JP2006513974A - Polycyclic fused heterocyclic compound, metal complex and polymerization method - Google Patents

Abstract

The present invention relates to a polycyclic heteroatom-containing fused ring having a cyclopentadienyl ring fused to a 5-membered polyatomic ring having at least one ring atom selected from Group 15 or 16 of the periodic table The present invention relates to a metal complex containing a compound, a polymerization catalyst, and an olefin polymerization method using them.

Description

This application was filed with priority on US Provisional Application No. 60/364809 (filed on Mar. 14, 2002).

The present invention relates to a metal complex containing a polycyclic fused ring ligand containing at least one group 15 or 16 atom, and a copolymer comprising an α-olefin and ethylene or a monovinyl aromatic monomer and ethylene. Polymerization obtained from the complex particularly suitable as a polymerization catalyst for producing a homopolymer or copolymer of an olefin or diolefin, including a copolymer comprising at least two olefins or diolefins such as a polymer Relates to the catalyst.

U.S. Pat. No. 5,703,187 discloses a constrained geometric metal complex and a method for its production. This patent further teaches a process for the preparation of new copolymers of ethylene and geometrically constrained vinyl monomers (including monovinyl aromatic monomers having a pseudo-random structure). Also, U.S. Pat.No. 5,321,106, U.S. Pat.No. 5,721,185, U.S. Pat.No. 5,774,696, U.S. Pat.No. 5,470,993, U.S. Pat.No. 5,541,349, U.S. Pat. Furthermore, international patent application WO 97/15583, international patent application WO 97/19463, etc. have further teachings on constrained geometric catalysts.

US Pat. Nos. 6034022 and 6329486 disclose certain active polycyclic aromatic metal complexes, in particular derivatives of s-indacenyl or cyclopentaphenanthrenyl ligand groups. US patent application specification (filed June 12, 2001: application number 09/979463; published May 23, 2002: publication number 2002/0062011) is derived from other non-aromatic polycyclic ring systems Complexes are disclosed. International patent application WO01 / 53360 specification, international patent application WO01 / 44318 specification, international patent application WO01 / 47939 specification, international patent application WO01 / 48039 specification, international patent application WO01 / 48040 specification, international patent application WO 98/06728 and US Pat. No. 6,626,444 disclose disclosures of heteroatom-containing metallocenes having a delocalized fused ring system, and US patent application (Application No. 10/12469; 2002 10 Published May 17th: Publication number 2002/0151662).

Despite the technological advances obtained with such metal complexes, further improvements in catalyst performance are still desired in the industry. In particular, it is desired to provide a metal complex with improved catalytic performance that can be easily synthesized. Therefore, it would be desirable to provide a metal complex that is easy to synthesize and has good catalytic properties.

Problems of the Invention and Means for Solving the Problems

The present invention provides a polycyclic heteroatom-containing fused ring compound represented by the following formula (I).
C _p M (Z) (X) _x (T) _t (X ') _x' (I)
In the formula, C _p is a polycyclic fused ring ligand having up to 60 atoms other than hydrogen or an inert substituted derivative thereof having at least a cyclopentadienyl ring bonded to M by a delocalized π electron. And a 5-membered polyatomic ring having at least one ring atom selected from Group 15 or 16 of the periodic table or a substituted derivative thereof, wherein the cyclopentadienyl ring is a second condensed ring. Without adjacent substituents that can form M is a metal selected from Groups 3 to 10 of the periodic table or lanthanum. Z is a divalent radical of the formula -Z'Y- involved in C _p and M, wherein, Z 'is ^{_{SiR 6 2, CR 6 2,}} SiR 6 2 SiR 6 2, R 6 2 CR 6 ₂ , CR ⁶ = CR ⁶ , CR ⁶ ₂ SiR ⁶ ₂ , BR ⁶ or GeR ⁶ ₂ . Y is —O—, —S—, —NR ⁵ —, —PR ⁵ —, —NR ⁵ ₂ or —PR ⁵ ₂ . Hydrocarbyl, each R ⁵ is exists independently trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, up to 20 have a non-hydrogen atoms, optionally the ring by a and Y 2 amino or R ⁵ by R ⁵ groups Can be formed. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 30 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X is hydrogen or a monovalent anionic ligand group having up to 60 atoms other than hydrogen. T is a neutral coordination compound that exists independently, and T and X or T and R ⁵ may be bonded together. X ′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen. x is 0, 1, 2 or 3, t is 0 to 2, and x ′ is 0 or 1.

The above compounds may exist as crystals isolated in the form of a solvate adduct dissolved in a solvent (especially an organic liquid solvent), as a mixture with other compounds, or in the form of a dimer And may be present as a chelating derivative (especially an organic substance such as ethylenediaminetetraacetate (EDTA) as a chelating agent).

The present invention also provides an olefin polymerization catalyst containing the following A or B.
(A) (i) a metal compound represented by formula (I) and (ii) an activated cocatalyst (where i: ii molar ratio is 1: 10,000 to 100: 1);
(B) A reaction product obtained by converting a compound of formula (I) to an active catalyst using activation techniques.

Furthermore, the present invention provides an olefin polymerization method comprising contacting at least one olefin containing 2 to 20 carbon atoms (including a cyclic olefin) under polymerization conditions using a catalyst containing A or B below. .
(A) (i) a metal compound represented by formula (I) and (ii) an activated cocatalyst (where i: ii molar ratio is 1: 10,000 to 100: 1);
(B) A reaction product obtained by converting a compound of formula (I) to an active catalyst using activation techniques.

The catalyst and polymerization process of the present invention comprises in particular a homopolymer of olefins, a copolymer of at least two olefins, in particular a copolymer of ethylene and a vinyl aromatic monomer such as a carbon 3-8 containing α-olefin or styrene, Is efficient for the production of interpolymers of at least three such polymerizable monomers under a wide range of polymerization conditions (especially at elevated temperatures). The catalyst and polymerization method of the present invention include, in particular, ethylene homopolymers and copolymers of ethylene and at least one carbon 3-8 containing α-olefin (ethylene, propylene and diene terpolymers (EPDM copolymers), etc. Is also useful in the production of Suitable diene monomers include, for example, ethylidene norbornene, 1,4-hexadiene or similar conjugated or non-conjugated dienes.

The catalyst of the present invention may be used while being supported on a solid material, or may be used for olefin polymerization in a slurry or gas phase. The catalyst of the present invention may be prepolymerized in advance in a polymerization reactor using at least one olefin monomer, or the prepolymerized catalyst in an intermediate stage may be recovered in a separate step before the main polymerization reaction. May be. The catalyst of the present invention may also be used in combination with at least one other catalyst such as a metallocene catalyst or a Ziegler-Natta catalyst, in which case they may be used together or the process of the present invention. According to the above, it may be used continuously in at least one polymerization reactor. In addition to use as a polymerization catalyst, the compounds of the present invention are also used for dehydrogenation, hydrogenation or oligomerization.

In this specification, all the symbols of the periodic table are given based on the periodic table of elements authored and published (1995) by CRCPress Inc. Moreover, the code | symbol with respect to each family of a periodic table is provided according to the IUPAC nomenclature. Disclosure of the contents of patents, patent applications or publications cited herein, in particular the structure of organometallics, synthesis techniques, and general recognition in the art, is their U.S. edition in light of the operational aspects of U.S. patents. It is based on. As used herein, the term “aromatic” means a polyatomic cyclic ring system containing (4δ + 2) π electrons (δ is an integer greater than or equal to 1). The term “fused” as used with reference to ring systems containing at least two or more polyatomic ring rings means that for at least two rings, at least one pair of adjacent atoms is present in both rings.

As used herein, the terms “comprising” and its derivatives refer to other additional ingredients, steps or methods, whether or not otherwise stated herein. The existence of is not excluded. For the avoidance of doubt, all compositions claimed using the term “comprising” shall include any other additional additives, adjuvants or compounds, unless otherwise specified. You may contain. On the contrary, the term “consistingessentially of” is excluded from the scope of the claims, unless the other ingredients, steps or methods are not operationally essential. . Also, the term “consisting of” excludes any other component, step or method, unless specifically stated otherwise. The term “or” means any combination with other ingredients, not just those listed, unless otherwise specified.

The compounds of the present invention desirably contain a cyclopentadienyl ring fused to the 5-membered ring at a position adjacent to at least one nitrogen, sulfur or oxygen heteroatom present in the 5-membered ring. .

The compound (metal complex) recommended in the present invention is a compound represented by the following formula.

Wherein J is independently present for hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis (trihydrocarbylsilyl) amino, di (hydrocarbyl) amino, hydrocarbylene. Amino, hydrocarbylimino, di (hydrocarbyl) phosphino, hydrocarbylenephosphino, hydrocarbyl sulfide, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis (trihydrocarbylsilyl) amino-substituted hydrocarbyl , Di (hydrocarbyl) amino substituted hydrocarbyl, hydrocarbylene amino substituted hydrocarb Bill, di (hydrocarbyl) phosphino substituted hydrocarbyl, hydrocarbylene phosphino substituted hydrocarbyl, or hydrocarbyl sulfide substituted hydrocarbyl having up to 40 atoms other than hydrogen. A is a divalent residue of an aromatic 5-membered ring group or a substituted derivative thereof, and has at least one group 15 or 16 ring atom. M is a Group 4 metal, Y is -O -, - S -, - NR 5 -, - PR 5 -, - NR 5 2 or -PR ⁵ _2, Z 'is _{^{SiR 6 2, CR 6 2,}} SiR 6 ₂ SiR ⁶ ₂ , CR ⁶ ₂ CR ⁶ ₂ , CR ⁶ = CR ⁶ , CR ⁶ ₂ SiR ⁶ ₂ , BR ⁶ or GeR ⁶ ₂ , R ⁵ is independently present hydrocarbyl, trihydrocarbyl silyl or Trihydrocarbyl silylhydrocarbyl, which has up to 20 atoms other than hydrogen and can optionally form a ring by two R ⁵ groups or by R ⁵ and Y. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 20 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X, T and X ′ are as defined in claim 1, x is 0, 1 or 2, t is 0 or 1, and x ′ is 0 or 1.

In a preferred embodiment, when x is 2 and x ′ is 0, the oxidation state of M is +4 (or when Y is —NR ⁵ ₂ or —PR ⁵ ₂ , the oxidation state of M is +3). And X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide and silyl groups, and also their halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (Hydrocarbyl) an anionic ligand selected from the group consisting of phosphino-substituted derivatives having up to 30 atoms other than hydrogen.

When x is 0 and x ′ is 1, the oxidation state of M is +4, and X is a dianion coordination selected from the group consisting of hydrocarbadiyl, silane, oxyhydrocarbylene and hydrocarbylenedioxy groups It is a child and has up to 30 atoms other than hydrogen.

When x is 1 and x ′ is 0, the oxidation state of M is +3, X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) phenyl and It is a stabilized anionic ligand group selected from the group consisting of 2- (N, N-dimethylamino) benzyl.

When both x and x 'are 0 and t is 1, the oxidation state of M is +2, and T is a neutral conjugated or non-conjugated diene (sometimes substituted with at least one hydrocarbyl group) And L has up to 40 carbon atoms and is bonded to M by its delocalized π electrons.

In metal complexes, the recommended T groups are carbon monoxide, phosphine (especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis (1,2-dimethylphosphino) ethane), P (OR ⁴ ) ₃ (wherein R ⁴ is a hydrocarbyl containing 1-20 carbons), ether (especially tetrahydrofuran), amines (especially pyridine, bipyridine, tetramethylethylenediamine (TMEDA) and triethylamine), olefins, and carbon 4-40 ( Preferably, it is a neutral conjugated diene containing 5 to 40). The oxidation state of the metal in the complex containing the neutral diene T group is +2.

In the code assigned to the metal complex, X is desirably selected from the group consisting of hydro, halo, hydrocarbyl, silyl and N, N-dialkylamino substituted hydrocarbyl. The number of K groups depends on the oxidation state of M, whether Z is divalent, or whether a neutral diene group or a divalent X 'group is present. Those skilled in the art already understand that charge balance is achieved by selecting and specifying the amount of various substituents and Z, resulting in the formation of a neutral metal complex. For example, when Z is divalent and x is 0, x 'is 2, which is smaller than the normal oxidation state of M. When Z has one neutral two-electron coordination covalent bond and M is in the normal oxidation state of +3, x and x 'are both 0, or x is 2 and x' is 0. In the last example, when the oxidation state of M is +2, Z may be a divalent ligand group. At this time, x and x 'are both 0, and one neutral T ligand group may be present.

A more recommended compound of formula (I) is when M is titanium. Examples of suitable A residues include those shown in the following a to e.

More preferred compounds of the formula (I) and metal complexes are those represented by the following formulae.

In the formula, M is titanium and R1 is independently present hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amino, hydrocarbyleneamino, di (hydrocarbyl) amino substituted hydrocarbyl group, or hydrocarbyleneamino substituted hydrocarbyl. Group having up to 30 atoms other than hydrogen. Y is -O -, - S -, - NR 5 -, - PR 5 -, - NR 5 2 or -PR ⁵ _2, Z 'is _{^{SiR 6 2, CR 6 2,}} SiR 6 2 SiR 6 2, CR 6 ₂ CR ⁶ ₂ , CR ⁶ = CR ⁶ , CR ⁶ ₂ SiR ⁶ ₂ , BR ⁶ or GeR ⁶ ₂ , R ⁵ is each independently present hydrocarbyl, trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, It has up to 20 atoms other than hydrogen and can optionally form a ring with two R ⁵ groups or with R ⁵ and Y. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 20 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X, T and X ′ are as defined in claim 1, x is 0, 1 or 2, t is 0 or 1, and x ′ is 0 or 1.

When x is 2 and x 'is 0, the oxidation state of M is +4 (or when Y is -NR ⁵ ₂ or -PR ⁵ ₂ , the oxidation state of M is +3), and X is Halides, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide and silyl groups, as well as their halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (hydrocarbyl) phosphino- An anionic ligand selected from the group consisting of substituted derivatives and having up to 30 atoms other than hydrogen.

When x is 0 and x ′ is 1, the oxidation state of M is +4, and X is a dianion coordination selected from the group consisting of hydrocarbadiyl, silane, oxyhydrocarbylene and hydrocarbylenedioxy groups It is a child and has up to 30 atoms other than hydrogen.

When x is 1 and x ′ is 0, the oxidation state of M is +3, X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) phenyl and It is a stabilized anionic ligand group selected from the group consisting of 2- (N, N-dimethylamino) benzyl.
A conjugated or non-conjugated diene in which x and x ′ are both 0, t is 1, M is in oxidation state +2, and T is a neutral (including optionally substituted with at least one hydrocarbyl group) Where L has up to 40 carbon atoms and is bonded to M by its delocalized π electrons.

Most preferably, R ¹ is each independently present hydrogen, Y is NR ⁵ (R ⁵ is alkyl or cycloalkyl containing 1 to 10 carbons, preferably t-butyl) and Z ′ is dimethylsilane. . When x is 2 and t and x ′ are both 0, the oxidation state of M is +4, X is independently present methyl, benzyl or halide, x and t are 0, x ′ is 1, When the oxidation state of M is +4, X ′ is —CH ₂ Si (CH ₃ ) ₂ CH ₂ — or a 1,4-butenediyl group that forms a metallocyclopentene ring together with M, x is 1, and t and x ′ When both are 0, the oxidation state of M is +3, X is 2- (N, N-dimethylamino) benzyl, and when x and x ′ are both 0 and t is 1, the oxidation state of M is +2, T is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

The most recommended metal complex represented by the formula (I) used in the present invention is a compound represented by the following formula.

Wherein R 1 is a carbon 1-30 containing hydrocarbyl (preferably methyl) or a carbon 4-30 containing alkyl or aralkyl group having a secondary or tertiary substituent pattern at the β-carbon position, most preferably Methyl, 2,2-dimethylpropan-1-yl, 2,2-dimethylbutan-1-yl, 2,2-diethylpropan-1-yl, 2,2-diethylbutan-1-yl, benzyl or pentafluoro It is a phenylmethyl group.

Metal complexes can be prepared by combining metal halide salts with the corresponding fused polycyclic ring system ligand dianion in an inert diluent, or corresponding metal amides in an inert diluent. Can be produced by combining with a neutral fused polycyclic ring system

Reducing agents can optionally be used to produce lower oxidation state complexes, and different ligand substituents can be produced using standard ligand exchange methods. The preferred method used in the present invention is well known to synthetic organometallic chemists. Such synthesis is preferably carried out in a suitable non-interfering solvent at a temperature range of −100 to 300 ° C., preferably −78 to 100 ° C., most preferably 0 to 50 ° C. As used herein, the term “reducing agent” refers to a metal or compound that can bring the oxidation state of the metal to a lower state under reducing conditions. Examples of suitable metal reducing agents include, for example, alkali metals, alkaline earth metals, aluminum and alkali metal or alkaline earth metal alloys such as sodium zinc or mercury amalgam, and sodium or potassium alloys. . Examples of suitable reducing agents include, for example, sodium naphthalenide, potassium graphite, lithium alkyl, lithium or potassium alkadienyl, and a griniard reagent. The most preferred reducing agents are alkali metals or alkaline earth metals, especially lithium and magnesium metals.

Suitable media for use in preparing the complex include, for example, aliphatic and aromatic hydrocarbons, ethers and cyclic ethers, especially branched chain hydrocarbons such as isobutane, butane, pentane, hexane, octane and mixtures thereof. Cyclic and alicyclic hydrocarbons such as cyclohexane, cyclopentane, methylcyclohexane, methylcycloheptane and mixtures thereof, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene and xylene, carbon 1-4 containing dialkyl ethers, (Poly) alkylene glycol and carbon 1-4 containing dialkyl ether derivatives of tetrahydrofuran and the like. Note that the above mixtures are also recommended.

As a metal complex in this invention, what is illustrated below is mentioned, for example. [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate ( 2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N -(1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [ b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a , 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- ( 1,1-dimethylethyl) -1,1-dimethyl Ranameto (2 -) - κN] titanium (III) 2- (N, N- dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H- Cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5 , 6,6a-η) -3-Phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a -η) -3-phenyl-4 H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethyl Amino) benzyl)

[1-[(3a, 4,5,6,6a-η) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl)- 1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5-methyl-4H-cyclopenta [b] thien -6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η ) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyl Titanium, [1-[(3a, 4,5,6,6a-η) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5- Methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl -1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1 , 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl ) -1,1-Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6 , 6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2- ) -κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N -(1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η ) -2,5-Dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titaniu (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien -6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro- Cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5 , 6,6a-η) -1,4-Dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a -η) -1,4- Hydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethyl Amino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl)- 1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrole -4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η ) -1,4-Dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyl Titanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro- 1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II ) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl ] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1- Dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1 -Phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4 , 5,6,6a-η) -1,4-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] Pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4 , 5,6,6a-η) -1,4-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1 , 1-Dimethylsilanamate (2-)-κN] Titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -1,4 -Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5 -Dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1- [ (3a, 4,5,6,6a-η) -1,4-Dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl- 1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1, 1 -Dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a- η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2 -)-[kappa] N] Titanium (III) 2- (N, N-dimethylamino) benzyl and mixtures thereof, especially mixtures of positional isomers.

Those skilled in the art will recognize that any of the above-described specific examples or those obtained by substitution of different Group 3-10 metals are also within the scope of the present invention. Furthermore, it is recognized that all possible electron distributions in the molecule such as η ³ , η ⁴ or η ⁵ are also encompassed by the compound.

The complex of the present invention exhibits catalytic activity in combination with an activated cocatalyst as conventionally known in combination with a Group 4 metal olefin polymerization complex in the art or by an activation technique. Suitable activated cocatalysts for use in the present invention include, for example, polymeric or oligomeric alumoxanes, particularly methylalumoxane, triisobutylaluminum modified methylalumoxane or isobutylalumoxane, carbon 1-30 containing hydrocarbyl substituted group 13 Neutral Lewis acids such as compounds, especially tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds, and their halogenated (including perhalogenated) derivatives (number of carbons in each hydrocarbyl or halogenated hydrocarbyl group) 1-10), more specifically perfluorinated tri (allyl) boron compounds, more specifically tris (pentafluorophenyl) borane, non-polymeric and compatible non-coordinating ion-forming compounds (oxidation) Including the use of such compounds under conditions In particular, compatible non-coordinating anion ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts, or compatible non-coordinating anionic ferrocenium salts, bulk electrolysis (below And a combination of the above-mentioned activated cocatalysts and methods. Recommended ion-forming compounds include, for example, tris (carbon 1-20 containing hydrocarbyl) ammonium salts of tetrakis (fluoroallyl) borate, in particular tetrakis (pentafluorophenyl) borate. Said activation cocatalysts and activation techniques are taught for different metal complexes, for example in the patents listed below. European Patent EP-A-277003 specification, US Pat.No. 5,153,157 specification, US Pat.No. 5,048,802 specification, US Pat.No. 5,321,106 specification, US Pat.No. 5,721,185 specification, US Pat.No. 5,350,723 specification, U.S. Pat.No. 5425872, U.S. Pat.No. 5625087, U.S. Pat.No. 5883204, U.S. Pat.No. 5919983, U.S. Pat.No. 5783512, International Patent WO99 / 15534 No. 09/251664 (United States application on Feb. 17, 1999: corresponding international patent WO99 / 42467).

Particularly preferred activating cocatalysts are, for example, combinations of neutral Lewis acids, particularly trialkylaluminums containing 1 to 4 carbons in each alkyl group and trihalides containing 1 to 20 carbons in each hydrocarbyl group ( Hydrocarbyl) boron (especially tris (pentafluorophenyl) borane), such neutral Lewis acid mixtures and polymeric or oligomeric alumoxanes, and also one neutral Lewis acid (especially tris (pentafluoro) And a combination of phenyl) borane) and polymeric or oligomeric alumoxane. The recommended molar ratio of Group 4 metal complex to tris (pentafluorophenyl) borane to alumoxane is 1: 1: 1 to 1:10:30, more preferably 1: 1: 1.5 to 1: 5: 10. It is.

An ion forming compound useful and suitable as a cocatalyst in one embodiment of the present invention comprises a cation (a Bronsted acid having proton donating ability) and a compatible non-coordinating anion A ⁻ . As used herein, the term “noncoordinating” means that the anion or substance does not coordinate to a Group 4 metal containing a precursor complex and a catalytic derivative derived therefrom, or neutral Lewis It is used in the sense that it is only weakly coordinated to such a complex that sufficiently retains the substitution adaptability with a base. Specifically, the non-coordinating anion refers to an anion that does not convert an anionic substituent or a fragment thereof into such a cation that acts on the formation of a neutral complex when functioning as an anion that balances the charge in the cationic metal complex. Sure. A “compatible anion” refers to an anion that is not degraded to a neutral state when the initially formed complex decomposes and that does not participate in any subsequent polymerization or other use of the complex.

Recommended anions are those containing a single coordination complex comprising a charged metal or metalloid core that can balance the charge of the active catalytic species (metal cations) formed when the two components are combined. Further, such anions should be sufficiently substituted with olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis acids such as ethers and nitriles. Suitable metals are not limited to those shown below, and examples include aluminum, gallium, niobium, and tantalum. Suitable metalloids are not limited to those shown below, but examples include boron (boron), phosphorus and silicon. As a compound containing an anion containing a coordination complex having a single metal or metalloid atom, there are, of course, many known compounds. A compound containing one boron atom.

A preferred cocatalyst can be represented by the general formula (L * -H) _d ⁺ (A) ^{d −} . Where L * is a neutral Lewis base, (L * -H) ⁺ is a conjugated Bronsted acid of L *, A ^d− is a non-phase compatible anion having a d− charge, and d is 1 to 3 It is an integer. A ^d− is more preferably represented by the formula [M′Q ₄ ] ⁻ . Where M ′ is boron or aluminum in the +3 oxidation state, Q is independently present, hydride, dialkylamide, halide, hydrocarbyl, hydrocarbyl oxide, halo-substituted hydrocarbyl, halo-substituted Selected from hydrocarbyloxy and halo-substituted silylhydrocarbyl groups (including perhalogenated hydrocarbyl, perhalogenated hydrocarbyloxy and perhalogenated silylhydrocarbyl groups). Q has a maximum of 20 carbons except for halides. US Pat. No. 5,296,433 discloses examples of suitable hydrocarbyl oxide Q groups.

In a more recommended embodiment, d is 1. That is, the counter ion has a −1 valence charge and corresponds to A ⁻ . An activated cocatalyst containing boron, which is particularly useful for the production of the catalyst of the present invention, is represented by the general formula (L * -H) ⁺ (BQ ₄ ) ⁻ . Where L * is as previously defined, B is boron in oxidation state 3, Q is hydrocarbyl, hydrocarbyloxy, fluorohydrocarbyl, fluorohydrocarbyloxy, hydroxyfluorohydrocarbyl, dihydrocarbylaluminumoxyfluorohydrocarbyl or fluorosilylhydrocarbyl group And has a maximum of 20 non-hydrogen atoms in cases other than hydrocarbyl. Q is most preferably a fluoroallyl group, in particular a pentafluorophenyl group.

Recommended Lewis base salts are ammonium salts, more preferably trialkylammonium or dialkylallylammonium salts containing at least one or more carbon 12-40 containing alkyl groups. It has been found that the latter cocatalyst is preferably used in combination with not only the metal complex of the present invention but also other Group 4 metallocenes.

The boron compound used as the activating cocatalyst in the production of the improved catalyst of the present invention (similar to the conventionally known Group 4 metal catalyst) is not limited to the following, but examples include the following: Can be mentioned.

Trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec- Butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium-n-butyltris (pentafluorophenyl) borate, N, N-dimethylanily Ni-benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) boret N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetradecylammonium tetrakis (pentafluorophenyl) borate Dimethylhexadecyl ammonium tetrakis (pentafluorophenyl) borate, dimethyl octadecyl ammonium tetrakis (pentafluorophenyl) borate, methyl ditetradecyl ammonium tetrakis (pentafluorophenyl) borate, methyl dite Tradecyl ammonium (hydroxyphenyl) tris (pentafluorophenyl) borate, methyl ditetradecyl ammonium (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, methyl dihexadecyl ammonium tetrakis (pentafluorophenyl) borate, methyl dihexadecyl Ammonium (hydroxyphenyl) tris (pentafluorophenyl) borate, methyl dihexadecyl ammonium (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, methyl dioctadecyl ammonium tetrakis (pentafluorophenyl) borate, methyl dioctadecyl ammonium (hydroxyphenyl) ) Tris (pentafluorophenyl) borate, methyldioctadecylan Ni (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, methyldioctadecylammonium tetrakis (pentafluorophenyl) borate, phenyldioctadecylammonium tetrakis (pentafluorophenyl) borate, phenyldioctadecylammonium (hydroxyphenyl) tris (pentafluoro) Phenyl) borate, phenyldioctadecylammonium (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, (2,4,6-trimethylphenyl) dioctadecylammonium tetrakis (pentafluorophenyl) borate, (2,4,6-trimethyl) Phenyl) dioctadecylammonium (hydroxyphenyl) tris (pentafluorophenyl) borate, (2,4,6-trimethylphenyl) Enyl) dioctadecylammonium (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, (2,4,6-trifluorophenyl) dioctadecylammonium tetrakis (pentafluorophenyl) borate, (2,4,6-trifluorophenyl) ) Dioctadecyl ammonium (hydroxyphenyl) tris (pentafluorophenyl) borate, (2,4,6-trifluorophenyl) dioctadecyl ammonium (diethylaminoxyphenyl) tris (pentafluorophenyl) borate, (pentafluorophenyl) dioctadecyl Ammonium tetrakis (pentafluorophenyl) borate, (pentafluorophenyl) dioctadecylammonium (hydroxyphenyl) tris (pentafluorophenyl) borate, (pentaful Olophenyl) dioctadecylammonium (diethylaluminoxyphenyl) tris (pentafluorophenyl) borate, (p-trifluoromethylphenyl) dioctadecylammonium tetrakis (pentafluorophenyl) borate, (p-trifluoromethylphenyl) dioctadecylammonium ( Hydroxyphenyl) tris (pentafluorophenyl) borate, (p-trifluoromethylphenyl) dioctadecylammonium (diethylaluminoxyphenyl) tris (pentafluorophenyl) borate, p-nitrophenyldioctadecylammonium tetrakis (pentafluorophenyl) borate , P-nitrophenyl dioctadecyl ammonium (hydroxyphenyl) tris (pentafluorophenyl) volley , P- nitrophenyl dioctadecylammonium (diethyl aluminosilicate hydroxyphenyl) tris (pentafluorophenyl) borate, and tri including mixtures thereof - substituted ammonium salts.

Such as di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, methyl octadecyl ammonium tetrakis (pentafluorophenyl) borate, methyl octadodecyl ammonium tetrakis (pentafluorophenyl) borate, and dioctadecyl ammonium tetrakis (pentafluorophenyl) borate Dialkylammonium salt.

Such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate Tri-substituted phosphonium salt.

Di-substituted oxonium salts such as diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, and di (octadecyl) oxonium tetrakis (pentafluorophenyl) borate.

Di-substituted sulfonium salts such as di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate and methyloctadecylsulfonium tetrakis (pentafluorophenyl) borate.

Recommended trialkylammonium cations are methyl dioctadecyl ammonium and dimethyl octadecyl ammonium. The use of the Bronsted acid as an activating cocatalyst for use with an addition polymerization catalyst is known, such as US Pat. No. 5,046,802, US Pat. No. 5919983, US Pat. Others are disclosed. Recommended dialkylammonium cations are fluorophenyl dioctadecyl ammonium-, perfluorophenyl dioctadecyl ammonium-, and p-trifluoromethylphenyl di (octadecyl) ammonium cations. Certain cocatalysts, particularly cocatalysts having a hydroxyphenyl ligand in the borate anion, can be prepared with a Lewis acid, especially a trialkylaluminum compound, in the polymerization mixture or catalyst composition to produce an active catalyst composition. It may be added.

Other suitable ion-forming activation cocatalysts comprise a cationic oxidant and a non-phase compatible anion represented by the formula (Ox ^{e +} ) _d (A ^d− ) _e . In the formula, Ox ^{e +} is a cationic oxidant having a charge of e +, e is an integer of 1 to 3, and A ^d− and d are as defined above.

Examples of the cationic oxidizing agent include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag ⁺ or Pb ⁺² . Preferred embodiments of A ^d- include anions already defined for Bronsted acids containing activated cocatalysts, particularly tetrakis (pentafluorophenyl) borate. The use of the above salts as an activating cocatalyst for addition polymerization catalysts is already known in the art and disclosed in US Pat. No. 5,321,106.

Other suitable ion forming, activating cocatalyst compound is carbenium ion salt of the formula (c) ⁺ A ^- comprising a non-coordinating phase compatible anion represented by. In the formula, (c) ⁺ is a carbon 1-20 containing carbenium ion, and A ⁻ is as defined above. The recommended carbenium ion is the trityl cation, ie triphenylmethylium. The use of the above salts as an activating cocatalyst for an addition polymerization catalyst is already known in the art and disclosed in US Pat. No. 5,350,723.

Still other suitable ion-forming activation cocatalysts comprise a compound that is a silylium ion salt and a non-coordinating anion represented by the formula R ³ Si (X ′) _q ⁺ A ⁻ . Wherein R ³ is a carbon 1-10 containing hydrocarbyl and X ′, q and A ⁻ are as previously defined. Recommended silylium salt-activated cocatalysts include, for example, trimethylsilylium tetrakis (pentafluorophenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate and ether-substituted adducts thereof. The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is already known in the art and is disclosed, for example, in US Pat. No. 5625087.

Certain complexes of alcohols, mercaptans, silanols and oximes with tris (pentafluorophenyl) borane are also effective catalyst activators and can be used in the present invention. Such cocatalysts are disclosed in US Pat. No. 5,296,433.

Other suitable catalyst activators can be extended to anionic compounds of the formula (A ^{1 + a1} ) _b1 (Z ¹ J ¹ j ¹ ) ^-c1 _d1 . In the formula, A ¹ is a positively charged cation, Z ¹ is an anionic group having ¹ to 50, preferably 1 to 30 atoms (not counting hydrogen) and further having at least two Lewis base sites, J ¹ is An independently present Lewis acid, which is coordinated to at least one Lewis base site of Z ¹ and, optionally, at least two such J ¹ groups together It is possible to form a group having a Lewis acid functional group. j ¹ is an integer from 2 to 12, and a ¹ , b ¹ , c ¹ and d ¹ are integers from 1 to 3, respectively, when the product of a ¹ and b ¹ is equal to the product of c ¹ and d ¹ is there.

The cocatalyst (imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide or substituted benzimidazolide anion) is represented as follows.

In which A ¹⁺ is a monovalent cation as defined above, preferably an alkyl group containing 1 or 2 carbons 10-40 (especially methylbis (tetradecyl) ammonium- or methylbis (octadecyl) ammonium-cation). Containing trihydrocarbyl ammonium cations, each R ⁸ is independently present hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl or silyl group (mono-, di-) having up to 30 atoms (not counting hydrogen). -Or tri (hydrocarbyl) silyl), preferably an alkyl group containing 1-20 carbons, and J ¹ is tris (pentafluorophenyl) borane or tris (pentafluorophenyl) alumine.

Examples of these catalyst activators include, for example, bis (tris (pentafluorophenyl) borane) imidazolide, bis (tris (pentafluorophenyl) borane) -2-undecylimidazolide, bis (tris (pentafluorophenyl) ) Borane) -2-heptadecylimidazolide, bis (tris (pentafluorophenyl) borane) -4,5-bis (undecyl) imidazolide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) ) Imidazolide, bis (tris (pentafluorophenyl) borane) imidazolinide, bis (tris (pentafluorophenyl) borane) -2-undecylimidazolinide, bis (tris (pentafluorophenyl) borane) -2-heptadecylimidazo Linide, bis (tris (pentafluorophenyl) bora ) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluorophenyl) borane) -5,6-dimethyl Benzimidazolide, bis (tris (pentafluorophenyl) borane) -5,6-bis (undecyl) benzimidazolide, bis (tris (pentafluorophenyl) arman) imidazolide, bis (tris (pentafluorophenyl) arman)- 2-undecylimidazolide, bis (tris (pentafluorophenyl) arman) -2-heptadecylimidazolide, bis (tris (pentafluorophenyl) arman) -4,5-bis (undecyl) imidazolide, bis (tris ( Pentafluorophenyl) arman) -4,5-bis (heptadecyl) imidazo Bis (tris (pentafluorophenyl) arman) imidazolinide, bis (tris (pentafluorophenyl) arman) -2-undecylimidazolinide, bis (tris (pentafluorophenyl) arman) -2-heptadecylimidazolinini Bis (tris (pentafluorophenyl) arman) -4,5-bis (undecyl) imidazolinide, bis (tris (pentafluorophenyl) arman) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluoro) Phenyl) alman) -5,6-dimethylbenzimidazolide and trihydrocarbyl ammonium salt of bis (tris (pentafluorophenyl) arman) -5,6-bis (undecyl) benzimidazolide, especially methylbis (tetradecyl) Ammonium or methylbis (o (Tadecyl) ammonium salt and the like.

Yet another suitable activating cocatalyst is a cationic group 13 salt of the formula [M ″ Q ¹ ₂ L ′ _{1 ′} ] ⁺ (Ar ^f ₃ M′Q ² ) ⁻ . Where M ″ is aluminum, gallium or indium, M ′ is boron or aluminum, Q ¹ is a hydrocarbyl containing ¹ to 20 carbons or it may be substituted with at least one group, Hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino having 1 to 20 atoms (not counting hydrogen) present independently Hydrocarbyl sulfide group. Q ² may be an alkyl group or it may be substituted with at least one cycloalkyl or allyl group and has 1 to 30 carbons. L ′ is a monodentate (monodentate) or polydentate (polydentate) Lewis base, and preferably coordinates reversibly to a metal complex optionally substituted by an olefin monomer, but more preferably a monodentate Lewis base. 1 ′ is a number of 0 or more indicating the number of Lewis base parts L ′, Ar ^f is an anionic ligand group present independently, preferably a halide, a halohydrocarbyl containing 1-20 carbons, and Q ¹ selected from the group consisting of a ligand group, more preferably a fluorinated hydrocarbyl moiety having 1 to 30 carbon atoms, most preferably a fluorinated aromatic hydrocarbyl moiety having 6 to 30 carbon atoms, and more Most preferred is a perfluorinated aromatic hydrocarbyl moiety having 6 to 30 carbon atoms.

Examples of the Group 13 metal salt include aluminium tris (fluoroallyl) borate or gallicinium tris represented by the formula [M ″ Q ¹ ₂ L ′ _{1 ′} ] ⁺ (Ar ^f ₃ BQ ² ) ⁻ Fluoroallyl) borate. Where M '' is aluminum or gallium, Q ¹ is a hydrocarbyl containing ¹ to 20 carbons, preferably alkyl containing 1 to 8 carbons, Ar ^f is perfluoroallyl, preferably pentafluorophenyl, and Q ² is It is an alkyl containing 1 to 20 carbons, preferably an alkyl containing 1 to 8 carbons. Q ¹ and Q ² are both the same carbon 1-8 containing alkyl group, most preferably methyl, ethyl or octyl.

The activated cocatalysts may also be used in combination. A particularly recommended combination is a mixture of tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compounds and oligomers or polymeric alumoxane compounds containing 1 to 4 carbons in each hydrocarbyl group or ammonium borate.

The molar ratio of catalyst to cocatalyst used is preferably 1: 10,000 to 100: 1, more preferably 1: 5,000 to 10: 1, and most preferably 1: 1,000 to 1: 1. When used as an activating cocatalyst, alumoxane is used in large amounts, generally at least 100 times the metal complex on a molar basis. When used as an activating cocatalyst, tris (pentafluorophenyl) borane is used in a molar ratio to the metal complex of 0.5: 1 to 10: 1, more preferably 1: 1 to 6: 1, most preferably 1: 1 to 5: 1 is used. The remaining activated cocatalyst is generally used in approximately equimolar amounts with the metal complex.

The catalyst is used alone or in combination with other catalysts in polymerizing ethylenically unsaturated monomers having from 2 to 100,000 carbon atoms, whether supported by any suitable method. Recommended addition polymerizable monomers used in the present invention include, for example, olefins, diolefins and mixtures thereof. Recommended olefins include, for example, aliphatic or aromatic compounds containing vinylic unsaturation, but cyclic compounds containing ethylenic unsaturation are also used. Examples of the latter include cyclobutene, cyclopentene, norbornene, and norbornene derivatives substituted at the 5th and 6th positions with a hydrocarbyl group containing 1 to 20 carbons. Recommended diolefins include, for example, carbon 4-40 containing diolefin compounds including ethylidene norbornene, 1,4-hexadiene and norbornadiene. The catalyst and the polymerization process of the present invention are in particular ethylene / 1-butene, ethylene / 1-hexene, ethylene / styrene, ethylene / propylene, ethylene / 1-pentene, ethylene / 4-methyl-1-pentene and ethylene / It is suitable not only for the production of 1-octene copolymers but also for the production of ethylene, propylene and non-conjugated diene terpolymers (terpolymers) such as EPDM.

Most recommended monomers include, for example, carbon 2-20 containing α-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4- Examples include methyl-1-pentene, 1-octene, 1-decene, long-chain polymer α-olefin, and mixtures thereof. Examples of other recommended monomers include styrene, alkyl substituted styrene containing 1 to 4 carbon atoms, ethylidene norbornene, 1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene, and the like. Examples thereof include a mixture with ethylene. The long chain polymeric α-olefin is the vinyl terminated polymeric remainder formed in place during the continuous solution polymerization reaction. Under appropriate polymerization conditions, these long-chain polymer units are easily polymerized together with ethylene and other short-chain olefin monomers to form a polymer in order to introduce a small amount of long-chain branching into the final polymer. Things are obtained.

Examples of the recommended monomer include a combination of ethylene and at least one monomer selected from the following. Monomers used in combination with ethylene include monovinyl aromatic monomers, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidenenorbornene, carbon 3-10 aliphatic α-olefins (particularly propylene, isobutylene, 1- Butene), 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene) and carbon 4-40 containing dienes. The most recommended monomers are mixtures of ethylene and styrene, mixtures of ethylene, propylene and styrene, mixtures of ethylene, styrene and non-conjugated dienes (especially ethylidene norbornene or 1,4-hexadiene), and ethylene, propylene and Non-conjugated dienes (especially ethylidene norbornene or 1,4-hexadiene).

In general, the polymerization is carried out under conditions known in the art for Ziegler-Natta or Kaminsky-Sin type polymerization reactions, i.e. at temperatures of 0-250 ° C, preferably 30-200 ° C and pressures of 1-10,000 atmospheres. You may go on. Regarding the polymerization type, suspension, solution, slurry, gas phase, solid powder polymerization, and other conditions can be used as desired. Supports such as silica, alumina or polymers (eg, poly (tetrafluoroethylene) or polyolefins) can also be used, but such a support is preferably used when a catalyst is used in the gas phase polymerization. The preferred amount of the support, the catalyst in a weight ratio of (metal basis) and the support 1:10 ^6-1: 10 ^3, more preferably 1: 10 ^6-1: 10 ^4.

In most polymerization reactions, the molar ratio of the catalyst to be used and the polymerizable compound is 10 ⁻¹² : 1 to 10 ⁻¹ : 1 and more preferably 10 ⁻⁹ : 1 to 10 ⁻⁵ : 1.

The solvent used in the solution polymerization is preferably one that is substantially inert under the polymerization conditions. Examples of such solvents include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof, cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and the like. And perfluorinated hydrocarbons such as alkanes containing 4-10 perfluorinated carbons, and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, and ethylbenzene. . Liquid olefins that function as monomers or comonomers are also examples of suitable solvents.

The catalyst is used with at least one other homogeneous or heterogeneous polymerization catalyst in the same reactor or in another reactor connected in series or in parallel to produce a polymer blend having the desired properties. It can also be used in combination. An example of such a method is disclosed in the international patent application WO 94/00500.

The catalyst of the present invention is particularly advantageous for the production of ethylene homopolymers and ethylene / α-olefin copolymers having high levels of long chain branching. The use of the catalyst of the present invention in continuous polymerization, particularly continuous solution polymerization, results in an increase in reactor temperature that is convenient for the formation of vinyl-terminated polymer chains in the growing polymer resulting in the formation of long chain branches. Enable. To produce an ethylene / α-olefin copolymer having moldability similar to low density polyethylene produced by a high pressure free radical process, it is economically advantageous to use the catalyst composition of the present invention.

The catalyst composition of the present invention improves moldability by polymerizing ethylene alone or ethylene / α-olefin mixtures with low levels of H-branched derived dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene. It is advantageously used to produce a modified olefin polymer. The unique combination of elevated reactor temperature, high molecular weight (low melt index) at high reactor temperatures and high comonomer reactivity is advantageous for the production of polymers with excellent physical properties and moldability. is there. Such polymers preferably comprise ethylene, a C 3-20 containing α-olefin and a comonomer that provides H branching. Such polymers are preferably prepared by a solution process, most preferably a continuous solution process.

The catalyst composition of this invention may be manufactured as a homogeneous catalyst by adding an essential component to the solvent or diluent at the time of superposing | polymerizing. Such a catalyst composition is also produced and used as a heterogeneous catalyst by adsorbing, depositing, or chemically attaching essential components to an inorganic or organic particulate solid. Examples of such solids include silica, silica gel, alumina, clay, expanded clay (aerogel), aluminosilicate, trialkylaluminum compound, and organic or inorganic polymeric substances (particularly polyolefins). In one recommended embodiment, inorganic compounds (preferably tri (carbons containing 1-4) alkyl) aluminum compounds) are activated cocatalysts, in particular (4-hydroxy-3,5-di-t-butylphenyl) tris. A heterogeneous catalyst is prepared by reacting with an ammonium salt of hydroxyallyl (trispentafluorophenyl) borate, such as (pentafluorophenyl) borate or ammonium salt of (4-hydroxyphenyl) tris (pentafluorophenyl) borate. The activated cocatalyst is deposited on the support by coprecipitation, absorption, spraying or similar techniques, and by removing the solvent or diluent. The metal complex is added to the support by adsorption, precipitation, or chemical deposition continuously, simultaneously or prior to the addition of the activated cocatalyst.

The catalyst composition produced in a heterogeneous or supported form is used in slurry or gas phase polymerization. As one practical limitation, slurry polymerization is conducted in a liquid diluent in which the polymer product is substantially insoluble. A preferred diluent used in such slurry polymerization is at least one hydrocarbon having less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane are also used as all or part of the diluent. Similarly, α-olefin monomers or mixtures of different α-olefin monomers may be used as all or part of the diluent. Most preferably, at least the main part of the diluent contains an α-olefin to be polymerized. If desired, a dispersant, particularly an elastomer, may be dissolved in the diluent using techniques known in the art.

Individual components, including recovered catalyst components, must be protected from oxygen and moisture at any time. Therefore, both the catalyst component and the catalyst must be produced and recovered in an oxygen and moisture free atmosphere. Therefore, it is preferred that all reactions are dry and in the presence of an inert gas such as nitrogen.

The polymerization may be performed by either a batch method or a continuous method. A continuous process in which catalyst, ethylene, comonomer and optionally solvent are continuously fed to the reaction zone and the polymer product is continuously recovered is preferred.

Although the present invention is not particularly limited, one method for carrying out such a polymerization method is, for example, as follows. Into a tank reactor equipped with a stirring function, the monomer to be polymerized is continuously introduced together with a solvent and optionally a chain transfer agent. The reactor comprises a liquid phase that is substantially filled with monomer but with solvent or other diluent and dissolved polymer. If desired, small amounts of H-branched derived dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene may be added. Catalyst and cocatalyst are continuously introduced into the liquid phase of the reactor. The reactor temperature is controlled by adjusting the solvent / monomer ratio, catalyst addition rate, or cooling or heating the coil, jacket, or both. The polymerization rate is controlled by the rate of catalyst addition. The amount of ethylene in the polymer product is determined by the ratio of ethylene to comonomer introduced into the reactor, which ratio is controlled by scanning the feed rate of each component to the reactor. The molecular weight of the polymer product can optionally be controlled by other chain influencing factors such as temperature, monomer concentration or other chain transfer agents such as the hydrogen stream introduced into the reactor (this is the case) Control (known in the art). The effluent from the reactor is contacted with a catalytic activator such as water. By optionally heating the polymer solution and further desorbing the polymer product with residual solvent or diluent, etc. under reduced pressure, if necessary, in an apparatus such as a gaseous desorption extruder. Separated from the gaseous monomer and recovered. In continuous processes, the residence time of catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, preferably from 10 minutes to 6 hours.

The process of the present invention is particularly suitable when producing ethylene homopolymers and ethylene / α-olefin copolymers. Such polymers generally have a density of 0.85 to 0.96 g / ml. Typically, the molar ratio of α-olefin comonomer to ethylene in the polymerization is varied to adjust the density of the final polymer. When producing a polymer having a density of 0.91 to 0.93 g / ml, the comonomer to monomer ratio (ratio) is less than 0.2, preferably less than 0.05, more preferably less than 0.02, and even less than 0.01. May be. In the above polymerization method, it is known to use hydrogen in order to effectively control the molecular weight of the finally obtained polymer. Typically, the molar ratio of hydrogen to monomer is less than 0.5, preferably less than 0.2, more preferably less than 0.05, even less than 0.02, and may be less than 0.01.

The present invention may be practiced in the absence of components not specifically disclosed herein. The following examples are disclosed to illustrate the present invention and are not limited to such disclosure. Unless otherwise indicated, “parts” and “%” are on a weight basis. The term “one day and night” (if used) means a length of time of about 16-18 hours, and “room temperature” means a temperature of about 20-25 ° C., “mixed alkanes” "Refers to hydrogenated propylene oligomers, such as isoalkanes containing 6-12 carbons that are commercially available under the trade name IsoparE from Exxon Chemical Company. If a compound represented by a structural formula is erroneously named, it shall be interpreted according to the structural formula. All solvents were purified according to the procedure disclosed in Pangbornet al., Organometallics, 15, 1518-1520 (1996). ¹ H and ¹³ C NMR shifts are related to internal solvent resonances and are reported on a TMS basis.

Example 1 [1- (3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- ( 1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium

1-Phenylpyrrole-2- carbaldehyde 16.2 ml of dimethylformamide was charged into a nitrogen-filled 1 liter flask equipped with a mechanical stirrer and then 19 ml of POCl ₃ was slowly added. The mixture was stirred for 10 minutes and cooled to 0 ° C. 25 g of 1-phenylpyrrole solution dissolved in 25 ml of dichloromethane was added to the mixture. The mixture was returned to room temperature (10 minutes) and heated at 50 ° C. for 1 hour. Subsequently, after returning the contents to room temperature, the flask was opened to the atmosphere, 220 g of crushed ice was added, and 250 ml of 20% NaOH aqueous solution was further added. The mixture was immediately warmed to 85 ° C. and stirred for 10 minutes before the flask was cooled to room temperature using an ice bath. The reaction mixture was extracted with dichloromethane (3x100ml) and the organic fraction was washed with water (2x200ml). The organic fraction was then dried over sodium sulfate and volatiles were removed using a rotary evaporator, resulting in an orange oil (24.4 g, 82%). The product contained 10% 1-phenylpyrrole-3-carbaldehyde isomer (isomer) and was used without further purification.
¹ HNMR (CDCl3): 6.35 (dd, 1H), 7.0 (t, 1H), 7.1 (dd, 1H), 7.3 (m, 2H), 7.4 (m, 3H), 9.5 (s, 1H);
¹³ C { ¹ H} NMR (CDCl 3): 178.4, 138.2, 132.0, 130.6, 128.6, 127.7, 125.5, 121.5, 110.4

Ethyl- (2Z) -2-methyl-3- [1-phenylpyrrol-2-yl] prop-2-noate
To a 250 ml flask charged with a sodium hydride (4.8 g, 200 mmol) mixture of THF (tetrahydrofuran: 10 ml), THF (20 ml) in triethyl-2-phosphonopropionate (32 ml, 150 mmol) was added at 0 ° C. Slowly added. The slurry was returned to room temperature and stirred for 1 hour. At that time, the temperature dropped to -10 ° C. A solution of THF (50 ml) in 1-phenylpyrrole-2-carbaldehyde (24.4 g, 142 mmol) was then added over a period of 10 minutes. A precipitate slowly formed from the mixture. The precipitate was partially crushed with a spatula and the reaction mixture was slowly brought to room temperature over 30 minutes. A saturated aqueous solution of NH ₄ Cl (ammonium chloride: 20 ml) was carefully added. The product was extracted with ether (2 × 100 ml) and the ether extract was washed with brine (“brine”) and dried over sodium sulfate. The solvent was removed with a rotary evaporator and the crude product was washed with hexane to give an orange oil. The oil precipitated over several days, made into a powder using a small amount of hexane, filtered, and the solid was dried under reduced pressure to yield 25.8 g (71%) of a light brown crystalline material.
¹ HNMR (CDCl3): 7.4 (m, 4H), 7.3 (m, 2H), 7.0 (dd, 1H), 6.7 (dd, 1H), 6.4 (t, 1H), 4.1 (q, 2H), 2.2 ( d, 3H), 1.2 (t, 3H); ¹³ C { ¹ H} NMR (CDCl3): 168.8, 139.2, 129.6, 129.2, 127.6, 127.5, 126.3, 125.0, 122.9, 114.3, 110.2, 60.4, 14.3, 14.2

Ethyl [2-methyl-3- (1-phenylpyrrol-2-yl)] propanoate A 300 ml capacity Pearl reactor was charged with ethyl- (2Z) -2-methyl-3- [1-phenylpyrrole- 2-Iyl] prop-2-noate 12.0 g (47 mmol), 10% palladium on carbon (0.6 g) and 150 ml of methylene chloride were charged. The reactor was maintained at a pressure of 80 psig (660 kPa) with hydrogen and after 1 hour the pressure was reduced to 40 psig (380 kPa) and then charged again with hydrogen to increase the pressure to 100 psig (790 kPa) and the mixture was Stir 1 day and night. The next day, the residual hydrogen pressure was evacuated and the reactor was filled with nitrogen. The catalyst was filtered, and the filtrate was dried with a rotary evaporator to obtain 12.5 g (103%) of a liquid product.
¹ HNMR (CDCl3): 7.3-7.4 (m, 5H), 6.7 (m, 1H), 6.2 (m, 1H), 6.0 (m, 1H), 4.0 (q, 2H), 2.9 (m, 1H), 2.5 (m, 2H), 1.2 (t, 3H), 1.0 (d, 3H); ¹³ C { ¹ H} NMR (CDCl3): 175.8, 140.1, 130.7, 129.0, 127.1, 126.2, 121.8, 111.7, 107.9, 60.1, 39.4, 30.4, 17.0, 14.0

2-methyl-3- [1-phenylpyrrol-2-yl] propionic acid 12.5 g of ethyl [2-methyl-3- (1-phenylpyrrol-2-yl)] propanoate in a 500 ml flask (48.6 mmol) was added, then 250 ml of Claisen alkali (350 g KOH + 250 ml water; cooled and diluted to 1 liter with methanol) was added. The mixture was heated to 90 ° C. for 1 hour. The yellow solution was poured out on crushed ice and then acidity was adjusted to PH 1-2 by adding 6 molar hydrochloric acid. The free acid that precipitated was extracted with ether (3 × 300 ml), the ether washed with brine (“brine”) and dried over anhydrous sodium sulfate. Volatiles were removed on a rotary evaporator to give 9.5 g (85%) of yellow liquid product.
¹ HNMR (CDCl3): 9.6 (br, 1H), 7.3-7.4 (m, 5H), 6.7 (m, 1H), 6.2 (m, 1H), 6.1 (m, 1H), 3.5 (q, 2H), 3.0 (m, 1H), 2.6 (m, 2H), 1.2 (t, 3H), 1.1 (d, 3H); ¹³ C { ¹ H} NMR (CDCl3): 182.2, 140.0, 130.5, 129.1, 127.3, 126.3 , 122.2, 108.1, 108.0, 65.8, 39.5, 30.0, 16.8, 15.1

5,6-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4 (1H) -one 41 ° C. until completely dissolved 41 g phosphorus pentoxide (P2O5) in 250 g polyphosphoric acid To prepare super polyphosphoric acid (SPPA). The SPPA was cooled to 100 ° C. and then a solution of 9.5 g (41.4 mmol) of 2-methyl-3- [1-phenylpyrrol-2-yl] propionic acid in 20 ml of 1,2-dichloroethane was added dropwise. The mixture was stirred for 5 hours, then cooled to 60 ° C. and slowly poured into water. After thoroughly pulverizing the lumped reaction mixture, the product was extracted with dichloromethane, and the organic phase was washed with sodium bicarbonate and further dried over sodium sulfate. Volatiles were removed on a rotary evaporator to give a tan solid. Yield: 8.5 g (97%).
¹ HNMR (CDCl3): 1.34 (d, 3H), 2.65 (dd, 1H), 3.0 (pd, 1H), 3.3 (dd, 1H), 6.5 (d, 1H), 7.1 (d, 1H), 7.4 ( m, 3H), 7.5 (m, 2H); ¹³ C { ¹ H} NMR (CDCl3): 17.0, 30.7, 47.4, 104.0, 121.9, 127.0, 127.8, 129.7, 138.6, 156.4, 199.5

5,6-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrole-4 (1H) -one tosylhydrazone
5,6-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4 (1H) -one (8.5 g, 40.2 mmol), para-toluenesulfonic acid hydrazide (7.7 g, 41 mmol) and para-toluene A mixture containing sulfonic acid monohydrate (1 g, 5 mmol) was stirred in 70 ml ethanol at 70 ° C. overnight. The solution was cooled in the freezer for several hours, and the precipitate was collected, washed with ether and dried under reduced pressure to give a tan solid (7.7 g, 50%, melting point 175-6 ° C.).
¹ HNMR (CDCl3): 7.9 (d, 2H), 7.45 (m, 2H), 7.3 (m, 6H), 7.05 (d, 1H), 6.56 (d, 1H), 3.4 (pd, 1H), 3.2 ( dd, 1H), 2.55 (dd, 1H), 2.4 (s, 3H), 1.25 (d, 3H); ¹³ C { ¹ H} NMR (CDCl3): 19.6, 21.5, 32.3, 42.7, 105.5, 121.3, 121.7 , 126.3, 126.9,128.1, 129.2, 129.7, 135.4, 138.8, 143.5, 147.1, 162.3

1,6-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrole
5,6-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4 (1H) -one Hydrazone (7.55 g, 19.9 mmol) in 80 ml THF (tetrahydrofuran) mixture was mixed with n-butyllithium (1.6 M, hexane 2.1 equivalents, 41.8 mmol) 26 ml was added at -78 ° C over about 5 minutes. The dark brown mixture was slowly warmed to room temperature and stirred for 1 day. A saturated solution of ammonium chloride (10 ml) was added slowly and volatiles were removed on a rotary evaporator. Water (100 ml) was added to the solid residue and the mixture was extracted with ether (2 × 100 ml). The ether layer was collected and dried over sodium sulfate, and then the volatile components were removed with a rotary evaporator to obtain 4.7 g of a tan oil. To obtain the tan oil, 80 ml of hexane was added and the mixture was stirred for 30 minutes. This operation was repeated once more. The extracts obtained by filtration were collected and dried under reduced pressure to give an orange-yellow oil (2.4 g, 62%). NMR analysis confirmed the presence of two isomers.
¹ HNMR (CDCl3): 7.5 (m, 4H), 7.3 (m, 1H), 7.1 (d, 1H), 6.95 * (d, 1H), 6.55 * (br s, 1H), 6.4 (br s, 1H ), 6.35 * (d, 1H), 6.25 (d, 1H), 3.3 (br s, 1H), 3.1 * (br s, 1H), 2.21 * (s, 3H), 2.15 (s, 3H);
Peaks marked with “*” are attributed to isomers (at least 40% amount) in the final product.

1- (1,4-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl) -N-1,1-dimethylethyl-1,1-dimethylsilanamine
To a 50 ml hexane mixture of 1,6-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrole (2.41 g, 12.3 mmol) was added 7.9 ml butyllithium (1.6 M, hexane; 1.02 eq). The mixture was stirred overnight and filtered, and the resulting solid was washed with hexane and dried to give 2.3 g (92%) of solid, redissolved in 60 ml of THF. Then ₂₀ ml THF of Me ₂ SiCl (NH ^t Bu) (1.94 g, 1.03 eq, 11.7 mmol) was added and the solution was stirred overnight. Volatiles were removed and the residue was extracted with hexane and filtered. The filtrate was dried under reduced pressure to give 3.75 g (94%) of a dark orange oil.
¹ HNMR (C ₆ D ₆ ): 7.3 (m, 2H), 7.05 (m, 1H), 6.9 (m, 1H), 6.5 (m, 1H), 6.4 (d, 1H), 3.1 (s, 1H) , 2.2 (s, 3H), 1.1 (s, 9H), 0.5 (br s, 1H), 0.2 (s, 3H), -0.1 (s, 3H)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl-N- (1,1-dimethyl Ethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium
In a 100 ml container N- (1,1-dimethylethyl) -1- (1-phenyl-5-methyl-4H-cyclopenta [b] aza-4-yl) -1,1-dimethylsilanamine 0.50 g (0.41 mmol) was added, and 60 ml of hexane and 2.0 ml of butyllithium (1.6 M, hexane) were added. The mixture was stirred for 1 day. As a result, a small amount of solid precipitated. After removing the volatiles under reduced pressure, the residue was redissolved in 20 ml of THF. Thereafter, 0.57 g (0.41 mmol) of TiCl ₃ 3THF was added. After the mixture was stirred for 30 minutes, PbCl ₂ (300 mg, 1.3 electron equivalents) and then CH ₂ Cl ₂ (10 ml) were added respectively. After 1 hour, volatiles were removed under reduced pressure. The residue was then dissolved with hexane (60 ml) and filtered. A hexane-insoluble dark brown substance was extracted with benzene and filtered. The filtrate was then dried under reduced pressure. Yield: 0.37 g (54%).
¹ HNMR (C ₆ D ₆ ): 7.2 (d, 2H), 7.03 (t, 2H), 7.0 (d, 1H), 6.9 (t, 1H), 6.43 (s, 1H), 6.15 (d, 1H) , 2.2 (s, 3H), 1.4 (s, 9H), 0.6 (s, 3H), 0.5 (s, 3H); ¹³ C { ¹ H} NMR (C ₆ D ₆ ): 143.2, 135.2, 129.9, 126.0 , 121.0,107.3, 105.7, 61.5, 32.6, 20.0, 3.8, 3.4

Example 2 [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl-N- ( 1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium
[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl-N- (1 , 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium (obtained in Example 1) 0.37 g (0.84 mmol), ether 30 ml and THF 40 ml were added. Then MeMgI (3M, ether, 1.8 mmol) was added. The mixture was stirred for 1 hour, and volatile components were removed under reduced pressure. The residue was extracted with hexane, filtered, and dried under reduced pressure to obtain a solid (0.33 g). The solid was redissolved once more with hexane, filtered, and the filtrate was concentrated to about 5 ml. The solution was left in a freezer at -30 ° C for one day. The supernatant was separated to obtain crystals. Yield: 0.19 g (yellow crystals).
¹ HNMR (C ₆ D ₆ ): 0.1 (s, 3H), 0.50 (s, 3H), 0.52 (s, 3H), 1.8 (s, 9H), 2.0 (s, 3H), 6.1 (d, 2H) , 6.6 (s, 1H), 6.9 (t, 2H), 7.1 (m), 7.2 (d); ¹³ C { ¹ H} NMR (C ₆ D ₆ ): 4.2, 4.8, 18.6, 34.5, 49.5, 55.7 , 57.5,83.8, 103.7, 105.8, 119.4, 124.7, 129.9, 130.4, 131.6, 137.7, 140.5

Example 3 [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thio-6-yl-N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] bis (N, N-dimethylaminotitanium)

3-Bromo-2-methyl-thiophene
A 500 ml flask was charged with diisopropylamine (12 ml, 85 mmol) and 150 ml ether THF, and an addition funnel and septum were attached to the system and cooled to 0 ° C. with nitrogen flow. Next, 53.5 ml of n-butyllithium (85 mmol, 1.6 M, hexane) was added to this system over 20 minutes. After all reagents were added, the reaction was stirred for an additional 15 minutes and the solution was cooled to -78 ° C. To this solution, 100 ml of a THF solution containing 3-bromo-thiophene (8 ml, 85 mmol) was added over 30 minutes. After completion of the addition, the solution was returned to 0 ° C. and stirred for 15 minutes. The solution was cooled again to −78 ° C. and iodomethane (5.4 ml, 85 mmol) in THF (50 ml) was added. The solution was returned to room temperature and stirred for 1.5 hours. The solution was cooled to 0 ° C. and the system was quenched with 100 ml of 1 molar hydrochloric acid (aqueous solution). The aqueous layer was separated and washed with 100 ml of ether, and the ether layer was separated. The organic extracts were collected, dried over magnesium sulfate, filtered, and then the volatiles were removed on a rotary evaporator to give 13.7 g (90%) of an oil.
¹ HNMR (CDCl ₃ ): 7.08 (d, 1H), 6.90 (d, 1H), 2.44 (s, 3H); ¹³ C { ¹ H} NMR (CDCl ₃ ): 134.35, 130.15, 122.99, 109.65, 68.22, 31.88,25.90, 14.83

2-methyl-3-phenyl-thiophene
A 500 ml flask was charged with 3-bromo-2-methyl-thiophene (13.7 g, 77 mmol), NiCl ₂ (0.21 g, 0.40 mmol) and 250 ml ether. The addition funnel was charged with 26 ml of phenylmagnesium bromide (77 mmol, 3.0 M, ether) and the Grignard reagent was slowly added over 1 hour with cooling in an ice bath (used to cool the reaction during the addition). After all the Grignard reagent was added, the reaction system was stirred at room temperature for 3 hours, cooled to 0 ° C., and the system was quenched with 100 ml of 1 molar hydrochloric acid (aqueous solution). The organic layer was separated and the aqueous solution was extracted twice with 75 ml of diethyl ether. The organic extracts were collected, dried over magnesium sulfate and filtered, and then the volatiles were removed under reduced pressure to give 13.3 g (99%) of an orange oil.
¹ HNMR (CDCl ₃ ): 7.7-7.4 (m, 5H), 7.2 (m, 2H), 2.66 (s, 3H); ¹³ C { ¹ H} NMR (CDCl ₃ ): 139.06, 137.19, 134.50, 129.62, 129.08, 128.80,127.57, 127.07, 121.94, 14.53

5,6-Dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thiophen-4-one
A 500 ml three-necked flask was charged with pentoxide phosphate (8 g, 57 mmol) and polyphosphoric acid (45 g, 475 mmol). The system was equipped with a stirrer and was further equipped with an addition funnel, condenser and separation funnel and purged with nitrogen. The system was heated to 150 ° C. until the pentoxide phosphate was almost dissolved in the viscous mixture (about 1.5 hours). After almost all of the solid had dissolved, the system was cooled to 70 ° C. and 350 ml of a dichloromethane solution containing 2-methyl-3-phenyl-thiophene (8.3 g, 47.6 mmol) and methacrylic acid (7 g, 83 mmol) was added for 3 hours. It was added over the above. After further stirring for 2 hours, methacrylic acid (4 g) was added, and after 2 hours, the same amount of methacrylic acid (4 g, 46 mmol) was added. After stirring at 70 ° C. for 14 hours, the mixture was cooled to 0 ° C. and 100 ml of ice water was added. After stirring for 1 hour, the organic layer was separated and the aqueous phase was extracted twice with 75 ml of dichloromethane. The organic extracts were collected, concentrated and washed 3 times with 1 molar sodium hydroxide solution. The organic extract was then dried over magnesium sulfate and filtered, and then the volatile components were removed with a rotary evaporator to obtain 10.3 g (89%) of an oily product.
¹ HNMR (CD ₂ Cl ₂ ): 7.5-7.3 (m, 5H), 3.2 (d, 1H), 2.85 (d, 1H), 2.6-2.5 (m, 4H), 1.35-1.25 (d, 3H)

5,6-Dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thiophen-4-ol
A 500 ml flask was charged with 5,6-dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thiophen-4-one (9.9 g, 41 mmol) with 200 ml THF. The system was purged with nitrogen, cooled to 0 ° C., and 20 ml of a 1 molar solution of lithium aluminum hydride dissolved in ether (20.4 mmol) was added over 20 minutes. After completion of the addition, the reaction system was returned to room temperature and further stirred for 1.5 hours. The mixture was quenched with water (200 ml) and ether (150 ml) was added. The mixture was filtered to remove solids and the organic layer was separated. The aqueous layer was washed twice with ether (100 ml) and the extracts were collected and dried over magnesium sulfate. After the mixture was filtered, volatile components were removed with a rotary evaporator to obtain 10.3 g (104%) of an oily product.
¹ HNMR (CD ₂ Cl ₂ ): 7.8-7.2 (m, 5H), 4.95 (d, 0.4H), 4.82 (d, 0.6H), 3.1-2.6 (m, 4H), 2.6-2.2 (m, 3H ), 1.2-1.35 (m, 3H); ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): 148.40, 146.66, 140.6, 139.70, 139.30, 136.20, 134.05, 129.08, 128.56, 126.91, 80.70, 74.24, 48.88 , 43.77, 35.59, 35.37, 19.2, 15.13, 14.54

2,5-Dimethyl-3-phenyl-6H-cyclopenta [b] thiophene
In a 250 ml flask, 5,6-dihydro-2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thiophen-4-ol (9.1 g, 37 mmol) and para-toluenesulfonic acid (175 mg, 0.9 mmol) Charged with benzene (50 ml). The mixture was blown with nitrogen and heated to 45 ° C. for 15 minutes. The reaction was then cooled and quenched by the addition of 150 ml of a saturated water / sodium bicarbonate mixture cooled with ice. The organic layer was separated and the extract was dried over magnesium sulfate and filtered. Volatiles were removed under reduced pressure. The obtained compound was dissolved in hexane and purified by column chromatography to obtain the desired substance (4.2 g, 50%).
¹ HNMR (CD ₂ Cl ₂ ): 7.55-7.25 (m, 5H), 6.44 / 6.35 (2s, 1H), 3.14 (s, 2H), 2.5 (m, 3H), 2.15 (s, 3H); ¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): 145.72,145.65, 140.72, 136.76, 133.42, 129.22, 128.85, 126.92, 126.76, 122.08, 121.79,40.61, 16.88, 14.84, 14.18

2,5-Dimethyl-3-phenyl-6H-cyclopenta [b] thiophene (-1) lithium
A 125 ml container was charged with 2,5-dimethyl-3-phenyl-6H-cyclopenta [b] thiophene (3.29 g, 14.5 mmol) and hexane (75 ml). To this mixture was added 9.7 ml of a hexane solution of n-butyllithium (15.3 mmol, 1.6 M) over 5 minutes. The mixture was stirred at room temperature for several days and the resulting precipitate was filtered and washed twice with hexane (25 ml). The obtained solid was dried under reduced pressure for 2 hours to obtain a solid (3.1 g, 92%).

N- (1,1-dimethylethyl) -1- (2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-4-yl) -1,1-dimethylsilanamine
A 125 ml flask was charged with 2,5-dimethyl-3-phenyl-cyclopenta [b] thiophene (-1) lithium (1.12 g, 4.8 mmol) and to this was added THF (25 ml). To this solution was added 5 ml of a THF solution containing N- (t-butyl) -1,1-dimethyl-1- (chloromethyl) silanamine (0.95 g, 5.8 mmol). The mixture was stirred at room temperature for 3 hours and volatiles were removed under reduced pressure. The residue was extracted in hexane (40 ml) and filtered. Volatiles were removed under reduced pressure to give a yellow oil (1.62 g, 94%).
¹ HNMR (C ₆ D ₆ ): 7.47 (d, 2H), 7.26-7.1 (m, 3H), 6.52 (s, 1H), 3.29 (s, 1H), 2.37 (s, 3H), 2.09 (s, 3H), 1.10 (s, 9H), 0.09 (s, 3H), 0.04 (s, 3H); ¹³ C { ¹ H} NMR (C ₆ D ₆ ): 149.00, 146.59, 137.67, 137.23, 134.87, 129.55, 128.55, 126.54, 122.48, 50.86, 33.69, 18.04, 14.69, -0.61, -1.56

[1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl-N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] bis (N, N-dimethylaminotitanium)
N- (1,1-dimethylethyl) -1- (2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-4-yl) -1,1-dimethylsilanamine (1.51 g), Ti (NMe ₂ ) ₄ (990 mg) and octane (40 ml) were charged. The mixture was heated to reflux for 11 hours (a time during which almost all of the starting material could be converted to a crude diamide complex).
¹ HNMR (C ₆ D ₆ ): 7.40 (d, 2H), 7.27 (t, 2H), 7.10 (m, 1H), 2.97 (s, 6H, NMe ₂ ), 2.27 (s, 6H, NMe ₂ ), 5.93 (s, 1H), 2.12 (s, 3H), 2.08 (s, 3H), 1.30 (s, 9H), 0.77 (s, 3H), 0.58 (s, 3H)

Example 4 [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl-N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium)

The reaction mixture of Example 3 was diluted with toluene (20 ml) and chlorotrimethylsilane (15 ml) was added. After 6 hours, the volatiles were removed under reduced pressure, the residue was extracted into toluene, filtered and the volatiles were removed under reduced pressure. Hexane (10 ml) was added to the residue, and after stirring for 10 minutes, the suspension was concentrated to about 6 ml and cooled at −30 ° C. overnight. The mother liquor was decanted, the solid was washed twice with chilled hexane (5 ml) and the solid (primary yield: 220 mg) was dried under reduced pressure. The mother liquor of hexane was further concentrated to about 3 ml and cooled to −30 ° C. to obtain a secondary yield (680 mg). The hexane mother liquor was further concentrated and dried, the residue was triturated with hexane (3 ml), and the suspension was cooled to −30 ° C. to obtain a third yield (140 mg). The NMR spectra of these three crops were all equivalent. Total yield: 1.04g (51%)
¹ HNMR (C ₆ D ₆ ): 7.49 (d, 2H), 7.24-7.15 (m, 3H), 6.59 (s, 1H), 2.31 (s, 3H), 2.07 (s, 3H), 1.39 (s, 9H), 0.63 (s, 3H), 0.40 (s, 3H); ¹³ C { ¹ H} NMR (C ₆ D ₆ ): 147.06, 146.68, 144.97, 139.66, 134.51, 130.45, 129.89, 129.14, 128.80, 117.65 , 117.36, 62.01, 32.33, 19.79, 15.11,3.40, 3.18

Example 5 [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl-N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium
[1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl-N- (1,1 -Dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] bis (N, N-dichlorotitanium (0.14 g, 0.30 mmol) was charged to which ether (20 ml) was added and the solution The solution was cooled to −30 ° C. To this solution was further added 0.3 ml (0.9 mmol, 3.0 M) methylmagnesium bromide, after 40 minutes the volatiles were removed and the residual material was extracted into hexane (20 ml). After stirring for a minute, the suspension was filtered, the filtrate was concentrated and dried, the solid was extracted again into hexane (10 ml), filtered, and the filtrate was concentrated and dried to give 118 mg (0.3 mmol) of a yellow solid. 92%).
¹ HNMR (C ₆ D ₆ ): 7.47 (d, 2H), 7.25 (t, 2H), 7.13 (m, 1H), 6.72 (s, 1H), 2.19 (s, 3H), 1.92 (s, 3H) , 1.54 (s, 9H), 0.79 (s, 3H), 0.57 (s, 3H), 0.42 (s, 3H), 0.39 (s, 3H); ¹³ C { ¹ H} NMR (C ₆ D ₆ ): 141.97,141.04, 139.56, 135.78, 135.64, 129.97, 128.91, 128.88, 112.94, 57.74, 57.05,50.93, 34.36, 18.39, 14.89, 4.36, 4.01

(Basic polymerization conditions)
The mixed alkanes and liquid olefins were blown with purified nitrogen, then alumina (LaRoche Inc .: A-2) and Q5 reactants (Englehard Chemicals Inc.) under a pressure of 50 psig (450 kPa) using a purified nitrogen pad The product was purified by passing through a column packed with All solvents and solutions described below were transferred using a dry / purified nitrogen or argon gaseous pad. The gas supply to the reactor was purified by passing through a column packed with A-204 alumina (LaRoche Inc.) and Q5 reactant. The aluminas were previously activated by treatment with nitrogen at 375 ° C., and the Q5 reactant was activated by treatment at 200 ° C. with 5% hydrogen in nitrogen.

(Polymerization 1)
A 2 liter Pearl reactor with a stirrer was charged with 740 g of mixed alkane (Isopar E ^™ ) and 118 g of purified 1-octene comonomer. Hydrogen (25 psi (170 kPa), 5.7 mmol) as a molecular weight control agent was added from a 75 ml addition tank under pressure of 300 psig (2.2 MPa) using differential pressure expansion. The reactor was heated to 140 ° C. and saturated with ethylene (500 psig (3.5 MPa)). Pre-mixed methyldi (C14-18 alkyl) ammonium tetrakis (pentafluorophenyl) borate (MDPB) or trispentafluorophenylborane (FAB) as catalyst and cocatalyst in a glove box to prepare a 0.005 molar solution of toluene Then, it was transferred to a catalyst addition tank and injected into the reactor. The polymerization conditions maintained the required amount of ethylene during the polymerization. The reaction is allowed to proceed 15 minutes and the resulting solution and collecting receiver (isopropyl alcohol 100ml filled with nitrogen from the reactor, sterically hindered phenols antioxidant (Ciba Geigy Corporation, Inc. Irgafos ^TM 1010 and phosphorus-based stabilizer (Ciba Charged with 20 ml of a 10 wt% toluene solution of Irgafos ^™ 168) manufactured by Geigy Corporation, the polymer was dried in a programmed vacuum oven at a maximum temperature of 145 ° C. and a heating time of 20 hours. The results obtained are shown in Table 1.

Claims (9)

A polycyclic heteroatom-containing fused ring compound represented by the following formula (I):
C _p M (Z) (X) _x (T) _t (X ') _x' (I)
In the formula, C _p is a polycyclic fused ring ligand having up to 60 atoms other than hydrogen or an inert substituted derivative thereof having at least a cyclopentadienyl ring bonded to M by a delocalized π electron. And a 5-membered polyatomic ring having at least one ring atom selected from Group 15 or 16 of the periodic table or a substituted derivative thereof, wherein the cyclopentadienyl ring is a second condensed ring. Without adjacent substituents that can form
M is a metal selected from Groups 3 to 10 of the periodic table or lanthanum. Z is a divalent radical of the formula -Z'Y- involved in C _p and M, wherein, Z 'is ^{_{SiR 6 2, CR 6 2,}} SiR 6 2 SiR 6 2, CR 6 2 CR 6 _2, CR ⁶ = CR ^6, a ^{_{CR 6 2 SiR 6 2, BR}} 6 , or GeR ⁶ _2, Y is -O -, - S -, - NR 5 -, - PR 5 -, - NR 5 2 or - it is a PR ⁵ _2. Hydrocarbyl, each R ⁵ is exists independently trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, up to 20 have a non-hydrogen atoms, optionally the ring by a and Y 2 amino or R ⁵ by R ⁵ groups Can be formed. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 30 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X is hydrogen or a monovalent anionic ligand group having up to 60 atoms other than hydrogen. T is a neutral coordination compound that exists independently, and T and X or T and R ⁵ may be bonded together. X ′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen. x is 0, 1, 2 or 3, t is 0 to 2, and x ′ is 0 or 1. The compound of claim 1 wherein represented by the following formula (I ¹⁾ or (I ^2).


Wherein J is independently present for hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis (trihydrocarbylsilyl) amino, di (hydrocarbyl) amino, hydrocarbylene. Amino, hydrocarbylimino, di (hydrocarbyl) phosphino, hydrocarbylenephosphino, hydrocarbyl sulfide, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis (trihydrocarbylsilyl) amino-substituted hydrocarbyl , Di (hydrocarbyl) amino substituted hydrocarbyl, hydrocarbylene amino substituted hydrocarb Bill, di (hydrocarbyl) phosphino substituted hydrocarbyl, hydrocarbylene phosphino substituted hydrocarbyl, or hydrocarbyl sulfide substituted hydrocarbyl having up to 40 atoms other than hydrogen. A is a divalent residue of an aromatic 5-membered ring group or a substituted derivative thereof, and has at least one group 15 or 16 ring atom. M is a Group 4 metal, Y is -O -, - S -, - NR 5 -, - PR 5 -, - NR 5 2 or -PR ⁵ _2, Z 'is ^{_{SiR 6 2, CR 6 2,}} SiR 6 ₂ SiR ⁶ ₂ , CR ⁶ ₂ CR ⁶ ₂ , CR ⁶ = CR ⁶ , CR ⁶ ₂ SiR ⁶ ₂ , BR ⁶ or GeR ⁶ ₂ . Hydrocarbyl, each R ⁵ is exists independently trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, up to 20 have a non-hydrogen atoms, optionally the ring by a and Y 2 amino or R ⁵ by R ⁵ groups Can be formed. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 20 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X, T and X ′ are as defined in claim 1, x is 0, 1 or 2, t is 0 or 1, and x ′ is 0 or 1. The metal complex according to claim 1, which is represented by the following formula.

In the formula, M is titanium and R1 is independently present hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amino, hydrocarbyleneamino, di (hydrocarbyl) amino substituted hydrocarbyl group, or hydrocarbyleneamino substituted hydrocarbyl. Group having up to 30 atoms other than hydrogen. Y is -O -, - S -, - NR 5 -, - PR 5 -, - NR 5 2 or -PR ⁵ _2, Z 'is ^{_{SiR 6 2, CR 6 2,}} SiR 6 2 SiR 6 2, CR 6 ₂ CR ⁶ ₂ , CR ⁶ = CR ⁶ , CR ⁶ ₂ SiR ⁶ ₂ , BR ⁶ or GeR ⁶ ₂ , R ⁵ is each independently present hydrocarbyl, trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, It has up to 20 atoms other than hydrogen and can optionally form a ring with two R ⁵ groups or with R ⁵ and Y. R ⁶ is independently selected from hydrogen or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, allyl halide, —NR ⁵ ₂ — and combinations thereof, and has a maximum of 20 atoms other than hydrogen. In some cases, two R ⁶ groups may form a ring. X, T and X ′ are as defined in claim 1, x is 0, 1 or 2, t is 0 or 1, x ′ is 0 or 1, x is 2, and x ′ is 0 (when or Y is -NR ⁵ ₂ or -PR ⁵ _2, the oxidation state of M is +3) oxidation state of M is +4 a, and, X is a halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl ) Amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide and silyl groups, as well as their halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (hydrocarbyl) phosphino-substituted derivatives An anionic ligand with up to 30 atoms other than hydrogen. When x is 0 and x ′ is 1, the oxidation state of M is +4, and X is a dianion coordination selected from the group consisting of hydrocarbadiyl, silane, oxyhydrocarbylene and hydrocarbylenedioxy groups It is a child and has up to 30 atoms other than hydrogen. When x is 1 and x ′ is 0, the oxidation state of M is +3, X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) phenyl and It is a stabilized anionic ligand group selected from the group consisting of 2- (N, N-dimethylamino) benzyl. A conjugated or non-conjugated diene in which x and x ′ are both 0, t is 1, M is in oxidation state +2, and T is a neutral (including optionally substituted with at least one hydrocarbyl group) Where L has up to 40 carbon atoms and is bonded to M by its delocalized π electrons. The metal complex according to claim 1, wherein the metal complex is selected from the group consisting of the following compounds and mixtures thereof.

[1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate ( 2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N -(1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [ b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a , 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -4H-cyclopenta [b] thien-6-yl] -N- ( 1,1-dimethylethyl) -1,1-dimethyl Ranameto (2 -) - κN] titanium (III) 2- (N, N- dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H- Cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5 , 6,6a-η) -3-Phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a -η) -3-phenyl-4 H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethyl Amino) benzyl)

[1-[(3a, 4,5,6,6a-η) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl)- 1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5-methyl-4H-cyclopenta [b] thien -6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η ) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyl Titanium, [1-[(3a, 4,5,6,6a-η) -3-Phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5- Methyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl -1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -3-phenyl-5-methyl-4H-cyclopenta [b] thien-6-yl] -N- (1 , 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl ) -1,1-Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6 , 6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2- ) -κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N -(1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η ) -2,5-Dimethyl-3-phenyl-4H-cyclopenta [b] thien-6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titaniu (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -2,5-dimethyl-3-phenyl-4H-cyclopenta [b] thien -6-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro- Cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5 , 6,6a-η) -1,4-Dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] Titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-cyclopenta [b] pyrrol-4-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a -η) -1,4- Hydro-cyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethyl Amino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl)- 1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrole -4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4,5,6,6a-η ) -1,4-Dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dibenzyl Titanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro- 1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II ) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-1-phenylcyclopenta [b] pyrrol-4-yl ] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III) 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1- Dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1 -Phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1-[(3a, 4 , 5,6,6a-η) -1,4-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1- Dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-5-methyl-1-phenylcyclopenta [b] Pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4 , 5,6,6a-η) -1,4-Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1 , 1-Dimethylsilanamate (2-)-κN] Titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a-η) -1,4 -Dihydro-5-methyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (III 2- (N, N-dimethylamino) benzyl)

[1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1, 1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dichlorotitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5 -Dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] dimethyltitanium, [1- [ (3a, 4,5,6,6a-η) -1,4-Dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl ) -1,1-dimethylsilanamate (2-)-κN] dibenzyltitanium, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl- 1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,3-pentadiene, [1-[(3a, 4,5,6,6a-η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1, 1 -Dimethylethyl) -1,1-dimethylsilanamate (2-)-κN] titanium (II) 1,4-diphenyl-1,3-butadiene, [1-[(3a, 4,5,6,6a- η) -1,4-dihydro-2,5-dimethyl-1-phenylcyclopenta [b] pyrrol-4-yl] -N- (1,1-dimethylethyl) -1,1-dimethylsilanamate (2 -)-κN] Titanium (III) 2- (N, N-dimethylamino) benzyl An olefin polymerization method comprising contacting at least one olefin monomer under polymerization conditions using a catalyst composition comprising the metal complex according to claim 1. 6. The polymerization method according to claim 5, wherein the catalyst composition further contains an activated cocatalyst. The polymerization method according to claim 5, which is carried out under a solution, slurry, or high pressure polymerization condition. 6. The polymerization method according to claim 5, which is carried out under slurry or gas phase polymerization conditions in the presence of a catalyst containing an inert particulate support. The polymerization method according to claim 6, wherein the activated cocatalyst is selected from the following.
Tris (pentafluorophenyl) borane, methylditetradecylammonium-tetrakis (pentafluorophenyl) borane, (pentafluorophenyl) ditetradecylammonium-tetrakis (pentafluorophenyl) borate, dimethyltetradecylammonium-tetrakis (pentafluorophenyl) ) Borate, methyldihexadecylammonium-tetrakis (pentafluorophenyl) borate, (pentafluorophenyl) dihexadecylammonium-tetrakis (pentafluorophenyl) borate, dimethylhexadecylammonium-tetrakis (pentafluorophenyl) borate, methyldi Octadecylammonium-tetrakis (pentafluorophenyl) borate, (pentafluorophenyl) dioctadecylammonium-tetrakis (pen Tafluorophenyl) borate, dimethyloctadecylammonium-tetrakis (pentafluorophenyl) borate, methylalumoxane, triisobutylaluminum modified methylalumoxane, or mixtures thereof