried over anhydrous magnesium sulfate. The desiccant was filtered off, the ether solution was replaced with nitrogen, and a small amount of iodine was added to perform a dehydration reaction. After leaving overnight under nitrogen, the mixture was heated under reflux for 3 hours to complete the reaction.

Next, wash twice with a 0.2N aqueous sodium hydroxide solution of 150 milliliters and twice with a saturated aqueous sodium chloride solution of 150 milliliters, and then wash with anhydrous magnesium sulfate. Dried. The desiccant was filtered off, the ether was removed, and yellow crude 1,2,4,5,6,7-hexamethylindene was obtained, which was then re-extracted into 300 milliliters of hexane. Dissolved in toluene and dried over anhydrous magnesium sulfate to give a yellow solution. After the desiccant was filtered off, hexane was distilled off to obtain a yellow solid, which was adsorbed on 20 g of silica gel from the hexane solution, and then flowed through a 8 O g silica gel column with hexane. Then, 28.8 g (144 mmol) of the desired 1,2,4,5,6,7-hexamethylindene was obtained as a pale yellow solid. Yield 80.4.

(3) Synthesis of 1- (chlorodimethylsilyl) -1,2,3,4,5,6,7-hexamethylindene

1,2,4,5,6,7-Hexamethylindene (14.4 g, 72 millimoles) was dissolved in dry tetrahydrofuran (150 milliliters), and then cooled under ice-cooling. t-Butyllithium (1.7 MZ pentane solution) 4 7 7 milliliters were added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the hexane-insoluble matter was collected by filtration, washed with hexane, and dried to obtain a yellow-white solid. This was dissolved in 150 milliliters of dehydrated tetrahydrofuran (red solution), and 10.9 g of dimethylchlorosilane (85 millimoles, 10.3 milliliters) was distilled at 178 ° C. (Little), and the mixture was returned to room temperature. After standing overnight, the obtained yellow solution was subjected to removal of volatile components under reduced pressure. Then, hexane-insoluble components were removed by filtration, and hexane-soluble components were removed. Was distilled off under reduced pressure, and 19.8 g of 1_ (chlorodimethylsilyl) 1-2,3,4,5,6,7-hexamethylindene was recovered as a white solid.

(4) Synthesis of 1- (t-butylamino-dimethylsilyl) -1,2,3,4,5,6,7-hexamethylindene

1 1 (Chlorodimethylsilyl) -2,3,4,5,6,7-Hexamethylindene 19.8 g is dissolved in 150 ml of dehydrated ether, and cooled under ice-cooling. 13.2 g of 1-butylamine was added, and the mixture was returned to room temperature and stirred for two days. After evaporating the volatiles under reduced pressure, extracting with hexane 300 milliliters, filtering out the insoluble salts, and distilling off the solvent from the hexane solution under reduced pressure, a pale yellow oil was obtained. Was obtained and left at room temperature to obtain 22.0 g of a white solid.

(5) Synthesis of (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitanium dichloride

1 (t-Butylaminodimethylsilyl) 1,2,3,4,5,6,7-Hexamethylindene 10.1 g is dissolved in 150 ml of dehydrated ether and cooled on ice. 1.6 M n-butyllithium Z hexane solution 31 1 milliliter was added dropwise, and the mixture was stirred for two days at room temperature. The solvent was distilled off from the obtained red solution under reduced pressure, and the hexane-insoluble part was removed. After filtering Further washing with hexane gave a yellow solid. This yellow lithium salt and TiCl ₃ (thf) 31.1 .5 g were mixed as a solid, dried tetrahydrofuran 200 milliliters were added, and the mixture was stirred for 1 hour. 4.7 g was added thereto, and the mixture was further stirred for 2 hours. Then, volatile components were distilled off under reduced pressure, and ether-insoluble components were separated by filtration. After ether was distilled off from the solution, recrystallization from a toluene hexane solution gave pure (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitanium dichloride. The lid was obtained. The compound was found to be 2.70 ρ ρ m (3 hydrogen), 2.575 p pm (3 hydrogen), 2.452 ρ P m (3 hydrogen) by NMR in a double-mouthed form solvent. , 2.338 ppm (3 hydrogen), 2.305 ppm (3 hydrogen), 2.266 ppm (3 hydrogen), 1.372 ppm (9 hydrogen), 0.853 ppm (3 hydrogen) Hydrogen) and 0.735 ppm (3 hydrogen).

Example 2

(t-Butylamide) (2,3,4,5,6,7-hexamethylindenyl) 1-dimethylsilylzirconium dichloride

Production of CM e 2 S i (Me _e Ind) (t-BuN) ZrCl ₂ Example 1 — 1- (t-butylamino-dimethylsilyl) 1,2,3, obtained in (4) Dissolve 10.0 g of 4,5,6,7-hexamethylindene in 150 milliliters of dehydrated ether, and add 1.6 M n-butyllithium / hexane solution under ice-cooling (Wako Pure Chemical Industries, Ltd.) 50 milliliters were added dropwise and stirred at room temperature for 24 hours. The volatile components were distilled off from the obtained solution under reduced pressure at room temperature, and the solvent was replaced with 100 mil of hexane. Next, the hexane-insoluble portion is filtered off, washed with hexane and dried under reduced pressure to obtain 1- (t-butylamidodimethylsilyl) —2,3, 4,5,6,7-Hexamethylindenyl dilithium was obtained as a yellow solid.

Next, this solid was dissolved in 50 milliliters of dehydrated ether and cooled in a dry ice Z ethanol bath. In a separate container, 7.2 g of zirconium tetrachloride was suspended in dehydrated toluene, cooled in a dry ice ethanol bath, and 70 milliliters of dehydrated ether was added. Butylamide dimethylsilyl) 1,2,3,4,5,6,7-hexamethylindenyl dilithium ether solution was added, and the mixture was stirred and stirred for 1 hour while cooling. Thereafter, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for two days and nights. After evaporating volatiles from the resulting solution at room temperature under reduced pressure, 240 ml of dehydrated toluene was added thereto to extract soluble components. Next, the extract phase was concentrated under reduced pressure to a total volume of 30 milliliters, and then added with 120 milliliters of hexane, filtered, and the solvent was distilled off from the filtrate under reduced pressure. As a result, a highly viscous oil was obtained.

Add 50 milliliters of hexane to this oil and add 160 milliliters. The insolubles were filtered off with C and washed with 30 ml of cold hexane to give (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl). 5.06 g of -dimethylsilyl zirconium dichloride was obtained.

This compound ^than] H- NMR in dichromate Holm solvent, 2. 7 0 ppm (3 H , s), 2. 6 4 ppm (3 H, s), 2. 4 9 ρ P m (3 H, s), 2.34 ppm (3H, s), 2.28 ppm (3H, s), 2.25 ppm (3H, s), 1.34 ppm (9H, s) s), 0.80 ppm (3H, s) and 0.76 ppm (3H, s). Example 3

To one liter of autoclave, add toluene 395 milliliters and 1-octene 5 milliliters, heat at 80, and add 1 mole of methyl in terms of aluminum. Aluminoxane (M AO) (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) obtained in Example 1 with 3 milliliters and 1 millimol Z liter ) over dimethylsilyl titanium dichloride Li de _{[M e 2 S i (M e} 2 I nd) ( 't one B u N) T i C 1 2 ] 0.5 ml (all in toluene) was added, Ethylene was introduced, and polymerization was carried out for 10 minutes while maintaining the total pressure at 0.8 MPa and 80 ° C. The unreacted gas was depressurized, the reaction was stopped by adding a small amount of methanol, and after cooling, the contents were washed with 5 liters of methanol.

The dry weight of the obtained ethylene Z 1 -octene copolymer was 27.5 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Example 4

To a one liter bottle of toluene, add 395 milliliters of toluene and 5 milliliters of one octene, heat to 80 ° C, and add 1 mole of Z Lithobutylaluminum (TIBA) (t-butylamide) obtained in Example 1 at 1 milliliter and 1 millimol / liter (to 2,3,4,5,6,7-) Kisa methylindenyl) over dimethylsilyl titanium dichloride Li de _{[M e 2 S i (M e} 6 I nd) (t - B u N) T i C 12 ] 0.5 ml and 1 Mi Rimoru Z Li Tsu torr N, N-dimethyl § two linear © beam tetrakis (pen evening full Orofeniru) volley bets ([N, N-Me 2 P hNH] [B (C ₆ F ₅₎ _4]) 0.5 ml ( In each case, a toluene solution) was added, ethylene was introduced, and the total pressure was maintained at 0.8 MPa, 80 MPa for 30 minutes. I combined. The unreacted gas was depressurized, the reaction was stopped by adding a small amount of methanol, and after cooling, the contents were washed with 5 liters of methanol. The dry weight of the obtained ethylene 1-octene copolymer was 15.0 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Example 5

To one liter of autoclave was added 460 milliliters of toluene and 40 milliliters of 1-octene, and the mixture was heated to 150 ° C and ethylene was introduced at a total pressure of 2.4 MPa. . In addition, 1 mole of methylaluminoxane (MA0) in terms of aluminum was obtained in Example 1 with 6 milliliters and 1 milliliter of methylaluminoxane (t-butylamide) (2, 3). , 4, 5, 6, hexa-methylindenyl) Jimechiru silyl titanium to 7 dichloride Li de _{_{[Me 2 S i (Me 6 I}} nd) (t - B u N) T i C 1 2 ] 1.0 millimeter Li Tsu Torr (all in toluene solution) was added, and the mixture was maintained at 150 ° C and polymerized for 8 minutes. The unreacted gas was depressurized, the reaction was stopped by adding a small amount of methanol, and after cooling, the contents were washed with 5 liters of methanol.

The dry weight of the obtained ethylene Z 1 -octene copolymer was 49.5 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Example 6

In Example 3, toluene 360 milliliters, 1-octene 40 milliliters, and methylaluminoxane (MAO) were converted to 0.2 millimoles of aluminum, (t-butylamide) (2,3 , 4, 5, 6, hexa-methylindenyl to 7) dimethylsilyl titanium Axis B Li de _{_{[M e 2 S i (Me 6}} I nd) ( Bok B uN) T i C l _2] 1.0 Maiguromoru, Polymerization was carried out in the same manner as in Example 3 except that 1.5 mM triisobutylaluminum was used. Stopped.

The dry weight of the obtained ethylene 1-octene copolymer was 83.7 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Comparative Example 1

In Example 3, (t-butylamide) (2,3,4,5,67-hexamethylindenyl) -dimethylsilyltitanium dichloride [Me ₂ Si (Me ₆ Ind) (t - B uN) T i C ( t one butylamine de instead of l _2]) (2, 3, 4, 5 Tetoramechirushi black penta Genis Le) over dimethylsilyl titanium dichloride Li de _{CM e 2 S i (Me 4} C p) (t - B u N ) except for using T i C 1 _2] include ethylene 1 in the same manner as in example 3 - were prepared Okuten copolymer.

The dry weight of the obtained ethylene Z 1 -octene copolymer was 22.0 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Comparative Example 2

In Example 4, (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyltitanium dichloride [Me ₂ Si (Me ₆ Ind) ( t one B uN) T i C l ( t one butylamine de instead of _2]) (2, 3, 4, 5 Tetoramechirushi black penta Genis Le) over dimethylsilyl titanium dichloride Li de CM e 2 S i (Me 4 An ethylene Z 1 -octene copolymer was produced in the same manner as in Example 4 except that C p) (t−BυN) TiC ₁₂ ] was used.

The dry weight of the obtained ethylene 1-octene copolymer was 11.4 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Comparative Example 3 In Example 5, (t one butylamine de) (2, 3, 4, 5, 6, hexa-methylindenyl to 7) Single dimethylsilyl titanium dichloride Li de _{_{[Me 2 S i (Me 6 I}} nd) (t - B uN) T i C instead (t-butylamine de of l _2]) (2, 3, 4, 5 Tetoramechirushi black penta Genis Le) Single dimethylsilyl titanium dichloride Li de _{CM e 2 S i (Me 4} C p) (t - B u N ) except for using T i C 1 _2] include ethylene Z 1 in the same manner as in example 5 - was produced Okuten copolymer.

The dry weight of the obtained ethylene Z 1 -octene copolymer was 47.1 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Example 7

In Example 6, a tetra isobutyl aluminum Nokisan _{(i B u 2 A 1 0} A 1 i Β υ 2) 3. using 0 Mi Rimoru in terms of aluminum in place of methyl aluminoxane (MAO), and preparative Riisobuchiru aluminum Polymerization was carried out in the same manner as in Example 6 except that (TIΒ) was not used, and the polymerization reaction was stopped in 60 minutes.

The dry weight of the obtained ethylene 1-octene copolymer was 56.0 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Example 8

In Example 6, in place of methylaluminoxane (MAO), tris (dimethylalumino) boroxane [B (0A1Me2) 3] was used in an amount of 3.0 mmol in terms of aluminum, and triisobutylaluminum was used. Polymerization was carried out in the same manner as in Example 6, except that 1.0 mmol of (TIBA) was used, and the polymerization reaction was stopped in 60 minutes.

The dry weight of the obtained ethylene Z 1 -octene copolymer was 29.3 g. Table 1 shows the polymerization conditions, catalytic activity, and physical properties of the polymer. Table 1

(Note) (A) component (t-butylamide) (2, 3, 4, 5, 6,

7-Hexamethylindenyl) 1-dimethylsilyltitanium dichloride

MAO methylaluminoxane

[N] [B] Ν, Ν-dimethylaniline

(Penyu fluorophenyl) borate

T I BA triisobutyl aluminum

T I B A O Te trisobutylaluminoxane

TDMAB Tris (dimethylalumino) boroxane Table 1 I 2

Table 1-3

Example 9

One milliliter of toluene is charged with 400 milliliters of toluene, heated to 50 ° C, and then added with 1 molnoliter of methylaluminoxane (MAO) 3 in terms of aluminum. (T-Phtylamide) (2,3: 4,5,6,7-hexamethylindenyl) -dimethylsilyl tita dimethyl dichloride obtained in Example 1 of 1 milliliter and 1 milliliter Li de _{[M e 2 S i (M e} 6 I nd) (t - Β υ N) T i C 1 2 ] 5 ml (all in toluene) was added, the flop propylene total pressure 0. The introduction was continued at 8 MPa, and the polymerization was maintained at 50 ° C. for 15 minutes. Unreacted gas was depressurized, the reaction was stopped by adding a small amount of methanol, and after cooling, the contents were washed with 5 liters of methanol. The dry weight of the obtained polymer was 71.5 g. This polymer had no melting point (Tm) by differential scanning calorimetry (DSC), was amorphous, and had a glass transition point (Tg) of 0 ° C. In addition, isotope carbon nuclear magnetic resonance ( ^13C- NMR) spectroscopy showed that atactic tritium [rr] was 18 mol% and racemic triad [rr] was 34 mol% atactic. It was polypropylene. Table 2 shows the polymerization conditions, catalyst activity, and physical properties of the polymer.

Example 10

In Example 9, a toluene solution of methylaluminoxane (MAO) (manufactured by Ethyl) was converted to 3.0 mmol in terms of aluminum, triisobutylaluminum (TIBA) was 0.5 mmol, and (t-butylamido) (2, 3, 4, 5, 6, hexa-methylindenyl) over di-methyl silyl titanium to 7 dichloride Li de _{[M e 2 S i (M e} e I nd) (t one B uN) T i C 12] 2.0 The procedure was performed in the same manner as in Example 9 except that polymerization was performed for 60 minutes using micromolar.

The dry weight of the obtained polymer was 72.9 g. This polymer had no melting point (Tm) as in Example 9, was amorphous, had a glass transition point (Tg) of 0, a mesopentad fraction (mmmm) of 2 mol%, and a mesotriat. de (mm) 1 6 mol%, indicating racemization TRIAL head [rr] 3 7 mol% of Atakuchi' click polypropylene and a _{c-polymerization} conditions, catalytic activity, the physical properties of the polymer in table 2.

Example 1 1

A stainless steel pressure-resistant reactor with an internal volume of 500 milliliters equipped with a stirrer was dried under reduced pressure, purged with nitrogen, and then toluene 160 milliliters and 1-octene 5 milliliters. , Triisobutylaluminum (TIBA) 0.3 mmol, methylaluminoxane (MAO) (East 1.5 mmol in terms of aluminum, (t-butylamide) (2,3,4,5,6,7-hexamethylindenyl) -dimethylsilyl obtained in Example 1 Titanium dichloride CM e ₂ S i (Me _e Ind) (t — Bu N) T i C l ₂ ] 1.07 micromoles are added, propylene is continuously supplied at 50 ° C, and the internal pressure is reduced. While maintaining at 0.8 MPa, polymerization was performed for 1 hour. After the completion of the polymerization reaction, the excess propylene was depressurized and removed, and the reaction was stopped by adding 5 milliliters of methanol. The contents were stirred in 150 ml of acidic methanol for 2 hours, and insolubles were collected by filtration. The insolubles were washed again in 1500 milliliters of methanol, and the resulting polymer was dried at 80 ° C under reduced pressure.

The dry weight of the polymer was 16.6 g. This polymer had no melting point (Tm) as in Example 9, was amorphous, and had a glass transition point (T g) of -1 ° C. Table 2 shows the polymerization conditions, catalytic activity, and physical properties of the polymer.

No. 2

(Note) Component (A) (t-butyl amide) (2, 3, 4, 5, 6,

7-Hexamethylindenyl) 1-dimethylsilyltitanium dichloride

(B) Component Methylaluminoxane

T I BA Triisobutylaluminum

Mw gel permeation chromatography (G

PC) Weight average molecular weight

Mw / Mn: weight average molecular weight measured by the GPC method

Example 1 2

A 500-milliliter stainless steel pressure-resistant reactor equipped with a stirrer was dried under reduced pressure and purged with nitrogen, and then toluene 200-milliliter and methylaluminoxane (MAO) (MAO) 1.0 mg in terms of aluminum salt, (t-butyl amide) obtained in Example 2 (2,3,4,5,6,7-hexamethylindenyl) - dimethylsilyl zirconium dichloride Li de _{[M e 2 S i (M e} 6 I nd) (t - B uN) Z r C 1 2 ] 1. put 0 micromolar, ethylene continuously at 8 0 ° C The mixture was supplied, the internal pressure was maintained at 0.8 MPa, and polymerization was performed for 1 hour. After the completion of the polymerization reaction, excess ethylene was depressurized and removed, and the reaction was stopped by adding 5 ml of methanol. The contents were stirred in 150 ml of acidic methanol for 2 hours, and insolubles were collected by filtration. The insolubles were washed again in methanol 150 ml and the obtained polymer was dried under reduced pressure at 80 to obtain 4.74 g of polyethylene.

In this polyethylene, the unsaturated bond observed by infrared spectroscopy (IR) was only a terminal vinyl group of 910 cm- ^1. The content of this vinyl group was 7.87 per 100 carbon atoms. Was individual. Table 3 shows the polymerization conditions, polymer yield, and polymer properties.

Example 13

Example 12 was carried out in the same manner as in Example 12 except that the amount of methylaluminoxane (MAO) was changed to 6.0 mmol in terms of aluminum. Table 3 shows the polymerization conditions, polymer yield, and polymer properties. You.

Example 14

Example 12 was carried out in the same manner as in Example 12, except that 0.4 mmol of triisobutylaluminum (TIBA) was further used. Table 3 shows the polymerization conditions, polymer yield, and polymer properties. Comparative Example 4

A 500-milliliter stainless steel pressure-resistant reactor equipped with a stirrer was dried under reduced pressure and purged with nitrogen, and then toluene 200-milliliter and triisobutylaluminum (TIBA ) 0.2 mmol, methylaluminoxane (MAO) (manufactured by Tosoh Aguso Co., Ltd.) in terms of aluminum is 1.0 mmol, (t-butylamide) (tetramethylcyclopentyl phenol) Dimethylsilyl titanium dichloride

CM e 2 S i (M e 4 C p) (t - B u N) T i C 1 2 ] 1. Put 0 My Kuromoru, continuously feeding Echiren at 8 0 ° C, the internal pressure 0. While maintaining the pressure at 4 MPa, polymerization was performed for 1 hour. After the completion of the polymerization reaction, the excess ethylene was depressurized and removed, and the reaction was stopped by adding 5 milliliters of methanol. The contents were stirred in 150 ml of acidic methanol for 2 hours, and the insolubles were collected by filtration. The insolubles were washed again in methanol 150 liter, and the obtained polymer was dried under reduced pressure at 80 ° C. to obtain 31.7 g of polyethylene.

The polyethylene, unsaturated bond in IR analysis indicates _c polymerization conditions were not observed, polymer yield, the physical properties of the polymer in Table 3. Table 3

(Note) A—I: (t-butylamide) (2,3,4,5,6,7 hexamethylindenyl) -dimethylsilyldilconidium dichloride

A-II: (t-butylamide) (tetramethylcyclopentenyl) -dimethylsilyltitanium dichloride,

(B) Component Methylaluminoxane

TI BA triisobutyl aluminum M: Weight average molecular weight measured by gel permeation chromatography (GPC)

Mw / Mn: Weight average molecular weight measured by the GPC method Number average molecular weight

Example 15

In a nitrogen atmosphere, dry hexane 64 million liters and methylaluminoxane (MAO) were converted to aluminum in 1.5 liters in a 2-liter autoclave heated to 150 ° C. 300 milliliters of a hexane solution containing 70 mol of 2-molbornene and 2-molbornene (1.74 mol as 2-norbornene) were charged in this order. Next, 120 mil dry hexane, 1.5 millimol of methylaluminoxane (MAO) (in terms of aluminum), and the t-butylamide (2,3) obtained in Example 1 were introduced into the catalyst inlet tube. 4, 5, 6, Kisamechiru indenyl) over dimethylsilyl titanium dichloride Li de to 7- _{[M e 2 S i (M ee} I nd) (t - Β υΝ) a T i C l ₂ 6 micromolar in the order of this added.

Next, after introducing ethylene so that the ethylene partial pressure becomes 3. O MPa, a catalyst solution is introduced from the catalyst inlet tube, and continuously ethylene is introduced so that the ethylene partial pressure becomes 3.0 MPa. The reaction was carried out for 5 minutes while introducing. After completion of the reaction, the polymerization was stopped with isopropyl alcohol, and the mixture was flushed with a flash drum to obtain 65.6 g of a powdery ethylenino 2-norbornene copolymer. The catalytic activity was 229 kg Zg T i.

This copolymer has a 2-norbornene unit content of 5.6 mol% and an intrinsic viscosity of? ? 2.83 deciliter Zg, melting point (Tm) 83 (Broad), molecular weight measured by GPC method is weight average molecular weight The amount (Mw) was 196,000, the number average molecular weight (Mn) was 60.5 000, and the MwZMn was 3.24. In addition, Meltoindex

MI _2] . ₆ (load 21.6 kg) was 0.34 10 minutes, and MI ₂ · ₁₆ (load 2.16 kg) was 0.007 g / 10 minutes.

Table 4 shows the polymerization conditions, catalytic activity, and physical properties of the polymer.

Example 16

Dry hexane 120 milliliters, methylaluminoxane (MA0) 1.5 millimoles (in terms of aluminum) and (t-butylamide) (2,3,4) obtained in Example 1 , 5,6,7-Hexamethylindenyl) 6-micromol of 1-dimethylsilyltitanium dichloride was mixed and left for 24 hours at room temperature under nitrogen, and the mixture was added to the catalyst charging tube. The same operation as in Example 15 was performed except that the value was set to 0.

Examples 17 to 19

Under the polymerization conditions shown in Table 4, an ethylene / 2-norpoleneene copolymer was produced in the same manner as in Example 15.

Comparative Example 5

As the catalyst for the component (A), (t-butylamide) (tetramethylcyclopentagenenyl) -dimethylsilyltitanium dichloride is used.

CM e 2 S i (M e ₄ C p) (t -B uN) T i C l ₂ ] Using 6 mic moles, under the polymerization conditions shown in Table 4, in the same manner as in Example 15 An ethylene // 2-norbornene copolymer was produced. Table 4 shows the polymerization conditions, catalyst activity, and physical properties of the polymer. Table 4 1

(Note) A—III: (t-butylamide) (2, 3, 4, 5, 6, 7,

1-hexamethylindenyl) -dimethylsilyl chloride

A-II: (t-butylamide) (tetramethylcyclopentene genyl) 1-dimethylsilyltitanium dichloride,

(B) component: methylaluminoxane

NB: 2-norbornene Use 64 ml of hexane as solvent, polymerization time is 5 minutes Table 4 2

(Note) *: The unit is kg 'volima-Ti · MPa · hour,

**: NB unit is 2-norbornene unit, Table 4 3

(Note) MwZMn: Weight average molecular weight measured by GPC method Number average molecular weight Industrial applicability

The transition metal compound of the present invention is a novel transition metal compound having, as a 7Γ ligand, a substituted indenyl group having at least one substituent in addition to a substituent bonded to a transition metal element on the five-membered ring side. It is useful as a catalyst component for olefin polymerization. The catalyst for polymerization of the olefin of the present invention containing the transition metal compound has high activity and a good quality of a normal olefin homopolymer, copolymer, or elastomer having a small amount of residual metal. Polymers with an excellent balance between modulus and elastic recovery, improved low-temperature properties, and improved moldability. These polymers are useful as narrow-chain copolymers, elastomers, etc., and have a narrow molecular weight distribution. Low-molecular-weight olefin-based polymers having a high vinyl group content useful as propylene-based polymers and macromonomers can be economically and efficiently provided.

Claims

The scope of the claims

(1) A transition metal compound having, as a 7Γ ligand, a substituted indenyl group having at least one substituent in addition to a substituent bonded to a transition metal element on the five-membered ring side.

(2) For olefin polymerization containing a transition metal compound having a substituted indenyl group having at least one substituent as a 7Γ ligand in addition to the substituent bonded to the transition metal element on the 5-membered ring side catalyst.

(3) (A) General formula (II)

And the general formula (III)

[In the formula, R ′, R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon having 6 to 20 carbon atoms, respectively. Group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, thioallyloxy group having 6 to 20 carbon atoms, amino group, amino group R ¹ and R ³ each represent a group other than a hydrogen atom, and a plurality of R ¹ , a plurality of R ² , a plurality of R ³ and a plurality of R ⁴ in each may be the same or different. M ² and VI ³ are metal elements of the periodic table 3 to 10 or lanthanide series, X ² and X ³ are ligands, L ² and L ³ are Lewis bases, Q ¹ And Q ² are an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a silylene group having 1 to 5 silicon atoms, or a 1 to 5 carbon atoms, respectively. Germylene group, J ^] and J ² represent an amide group, a phosphide group, an oxygen atom, a sulfur atom or an alkylidene group, respectively, a plurality of X ² , a plurality of X ³ , a plurality of L ² and a plurality of L ² ³ may be the same or different in each. c and e each represent the valence of M ² and M ^3, the d and f is 0, 1 or 2. ]

At least one selected from the transition metal compounds represented by

(B) for organic polymerization comprising a combination of at least one selected from the group consisting of (a) an organic boron compound, (b) an aluminoxane and (c) an ionic compound comprising a non-coordinating anion and a cation. catalyst.

(4) (A) at least one selected from the transition metal compounds represented by the general formulas (II) and (II); and (B) (a) an organic boric acid compound; Aluminoxane and (c) non-coordinating anion and force A catalyst for polymerization of olefins comprising a combination of at least one selected from ionic compounds comprising thione and (C) a Lewis acid.

(5) In the presence of the catalyst according to claim 2, 3, or 4, homopolymerization of orefins, copolymerization of two or more orefins, or copolymerization of orefins with other polymerizable unsaturated compounds. A method for producing an olefin polymer, which comprises polymerizing.

(6) The method according to claim 5, wherein the orefins and the cyclic orefins are copolymerized to produce an oreforecyclic orefin copolymer.

(7) Orefin Z The cyclic orefin copolymer has the following properties: (1) the ratio MwZMn of the weight average molecular weight (M) to the number average molecular weight (Mn) measured by gel permeation chromatography is 6 or less; Intrinsic viscosity [7?] Measured at 135 ° C in decalin and a load of 2.16 kg were measured in a unit content of 0.1 to 95 mol% in decalin. the melt index relationship between the (MI _2.] _6), formula

[7?] ≤ 1.3 3 3— 0.6 2 0 X 1 og MI ₂ .ie

7. The method according to claim 6, which satisfies the following.

(8) The polymerization catalyst according to claim 3 or 4, wherein in the transition metal compound of the component (A), M ² and M ³ in the general formulas (II) and (III) are each titanium.

(9) In the transition metal compound of the component (A), M ² and M ³ in the general formulas (Π) and (III) are each zirconium or hafnium. 5. The polymerization catalyst according to claim 3, which is a rubber.

(10) In the presence of the catalyst according to claim 8, propylene is homopolymerized, or propylene is used.

6. The method according to claim 5, wherein at least one selected from 20 other unsaturated compounds for polymerization is copolymerized to produce an amorphous high molecular weight propylene-based polymer.

(11) The amorphous high-molecular-weight propylene polymer has (1) an intrinsic viscosity [7?] Measured at 135 in decalin larger than 1.0 deciliter. (2) Gel permeation The ratio MwZMn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the chromatographic method is less than 3, and ③ has no melting point (Tm) and a glass transition point (Tg) of 1 The method according to claim 10, wherein the temperature is lower than 0 ° C.

(12) In the presence of the catalyst according to claim 9, homopolymers of C 2 to C 20 olefins, copolymerization of two or more C 2 to C 20 olefins, or C 2 to C 2 olefins The low molecular weight olefin polymer having a high vinyl group content is produced by copolymerizing an olefin having 20 and another polymerizable unsaturated compound having 2 to 20 carbon atoms. the method of

(13) A low-molecular-weight olefin polymer having a high vinyl group content is obtained by mixing an ethylene homopolymer or ethylene with an olefin having 3 to 20 carbon atoms and other olefins having 2 to 20 carbon atoms. It is a copolymer with at least one selected from polymerizable unsaturated compounds, and has the following characteristics: (1) Weight average molecular weight in terms of polyethylene measured by gel permeation-short chromatography (Mw) in the 2 0 0 to 10, 0 0 0, ② density is the 0. 9 2 5 gZc m ³ or more on, and ③ the proportion of vinyl groups to the total unsaturated group is 7 0 mol% or more 13. The method according to claim 12, wherein the vinyl group content measured by infrared spectroscopy is 1.5 or more per 100 carbon atoms.

(14) ① The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) measured by gel permeation chromatography is MwZMn of 6 or less, and ② the content of cyclic orefine units is 0.1 to 9 5 the mole%, and ③ in deca Li down, 1 3 5 ° intrinsic viscosity measured in C [7?] and load weight 2. melt index was measured at _{_{1 6 kg (MI 2. 1}} β) and Is the relationship

C T?) ≤ 1.3 3 3-0.6.20 X 1 o gM I 2.le

A cyclic Z-olefin copolymer that satisfies

(15) In decalin, the intrinsic viscosity [] measured at 135 is greater than 1.0 deciliter / g, ② weight average molecular weight measured by gel permeation chromatography ( Mw) and number average molecular weight

A propylene polymer having a ratio of (Mn) to MwZMn of less than 3, (3) having no melting point (Tm), and having a glass transition point (Tg) of less than 10 ° C.