KR20010020425A - Olefin polymers prepared with substituted indenyl containing metal complexes - Google Patents

Abstract

The present invention relates to an indenyl group substituted at position 2 or 3 with at least one group selected from hydrocarbyl, perfluoro-substituted hydrocarbyl, silyl, germanyl and mixtures thereof. In the presence of a Group 4 metal complex comprising a divalent ligand group comprising nitrogen or phosphorus having an aliphatic or cycloaliphatic hydrocarbyl group covalently bonded thereto by a secondary carbon) It relates to an olefin polymer produced by polymerizing α-olefins. Preferred olefin polymers of the present invention will be characterized by having a high molecular weight, narrow molecular weight distribution, high vinyl content and biphasic DSC melt curves or delineated ATREF or GPC curves showing at least two distinct narrow peaks. Olefin polymers will have utility in a variety of applications, including but not limited to films, fibers, foams, molded parts, and as components of formulations such as adhesives, sealants, coatings, cokes and asphalt.

Description

Olefin polymer prepared using substituted indenyl-containing metal complexes {OLEFIN POLYMERS PREPARED WITH SUBSTITUTED INDENYL CONTAINING METAL COMPLEXES}

Constrained geometric metal complexes and methods for their preparation are described in EP-A-416,815; EP-A-468,651; EP-A-514,828; EP-A-520,732; And WO 93/19104, as well as US-A-5,055,438, US-A-5,057,475, US-A-5,096,867, US-A-5,064,802, US-A-5,132,380, US-A-5,470,993, WO 95/00526 and US Provisional application 60-005913 is disclosed. Various substituted indenyl containing metal complexes have been taught in WO 95/14024 as well as in US application 592,756, filed Jan. 26, 1996.

Constrained geometric catalysts and other single site or metallocene catalysts are useful for preparing homogeneous olefin polymers. The term "homogeneous olefin polymer" refers to a narrow polydispersity, i.e., M _w / M _n of 1.5 to 3.0, and in the case of an interpolymer, a homogeneous short chain branching distribution, i.e. each molecule is about the same It refers to a homopolymer or interpolymer of at least one α-olefin, which is characterized by having a number of short chain branches. Homogeneous olefin polymers are advantageous over Ziegler Natta produced polymers in the absence of low molecular weight residue fractions resulting in improved strength and stiffness. Homogeneous olefin polymers also provide a cost-effective production of polymers having a density of less than 0.910 g / cm ³ , in which catalysts useful for preparing such polymers, in particular restraint geometry catalysts, readily and effectively incorporate comonomers to provide good elasticity. It is advantageous over the polymers produced by Ziegler Natta in that it is possible.

Homogeneous polymers, despite their advantageous features, are typically more difficult to process than their Ziegler-Natta counterparts, in part due to the absence of low molecular weight fractions and in part due to the narrowing of the melting zone.

One preferred class of homogeneous olefin polymers is nearly linear, characterized by having a narrow polydispersity, homogeneous short chain branch distribution, and the presence of long chain branches sufficient to provide improved rheological properties and resistance to melt grinding. Polymer class. Nearly linear polymers are described in US Pat. No. 5,272,236; 5,278,272; 5,380,810; And EP 659,773; EP 676,421; And WO 94/07930.

Another approach to using the preferred near linear olefin polymers has been to incorporate an effective amount of polymeric processing aid into the homogeneous olefin polymer prior to making into a film or article. This method is disadvantageous in that it requires additional processing steps and adds cost to the final product.

Whereas homogeneous olefin-based elastomers, and in particular nearly linear olefin polymers, show considerable commercial utility, the low density of the elastomers associated with the absence of higher transparency non-short chain branching fractions, in terms of upper service temperature and thermal , For example, makes the polymer considerably poor in terms of being prone to deformation under a clothes dryer.

In order to improve the top service temperature of homogeneous olefin polymers that are elastomers, the polymers may be prepared in physical blends or in US Application Nos. 510,527 (August 2, 1995, WO 94/171112) and US Application Nos. 208,068 (1994). 3. The mixture can be blended with homogeneous or heterogeneous olefin polymers of higher clarity via the in-reactor mixture produced in a dual reactor system as disclosed in EP. 619827).

However, the industry has sought great advantages in polymers having elasticity that exhibit resistance to deformation under heat, which is greater than physical or in-reactor blends of the same overall density. The industry has sought to find particular advantages in polymers having an overall polydispersity of 1.5 to 3.0 but with excellent processability, as evidenced by resistance to melt grinding and / or I ₁₀ / I _{2 of} at least ₁₀ . The industry has sought to find very particular advantages in polymers that can be produced in a single reactor using highly effective catalysts that are resistant to degradation at elevated temperatures.

US Pat. No. 5,621,126, issued to Exxon Chemical Patents, Inc., uses mono (cyclopentadienyl) Group 4B metal compounds to produce ethylene / α-olefin copolymers. It should be noted that it is disclosed. U.S. Patent 5,621,126 discloses a catalyst containing an amido group which is aliphatic or cycloaliphatic and has a hydrocarbyl ligand R 'bonded to a nitrogen atom via a primary or secondary carbon, wherein the hydrocarbyl ligand R' is a tertiary carbon. It is claimed to produce copolymers having an α-olefin incorporation rate which is bonded via a atom to a nitrogen atom or R 'is larger than a catalyst having an aromatic carbon atom. U.S. Pat.No. 5,621,126 discloses that when the R 'ligand is bonded to the nitrogen atom via a secondary carbon atom, the catalytic activity is R' is greater than that when the R 'ligand is bonded to nitrogen through a primary carbon atom of an aliphatic group of the same carbon number It is claimed to be larger when it is alicyclic. U.S. Pat.No. 5,621,126 discloses that as the number of carbon atoms of R 'increases, the productivity of the catalyst system and the molecular weight of the ethylene / a-olefin copolymer increase while the amount of incorporated alpha -olefin comonomer remains approximately the same or Or claim to increase. U.S. Patent 5,621,126 claims that the more preferred R 'ligand is cyclododecyl.

The compositions of U. S. Patent No. 5,621, 126 are disadvantageous in that they lack long chain branching, making them easy to melt pulverize and are therefore considered to be less commercially desirable.

The present invention is particularly suitable for use in polymerization processes for polymerizing a mixture of α-olefins and α-olefins to produce polymers, Group 4 metal complex classes and olefin polymerization catalysts derived therefrom, and α-olefins produced therefrom and It relates to a mixture of α-olefins.

1 is a diagram of a catalyst, cocatalyst and scavenging compound implemented in the examples shown herein.

FIG. 2 is a DSC endogram of the ethylene / octene interpolymer of Comparative Example C-3a prepared using Catalyst (III).

FIG. 3 is a DSC endogram of the ethylene / octene interpolymer of Example 1a prepared using catalyst (I).

FIG. 4 is a DSC endogram of the ethylene / octene interpolymer of Example 2a prepared using catalyst (II).

FIG. 5 is a transmission electron micrograph of the ethylene / octene interpolymer of Example 2a prepared using catalyst (II).

6 is a transmission electron micrograph of the ethylene / octene interpolymer of Comparative Example C-3a prepared using Catalyst (III).

FIG. 7A shows two ethylene / octene interpolymers of the invention prepared using catalyst (I) (Example 1b) and catalyst (II) (Example 2a), respectively, and a comparison made using catalyst (III) ATREF curves of the ethylene / octene interpolymer of Example C-3a.

FIG. 7B shows an ethylene / octene interpolymer prepared using catalyst (II), and a density of 0.895 g / cm ³ prepared using catalyst (III) and a melt index (I ₂ ) of 1.6 g / 10 min. ATREF curves of the comparative ethylene / octene interpolymer.

7C is the ATREF and differential viscosity curves of the ethylene / octene interpolymer of Example 45 (e) prepared using catalyst (II).

7D is a plot of ATREF shape factor versus average ATREF elution temperature.

8A and 8B show ethylene / octene interpolymers prepared using Catalyst (I) (Example 1a) and Catalyst (II) (Example 2a), respectively, and Catalyst (III) (Comparative Example C-3a). Dynamic mechanical data for ethylene / octene interpolymers prepared using.

9A shows an ethylene / octene interpolymer made using catalyst (II) and a comparative ethylene / octene interpolymer made using catalyst (III), and two ethylene / octene made using catalyst (III). Plot of the upper service temperature (UST) of the mixture of interpolymers.

FIG. 9B plots the difference between UST of various blends of ethylene / octene interpolymers prepared using catalyst (III) and UST of the inventive interpolymer shown in FIG. 9A.

FIG. 10 is a delineated gel permeation chromatogram of the ethylene / octene interpolymer of Example 1b prepared using catalyst (I).

FIG. 11 is a delineated gel permeation chromatogram of the ethylene / octene interpolymer of Example 2b prepared using catalyst (II).

12 is a delineated gel permeation chromatogram of ethylene / octene interpolymer of Comparative Example C-2a prepared using Catalyst (II) and Batch Polymerization Process.

13 is the ethylene / octene interpolymer of Example 2a prepared using catalyst (II) in a continuous liquid phase polymerization process, and ethylene of Comparative Example C-2a prepared using catalyst (III) in a liquid phase batch polymerization process. Viscosity curves of the / octene interpolymer.

14 is a graph of a compressed set of ethylene / octene interpolymers prepared using catalysts (I) and (II), and ethylene / octene interpolymers prepared using catalyst (III), respectively.

15 and 16 are DSC curves for the EPDM of the present invention.

All references to the Periodic Table of Elements herein relate to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1989. In addition, any reference sign to the group or groups should be for the group or groups as indicated in the Periodic Table of the Elements using the IUPAC system to number groups.

Unless otherwise stated, the following procedure is used:

Density is measured according to ASTM D-792. The sample is annealed at ambient temperature for 24 hours before measurement.

Melt index (I ₂ ) is measured according to ASTM D-1238, Condition 190 ° C./2.16 kg (formally known as “Condition (E)”).

I ₁₀ is measured according to ASTM D-1238, Condition 190 ° C./10 kg (formally known as “Condition (N)”).

Molecular weight is gel permeation chromatography (GPC) on a Waters 150 ° C. high temperature chromatography unit equipped with three mixed porous columns (polymer laboratories 103, 104, 105 and 106), operating at a system temperature of 140 ° C. Measure with). The solvent is 1,2,4-trichlorobenzene from which a 0.3 wt% solution of the sample is prepared for injection. The flow rate is 1.0 ml / min and the injection size is 100 μl.

Molecular weight measurements, along with their elution volume, are inferred using polystyrene standards (polymer laboratories) of narrow molecular weight distribution. Equivalent polyethylene molecular weights are described by using appropriate Mark-Houwink coefficients for polyethylene and polystyrene (Williams and Word, Journal of Polymer Science, Polymer Letters, 6 (621) (1968)). Determine by deriving the following equation:

M _polyethylene = a * (M _polystyrene ) ^b _.

In the equation, a is 0.4316 and b is 1.0. The weight average molecular weight, M _w , is calculated in the usual manner according to the following formula: M _w = Σw _i * M _i , where w _i and M _i are each the weight fraction and molecular weight in its fraction eluted from the GPC column. .

Transparency% is an equation:% C = (A / 292 J / g) x 100 [where% C represents transparency% and A is in joules per gram (J / g) as measured by differential scanning calorimetry (DSC) Represents the heat of fusion of ethylene].

Place each sample (5 mg) in an aluminum pan to produce differential scanning calorimeter (DSC) data, heat the sample to 160 ° C., cool to 10 ° C./min, and use -30 with Perkin Elmer DSC 7 The endotherm was recorded by scanning from 140 ° C to 140 ° C. DSC exotherm (cooling curve) was also recorded by scanning from 140 ° C. to −30 ° C. at 10 ° C./min.

The morphology of the copolymer was examined by transmission electron microscopy (TEM). Samples are stained with ruthenium chloride- hypochlorite and then thin slices are made with a glass knife on a microtome at room temperature. Micrographs were recorded at 150000x magnification on a JEOL 2000FX microscope.

Analytical Temperature Rise Elution Classification (ATREF) data was generated using standard equipment in polyolefin research. Polymer samples (dissolved in hot trichlorobenzene) were crystallized in a column containing an inert support (steel shot) by slowly decreasing the temperature. Subsequently, the temperature of the eluting solvent and trichlorobenzene was gradually raised to elute the crystallized sample from the column to prepare an ATREF chromatogram. The ATREF curve showed several important structural features of the resin. For example, the reaction from the refractive index detector provides a short chain branching distribution, while the reaction from a differential viscometer detector provides an evaluation of the viscosity average molecular weight.

Dynamic mechanical spectroscopy measurements were performed on an RMS-800 synchronous spectrometer using a 25 mm diameter parallel plate (2 mm spacing) in an oscillatory shear method. Frequency sweeps were carried out over a shear rate range of 0.1 to 100 rad / s at 190 ° C. under 15% strain in a nitrogen atmosphere. Temperature sweep was also performed on the RDAII power analyzer. In this case, 12.5 mm diameter parallel plates (1.5 mm spacing) were used over a temperature range of -100 to 200 ° C. at a frequency of 1 rad / s in a nitrogen atmosphere. The sample was loaded at room temperature and heated to 60 ° C. to ensure good contact between the sample and the plate, then cooled to −100 ° C. and the temperature sweep experiment started.

Processability was evaluated using a gas extrusion rheometer (GER). The resin was filled into a capillary rheometer equipped with a 20 L / D cylindrical die of 0.0296 in diameter operating at 190 ° C. Nitrogen gas was used to pressurize the rheometer and extrudate samples were collected when the pressure was reduced from 5500 psi to 1000 psi (38 MPa to 6.9 MPa) in steps of 250 psi (1.7 MPa), typically 19 air. The coalescing samples were collected. After solidification, the surface of each extrudate was visually inspected for surface flow defects, for example measuring the point where each resin lost surface gloss (LSG) and the point where each resin was severely melt crushed (OGMF). It was.

Olefins as used herein include cyclobutene, cyclopentene, including norbornenes substituted at positions 5 and 6 with C _1-20 hydrocarbyl groups, as well as C _2-20 aliphatic or aromatic compounds containing vinyl unsaturated groups And cyclic compounds such as norbornene. In addition to the mixture of the olefins, mixtures of the olefins with C _4-40 diolefin compounds are also included. Examples of the latter compound include ethylidene norbornene, 1,4-hexadiene, norbornadiene and the like. The catalysts and methods herein are only ethylene / propylene, ethylene / 1-butene, ethylene / 1-pentene, ethylene / 4-methyl-1-pentene, ethylene / 1-hexene, ethylene / 1-octene and ethylene / styrene interpolymers. Rather, the interpolymers of ethylene and C ₃ -C ₂₀ α-olefins, preferably C ₄ -C ₂₀ α-olefins, more preferably C ₆ -C ₁₀ α-olefins, and ethylene, propylene and nonconjugated dienes Particularly suitable for use in the preparation of terpolymers, ie EPDM terpolymers, ethylene / 1-octene polymers are particularly preferred.

Interpolymers of the invention will preferably be prepared using a catalyst system derived from a metal complex corresponding to formula (1)

Formula 1

Where

M is titanium, zirconium or hafnium in the +2, +3 or +4 type oxidation state;

A ′ is at least 2 or 3 in a group selected from hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germanyl and mixtures thereof A substituted indenyl group containing up to 40 non-hydrogen atoms, wherein A 'is also covalently bonded to M by a divalent Z group;

Z is a divalent moiety attached to both A 'and M by σ-bond and comprises a member of Group 14 of the boron or periodic table of elements, and also includes nitrogen or phosphorus, wherein the aliphatic or cycloaliphatic hydrocarbyl group is Covalently bound to nitrogen or phosphorus by primary or secondary carbon;

X is an anionic or anionic ligand group having up to 60 atoms except for the ligand class which is a cyclic delocalized π-binding ligand group;

X 'is each independently a neutral linking compound having up to 20 atoms;

p is 0, 1 or 2, and 2 is less than the formal oxidation state of M, provided p is 1 when X is an anionic ligand;

q is 0, 1 or 2.

Preferred X 'groups are carbon monoxide; Phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis (1,2-dimethylphosphine) ethane; P (OR) ₃ , where R is as defined above; Ethers, in particular tetrahydrofuran; Amines, in particular pyridine, bipyridine, tetramethylethylenediamine (TMEDA) and triethylamine; Olefins; And conjugated dienes having 4 to 40 carbon atoms. Complexes containing the latter X 'group include complexes in which the metal is in the +2 type oxidation state.

In the case of the metal complex as well as in the case of other metal complexes disclosed herein, M is preferably zirconium or titanium, more preferably titanium.

Preferred substituted indenyl coordination complexes used according to the invention are the complexes corresponding to formula (II):

Where

R ₁ and R ₂ are groups containing up to 20 non-hydrogen atoms independently selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germanyl and mixtures thereof, provided that R ₁ and At least one of R ₂ is not hydrogen;

R ₃ , R ₄ , R ₅ and R ₆ are groups containing up to 20 non-hydrogen atoms independently selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germanyl and mixtures thereof ;

M is titanium, zirconium or hafnium;

Z is a divalent residue comprising boron or a Group 14 member of the Periodic Table of the Elements, and also comprising nitrogen or phosphorus, and having up to 60 non-hydrogen atoms, wherein the aliphatic or cycloaliphatic hydrocarbyl group is a primary or 2 Covalently bonded to nitrogen or phosphorus by grade carbon;

p is 0, 1 or 2;

q is 0 or 1; only

When p is 2, q is 0, M is a +4 type oxidation state, X is a halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphido, hydrocarbyl sulfi And an anionic ligand selected from the group consisting of halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (hydrocarbyl) phosphino-substituted derivatives thereof, as well as the X and Has up to non-hydrogen atoms;

When p is 1, q is 0, M is a +3 type oxidation state, X is allyl, 2- (N, N-dimethylaminomethyl) phenyl and 2- (N, N-dimethyl) -aminobenzyl A stabilizing anionic ligand group selected from the group consisting of: or M is a +4 type oxidation state, X is a divalent derivative of conjugated diene, and M and X together form a metal cyclocyclopentene group;

When p is 0, q is 1, M is a +2 type oxidation state, X 'is a neutral conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, and has up to 40 carbon atoms Form M-pi complexes.

More preferred coordinating complexes used according to the invention are the complexes corresponding to the formula

Where

R ₁ and R ₂ are hydrogen or C _1-6 alkyl, provided that at least one of R ₁ and R ₂ is not hydrogen;

R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen or C _1-6 alkyl;

M is titanium;

Y is -NR ^** -, -PR ^** -;

Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ ;

R ^* in each occurrence is independently hydrogen or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl and mixtures thereof, having up to 20 non-hydrogen atoms, optionally from Z (when R ^* is not hydrogen), two R ^* group, or an R ^* group from one of the R ^* groups from Y, and Z forms a ring system;

R ^** is an aliphatic or cycloaliphatic hydrocarbyl group covalently bonded to nitrogen or phosphorus of Y by primary or secondary carbon;

p is 0, 1 or 2;

q is 0 or 1; only

when p is 2, q is 0, M is a +4 type oxidation state and X is independently at each occurrence methyl or benzyl;

When p is 1, q is 0, M is a +3 type oxidation state, X is 2- (N, N-dimethyl) aminobenzyl, or M is a +4 type oxidation state, and X is 1,4 -Butadienyl;

When p is 0, q is 1, M is a +2 type oxidation state, and X 'is 1, 4- diphenyl- 1, 3- butadiene or 1, 3- pentadiene. The latter diene is an example of an asymmetric diene group that produces a metal complex that is substantially a mixture of each geometric isomer.

Preferred substituted indenesyl metal complexes correspond to formula IIa or IIIa:

Where

R 'is a hydrocarbyl, di (hydrocarbylamino) or hydrocarbyleneamino group and has up to 20 carbon atoms;

R ″ is C _1-20 hydrocarbyl or hydrogen;

M is titanium;

Y is -O-, -S-, -NR ^* -, -PR ^* -, -NR ^* ₂ -or -PR ^* _2- ;

Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ ;

R ^* in each occurrence is independently hydrogen or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl and mixtures thereof, having up to 20 non-hydrogen atoms, optionally from Z (when R ^* is not hydrogen), two R ^* group, or an R ^* group from one of the R ^* groups from Y, and Z forms a ring system;

X, X 'and X "are as defined above;

p is 0, 1 or 2;

q is 0 or 1;

r is 0 or 1; only

When p is 2, q and r are 0, M is a +4 type oxidation state (or M is a +3 type oxidation state when Y is -NR ^* ₂ or -PR ^* ₂ ), X is a halide, Hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphido, hydrocarbyl sulfido and silyl groups, as well as halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and An anionic ligand having up to 30 non-hydrogen atoms, selected from the group consisting of di (hydrocarbyl) phosphino-substituted derivatives;

When r is 1, q and q are 0, M is a +4 type oxidation state and X "is no more than 30 ratios selected from the group consisting of hydrocarbodiyl, oxyhydrocarbyl and hydrocarbylenedioxy groups -Anionic ligands with hydrogen atoms;

When p is 1, q and r are 0, M is a +3 type oxidation state, X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N-dimethylaminomethyl) phenyl And a stabilizing anionic ligand group selected from the group consisting of 2- (N, N-dimethylamino) benzyl;

When p and r are 0, q is 1, M is a +2 type oxidation state and X 'is a neutral conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, up to 40 carbon atoms And form M and π-complex compound.

Most preferred metal complexes are as defined above for M, X, X ', X ", R', R", Z ^* , Y, p, q and r; Provided that when p is 2, q and r are 0, M is a +4 type oxidation state and X is independently at each occurrence methyl, benzyl or halide; when p and q are 0, r is 1, M is a +4 type oxidation state and X "is a 1,4-butadienyl group forming a metalcyclocyclopentene ring with M; when p is 1 when q and r are 0, M is in a +3 form oxidation state, X is 2- (N, N-dimethylamino) benzyl; and when p and r are 0, q is 1 and M is of +2 type A metal complex corresponding to the above formula (IIa) or (IIIa) in the oxidation state, wherein X 'is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene

Particularly preferred coordination complexes corresponding to the above formulas (IIa) and (IIIa) are specifically substituted according to their particular end use. In particular, metal complexes which are very useful for use in catalyst compositions for the copolymerization of ethylene, one or more monovinyl aromatic monomers, and optionally α-olefins or diolefins, are those wherein R 'is C _6-20 aryl, in particular phenyl, biphenyl or naph Til and R < 2 > is hydrogen or methyl, in particular hydrogen, said complex compound (IIa) or (IIIa).

Metal complexes that are very useful for use in catalyst compositions for homopolymerization of ethylene or copolymerization of ethylene with one or more α-olefins, in particular 1-butene, 1-hexene or 1-octene, are those wherein R 'is C _1-4 alkyl, N And N-dimethylamino or 1-pyrrolidinyl, wherein R " is hydrogen or C _1-4 alkyl, wherein the complex is (IIa) or (IIIa). In addition, in the complex, Y is preferably cyclohexyl Amido group, X is methyl, p is 2, q and r are both 0. Most preferably, the complex is 2,3-dimethyl-substituted s- corresponding to formula VI or VII Senyl complexes are:

Finally, for use in catalyst compositions for the copolymerization of ethylene, α-olefins and dienes, in particular ethylene, propylene and non-conjugated dienes such as ethylidene norbornene or 1,4-hexadiene or conjugated diene piperylene Very useful metal complexes include the above complexes (IIa) or (IIIa) wherein R 'is hydrogen and R "is C _1-4 alkyl, in particular methyl.

Very preferred metal complexes are:

2-methylindenyl complex:

(n- butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -2- methyl-indenyl) a silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Isopropyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Isopropyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Iso-butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Iso-butylamido) dimethyl (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) di isopropoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) di isopropoxy (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-2-methyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene, the

(n- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- inde-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- methyl-indenyl) silane titanium (IV) dibenzyl,

2,3-dimethylindenyl complex:

(n-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silane titanium (IV) dimethyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silane titanium (IV) dimethyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3-dimethylindenyl) silanetitanium (IV) dibenzyl,

3-methylindenyl complex:

(n- butylamido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV), dimethyl

(n- butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Isopropyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Diisopropyl amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Isopropyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethylsilyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Iso-butylamido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Iso-butylamido) dimethyl (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) di isopropoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) dimethoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ inde-3-methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

ethoxymethyl (n- butylamido) (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -3- inde-methyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -3- methyl-indenyl) silane titanium (IV) dibenzyl,

2-methyl-3-ethylindenyl complex:

(n-butylamido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Isopropyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Isopropyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Isopropyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Iso-butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Iso-butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Iso-butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Iso-butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Iso-butylamido) dimethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) di isopropoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(n- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethoxy (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n- butylamido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) ethoxymethyl (η ⁵ -2- inde-methyl-3-ethyl-indenyl) silane titanium (IV) dimethyl,

(n- butylamido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2- inde-methyl-3-ethyl-indenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2-methyl-3-ethylindenyl) silanetitanium (IV) dimethyl,

(Cyclo-dodecyl amido) ethoxymethyl (η ⁵ -2--methyl-3-ethyl-indenyl) silane titanium (IV) dibenzyl,

2,3,4,6-tetramethylindenyl complex:

(n-butylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silane titanium (IV) dimethyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dibenzyl,

2,3,4,6,7-pentamethylindenyl complex:

(n-butylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Isopropylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Isobutylamido) dimethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silane titanium (II) 1,3-pentadiene,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silane titanium (IV) dimethyl,

(Cyclododecyl amido) diisopropoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethoxy (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dimethyl,

(n-butylamido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silane titanium (IV) dimethyl,

(Cyclododecyl amido) ethoxymethyl (η ⁵ -2,3,4,6,7-pentamethylindenyl) silanetitanium (IV) dibenzyl,

3-phenyl-s-indasen-1-yl complex (or [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s-indacene-1- Also referred to as a general complex):

(i- propyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl -s- indazol enyl) silane titanium (IV) dibenzyl,

3-naphthyl-s-indasenyl complex:

(i- propyl amido) dimethyl (η ⁵ -3- naphthyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- naphthyl -s- indazol enyl) silane titanium (IV) dimethyl,

3-biphenyl-s-indasenyl complex:

(i- propyl amido) dimethyl (η ⁵ -3- biphenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- biphenyl -s- indazol enyl) silane titanium (IV) dimethyl,

2-Methyl-3-biphenyl-s-indasenyl complex:

(i- propyl amido) dimethyl (η ⁵ -2- methyl-3-biphenyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-biphenyl -s- indazol enyl) silane titanium (IV) dimethyl,

2-Methyl-3-naphthyl-s-indasenyl complex:

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-naphthyl -s- indazol enyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-naphthyl -s- indazol enyl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-naphthyl -s- indazol enyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-naphthyl -s- indazol enyl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl-3-naphthyl -s- indazol enyl) silane titanium (IV) dibenzyl,

3-phenyl-gem-dimethylacenaphthalenyl complex [(1,2,3,4,5-η) (5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-1H Benz (f) in-1-yl) complex)

(n- butylamido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- phenyl-Gem-dimethyl-acetoxy-naphthalenyl) silane titanium (IV) dibenzyl,

2-methyl-s-indasen-1-yl complex:

(n- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol sensor yl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Isopropyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclopentylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Iso-butylamido) dimethyl (η ⁵ -2- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

2,3-dimethyl-s-indasen-1-yl complex:

(n-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(n-butylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(Cyclohexyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(Isopropylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclopentyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(Cyclopentylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(Cyclopentylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(Cyclododecyl amido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,4-diphenyl-1,3-butadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (III) 2- (N, N-dimethylamino) benzyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dimethyl,

(Isobutylamido) dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silanetitanium (IV) dibenzyl,

3-methyl-s-indasen-1-yl complex:

(n- butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(n- butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(n- butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(n- butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(n- butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Cyclohexyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Isopropyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Cyclopentyl-amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl,

(Cyclo-dodecyl amido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,4- diphenyl-1,3-butadiene,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (II) 1,3- pentadiene,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (III) 2- (N, N- dimethylamino) benzyl,

(Iso-butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dimethyl, and

(Iso-butylamido) dimethyl (η ⁵ -3- methyl -s- indazol metallocene-1-yl) silane titanium (IV) dibenzyl.

Complexes can be prepared using known synthetic techniques. Optionally, reducing agents can be used to produce complexes in low oxidation states. The process is disclosed in US patent application 8 / 241,523, filed May 13, 1994 and published as WO 95-00526. The reaction is carried out in a suitable non-interfering solvent at a temperature of -100 to 300 ° C, preferably -78 to 100 ° C, most preferably 0 to 50 ° C. As used herein, the term "reducing agent" means a metal or compound that causes the metal M to be reduced from a high oxidation state to a low oxidation state under reducing conditions. Examples of suitable metal reducing agents are alloys of alkali metals, alkaline earth metals, aluminum and zinc, alkali metals or alkaline earth metals, for example sodium / mercury amalgam and sodium / potassium alloys. Examples of suitable reducing agent compounds include sodium naphthalenide, potassium graphite, lithium alkyl, lithium or potassium alkadienyl; And Grignard reagents. Most preferred reducing agents are alkali or alkaline earth metals, in particular lithium and magnesium metals.

Suitable reaction media for complex formation include aliphatic and aromatic hydrocarbons, ethers and cyclic ethers, especially branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; Cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; Aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene and xylene, C _1-4 dialkyl ethers, C _1-4 dialkyl ether derivatives of (poly) alkylene glycols and tetrahydrofuran . Mixtures of the foregoing media are also suitable.

The complex is made catalytically active by mixing with an activation promoter or by using an activation technique. Suitable activating promoters for use in the present invention include polymeric or oligomeric alumoxanes, in particular methylalumoxane, triisobutyl alumoxane-modified methylalumoxane or isobutylalumoxane; Neutral Lewis acids, for example C_1-30 Hydrocarbyl substituted Group 13 compounds, in particular tri (hydrocarbyl) aluminum- or tri (hydrocarbyl) boron-compounds, and their halogenation (including perhalogenation) having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group ) Derivatives, more particularly perfluorinated tri (aryl) boron compounds, most particularly tris (pentafluorophenyl) borane; Nonpolymeric, compatible, non-coordinating ion generating compounds (including the use of these compounds under oxidizing conditions), especially ammonium-, phosphonium-, oxonium-, carbonium-, silyllium- Or the use of sulfonium-salts, or ferrocenium salts of compatible coordinating anions; Bulk electrolysis (described in more detail below); And combinations of the above-described activation promoters and techniques. Combinations of the foregoing activation promoters and techniques can also be used as desired. The aforementioned activation promoters and activation techniques have already been taught in connection with different metal complexes in the following references: EP-A-277,003; US-A-5,153,157; US-A-5,064,802; EP-A-468,651 (corresponds to US application 07 / 547,718); EP-A-520,732 (corresponds to US application 07 / 876,268); And EP-A-520,732 (corresponding to US patent application Ser. No. 07,884,966, filed May 1, 1992).

Mixtures of neutral Lewis acids, in particular trialkyl aluminum compounds having 1 to 4 carbons in each alkyl group and tri (hydrocarbyl) boron compounds having 1 to 20 carbons in each hydrocarbyl group, in particular tris (pentafluor Mixtures of rophenyl) borane, also mixtures of polymeric or oligomeric alumoxanes with the neutral Lewis acid mixture, and mixtures of polymeric or oligomeric alumoxanes with a single neutral Lewis acid, in particular tris (pentafluorophenyl) borane This is a particularly preferred activation promoter. An advantage according to the invention is the discovery that the most effective catalytic activation using this mixture of tris (pentafluorophenyl) borane / alumoxane mixtures occurs with reduced amounts of alumoxane. The preferred molar ratio of Group 4 metal complex: tris (pentafluorophenyl) borane: alumoxane is 1: 1: 1 to 1: 5: 5, more preferably 1: 1: 1.5 to 1: 5: 3. The surprisingly effective use of smaller amounts of alumoxane in accordance with the present invention enables the production of olefin polymers under high catalyst efficiency using less expensive alumoxane cocatalyst. In addition, less amount of aluminum residue is produced to obtain a polymer with greater transparency.

Suitable ion-generating compounds useful as cocatalysts in one embodiment of the present invention is capable of donating a proton possible Bronsted acid cations, and commercial, it includes a non-coordinating anion A ^_. As used herein, the term "non-coordinating" is not coordinating to Group 4 metals containing precursor complexes and catalytic derivatives derived therefrom, or remains only weakly coordinating to the complexes and sufficiently susceptible to substitution by neutral Lewis acids. Means an anion or substance. Non-coordinating anions refer to anions that form neutral complexes by not transferring anionic substituents or fragments thereof to the anions, particularly when they act as charge balance negative silver in the cationic metal complex. A “compatible anion” is an anion that does not degrade to neutrality when the initially produced complex compound decomposes and does not interfere with the desired subsequent polymerization or other uses of the complex compound.

Preferred anions are those containing a single coordination complex comprising a charge-containing metal or metalloid core with an anion capable of balancing the charge of the active catalytic species (metal cations) that can be produced when the two components are mixed. . In addition, the anion should be easy to be sufficiently substituted by olefins, diolefins and acetylenically unsaturated compounds, or neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus and silicon. Compounds containing anions, including coordinating complexes containing single metals or metalloid atoms, are known and many such compounds, especially those compounds containing a single boron atom in the anion moiety, are commercially available.

Preferably, the promoter may be represented by the following formula (4):

(L ^* -H) _d ⁺ (A) ^d-

Where

L ^* is a neutral Lewis base;

(L ^* -H) ⁺ is Bronsted acid;

A ^d- is an uncoordinated, compatible anion with a charge of d-;

d is an integer of 1 to 3.

More preferably, A ^d- is the formula [M'Q ₄ ] ^- (wherein M 'is boron or aluminum in the +3 type oxidation state; Q is independently in each occurrence a hydride, dialkylamido, halide, Hydrocarbyl, hydrocarbyl oxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy and halo-substituted silylhydrocarbyl radicals (perhalogenated hydrocarbyl-, perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals) Q) has up to 20 carbons, but only once Q is a halide). Examples of suitable hydrocarbyoxide Q groups are disclosed in US Pat. No. 5,296,433.

In a more preferred aspect, d is 1, ie the counter ion has a single negative charge and is A ⁻ . Activation promoters comprising boron which are particularly useful in the preparation of the catalysts of the invention can be represented by the formula:

(L ^* -H) ⁺ (BQ ₄ ) ^-

Where

L ^* is as defined above;

B is boron in the formal oxidation state of 3;

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy- or fluorinated silylhydrocarbyl- group having up to 20 non-hydrogen atoms, provided that only once Q is Hydrocarbyl).

Most preferably, Q is in each case a fluorinated aryl group, in particular pentafluorophenyl group.

Representative, non-limiting examples of boron compounds that can be used as activating cocatalysts in the preparation of the improved catalysts of the present invention are tri-substituted ammonium salts such as: trimethylammonium tetrakis (pentafluorophenyl) borate, triethyl Ammonium Tetrakis (pentafluorophenyl) borate, Tripropylammonium Tetrakis (pentafluorophenyl) borate, Tri (n-butyl) ammonium Tetrakis (pentafluorophenyl) borate, Tri (tert-butyl) ammonium tetra Kis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethyl Anilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N Dimethylanilinium tetraki (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxycitries (pentafluorophenyl) borate, N, N- Diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate , N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) Bo Byte and N, N- dimethyl (2,3,4,6-tetrafluoro-phenyl) dimethylanilinium tetrakis not 2,4,6-trimethyl borate; Dialkyl ammonium salts such as di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; Triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl Tri-substituted phosphonium salts such as borate; Diphenyloxonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate and di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl Di-substituted oxonium salts such as borate; Diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate and bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl Di-substituted sulfonium salts such as borate.

Preferred (L ^* -H) ⁺ cations are N, N-dimethylanilinium and tributylammonium.

Still other suitable ion generating, activating promoters include salts of non-coordinating, compatible anions with cationic oxidants represented by the formula:

(O _X ^{e +} ) _d (A ^d- ) _e

Where

O _x ^{e +} is a cationic oxidant with a charge of e +;

e is an integer from 1 to 3;

A ^d- and d are as defined above.

Examples of cationic oxidants include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag ⁺ or Pb ⁺² . Preferred embodiments of A ^d- are the anions defined above in connection with Bronsted acid containing an activating promoter, in particular tetrakis (pentafluorophenyl) borate.

Still other suitable ion generating, activating promoters include compounds which are salts of non-coordinating, compatible anions with carbenium ions represented by the formula:

Ⓒ ^＋ A ^－

Where

Ⓒ⁺C_1-20 Carbenium ions;

A ⁻ is as defined above.

Preferred carbenium ions are trityl cations, ie triphenylmethyllium.

Still other suitable ion generating, activating promoters include compounds that are salts of noncoordinating, compatible anions with silyllium ions, represented by the formula:

_{R 3 Si (X ') q} + A -

Wherein R is C _1-10 hydrocarbyl and X ′, q and A ⁻ are as defined above.

Preferred silyllium salt activation cocatalysts are trimethylsilyllium tetrakispentafluorophenylborate, triethylsilyllium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts are described in J. Chem. Chem. Soc. Chem. Comm., 383-384 (1993); And Lambert, J. B., et al., Organometallics, 13, 2430-2443 (1994). The use of such silyllium salts as activation promoters for addition polymerization catalysts is claimed in US Pat. No. 5,625,087.

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

Particularly preferred promoters are characterized by a cation which is a Bronsted acid capable of donating both, and a solubility at 25 ° C. in at least 5% by weight, preferably at least 7.5% by weight of hexane, cyclohexane or methylcyclohexane. It will include inert, compatible, uncoordinated anions. By the use of the catalyst activators described above, improved catalyst activation is provided. More particularly, increased catalyst efficiency and polymerization rate are obtained, in particular under liquid phase polymerization conditions, most particularly under continuous liquid phase polymerization processes.

Preferred embodiments of the promoter can be represented by the following general formula (4):

Formula 4

(L ^* -H) _d ⁺ (A ^d- )

Where

L ^* is a neutral Lewis base;

(L ^* -H) ⁺ is Bronsted acid;

A ^d- is an uncoordinated, compatible anion with a charge of d-;

d is an integer of 1 to 3.

Examples of suitable anions of the formula A ^d- include stericly protected diboron anions corresponding to Formula 5:

Where

S is alkyl, fluoroalkyl, aryl or fluoroaryl (also hydrogen if two S groups are present);

Ar ^F is fluoroaryl;

X ¹ is hydrogen or halide.

Such diboron anions are disclosed in US Pat. No. 5,447,895.

Another example of an A ^d- anion is an anion corresponding to Formula 6:

[M ' ^{k +} Q _n' ] ^d-

Where

k is an integer from 1 to 3;

n 'is an integer from 2 to 6;

n'-k is d;

M 'is an element selected from Group 13 of the Periodic Table of the Elements;

Q is independently at each occurrence selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl and halosubstituted hydrocarbyl radicals, having up to 20 carbons, with only one time Q being a halide to be.

In a more preferred aspect d is 1, ie the counter ion has a single negative charge and corresponds to the formula A ⁻ . Particularly useful activating promoters comprising boron in the present invention can be represented by the formula:

[L ^* -H] ⁺ [BQ ' ₄ ] ^－

Where

L ^* is a neutral Lewis base containing nitrogen, sulfur or phosphorus;

B is boron in the oxidation state of 3;

Q 'is a fluorinated C _1-20 hydrocarbyl group.

Most preferably, Q 'is in each case a fluorinated aryl group, in particular a pentafluorophenyl group.

In general, the solubility of the catalyst activators of the present invention in aliphatic compounds is determined by one or more lipophilic groups such as long chain alkyl groups; Long chain alkenyl groups; Or by incorporating halo-, alkoxy-, amino-, silyl- or germanyl- substituted long chain alkyl groups or long chain alkenyl groups into the Bronsted acid, L. The term "long chain" means a group having 10 to 50 non-hydrogen atoms, preferably in non-branched form. Preferably, the L group contains 1 to 3 C _10-40 n-alkyl groups having 12 to 100 carbons in total, more preferably 2 C _10-40 alkyl groups having 21 to 90 carbons in total do. The presence of the lipophilic group is believed to make the activator more soluble in the aliphatic liquid, thus improving the effect upon catalyst activation. It should be noted that the catalyst activator may comprise a mixture of lipophilic groups of different lengths. For example, one suitable activator is a quantized ammonium salt derived from a commercially available long chain amine comprising a mixture of two C ₁₄ , C ₁₆ or C ₁₈ alkyl groups and one methyl group. The amine is marketed under the tradename Kemamine ^™ T9701 at Witco Corp. and under the name Armeen ^™ M2HT at Akzo-Nobel. The promoters of the present invention can be used at reduced concentrations based on the amount of metal complex compared to the amount of conventionally known promoters previously required while maintaining equivalent or improved catalyst efficiency.

Representative, non-limiting examples of boron compounds that can be used as ionic activation promoters useful in the preparation of the polymers of the present invention are tri-substituted ammonium salts such as: decyldi (methyl) ammonium tetrakis (pentafluorophenyl Borate, dodecyldi (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetradecyldi (methyl) ammonium tetrakis (pentafluorophenyl) borate, hexadecyldi (methyl) ammonium tetrakis (pentafluorophenyl) ) Borate, octadecyldi (methyl) ammonium tetrakis (pentafluorophenyl) borate, eicosyldi (methyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi (decyl) ammonium tetrakis (pentafluorophenyl) Borate, methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi (tetradecyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi ( Hexadecyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi (octadecyl) ammonium tetrakis (pentafluorophenyl) borate, methyldi (eicosyl) ammonium tetrakis (pentafluorophenyl) borate, tridecyl Ammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, tritetradecylammonium tetrakis (pentafluorophenyl) borate, trihexadecylammonium tetrakis (pentafluorophenyl ) Borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, trieicosylammonium tetrakis (pentafluorophenyl) borate, decyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, dode Sildi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) bore , N, N-didodecylanilinium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate, N, N-di (octadecyl) ( 2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, cyclohexyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate and methyldi (dodecyl) ammonium tetrakis (pentafluoro Rophenyl) borate.

Suitable similarly substituted sulfonium or phosphonium salts such as di (decyl) sulfonium tetrakis (pentafluorophenyl) borate, (n-butyl) dodecylsulfonium tetrakis (pentafluorophenyl) borate, Tridecylphosphonium tetrakis (pentafluorophenyl) borate, di (octadecyl) methylphosphonium tetrakis (pentafluorophenyl) borate and tri (tetradecyl) phosphonium tetrakis (pentafluorophenyl) borate also Can be mentioned.

Preferred activators are di (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate and di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate.

The cocatalyst may also contain 1 to 20 carbons in each hydrocarbyl group, a tri (hydrocarbyl) aluminum compound having 1 to 10 carbons, an oligomeric or polymeric alumoxane compound, each hydrocarbyl or hydrocarbyloxy group. Di (hydrocarbyl) (hydrocarbyloxy) aluminum compound having, or, optionally, a mixture with the above-mentioned compounds. The aluminum compounds are usefully used because of their advantageous ability to remove impurities such as oxygen, water and aldehydes from the polymerization mixture.

Suitable di (hydrocarbyl) (hydrocarbyloxy) aluminum compounds are represented by the formula T ¹ ₂ AlOT ² , wherein T ¹ is C _3-6 secondary or tertiary alkyl, most preferably isopropyl, isobutyl or tertiary- Butyl; T ² is a C _12-30 alkyl radical or an aralkyl radical, most preferably 2,6-di (t-butyl) -4-methylphenyl, 2,6-di (t-butyl) -4-methyltolyl, 2 , 6-di (i-butyl) -4-methylphenyl, or 4- (3 ', 5'-di (t-butyl) tolyl) -2,6-di (t-butyl) phenyl].

Preferred aluminum compounds are C _2-6 trialkyl aluminum compounds, especially those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, 1 to 6 carbons in the alkyl group And dialkyl (aryloxy) aluminum compounds containing 6 to 18 carbons in the aryl group (particularly (3,5-di (t-butyl) -4-methylphenoxy) diisobutylaluminum), methylalumoxane , Modified methylalumoxane and diisobutylalumoxane. The molar ratio of aluminum compound to metal complex is preferably 1: 10,000 to 1000: 1, more preferably 1: 5000 to 100: 1 and most preferably 1: 100 to 100: 1.

Bulk electrolysis techniques include electrochemical oxidation of metal complexes under electrolysis conditions in the presence of uncoordinated, supportive electrolytes containing inert anions. In this technique, solvents, supporting electrolytes, and electrolyte potentials for electrolysis are used so that little electrolysis by-products that cause the metal complexes to be catalytically inactivated are produced in the reaction. More particularly, suitable solvents are liquids under electrolysis conditions (typically temperatures of from 0 to 100 ° C.) and are inert materials capable of dissolving the supporting electrolyte. "Inert solvent" is a solvent that does not reduce or oxidize under the reaction conditions used for electrolysis. In general, it is possible to select solvents and supporting electrolytes that are not affected by the potential used for the desired electrolysis in terms of the desired electrolysis reaction. Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME) and mixtures thereof.

Electrolysis can be carried out in a standard electrolysis cell containing an anode and a cathode (also referred to as working electrode and counter electrode, respectively). Suitable materials for constructing the cells are glass, plastics, ceramics and glass coated metals. The electrode is made of an inert conductive material, ie a conductive material that is not affected by the reaction mixture or reaction conditions. Platinum or palladium is the preferred inert conductive material. Usually, an ion permeable membrane, such as a fine glass frit, separates the cell into separate compartments, namely the working electrode compartment and the counter electrode compartment. The working electrode is immersed in a reaction medium comprising the metal complex to be activated, the solvent, the supporting electrolyte and any other material desired to control the electrolyte or to stabilize the resulting complex. The counter electrode is immersed in a mixture of solvent and supporting electrolyte. Preferred voltages may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte. Background cell current, i.e. current release in the absence of the desired electrolysis, is also measured. Electrolysis is completed when the current drops from the desired level to the background level. In this way, complete conversion of the initial metal complex can easily be detected.

Suitable supporting electrolytes are salts comprising cations and compatible, non-coordinating anions A ⁻ . Preferred supporting electrolytes are salts corresponding to the formula G ⁺ A ^- where G ⁺ is a cation which is unreactive to the starting and forming complexes, and A ^- is as defined above.

Examples of the cation G ⁺ include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 non-hydrogen atoms. Preferred cations are tetra (n-butylammonium)-and tetraethylammonium- cations.

During activation of the complex compounds of the present invention by bulk electrolysis, the cations of the supporting electrolyte migrate to the counter electrode and A ⁻ moves to the working electrode to become the anion of the resulting oxidation product. The cations of the solvent or supporting electrolyte are reduced at the counter electrode in an amount equivalent to the amount of the metal oxide complex produced at the working electrode. Preferred supported electrolytes are tetrahydrocarbylammonium salts of tetrakis (perfluoroaryl) borate having 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, in particular tetra (n-butylammonium) tetrakis (penta) Fluorophenyl) borate.

A more recently developed electrochemical technique for producing activating promoters is the electrolysis of disilane compounds in the presence of an uncoordinated, compatible anion source. This technique is described in more detail in the aforementioned US Pat. No. 5,625,087.

The aforementioned electrochemical activation techniques and activation promoters can also be used together. Particularly preferred combinations are mixtures of tri (hydrocarbyl) aluminum or tri (hydrocarbyl) borane compounds with oligomeric or polymeric alumoxane compounds having 1 to 4 carbons in each hydrocarbyl group.

The molar ratio of catalyst / cocatalyst used is preferably in the range from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1 and most preferably from 1: 1000 to 1: 1. Alumoxane, when used as an activating promoter by itself, is generally used in a quantity of at least 100 times the amount of the metal complex on a molar basis. Tris (pentafluorophenyl) borane, when used as an activating promoter, is from 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, most preferably from 1: 1 to 5: 1 Used as molar ratio for metal complexes. The remaining activating promoter is generally used in approximately equimolar amounts with the metal complex.

The process can be used to polymerize ethylenically unsaturated monomers having 3 to 20 carbon atoms alone or in mixtures. Preferred monomers include monovinylidene aromatic monomers, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene and C _3-10 aliphatic α-olefins (especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene), C _4-40 dienes and mixtures thereof. Most preferred monomers are ethylene and mixtures of ethylene, propylene and nonconjugated dienes, especially ethylidenenorbornene.

In general, the polymerization is carried out under conditions known in the prior art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, i.e. 0 to 250 ° C, preferably 30 to 200 ° C. Temperature and atmospheric pressure may be performed at a pressure of 10,000 atmospheres (100 MPa). Suspensions, solutions, slurries, gas phase, solid state powder polymerization or other process conditions may optionally be used. Supports, in particular silica, alumina or polymers (particularly poly (tetrafluoroethylene) or polyolefins) can be used and are preferably used when the catalyst is used in a gas phase polymerization process. The support preferably provides a weight ratio of catalyst (metal based): support from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20, most preferably from 1: 10,000 to 1:30. Used in quantity.

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

Suitable solvents for the polymerization are inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; Cyclic and cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; Perfluorinated hydrocarbons such as perfluorinated C _4-10 alkanes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like. Suitable solvents also include liquid olefins which can act as monomers or comonomers, for example ethylene, propylene, butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl- 1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene and vinyltoluene (including all isomers alone or in mixtures) and the like. Also suitable as mixtures of the foregoing compounds.

The catalyst can be used with one or more additional homogeneous or heterogeneous polymerization catalysts in separate reactors connected in series or in parallel to produce a polymer blend with the desired properties. Examples of such processes are disclosed in WO 94/00500, corresponding to US patent application 07 / 904,770, as well as WO 94/17112, corresponding to US patent application 08/10958 (filed Jan. 29, 1993). It is.

Using the catalyst of the present invention, copolymers having a low melt index, while having a high comonomer incorporation and a correspondingly low density, can be readily prepared. That is, high molecular weight polymers are readily obtained using the catalysts of the present invention even in elevated reactors. This result can easily be reduced by the use of hydrogen or similar chain transfer agents, but increasing the molecular weight of the α-olefin copolymer can usually only be achieved by reducing the polymerization temperature of the reactor. It is very desirable because it can. Disadvantageously, operating the polymerization reactor at a reduced temperature significantly increases the operating cost because it must remove heat from the reactor to maintain the reduced reaction temperature while simultaneously applying heat to the reaction effluent to volatilize the solvent. . In addition, productivity is increased due to improved polymer solubility, reduced solution viscosity and higher polymer concentration. Using the catalyst of the present invention, α-olefin homopolymers or copolymers having a density of 0.85 to 0.96 g / cm ³ and a melt flow rate of 0.001 to 10.0 dg / min are easily obtained in high temperature processes.

The polymers of the present invention will preferably have a high level of long chain branching. Using the catalysts described herein to prepare the polymers of the invention in a continuous polymerization process, in particular in a continuous liquid phase polymerization process, advantageously results in the production of vinyl terminated polymer chains that can be incorporated into the growth polymer to provide long chain branching. Enabling elevated reactor temperatures. The use of the catalysts described herein in the preparation of the polymers of the invention advantageously allows economic production of ethylene / a-olefin copolymers having similar processability to high pressure, free radical produced low density polyethylene.

The polymers of the invention, as measured by FTIR, will have preferably at least 0.03, more preferably at least 0.04, vinyl per 1000 carbons.

The polymers of the invention will preferably be characterized as having long chain branches, preferably from 0.01 to 3 long chain branches per 1000 carbons. Methods for measuring both the amount of long chain branching present qualitatively and quantitatively are known in the art.

For qualitative measurement methods, see, for example, US Pat. Nos. 5,272,236 and 5,278,272, which disclose the use of an apparent shear stress versus apparent shear rate plot to identify melt grinding phenomena. Preferred polymers of the present invention will have the following gas extrusion rheology: (a) having the same comonomer or comonomers, having I ₂ , M _w / M _n and density falling within 10% of the polymer of the present invention; Critical shear rate at the start of surface melt grinding for the polymer of the invention at least 50% greater than the critical shear rate at the beginning of surface melt grinding for the linear polymer, wherein each critical of the inventive polymer and linear polymer Shear rate is measured at the same melt temperature using a gas extrusion rheometer); Or (b) critical shear rate at the start of the global melt milling, as measured by a gas extrusion rheometer, greater than 4 × 10 ⁶ dyn / cm ² .

For quantitative measurement methods, see, for example, US Pat. No. 5,272,236 and Randall, Rev., which review long chain branching measurements using ¹³ C nuclear magnetic resonance spectroscopy. Macromol. Chem. Phys., C29 (2 & 3), 285-297], gel permeation chromatography coupled with low angle laser light scattering detector (GPC-LALLS) and gel permeation chromatography coupled with differential viscometer detector (GPC-DV) In consideration of the use of Zimm, GH and Stockmayer, WH, J. Chem. Phys., 17, 1301 (1949); and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York, 103-112 (1991).

The polymers of the invention are also characterized by having a polydispersity index, ie a melt flow ratio (I ₁₀ / I ₂ ) which can vary independently of the molecular weight distribution M _w / M _n . This feature gives the polymers of the present invention a high degree of processability despite the narrow molecular weight distribution. Preferably, the polymers of the present invention will have an I ₁₀ / I _{2 of} at least 10, preferably at least 15, with I ₁₀ / I ₂ values exceeding 20 being possible.

ATREF / DV can also be used to illustrate that the preferred copolymers of the present invention are characterized by having a bimodal molecular weight distribution. It is important to note that the ATREF peak is very sharp and distinguishes from the copolymer produced using the supported catalyst system. In particular, (i) measuring the maximum ATREF peak height, (ii) measuring the width of the overall ATREF peak at half the point of the maximum peak height, and calculating the ATREF shape factor, i.e. ratio (ii) / (i) The average ATREF elution temperature is measured, i.e., (minimum ATREF elution temperature + maximum ATREF elution temperature) / 2. The polymers of the present invention have an ATREF curve that satisfies the following inequality:

ATREF shape factor ≤ 0.90-0.00626 (average elution temperature),

Preferably, the ATREF curve satisfies the following inequality:

ATREF shape factor ≤ 0.75-0.00626 (average elution temperature),

Most preferably it will be characterized by having an ATREF curve that satisfies the following inequality:

ATREF shape factor <0.70-0.00626 (average elution temperature).

The polymer composition of the present invention is characterized by having a fraction having a higher transparency than the other fractions. The presence of high transparency fractions results in an improvement in the upper service temperature of the polymer composition of the present invention over the comparative composition. The upper service temperature can be defined as the intersection of the line drawn across the non-melted flat area at the top of the log G1 vs. temperature plot and the melting transition area falling. Preferably the upper service temperature of the olefin cross polymer [UST (cross-polymer) is provided in the first weight percent having a density, a first I ₂ comparable to the I ₂ which, comparable to the first density, depending on, for inequality a first homogeneous olefin polymer, and an upper service temperature of the second physical blend of a homogeneous olefin polymer is provided as a density, a second weight% has an I _2, comparable to the 2 I _2, comparable to the second density which is [ Greater than UST (blend)]:

UST (Interpolymer)-UST (Blend) ≥ 256-275 (density of olefin interpolymer)

The polymers of the present invention are preferably such that they polymerize ethylene alone or in small amounts of "H" branches, including dienes such as norbonadiene, 1,7-octadiene or 1,9-decadiene. Whether produced by polymerizing ethylene / a-olefin mixtures having, will have improved processing properties. The unique combination of elevated reactor temperature, high molecular weight (or low melt index) and high comonomer reactivity at high reactor temperatures advantageously enables economic production of polymers with excellent physical properties and processability. Preferably, the polymer comprises ethylene, C _3-20 α-olefins and “H” -branched comonomers. Preferably, the polymer is produced in a liquid phase process, most preferably in a continuous liquid phase process.

As mentioned above, the polymers of the present invention can be prepared by liquid phase processes or slurry processes already known in the art. Kaminsky, J. Poly. Sci., 23, 2151-2164 (1985) reported the use of a soluble bis (cyclopentadienyl) zirconium dimethyl-alumoxane catalyst system for the liquid phase polymerization of EP and EPDM elastomers. U.S. Patent 5,229,478 discloses a slurry polymerization process using a similar bis (cyclopentadienyl) zirconium based catalyst system.

In general terms, it is desirable to produce the EP and EPDM elastomers under conditions of increased reactivity of the diene monomer component. The reason is described in US Pat. No. 5,229,478 in the following manner, which remains true despite the advantages achieved in the above references. The main factor influencing the cost of production and hence the availability of EPDM is the diene monomer cost. Dienes are monomer materials that are more expensive than ethylene or propylene. In addition, the reactivity of the diene monomer with the metallocene catalyst known in the art is lower than that of ethylene and propylene. As a result, in order to achieve the degree of diene incorporation necessary to produce EPDM under an acceptable curing rate as fast as possible, substantially as compared to the percentage of diene desired to be incorporated into the final EPDM product, expressed as a percentage of the total concentration of monomer present. It is necessary to use excess diene monomer concentration. Since a sufficient amount of unreacted diene monomer must be recovered from the polymerization reactor effluent for recycle, the production cost is inevitably increased.

Adding to the EPDM production cost is generally the exposure of the olefin polymerization catalyst to the diene, especially the high concentration of diene monomer needed to provide the required level of diene incorporation in the final EPDM product, often resulting in the rate at which the catalyst proceeds to polymerize the ethylene and propylene monomers. Or reduces activity. Correspondingly, lower runoff and longer reaction times are required as compared to the production of ethylene-propylene copolymer elastomers or other α-olefin copolymer elastomers.

The catalyst system of the present invention advantageously allows for increased diene reactivity to make EPDM polymers produced in high yields and productivity. In addition, the catalyst system of the present invention achieves economical production of EPDM polymers with very high fast cure rates, having a diene content of 20% by weight or less.

Non-conjugated diene monomers may be straight, branched or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include straight chain acyclic dienes such as 1,4-hexadiene and 1,6-octadiene: branched chain acyclic dienes such as 5-methyl-1,4-hexa Dienes; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroocyene: single ring alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene: and multi-ring alicyclic fused and crosslinked ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene; Bicyclo- (2,2,1) -hepta-2,5-diene; Alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5- Vinyl-2-norbornene and norbornadiene. Another preferred diene is piperylene.

Among the dienes typically used to prepare EPDM, particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB) , 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD). Particularly preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD). Another preferred diene is piperylene.

Preferred EPDM elastomers may contain 20 to 90% by weight, more preferably 30 to 85% by weight, most preferably 35 to 80% by weight of ethylene.

Suitable α-olefins for use in the preparation of elastomers with ethylene and dienes are preferably C _3-16 α-olefins. Representative non-limiting examples of such α-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene. α-olefins are generally incorporated in EPDM polymers at 10 to 80% by weight, more preferably 20 to 65% by weight. Non-conjugated dienes are generally incorporated in EPDM at 0.5 to 20% by weight, more preferably 1 to 15% by weight and most preferably 3 to 12% by weight. In some cases, one or more dienes, for example HD and ENB, may be incorporated simultaneously, with the total diene incorporation within the limits specified above.

The catalyst system can be prepared as a homogeneous catalyst, by adding the necessary components to the solvent in which the polymerization is to be performed by the liquid phase polymerization procedure. The catalyst system can also be prepared and used as a heterogeneous catalyst by adsorbing the necessary components onto a catalyst support material, such as silica gel, alumina or other suitable inorganic support material. When produced in heterogeneous or supported form, it is preferred to use silica as the support material. Heterogeneous forms of the catalyst system are used in slurry polymerization. Due to conventional limitations, slurry polymerization takes place in liquid diluents in which the polymer product is almost insoluble. Preferably, the diluent for slurry polymerization is one or more hydrocarbons having less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or in part as diluents. Likewise, α-olefin monomers or mixtures of different α-olefin monomers may be used in whole or in part as diluents. Most preferably, the diluent comprises at least a majority of the α-olefin monomer or monomers to be polymerized.

In contrast, liquid phase polymerization conditions use solvents for the respective components of the reaction, in particular EP or EPDM polymers. Preferred solvents include mineral oils and various hydrocarbons that are liquid at reaction temperatures. Representative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as isopa (available from kerosene and Exxon Chemical Inc.). Isopar) mixtures of alkanes including E ^™ ; Cycloalkanes such as cyclopentane and cyclohexane; And aromatic compounds such as benzene, toluene, xylene, ethylbenzene and diethylbenzene.

At any time, the recovered components as well as the individual components must be protected from oxygen and moisture. Therefore, the catalyst components and the catalyst must be prepared and recovered in an atmosphere free of oxygen and moisture. Therefore, preferably, the reaction is carried out in the presence of anhydrous, inert gas, such as for example nitrogen.

Ethylene is added to the reaction vessel in an amount that maintains a differential pressure above the combined vapor pressure of the α-olefin and diene monomers. The ethylene content of the polymer is determined by the ratio of ethylene differential pressure to total reactor pressure. Generally, the polymerization process is carried out under ethylene differential pressure of 10 to 1000 psi (70 to 7000 kPa), most preferably 40 to 400 psi (30 to 300 kPa). The polymerization is generally carried out at a temperature of 25 to 200 ° C, preferably 75 to 170 ° C and most preferably 95 to 140 ° C.

The polymerization can be carried out in batch or continuous polymerization fixation. Preference is given to a continuous process in which the catalyst, ethylene, α-olefin, and optionally solvent and diene are continuously fed to the reaction zone and the resulting polymer is continuously removed therefrom.

Without limiting the scope of the invention in any way, one method for carrying out the polymerization process is as follows. The propylene monomer is continuously introduced into the stirred-tank reactor together with the solvent, diene monomer and ethylene monomer. The reactor contains a liquid phase consisting of ethylene, propylene and diene monomers with substantially any solvent or additional diluent. If desired, small amounts of “H” -branches may also be added, including dienes such as norbornadiene, 1,7-octadiene or 1,9-decadiene. The catalyst and cocatalyst are introduced continuously into the reactor liquid phase. Reactor temperature and pressure can be controlled by cooling or heating coils, quenches or both, as well as controlling solvent / monomer ratios, catalyst addition rates. The rate of polymerization is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the feed rate of each of these components in the reactor. The polymer product molecular weight is optionally controlled by other polymerization parameters such as temperature, monomer concentration, or by a hydrogen stream introduced into the reactor, as is known in the art. The reactor effluent is contacted with a catalyst kill agent such as water. The polymer solution is optionally heated and the polymer product is recovered by flashing off gaseous ethylene and propylene as well as residual solvents or diluents at reduced pressure and optionally further devolatilizing in a device such as a devolatilizing extruder. . In a continuous process, the average residence time of the catalyst and polymer in the reactor is generally 5 minutes to 8 hours, preferably 10 minutes to 6 hours.

In a preferred mode of operation, the polymerization is carried out in a continuous liquid phase polymerization system comprising two reactors connected in series or in parallel. In one reactor, a product having a molecular weight (M _w ) of 300,000 to 600,000, more preferably 400,000 to 500,000 is produced, while a product having a second molecular weight (M _w ) of 50,000 to 300,000 is produced in a second reactor. Is generated. The final product is a blend of two reactor effluents combined prior to devolatilization to produce a uniform blend of the two polymer products. The dual reactor process allows polymers with improved properties to be made. In a preferred embodiment, the reactors are connected in series, ie effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen are charged to the second reactor. Reactor conditions are controlled such that the weight ratio of polymer produced in the first reactor to polymer produced in the second reactor is from 20:80 to 80:20. In addition, the temperature of the second reactor is controlled to produce a low molecular weight product. The system advantageously allows the production of EPDM products with a wide range of Mooney viscosities as well as excellent strength and processability. Preferably, the Mooney viscosity (ASTM D1646-94, ML1 + 4 at 125 ° C.) of the resulting product is adjusted to fall in the range of 1 to 200, preferably 5 to 150, most preferably 10 to 110.

In addition, while mono (cyclopentadienyl) group 4B metal compounds may find significant commercial advantages in the polymerization of ethylene / α-olefin interpolymers in fact, they are constantly looking for improvements in the industry, in particular mono (cyclopenta) It was intended to find an advantage in catalysts that withstand higher reaction temperatures than those of dieneyl) catalysts. Such high reaction temperatures convert them into polymers exhibiting high vinyl unsaturation, making them particularly useful as precursors to functionalized polymers and increasing long chain branch incorporation when suitable polymerization conditions are used.

According to the present invention, (1) a metal complex corresponding to formula (1); And (2) the activating promoter (the molar ratio of (1) :( 2) is 1: 10,000 to 100: 1), or the reaction product produced by converting (1) to an active catalyst using an activation technique. There is provided a product produced by a process for preparing a polymer of an olefin monomer comprising contacting a catalyst with at least one such monomer:

Where

M is titanium, zirconium or hafnium in the +2, +3 or +4 type oxidation state;

A ′ is at least 2 or 3 in a group selected from hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germanyl and mixtures thereof A substituted indenyl group containing up to 40 non-hydrogen atoms, wherein A 'is also covalently bonded to M by a divalent Z group;

Z is a divalent moiety bonded to both A 'and M by σ-bond, and comprises boron or a group 14 member of the periodic table of elements, and also includes nitrogen, phosphorus, sulfur or oxygen, preferably hydrocarbyl Z has an aliphatic or cycloaliphatic hydrocarbyl or substituted hydrocarbyl group covalently bonded thereto so that the group is covalently bonded to Z by primary or secondary carbon;

X is an anionic or anionic ligand group having up to 60 atoms except for the ligand class which is a cyclic delocalized π-binding ligand group;

X 'is each independently a neutral linking compound having up to 20 atoms;

p is 0, 1 or 2, and 2 is less than the formal oxidation state of M, provided p is 1 when X is an anionic ligand;

q is 0, 1 or 2.

(1) a metal complex corresponding to formula (Ia) below; And (2) the activating promoter (the molar ratio of (1) :( 2) is 1: 10,000 to 100: 1), or the reaction product produced by converting (1) to an active catalyst using an activation technique. Also disclosed is a product produced by a process comprising reacting at least one α-olefin in the presence of a catalyst:

Where

M is titanium, zirconium or hafnium in the +2, +3 or +4 type oxidation state;

R 'and R "are independently at each occurrence hydride, hydrocarbyl, silyl, germanyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbyl) amino, hydrocarbyleneamino, Di (hydrocarbyl) phosphino, hydrocarbylene-phosphino, hydrocarbyl sulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted Hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl, di (hydrocarbyl) amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di (hydrocarbyl) phosphino-substituted hydrocarbyl, hydrocar Bilylene-phosphino-substituted hydrocarbyl, or hydrocarbyl sulfido-substituted hydrocarbyl, wherein the R 'or R "group has a ratio of up to 40 -Have a hydrogen atom, and optionally two or more of the aforementioned groups can together form a divalent derivative;

R ″ ′ is a divalent hydrocarbylene- or substituted hydrocarbylene group that forms a fusion system with the rest of the metal complex and contains 1 to 30 non-hydrogen atoms;

Z is a divalent moiety or a moiety comprising one σ-bond and a neutral two electron pair capable of forming a coordination-covalent bond to M, wherein Z comprises a boron or group 14 member of the Periodic Table of the Elements, Also includes nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms except for the ligand class which is a cyclic delocalized π-binding ligand group;

X 'is each independently a neutral linking compound having up to 20 atoms;

X ″ is a divalent anionic ligand group having up to 60 atoms;

p is 0, 1, 2 or 3;

q is 0, 1 or 2,

r is 0 or 1;

Preferably, by means of a liquid phase polymerization process, the catalysts and methods of the invention used for the polymerization of the polymers of the invention are characterized in that the high molecular weight olefin polymers, in particular ethylene / α-olefin interpolymers, ethylene / propylene at a wide range of polymerization conditions and especially at elevated temperatures / Diene interpolymers (EPDM), where dienes are ethylidenenorbornene, 1,4-hexadiene or similar nonconjugated dienes. The use of elevated temperatures not only allows the increased solubility of the polymer at elevated temperatures to enable the use of increased conversions (higher concentrations of polymer product) without exceeding the solution viscosity limit of the polymer equipment, as well as the energy required to devolatilize the reaction product. The fact that the cost is reduced dramatically increases the productivity of the process.

The invention also provides an olefin interpolymer, preferably an ethylene and at least one C ₃ -C ₂₀ α-olefin, characterized in that it satisfies at least four of the following criteria, in particular all five of the following criteria:

(a) I ₂ of 100 g / 10 min or less,

(b) M _w / M _n between 1.5 and 3.0,

(c) at least 0.03 vinyl / 1000 carbon, as measured by FTIR, and

(d) two or more distinct ATREF peaks, each satisfying the following inequality: ATREF shape factor <0.90-0.00626 (average elution temperature).

The use of indenyl and insenenyl catalysts as disclosed herein results in the production of polymers with high vinyl termination rates. The high levels of vinyl / 1000 carbons produced make the polymer of the present invention particularly useful for applications in which the polymer is functionalized continuously. The resulting high levels of vinyl / 1000 carbons also make the polymer able to achieve higher levels of long chain branching when the appropriate polymerization conditions are used.

Preferably, the polymers of the present invention will be characterized as having I ₁₀ / I _{2 of} at least ₁₀ , preferably at least 12, most preferably at least 15.

As a more qualitative label of long chain branching, the polymers of the invention preferably have a critical shear rate at the start of surface melt grinding at least 50% greater than the critical shear rate at the beginning of surface melt grinding for linear interpolymers. It will also be characterized, wherein the nearly linear interpolymer and the linear interpolymer comprise the same comonomer or comonomers, the linear interpolymer being I ₂ , M _w / M which falls within 10% of the nearly linear interpolymer. The critical shear rate for each of the linear and linear interpolymers with _n is measured at the same melt temperature using a gas extrusion rheometer.

The olefin interpolymers of the present invention are characterized in particular as bimodal in terms of short chain branch distribution and molecular weight, as evidenced by differential scanning calorimetry and ATREF curves as well as deconvoluted gel permeation chromatography. do. This effect is especially true for interpolymers having a density of up to 0.910 g / cm ³ .

It has been found that interpolymers of the invention having a density of less than 0.890 g / cm ³ , in particular a density of 0.880 g / cm ³ or less, more particularly a density of less than 0.870 g / cm ^3, have a particularly good and very unique balance of properties. . In particular, the polymer is associated with an upper service temperature exceeding that of the physical blend of interpolymers corresponding to the components of the interpolymers of the present invention as identified by the deconvolution of a typical gel permeation chromatograph. It has improved elastic properties, such as a compression set of less than%, preferably less than 85%, more preferably less than 80%. The uniqueness of the interpolymers of the present invention is demonstrated in micrographs obtained by transmission electron microscopy, which clearly shows that the presence of a thin film in the interpolymer, whose density suggests, should be completely amorphous.

The olefin interpolymers of the present invention are used in a variety of applications, including but not limited to films, fibers, foams, injection molded parts, rotomolded parts, and combinations of adhesives, sealants, coatings, caulks, and asphalts. It is expected to have great utility as components.

These and other aspects are described in more detail in the detailed description below.

Those skilled in the art will appreciate that the invention disclosed herein may be practiced in the absence of any component not specifically disclosed. The following examples are provided to further illustrate the invention and are not intended to be limiting. Unless stated otherwise, all parts and percentages are by weight.

¹ H and ¹³ C NMR spectra were recorded on a Varian XL (300 MHz) spectrometer. Chemical conversion was determined from the residual CHCl ₃ or C ₆ D ₆ residual C ₆ HD ₅ in CDCl ₃ of about about TMS, or TMS. Tetrahydrofuran (THF), diethyl ether, toluene and hexane, double charged with activated alumina and alumina supported mixed metal oxide catalysts (Q-5 ^R catalyst, commercially available from Engelhard Corp.) It was used to track the path through the column. Compound n-BuLi, KH, all Grignard reagents and 1,4-diphenyl-1,3-butadiene were all used as purchased from Aldrich Chemical Company. All synthesis was performed under anhydrous nitrogen atmosphere using a combination of glove box and high vacuum technique.

Preparation of Catalyst (I): [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl

Preparation of Dimethylsilyl (2,3,4,6-tetramethylindenyl) (isopropylamine):

Dimethylsilyl (2,3,4,6-tetramethylindenyl) Cl (22.29 g, 84.17 mmol) was stirred in THF with the addition of i-PrNH ₂ (28.68 mL, 336.7 mmol). The mixture was stirred for 16 hours. The volatiles were removed under reduced pressure. The residue was extracted with hexanes and filtered through diatomaceous earth filter aid on 10-15 mm glass frit. Hexane was removed under reduced pressure to give the product as a yellow oil. Yield: 17.23 g, 71%.

Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride:

In a dry box, 17.23 g (59.93 mmol) of dimethylsilyl (2,3,4,6-tetramethylinyl) (isopropylamine) was dissolved in 350 ml of hexane in a 500 ml round bottom Schlenk flask. I was. Then 2 equivalents of n-BuLi (47.94 mL, 2.5 M in hexane) were added by syringe. The reaction was stirred for 12 hours. The solvent was removed under reduced pressure to give an orange powder. The powder was dissolved in 250 ml of THF. TiCl ₃ (THF) ₃ (22.2 g, 59.93 mmol) was added as a solid. After 15 minutes, CH ₂ Cl ₂ (2.48 mL, 29.97 mmol) was added. After 2 hours, the solvent was removed under reduced pressure. The residue was extracted with toluene and filtered through a diatomaceous earth filter aid on a 10-15 mm glass frit. Toluene was removed under reduced pressure. The residue was slurried in hexanes and filtered over 10-15 mm glass frit. The residue was dried under reduced pressure to give a red powder. Yield: 12.3 g, 51%.

Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl:

In anhydrous box, [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride (6.92 g, 17.12 mmol) was charged in 150 ml of 250 ml round bottom flask. Dissolved in ml of Et ₂ O. Two equivalents of a 3.0 M THF solution of MeMgCl (11.41 mL, 34.23 mmol) were added. The mixture was stirred for 1 hour. The volatiles were removed under reduced pressure. The residue was extracted with hexanes and filtered through diatomaceous earth filter aid on 10-15 mm glass frit. Hexane was removed under reduced pressure to give an orange powder. Yield: 5.8 g, 93%.

Preparation of Catalyst Composition (II): [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl

Preparation of Dimethylsilyl (2,3,4,6-tetramethylindenyl) (cyclohexylamine):

Dimethyl silyl (2,3,4,6-tetramethylindenyl) Cl (9.95 g, 37.8 mmol) with addition of NEt ₃ (4.1 g, 40.6 mmol) followed by cyclohexylamine (4.05 g, 40.8 mmol) Was stirred in hexane. The mixture was stirred at 20 ° C for 24 h. After the reaction time, the mixture was filtered, volatiles were removed and the desired product was isolated as pale yellow oil (10.98 g, 89.3% yield).

Preparation of Dilithium (N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane:

In anhydrous box, 4.0 g (12.6 mmol) of (N-cyclohexylamino) (dimethyl) (2,3,4,6-tetramethylindenyl) silane was dissolved in 300 ml of hexane. To this solution was added dropwise 12.6 mL of n-BuLi (2.00 M) at 20 ° C. When the addition of n-BuLi was complete, the solution was stirred for 12 hours and then the solvent was removed under reduced pressure to give 4.12 g (96% yield) of a yellow-orange powder.

Preparation of [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride:

In anhydrous boxes, 4.63 g (12.5 mmol) TiCl ₃ (THF) ₃ was dissolved in 75 mL THF. To this solution, 4.12 g (12.5 mmol) of dilithium (N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane was added as a solid at 20 ° C. with stirring. The solution was then stirred for 45 minutes. After this time, 1.73 g (6.25 mmol) PbCl ₂ was added and the solution stirred for 45 minutes. Then, THF was removed under reduced pressure. The residue was then extracted with toluene, the solution was filtered and toluene was removed under reduced pressure. The residue was then triturated with hexanes and the solution volume reduced, at which time a red precipitate formed which was collected by filtration and washed with cold (0 ° C.) hexanes. The solid product was dried under vacuum to yield 1.70 g (31% yield) of the product.

Preparation of [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl:

In anhydrous box, 0.300 g of [(Nt-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride (0.675 mmol) at 50 ° C. was added 50 ml of Et It was suspended in ₂ O. 0.45 mL of MeMgI (3.0 M) was added dropwise to the suspension over 20 minutes with stirring. After the addition of MeMgI was complete, the solution was stirred for 40 minutes. Then Et ₂ O was removed under reduced pressure, the residue was extracted with hexane, the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to yield 0.27 g (100% yield) of the product.

Preparation of Catalyst Composition (III): [(tetramethylcyclopentadienyl) (dimethyl) (t-butylamido) silane] titanium 1,3-pentadiene

Preparation of TiCl ₃ (DME) _1.5 :

The device (called R-1) was mounted in a hood and purged with nitrogen; The apparatus consists of a 10 L glass kettle with a flush installed bottom valve, 5-neck head, polytetrafluoroethylene gasket, clamps and agitator components (bearings, shafts and paddles). The neck was mounted as follows: The stirrer components were placed on the central neck and the outer neck had a gas inlet / outlet, a solvent inlet, a thermocouple and a reflux condenser fitted with a stopper. Anhydrous, deoxygenated dimethoxyethane (DME) was added to the flask (about 5.2 L). In a dry box, 300 g of TiCl ₃ are metered into a homogenized powder addition funnel; The funnel was blocked and removed from the dry box and placed on the reaction kettle instead of the stopper. TiCl ₃ was added for about 10 minutes with stirring. After the addition was complete, the remaining TiCl ₃ was rinsed into the flask with additional DME. The procedure was then repeated with 325 g of additional TiCl ₃ to give a total of 625 g. Additional funnel was replaced with a stopper and the mixture was heated to reflux. The color changed from purple to light blue. The mixture was heated for about 5 hours, cooled to room temperature, then the solid was precipitated and the supernatant was poured off from the solid. TiCl ₃ (DME) _1.5 remained in R-1 as a light blue solid.

Preparation of [(Me ₄ C ₅ ) SiMe ₂ NtBu] [MgCl ₂ ]:

The apparatus (referred to as R-2) was mounted as described for R-1 except that the flask size was 30 liters. Seven necks on head; The central neck was equipped with an outer neck containing a stirrer and a condenser with nitrogen inlet / outlet, vacuum adapter, reagent tube, thermocouple and stopper. The flask was charged with 7 L toluene, 2.17 M iPrMgCl in 3.09 kg Et ₂ O, 250 ml THF and 1.03 kg (Me ₄ C ₅ H) SiMe ₂ NHtBu. The mixture was then heated and the ether was boiled into a trap cooled to -78 ° C. After 3 hours, the temperature of the mixture reached 80 ° C., at which time a white precipitate formed. The temperature was then raised to 90 ° C. over 30 minutes and held at this temperature for 2 hours. At the end of this time, the heater was turned off and 2 L of DME was added to the hot stirred solution to produce additional precipitate. The solution was cooled to room temperature, the material precipitated and the supernatant was poured from the solid. Toluene was added, stirred for a few minutes, a solid precipitated out and the toluene solution was poured off for further washing. [(Me ₄ C ₅ ) SiMe ₂ NtBu] [MgCl ₂ ] remained in R-2 as a gray solid.

Preparation of [(η ₅ -Me ₄ C ₅ ) SiMe ₂ NtBu] Ti (η ₄ -1,3-pentadiene):

The material remaining in R-1 and R-2 was slurried in DME (total volume of the mixture was 5 L at about R-1 and 12 L at R-2). The contents of R-1 were transferred to R-2 using a moving tube connected to one of the bottom valve of the 10 L flask and the head opening of the 30 L flask. The material remaining in R-1 was washed with additional DME. The mixture quickly darkened to dark red / brown. After 15 minutes, 1050 ml of 1,3-pentadiene and 2.60 kg of 2.03 M nBuMgCl in THF were added simultaneously. The maximum temperature reached in the flask during the addition was 53 ° C. The mixture was stirred for 2 hours and then about 11 L of solvent was removed under vacuum. Hexane was then added to the flask to make a total volume of 22 liters. The material was allowed to settle and the liquid layer (12 L) was poured into another 30 L glass kettle (R-3). Hexane was added to R-2, stirred for 50 minutes, precipitated again and poured off to collect an additional 15 L of product solution. The material was combined with the first extract in R-3. The solvent in R-3 was removed under vacuum leaving a red / black solid which was then extracted with toluene. The material was transferred to a storage cylinder. Analysis showed that the solution (11.75 L) was a 0.225 M solution in titanium, which was 3.0 moles or 1095 g of [(η ₅ -Me ₄ C ₅ ) SiMe ₂ NtBu] Ti (η ₄ -1,3-pentadiene) Corresponds to This is 74% yield based on titanium added as TiCl ₃ .

Preparation of Soluble Borate Cocatalyst ((bis (Hydrogenated-Tallowalkyl) methylamine)) (B-FABA)

Methylcyclohexane (1200 mL) was placed in a 2 L cylindrical flask. While stirring, bis (hydrogen-tallowalkyl) methylamine (ARMEEN ^R M2HT, 104 g, triturated in granule form) was added to the flask and stirred until complete dissolution. Aqueous HCl (1M, 200 mL) was added to the flask and the mixture was stirred for 30 minutes. A white precipitate formed immediately. At the end of this time, LiB (C ₆ F ₅ ) ₄ .Et ₂ O. 3LiCl (MW = 887.3; 177.4 g) was added to the flask. The solution began to turn milky white. The flask was equipped with a 6 inch (15 cm) Vigreux column equipped with a distillation apparatus and the mixture was heated (140 ° C. outer wall temperature). A mixture of ether and methylcyclohexane was distilled out of the flask. The two-phase solution was only slightly cloudy. The mixture was cooled to room temperature and the contents placed in a 4 L separating funnel. The aqueous layer was removed and discarded, the organic layer was washed twice with H ₂ O, and the aqueous layer was discarded again. The resulting solution was divided into two equal portions for evaluation of the two working procedures. The H ₂ O saturated methylcyclohexane solution was determined to contain 0.48% by weight of diethyl ether (Et ₂ O).

The solution (600 mL) was transferred to a 1 L flask, sparged thoroughly with nitrogen and transferred to anhydrous box. The solution was passed through a column (13 inches (2.5 cm) diameter, 6 inches (15 cm) high) containing 13-fold molecular sieves. This reduced the amount of Et ₂ O from 0.48% by weight to 0.28% by weight. The material was then stirred for 4 hours on fresh 13-fold molecular sieves (20 g). Subsequently, the amount of Et ₂ O was measured at 0.19 wt%. The mixture was then stirred overnight, further reducing the amount of Et ₂ O to about 40 ppm. The mixture was filtered using a funnel equipped with a glass frit having a pore size of 10-15 μm to give a clear solution (molecular sieve rinsed with additional anhydrous methylcyclohexane). Concentration was determined by gravimetric analysis to give a value of 16.7% by weight.

Polymerization of Polymers of Examples and Comparative Examples of the Invention:

The polymer product of the examples was produced in a liquid phase polymerization process using a well-mixed recycle loop reactor. For polymers produced using catalyst (I), the addition package contains 1500 ppm potassium stearate, 600 ppm Irganox ^™ 1076 hindered phenolic antioxidant, and 950 ppm PEPQ (tetrakis (2)). , 4-di-t-butylphenyl) -4,4'-biphenylene diphosphonite) (commercially available from Clarit Corp.). For the polymer produced using catalyst (II), the addition package was 1450 ppm calcium stearate, 600 ppm Irganox ^™ 1076 and 930 ppm PEPQ. For polymers produced using catalyst (III), the addition package was 640 ppm calcium stearate, 260 ppm Irganox ^™ 1076 and 400 ppm PEPQ.

Ethylene and hydrogen (as well as ethylene and hydrogen recycled from the separator) are combined in one stream, and then the diluent mixture, ie C ₈ -C ₁₀ saturated hydrocarbons, such as ISOPAR ^TM -E (Exon Chemical Company) Commercially available) and in the mixture of comonomer 1-octene.

The metal complexes and cocatalysts were combined into a single stream and continuously injected into the reactor. For Examples 1a, 1b and 1c, the catalyst was as prepared in Catalyst Preparation (I). For Examples 2a, 2b, 2c and 2d, the catalyst was as prepared in Catalyst Preparation (II). For Comparative Examples C-3a and C-3b, the catalyst was as prepared in Catalyst Preparation (III). In each and the comparative examples, the primary and secondary promoters were as prepared in promoter example 1 and promoter example 2.

Sufficient residence time allowed the metal complex and cocatalyst to react before being introduced into the polymerization reactor. The reaction pressure was kept constant at about 450 to 475 psig (3.1 to 3.3 MPa).

After the polymerization, the reactor effluent stream is introduced into the separator, where the molten polymer is separated from the unreacted monomer (s), unreacted ethylene, unreacted hydrogen and diluent mixture streams, which in turn is introduced into a reactor for fresh air. Recycle for mixing with monomer, ethylene, hydrogen and diluent. The molten polymer was subsequently cut or pelletized into strands, cooled in a water bath or pelletizer and the solid pellets collected. Table 1 describes the polymerization conditions and the resulting polymer properties.

Table 2 shows the melt composition (I ₂ ), density and melt flow ratio (I ₁₀ / I ₂ ) of the ethylene / octene copolymer prepared using the catalyst composition (III) to the catalyst compositions (I) and (II). Compared with the polymer of the present invention prepared using. Significantly higher molecular weight copolymers were produced using catalyst compositions (I) and (II) than those produced using catalyst composition (III). For example, at a reactor temperature of 122 ° C., catalyst (I) produced a polymer with I ₂ of 0.7 dg / min, while catalyst (III) produced a polymer with I ₂ of 116 dg / min. The use of catalysts (I) and (II) is advantageous in that it produces copolymers of specific molecular weight at higher reactor temperatures, reducing solution viscosity, reactor pressure drop, reactor contamination and improving the overall process economy.

As also illustrated in Table 2, the copolymers produced using catalysts (I) and (II) have higher melt flow ratios. The higher melt flow ratio is preferred in that copolymers with higher melt flow ratios are easier to process, for example, significantly lower pressures and currents are observed while the copolymer is converted to plastic parts. do.

Property Information for Polymers of Examples and Comparative Examples Example catalyst Reaction temperature (℃) I ₂ (g / 10 min) I ₁₀ I ₁₀ / I ₂ Annealing Density (g / cm ³ ) C-3a III 88.0 0.48 4.5 9.38 0.8667 1a I 122.0 0.71 8.22 11.58 0.8710 1b I 122.0 0.63 7.74 12.29 0.8700 1c I 122.0 0.82 8.95 10.91 0.8703 2a II 129.4 0.5 7.61 15.22 0.8606 2b II 129.4 0.43 5.84 13.58 0.8612 2c II 129.5 0.38 5.47 14.39 0.8612 2d II 129.0 0.38 3.84 10.11 0.8615 C-3b III 122.0 116 650 6.00 0.8612 C-2a ^* II 0.49 6.53 0.8635 * Samples prepared in a batch reactor

Batch polymerization experiments were performed using a 1 gallon stirred autoclave engineer reactor. The reactor was charged with 1440 g of Isowave E, the indicated amount of 1-octene and hydrogen, then heated to the desired temperature and saturated with ethylene to 450 psig (3.1 MPa). The catalyst was prepared in an anhydrous box by injecting the catalyst, cocatalyst, and scavenger solution with additional solvent together to provide a total volume of 17 ml. The catalyst solution was then transferred to the catalyst addition loop by syringe and injected into the reactor for about 4 minutes using a high pressure solvent stream. The polymerization was allowed to proceed for 10 minutes while feeding ethylene as needed to maintain a pressure of 445 psig (3.07 MPa). The amount of ethylene consumed during the reaction was investigated using a mass flow meter. The polymer solution was poured from the reactor into a nitrogen-purged glass kettle containing 10-20 ml of isopropanol. An aliquot of the addition solution described below was added to the kettle and the solution was stirred thoroughly (the amount of additive used was selected based on the total ethylene consumed during the polymerization). The polymer solution was poured into a tray, air dried overnight and then completely dried in a vacuum oven for 2 days. The weight of the polymer was recorded and the efficiency was calculated in grams of polymer per gram of transition metal.

Differential Scanning Calorimetry (DSC) data for the polymers of the Examples and Comparative Examples are shown in Table 3 below:

Differential Scanning Calorimetry (DSC) Data for Polymer Compositions of the Invention and Comparative Example Example catalyst DSC Calculation ASTM Annealing Density (g / cm ³ ) Tm1 (℃) Tm2 (℃) Tc1 (° C) Tc2 (° C) Tm1 density (g / cc) Tm2 density (g / cc) C-3a III 46.32 30.79 0.866 0.8667 1a I 74.73 63.39 0.884 0.8710 1b I 74.33 63.79 0.884 0.8700 1c I 77.99 65.93 0.886 0.8703 2a II 24.26 91.19 10.33 67.53 0.854 0.897 0.8606 2b II 26.85 91.19 11.66 67.59 0.855 0.897 0.8612 2c II 26.86 91.73 11.79 67.39 0.855 0.898 0.8612 2d II 29.06 91.79 13 67.6 0.856 0.898 0.8615 C-3b III 61.92 49.8 0.875 0.8612 C-2a ^* II 41.07 91.86 24.11 75.48 0.863 0.898 0.8635

When providing the total ASTM density of the copolymers produced using catalysts (I) and (II), the melting point (Tm) and crystallization point (Tc) of the copolymers of the comparative examples prepared using catalyst (III) Very different from the values. This distinction is also illustrated in the DSC endograms of copolymers C-3a (catalyst (III)) and 1a (catalyst (I)) shown in FIGS. 2 and 3.

First, the copolymer of the invention prepared using catalyst (I) has a Tm at least 10 ° C. higher than the polymer of the comparative example produced using catalyst (III), which will lead to an improved top service temperature. It is expected. The higher upper service temperature is clearly evidenced by the synchronous data discussed below.

In addition, as can be seen in Figures 4 and 3, the DSC thermograms of the copolymers produced using catalyst (II) have distinct dual phase characteristics. In fact, the DSC thermogram for the polymer of Example 1a corresponds to the DSC thermogram of the blend of two copolymers with densities of 0.855 and 0.897 g / cm ³ , respectively.

The bimodal properties of the polymers of the invention prepared using catalyst (II) are also illustrated in the micrographs of polymer 2a produced by transmission electron microscopy (TEM), where the higher density copolymer fractions are shown in the micrographs. The thin film produced by it can be clearly seen. For example, as can be seen in Figure 5, a well defined thin film was present in the polymer of Example 2a. The ribbon-like structure having an aspect ratio of about 16 (1120 Å × 70 Å) appears to be relatively isolated in a matrix of granule-like tuft-like colloidal structures having an aspect ratio close to 1 (70 Å). In contrast, as can be seen in FIG. 6 (although it has a kind of structure with an aspect ratio of about 6), a TEM micrograph made of the copolymer of Comparative Example C-3a prepared using catalyst (III) There was no well defined thin film. Despite the fact that the copolymer of Comparative Example C-3a has a higher density than the copolymer of Example 2a, it lacked a thin film.

Assuming that octenes are randomly incorporated into the copolymers of the present invention and the comparative examples, the final density can be calculated according to the following equation:

1 / ρ ₁ = w ₁ / ρ ₁ + w ₂ / ρ ₂

Wherein ρ ₁ is the final density, ρ ₁ and ρ ₂ are the densities of the first and second component fractions, and w ₁ and w ₂ are the weight fractions of the component fractions.

The polymers of Examples 1b and 2a and Comparative Examples C-3a and C-2a ^* were analyzed for short chain branching distribution by ATREF. The results are shown in Table 4 below:

Measurement of comonomer incorporation by ATREF Example catalyst ATREF Calculation ASTM Annealing Density (g / cm ³ ) Purge amount (%) Elution temperature (℃) Calculated Density (g / cc) Tm1 density (g / cc) Tm2 density (g / cc) C-3a III 100 0.866 0.8667 1b I 63.8 53.00 0.8855 0.884 0.8700 2a II 92.3 62.45 0.8950 0.854 0.897 0.8606 C-2a ^* II 90.1 60.85 0.8934 0.863 0.898 0.8635 Comparative Example C-2a was produced in a batch reactor.

The ATREF curves for Examples 1b and 2a and Comparative Examples C-3a are shown in FIG. 7A. Since the overall density of the copolymers is relatively low, most of the copolymer eluted with the purge, ie the copolymer did not crystallize from the solvent (trichlorobenzene). In fact, 100% of the copolymer of Comparative Example C-3a eluted with the purge. ATREF data showed that both catalysts (I) and (II) produced a bimodal copolymer in the short chain branching distribution. More particularly, most of the copolymers produced from these catalysts were low density copolymers eluted with purge, but there were also high density copolymers which produced peaks in the ATREF chromatogram shown in FIG. 7A. When comparing the copolymer of catalyst (I) with the copolymer of catalyst (II), catalyst (II) produced a smaller amount of high density copolymer. As can be seen in Table 4, the copolymer density calculated from ATREF was similar to the DSC estimate. For example, while the copolymer of Example 2a has a density of 0.861 g / cm ³ , the ATREF peak is typically prepared using catalyst (III) and almost linear ethylene / 1 having a density of 0.895 g / cm ³ . Corresponds to the value seen for the octene copolymer. This is typical for Example 1a of the copolymer is, the substantially linear ethylene / 1-octene copolymer prepared using the catalyst (III) has a density of 0.897 g / ㎝ ³ has a density of 0.871 g / ㎝ ³ The DSC endotherm corresponding to the value seen as is consistent with the finding. For the example, 0.895 g / ㎝ ³ density and 1.6 g / 10 minutes I ₂ and 9.9 of the I ₁₀ / I ₂ of which, carried out ATREF of the copolymers prepared using the catalyst (III) Example 2a of See FIG. 7b compared to the copolymer.

Similarly, while the copolymer of Example 1b has a density of 0.870 g / cm ³ , the ATREF peak is prepared using catalyst (III) and has a nearly linear ethylene / 1-octene air with a density of 0.886 g / cm ³ . Corresponds to the values typically seen for coalescing, which indicates that the copolymer of Example 1b is a nearly linear ethylene / 1-octene air prepared using catalyst (III), having a density of 0.884 g / cm ³ . This finding is consistent with the findings that indicate DSC endotherms corresponding to the values typically seen for coalescence.

ATREF / DV can also be used to illustrate the fact that the copolymers of the invention are characterized by having a bimodal molecular weight distribution. For example, as shown in FIG. 7C, the ATREF refractive index detector shows a single short chain branch distribution of the copolymer of Example 45e produced by catalyst (II). In addition, the ATREF differential viscometer detector (right vertical axis) has a 92% by weight low density component with copolymers eluting at about 71 ° C. and a weight average molecular weight of 417000 Daltons, and a weight average molecular weight of 174000 Daltons eluting at about 85 ° C. It contains about 8% by weight of the high density component. Thus, the ATREF M _w1 / M _n2 ratio was 2.40, which is similar to the value measured by the GPC delineation, ie 2.41, shown in Table 6.

7D below is a plot of ATREF shape factor versus average ATREF elution temperature. In the plot, the data were generated from the ATREF curve. Specifically, (i) the maximum ATREF peak height was measured, (ii) the width of the total ATREF peak at half the maximum peak height was measured, and the ATREF shape factor, ie, ratio (ii) / (i), was determined. The average ATREF elution temperature, i.e. (minimum ATREF elution temperature + maximum ATREF elution temperature) / 2, was determined. For the inventive copolymers produced using catalyst (II), the ATREF shape factor is described as the reference ATREF shape factor = 0.64-0.00626 (average ATREF elution temperature), which is an ATREF shape of 0.165 at an average elution temperature of 75.94 ° C. Point to an argument.

As the DSC and ATREF information illustrate, the polymer composition of the present invention is characterized by having a fraction having a higher transparency than the other fractions. The presence of the high transparency fraction improves the upper service temperature of the polymer composition of the present invention over the comparative composition prepared using catalyst (III). In particular, the synchronous data for the copolymers of Examples 1a and 2a and Comparative Examples C-3c are compared in FIG. 8. Figure 8a compares the storage modulus (G ') and tan d (G "/ G') as a function of temperature, of examples 1a and 2a produced using catalysts (I) and (II), respectively, at high temperatures. The copolymer was more elastic than the copolymer of Comparative Example C-3c produced using catalyst (III) High elasticity is a desirable attribute for applications such as thermoforming The upper service temperature is the intersections of Figure 8b. As can be seen, it can be defined as the intersection of a line drawn across the non-melted flat region and the falling melting transition region at the top of the log G1 vs. temperature plot The upper service temperature of the copolymer of Example 1a is 54 ° C. The upper service temperature of the copolymer of Comparative Example C-3a was 75 ° C., 21 ° C. higher than the copolymer of Comparative Example C-3a. C, which indicates that the copolymer of Example 2a Especially surprising in that it has a lower density than the polymer C-3c.

Moreover, it is important to note that the improvement in the upper service temperature exceeds that achieved by blending a separate near linear ethylene / 1-octene copolymer having a density corresponding to each of the fractions of the inventive copolymer. . 9A compares the top service temperature of the copolymer produced using catalyst (II) as a function of density with the copolymer produced using catalyst (III). The curve in FIG. 9A was a simple polynomial fit across the data. Copolymers prepared using catalyst (II) used in FIG. 9A include Example 2a, and examples prepared using the batch polymerization process shown above using catalyst (II) and the following reaction conditions:

Example Catalyst ¹ (μmol) Octene (g) Ethylene (g) H ₂ (mmol) Temperature (℃) efficiency Melt index, I ₂ (dg / min) Melt Flow Ratio (I ₁₀ / I ₂ ) ASTM Density (g / cc) 45a 15 37.5 117 20 170 0.042 0.31 6.56 0.9131 45j 7.5 253.7 132.7 5 155 0.168 1.36 6.94 0.8655 45n 7.5 140.5 125 20 155 0.181 0.36 22.87 0.8823 ¹ (2,3,4,6-tetramethyl-indenyl) dimethyl (cyclohexylamido) silane titanium dimethyl

For copolymers having a density of 0.87 g / cm ³ , the upper service temperature of the copolymer produced using catalyst (II) was 33 ° C. higher than the comparative polymer made using catalyst (III).

9B shows an increase in the upper service temperature (UST) that can be achieved by blending copolymers prepared using catalyst (III) and the UST achievable by copolymers of the invention prepared using catalyst (II). The increase is compared. The study shows that about 20% by weight of high density components resulted in the largest increase in UST for the blend. More particularly, if the blend contains less than 20% by weight of high density components, UST is reduced due to the reduced concentration of the high melt material, while if the blend contains more than 20% by weight of high melt material, the UST is high. It was reduced because it was necessary to reduce the density of the molten material (to keep the overall density of the blend constant at 0.875 g / cm ³ ). In sharp contrast to the embodiment of the blend, the copolymer of the present invention exhibited a single embodiment. For example, compared to blends containing about 10-wt% of high density copolymers (corresponding to the relative proportions of high density components in copolymers prepared using catalyst (II), as illustrated in FIG. 9A), The copolymer produced using catalyst (II) showed a higher service temperature of 24 ° C. than the copolymer of the comparative blend.

In addition to Examples 1a-1c and 2a-2d, the molecular weights (M _w and M _n ) and polydispersities (M _w / M _n ) for the copolymers of Comparative Examples C-3a and C-2a were measured It is shown in Table 5 below.

Gel Permeation Chromatography (GPC) Data Example catalyst GPC Fit M _w M _n M _w / M _n M _w M _n M _w / M _n C-3a III 146500 68700 2.132 142748 60643 2.354 1a I 122400 43100 2.840 121075 43348 2.793 1b I 132500 52900 2.505 127299 47828 2.662 1c I 125300 51100 2.452 119533 44934 2.660 2a II 143400 65400 2.193 139869 56994 2.454 2b II 136300 54100 2.519 136096 53206 2.558 2c II 142900 64300 2.222 138895 55961 2.482 2d II 146200 62400 2.343 143378 57570 2.491 C-3b III 37300 17000 2.194 36878 15846 2..327 C-2a ^* II 159700 77000 2.074 155539 67900 2.291 Comparative Example C-2a was produced in a batch reactor.

As illustrated in Table 5, the copolymers of Comparative Examples C-3a and C-3b have a GPC polydispersity (M _w / M _n ) of 2.16, while produced using catalysts (I) and (II) Copolymers have a polydispersity of 2.60 (catalyst I) and 2.32 (catalyst II).

The original GPC chromatogram was also suitable for the Bamford-Tompa distribution, from which the total M _n , M _w and M _w / M _n can be calculated. The suitable procedure showed a monomolecular weight distribution in which the amount of long chain branches varied to fit the original GPC chromatogram.

The Vampford-Tompa molecular weight distribution is calculated by the following equation:

In the above formula,

I ₁ (x) is a first-order modified Bessel function of the first order, defined by Equation 2 below,

ζ is an adjustable variable that broadens the molecular weight distribution, as shown in Equation 3:

As defined by Bamford and Tompa, ζ is related to the amount of long chain branches by the following equation:

In the above, M is the average molecular weight of the repeating unit. The b individual terms of the expanded Bessel function represent the molecular weight distribution of the polymer chains with b long chain branches per molecule. Vampford and Tompa also provide equations that calculate the average number of branching points in a molecule as a function of chain length (see, for example, CH Bamford and H. Tompa, "The Calculation of Molecular Weight Distributions from Kinetics Schemes"). , Trans. Faraday Soc., 50, 1097 (1954).

“Suitable” M _w / M _n provided a more consistent polydispersity assessment. The "suitable" polydispersities for the copolymers of Comparative Examples C-3a and C-3b, Examples 1a-1c and Examples 2a-2d were 2.34, 2.50 and 2.71, respectively.

In the case of the copolymers of Examples 2a to 2d produced by the continuous liquid phase polymerization process and the copolymers of Comparative Example C-2a produced by the batch liquid phase polymerization process, the former showed an increased polydispersity compared to the latter. . In particular, Comparative Example C-2a showed a polydispersity of 2.07, while Examples 2a to 2d showed an average polydispersity of 2.32 ± 0.15; Similarly, "suitable" polydispersities of 2.29 and 2.50 ± 0.04, respectively, were observed for the copolymers of Comparative Examples C-2a and Examples 2a to 2d, respectively.

The increased polydispersity as it moves from batch to continuous process correlates with an increase in melt flow rate. For example, the average I ₁₀ / I ₂ of the copolymers of Examples 2a to 2d was 13.3, while the copolymer of Comparative Example C-2a showed I ₁₀ / I ₂ of 6.5. Both of these observations suggest that higher M _w / M _n and I ₁₀ / I ₂ contain higher concentrations of long chain branches than the corresponding batch polymerized polymers. It is known that long chain branching dramatically increases the shear thinning aspect of the copolymer.

Deconvolution of Bimodal Molecular Weight Distribution

The molecular weight distribution of the copolymers produced by catalysts (I) and (II) exhibited a bimodal shape. In addition, the molecular weight distribution indicates that M _w / M _n of each component can be described by Equation 2. Thus, the GPC delineation procedure refers to the five variable goodness of fit, M _n1 , z ₁ , M _n2 , z ₂ and split (S), where subscripts 1 and 2 refer to primary and secondary copolymer components, respectively. , Split is defined as the weight fraction of the high molecular weight copolymer. Non-linear curve-fit subroutines in SigmaPlot + (v2.01) can be used to evaluate the variables. The subroutine used the Marquardt-Levenberg algorithm to measure variable values that minimized the sum of the squares of the differences between the distribution defined by the dependent variable values and the observed GPC data. The non-linear curve suitability algorithm requires an initial variable value, which is determined after visual inspection of the experimental GPC chromatogram. The converged variable estimates were not significantly affected by the initial variable values.

Given that the copolymers produced by catalysts (I) and (II) exhibit bimodality in molecular weight distribution, Table 6 summarizes the results of GPC delineation. As mentioned above, in the above procedure, the molecular weight distribution of the two components was found to follow the Vampford-Tompa distribution. Thus, the GPC delineation includes five parameter fits: M _n1 , ζ ₁ , M _n2 , ζ ₂ and the weight fraction (M _n1 ) of the high molecular weight copolymer. GPC off-line data is shown in Table 6 below.

GPC delineation results for ethylene / octene copolymers produced using catalysts (I) and (II) Example catalyst High molecular weight low density component Low Molecular Weight High Density Components Mn ratio M _n1 / M _n2 M _w1 M _n1 M _w / M _n weight% M _w2 M _n2 M _w / M _n 1a I 165383 72285 2.2879 62.6 56827 28272 2.0100 2.56 1b I 176274 78776 2.2377 60.0 64304 32152 2.0000 2.45 1c I 166456 72573 2.2936 60.3 61713 30855 2.0001 2.35 Average TMInd-N-iPr → 169371 74545 2.2731 61.0 60948 30426 2.0034 2.45 2a II 155074 65311 2.3744 84.1 79312 39654 2.0001 1.65 2b II 155959 65455 2.3827 81.5 62924 31459 2.0002 2.08 2c II 155235 65205 2.3807 83.0 76699 38348 2.0001 1.70 2d II 168193 73727 2.2813 77.1 67357 33678 2.0000 2.19 Average TMInd-N-CHEX → 158615 67425 2.3548 81.4 71573 35785 2.0001 1.88 5r ¹ II 296460 68670 2.3172 95.5 95134 47558 2.0004 1.44 10a ^1,2 TMCp-N-CHEX 77124 36015 2.1414 85.5 48108 24054 2.0000 1.50 10c ^1,2 2-Me-5,6,5-Ind-N-CHEX 164432 71648 2.2950 84.2 60634 30316 2.0001 2.36 10e ^1,2 3-Pyrol-Ind-N-CHEX 258038 114543 2.2528 89.1 142678 71339 2.0000 1.61 10j ^1,2 I 220854 98430 2.2438 68.5 105325 52662 2.0000 1.87 45e ^1,2 II 321517 143333 2.2432 89.7 118855 59424 2.0001 2.41 45f ^1,3 II 133488 58611 2.2775 86.6 64027 32009 2.0003 1.83 45h ^1,3 II 121666 53434 2.2769 89.6 57857 28926 2.0002 1.85 45i ^1,3 II 72715 32997 2.2037 89.9 39552 19776 2.0000 1.67 ¹ batch reactor

As can be seen in Table 6, 61% of the copolymer produced by the catalyst (I) was 169,000 Daltons, with the remainder 61000 Daltons. Likewise, 81.4% of the copolymers produced by catalyst (II) were 159,000 daltons and the rest was 72000 daltons. 10 and 11 illustrate these delineated results in graphical form. GPC off-line results for batch reactor samples are also summarized in Table 6.

Copolymers of the invention were analyzed for labeling long chain branches. In particular, rheological data was created using a Rheometrics RMS-800 Synchronous Spectrometer with a 25 mm diameter parallel plate in a vibratory shear method. Frequency sweeps were performed in a shear rate range of 0.1-100 rad / s under 15% strain in nitrogen atmosphere. Rheological data is shown in Table 7 below.

Viscosity Data for Copolymers of the Invention and Copolymers of Comparative Examples Example catalyst Melt index (dg / min) Melt Flow Rate (I ₁₀ / I ₂ ) h, viscosity (poise) tanδ at 0.1 Hz h _0.1Hz h _{100 Hz} h _0.1Hz / h _100Hz C-3a III 0.48 9.38 186030 20889 8.91 4.83 1a I 0.71 11.58 216860 15510 13.98 2.72 1b I 0.63 12.29 195830 14486 13.52 2.83 1c I 0.82 10.91 164620 14097 11.68 3.24 2a II 0.5 15.22 293030 17363 16.88 2.37 2b II 0.43 13.58 344890 18370 18.77 2.13 2c II 0.38 14.39 346910 18053 19.22 2.10 2d II 0.38 10.11 400840 18965 21.14 1.91 C-3b III 116 6.00 854 696 1.23 102.8 ¹ C-2a ^* II 0.49 6.53 171940 22021 7.81 6.06 ^{1 at} 0.631 Hz (not 0.1 Hz) ² Could not be measured ^* Copolymer C-2a was produced in a batch reactor is

FIG. 13 shows a plot of log viscosity versus log frequency for the copolymers of the present invention and comparative examples, measured by an RMS 800 rheometer according to the procedure shown above. As illustrated in FIG. 13, the copolymer of Example 2a exhibited an improved shear thinning aspect compared to the copolymer of Comparative Example C-2a, both of which were produced using catalyst (II). In addition, FIG. 13 shows that the copolymer of Example 2a prepared by the continuous process was lower than that of Comparative Example C-2a produced in a batch reactor, as can be seen by the low tan δ value of the copolymer of Example 2a. It shows elasticity. This embodiment exhibits a high level of long chain branching properties of the copolymers produced by the continuous liquid phase polymerization process.

The melt grinding aspect of the selected resins was also evaluated on a gas extrusion rheometer (GER). The shear stress and shear rate at which each resin lost surface gloss (LSG) shear stress (MPa) and shear rate (s ⁻¹ ) and severe melt grinding initiation point (OGMF) are shown in Table 8 below.

Gas Extrusion Rheometer (GER) Data for Copolymers of Examples and Comparative Examples Example catalyst Density (g / cc) Melt index (dg / min) Melt Flow Rate (I ₁₀ / I ₂ ) LSG ¹ OGMF ² Shear stress (MPa) Shear rate (s ^-1 ) Shear stress (MPa) Shear rate (s ^-1 ) 2a II 0.8606 0.50 15.22 0.151 56 0.302 432 C-3c ³ III 0.8680 0.51 8.01 <0.086 <24 0.237 280 1c I 0.8703 0.82 10.91 <0.086 <35 0.259 479 C-2a II batch reactor 0.8635 0.49 6.53 0.129 19 0.237 89 ¹ LSG = loss of surface gloss ² OGMF = Initiation of Severe Melt Grinding Nearly Linear Ethylene / 1-octene Interpolymer Prepared Using Catalyst (III) in ^Three Continuous Liquid Phase Polymerization Processes ^* Comparative Example C-2a were applied created in a batch reactor

As evidenced by the shear rate at the onset of severe melt grinding (OGMF), the copolymers produced using catalysts (I) and (II) were produced using comparative examples produced using catalyst (III) in a continuous reactor. It was more resistant to melt grinding than the copolymer of C-2a. Since the shear rate is proportional to the flow rate (i.e. lb / hr or parts / hr), the copolymer of Example 2a prepared using catalyst (II) is copolymer C-3c prepared using catalyst (III). It can be processed at a high speed compared to.

The advantage of using the continuous liquid phase polymerization process compared to the batch liquid phase polymerization process is that the copolymer of Example 2a produced by the continuous liquid phase polymerization process and the copolymer of Comparative Example C-2a produced by the batch liquid phase polymerization process Is illustrated. The copolymers had a similar melt index, but the copolymer (89 s ^-1 ) of Comparative Example C-2a showed a lower OGMF shear rate than the copolymer (432 s ^-1 ) of Example 2a.

Infrared analysis (FTIR) was performed on each of the copolymers of the Examples and Comparative Examples, and the results are shown in Table 9 below.

Fourier Transform Infrared (FTIR) Data for Copolymers of Examples and Comparative Examples Example catalyst Density (g / cc) Melt index (dg / min) Melt Flow Rate (I ₁₀ / I ₂ ) FTIR data vinyl Trans + vinylidene Vinyl Rain ¹ Trans + vinylidene ratio C-3a III 0.8667 0.48 9.38 0.025 0.220 1.000 1.000 1a I 0.8710 0.71 11.58 0.042 0.293 1.680 1.332 1b I 0.8700 0.63 12.29 0.046 0.298 1.840 1.355 1c I 0.8703 0.82 10.91 0.080 0.320 3.200 1.455 2a II 0.8606 0.50 15.22 0.052 0.602 2.080 2.736 2b II 0.8612 0.43 13.58 0.037 0.580 1.480 2.636 2c II 0.8612 0.38 14.39 0.051 0.556 2.040 2.527 2d II 0.8615 0.38 10.11 0.043 0.566 1.720 2.573 C-3b III 0.8712 116 6.00 0.130 0.311 5.200 1.414 ¹ Normalized vinyl concentration (for vinyl concentration of sample 4a)

The data shown in Table 9 shows that the copolymers of Examples 1a-1c and 2a-2d showed higher vinyl concentrations than the copolymers of Comparative Examples C-3a. Where high levels of vinyl terminating properties of the inventive copolymers are provided, they are believed to exhibit high levels of long chain branching due to the re-incorporation of vinyl-terminated macromolecules in the polymer chains to be propagated. While not wishing to be bound by theory, it is believed that the high level of vinyl terminating properties of the polymers of the invention is due to the higher reaction temperatures made possible by the use of catalysts such as catalysts (I) and (II) described herein. . For example, a comparison of Comparative Examples C-3b and C-3a indicates that as the reaction temperature increases, the amount of vinyl terminating is likewise increased. It should be noted that the copolymers of the examples were produced at a temperature of about 120 ° C. compared to 80 ° C. of the copolymer of Comparative Example C-3a.

The copolymers of the examples and comparative examples were further tested for compression sets according to the following procedure. A compression set button was made for each sample by cutting a 2.86 cm (1.125 inch) diameter disk from a 1.52 mm thick compression molded plate. The disks were stacked in a compression set mold (total stacked height of about 1.37 cm (0.54 inch)) (at room temperature) and the disks were fused at 176.7 ° C. (350 ° F) and 10,000 psi (69 MPa) for 10 minutes. The buttons were removed from the molds, equilibrated for 24 hours at ASTM conditions, and the thickness of each button measured in micrometers. A 1.27 cm (0.5 inch) thick button was placed in the compression set clamp and compressed to 0.953 cm (0.375 inch) by tightening the set screw until the upper platen contacted the 0.953 cm spacer. The cold compression set clamp was left in a 70 ° C. (158 ° F.) oven for 24 hours. The button was removed from the compression set clamp and equilibrated in ASTM conditions for 24 hours before the button thickness was measured. The compression set is shown as% unstrained strain. Additional information regarding the compression set test can be found in ASTM D-395-89 Method B.

A compressed set of inventive copolymers produced using catalysts (I) and (II) and comparative copolymers produced using catalyst (III) is summarized in FIG. 14. Compared to copolymer C-3c produced using catalyst (III), the compression set at 70 ° C. for the copolymer produced by catalysts (I) and (II) was lower despite the similar transparency of the copolymer . Low compression sets are preferred in that the compression set exhibits% strain that is not restored. Ideally, the compression set of the complete elastomer is 0%, ie the burnout is completely restored. The compression set of the inventive copolymers produced by catalysts (I) and (II) was due to the biphasic short chain branching distribution.

Preparation of Ethylene / Propylene Interpolymers and Ethylene / Propylene / Diene Interpolymers

Ethylene / propylene interpolymers are prepared according to the following procedure using the reactor conditions shown in the table below.

Terpolymerization of ethylene, propylene and ethylidene norbornene is carried out at 1450 g of isopa E ^* (mixed alkanes, commercially available from Exxon Chemicals), 207.3 g of propylene, 17.6 g of ethylidene norbornene and 13.8 mmol It was carried out using a 3.8 L stainless steel reactor filled with hydrogen. The reactor was heated to 100 ° C. and then saturated with 460 psig (3.2 MPa) with ethylene. 5.0 μmol (0.005 M solution) of metal complex (ispropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (V) dimethyl, 5 μmol (0.0075 M solution) Cocatalyst di (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, 50.0 μmol (0.050 M solution) scavenger (diisopropylamido) diethylaluminum, and additional isopa The catalysts were prepared in anhydrous boxes by injecting E ^* together to give a total volume of 18 ml. The catalyst solution was then transferred to the catalyst addition loop by syringe and injected into the reactor for about 4 minutes using a flow of high pressure solvent. The polymerization was allowed to proceed for 10 minutes while feeding ethylene as needed to maintain a pressure of 460 psig (3.2 MPa). The amount of ethylene consumed during the reaction was investigated using a mass flow meter. The polymer solution was then poured into a nitrogen-purged glass kettle from the reactor and a stabilizer (Irganox ^™ 1076) was added and mixed well with the solution. The polymer solution was poured into a tray, air dried overnight and then completely dried in a vacuum oven for one day. The yield of polymer was 37.0 g and the catalyst efficiency calculated as g of polymer per gram of transition metal was 0.15 × 10 ⁶ . The terpolymer obtained exhibited a composition of 54.7 wt% ethylene, 42.7 wt% propylene and 2.6 wt% ethylidene norbornene. The molecular weight was 147,200 under a molecular weight distribution of 2.18. The elastomer had a measured glass transition temperature of −53.9 ° C. and was 0.9% crystalline.

Sixteen ethylene / propylene copolymers were prepared using the component amounts shown in the following table, using the above apparatus and procedure except that the addition of ethylidene norbornene was omitted. The physical properties of the polymers are shown in the following table. The catalyst of Examples 1a to 1e is (cyclohexylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl. The catalyst of Examples 2a to 2f is (isopropylamido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl. The catalyst of the comparative example is (tetramethylcyclopentadiinyl) dimethyl (t-butylamido) silanetitanium 1,3-pentadiene. The cocatalyst of all examples is di (hydrogen-tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate. All of the scavengers of the examples are derivatives of diisobutyl aluminum.

Polymerization of Ethylene / Propylene / Diene Interpolymers

Ethylene / propylene / diene interpolymers were prepared according to the general polymerization procedure shown above using the reactor conditions shown below:

Al / Ti ratio: 10

Temperature: 101.6 ℃

Charged C ₃ (g): 207.3

H ₂ delta pressure: 150.6

Isopa ^TM Weight (g): 1455.9

Octene Weight (g): 0

Diene Weight (g): 17.6

C2 charge (g): 141.54

Total Pressure (psi (MPa)): 460.4 (3.174)

C ₂ partial pressure (psi (MPa)): 309.4 (2.133)

Max Ethylene Rate: 8.8

Consumed Ethylene: 27.5

Conduct period: 10

Ti (μ mol): 5

Dry weight: 37

Efficiency: 0.15

The resulting polymer contained 54.7 wt% ethylene, 42.7 wt% propylene, 2.6 wt% ENB. GPC-DV results show that the polymer has a M _w of 147200, M _{n of} 67500 and M _w / M _n of 2.18. Differential scanning calorimetry showed a Tc of 14.09 ° C., a DSC cooling peak at −22.8 ° C., a heat of DSC fusion of 2.685 J / g, a DSC melting peak at −30.58 ° C., and a transparency of 0.9%.

Ethylene / Propylene and Ethylene / Propylene / Diene Copolymers In the examples, the examples show that semi-crystalline EP and EPDM interpolymers (Examples 2f and 1e) having an ethylene content of greater than 45 wt. It shows the DSC properties observed for. In addition, amorphous materials having less than 45% by weight of ethylene prepared using the catalyst of the present invention may be prepared using (tetramethylcyclopentadienyl) dimethyl (t-butylamido) silanetitanium 1,3-pentadiene. It has a lower Tg and higher molecular weight than polymers prepared under the same conditions.

The following describes the details of the polymerizations carried out using the catalysts as well as the procedures for preparing further catalysts useful for the preparation of the polymers of the invention.

Example A Preparation of (2,3-dimethylindenyl) dimethyl (cyclo-dodecylamido) silanetitanium dichloride

Preparation of Li ₂ [(2,3-dimethylindenyl) (cyclododecylamido) dimethyl-silane] .0.75 Et ₂ O:

Diethyl ether (25) was added slowly with (2,3-dimethylinyl) (cyclododecylamido) dimethylsilane (5.47 g, 0.0142 mol) n-BuLi (0.030 mol, 11.94 ml of 2.5M solution in hexane). Ml). The mixture was then stirred for 16 hours. After the reaction time, the volatiles were removed and the residue was washed with hexane and then collected by filtration as a solid which was used without further purification or analysis (5.47 g, 85.2%).

Preparation of (2,3-dimethylindenyl) dimethyl (cyclododecylamido) silanetitanium dichloride:

TiCl ₃ (THF) in THF (75 mL) as Li ₂ [(2,3-dimethylindenyl) (cyclododecylamido) dimethylsilane] · 3/4 Et ₂ O (5.47 g, 0.0121 mol) as a solid ₃ slowly (4.48 g, 0.0121 mol) was added slowly. The mixture was stirred for 45 minutes. PbCl ₂ (1.68 g, 0.00604 mol) was then added to the mixture and stirred for 45 minutes further. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was then removed and the residue slurried in hexane and collected by filtration as a reddish brown crystalline solid. The filtrate was concentrated and cooled and then a second yield was obtained by second filtration. The obtained products were then combined and determined to be the desired product (0.457 g, 7.6%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ 0.52 (s, 3H), 0.63 (s, 3H), 1.51-1.91 (m, 23H), 2.11 (s, 3H), 2.23 (s, 3H ), 5.31 (m, 1H), 6.83-7.12 (m, 2H), 7.29 (d, 1H), 7.63 (d, 3H).

Example B. Preparation of (2,3-dimethylindenyl) dimethyl (cyclo-dodecylamido) silanetitanium dimethyl

(2,3-dimethylindenyl) dimethyl (cyclododecylamido) silane TiCl ₂ (0.200 g, 0.000400 mol) was added dropwise with methylMgI (0.00084 mol, 0.28 ml of 3.0M solution in diethyl ether) Stir in (50 mL). The mixture was then stirred for 30 minutes. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using hexane. The volatiles were removed and then filtered again using hexane to remove hexane and the desired product isolated as an orange crystalline solid (0.134 g, 73.2%).

¹ H NMR (300 MHz, C ₆ D ₆ ): δ-0.11 (s, 3H), 0.53 (s, 3H), 0.61 (s, 3H), 0.65 (s, 3H), 1.10-1.90 (m, 23H ), 1.98 (s, 3H), 2.26 (s, 3H), 5.12-5.25 (m, 1H), 6.91 (t, 1H), 7.09 (t, 1H), 7.45 (d, 1H), 7.58 (d, 1H).

Example C. Preparation of [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl

Preparation of Dimethylsilyl (2,3,4,6-tetramethylindenyl) (cyclohexylamine):

Dimethylsilyl (2,3,4,6-tetramethylindenyl) Cl (9.95 g, 37.8 mmol) was added, NEt ₃ (4.1 g, 40.6 mmol) was added, followed by cyclohexylamine (4.05 g, 40.8 mmol). Stirring in hexane (200 mL). The mixture was then stirred at 20 ° C for 24 h. After the reaction time, the mixture was filtered, the volatiles were removed and the desired product was isolated as pale yellow oil (10.98 g, 89.3%).

Preparation of Dilithium (N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane:

4.0 g (12.6 mmol) of (N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane was dissolved in 300 ml of hexane in a dry box. To this solution, 12.6 mL (25.2 mmol) of nBuLi (2.00 M) was added dropwise at 20 ° C. When the addition of nBuLi was complete, the solution was stirred for 12 hours and then the solvent was removed under reduced pressure to yield 4.12 g (96% yield) of yellow-orange powder.

Preparation of [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride:

4.63 g (12.5 mmol) TiCl ₃ (THF) ₃ was dissolved in 75 mL THF in a dry box. To this solution, 4.12 g (12.5 mmol) of dilithium (N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane was added as a solid at 20 ° C. with stirring. The solution was then stirred for 45 minutes. After this time, 1.73 g of PbCl ₂ (6.25 mmol) was added and the solution stirred for 45 minutes. Then, THF was removed under reduced pressure. The residue was then extracted with toluene, the solution was filtered and toluene was removed under reduced pressure. The residue was then triturated with hexane and the solution volume reduced, at which time a precipitate formed which was collected by filtration and washed with cold (0 ° C.) hexane. The solid product was dried under vacuum to yield 1.70 g (31% yield) of the product.

Example D. Preparation of [(N-cyclohexylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl

0.300 g of [(Nt-cyclohexylamino) (dimethyl) (2,3,4,6-tetramethylinyl) silane] titanium dichloride (0.675 mmol) in anhydrous box was then added to 50 ml of Et ₂ O at 20 ° C. Suspended in. 0.45 mL of MeMgI (3.0M) was added dropwise to the suspension with stirring for 20 minutes. After the addition of MeMgI was complete, the solution was stirred for 40 minutes. Then Et ₂ O was removed under reduced pressure, the residue was extracted with hexane, the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to yield 0.27 g (100% yield) of the product.

Example E. Preparation of [(N-cyclohexylamido) (dimethyl) (2,3-methylindenyl) silane] titanium (II) (1,4-diphenyl-1,3-butadiene)

In a 100 mL flask, 0.300 g of (N-cyclohexylamino) (dimethyl) (2,3-methylindenyl) silane] titanium dichloride (0.720 mmol, Example 23) was added 1,4 in 70 mL hexane at 0 ° C. Stir with 0.149 g of -diphenyl-1,3-butadiene. To the solution, 0.577 mL of 2.5M nBuLi (in hexanes) was added and the mixture was refluxed for 2 hours. After cooling the solution to 20 ° C., the solution was filtered. The filtrate residue was then washed with hexane. Hexane was then removed from the filtrate under reduced pressure to yield 0.109 g (27% yield) of the product.

Conduct polymerization

A 2 L Parr reactor was charged with 740 g of mixed alkane solvent (isopa ^TM -E) and 118 g of 1-octene comonomer. Hydrogen was added as molecular weight regulator by differential pressure expansion from about 75 ml addition tank at 25 psi (1070 Kpa). The reactor was heated to a polymerization temperature of 140 ° C. and saturated with ethylene at 500 psig (3.4 Mpa). 2.0 millimoles of catalyst and cocatalyst, respectively, as a 0.005 M solution in toluene were premixed in anhydrous boxes. After the desired premix time, the solution was transferred to a catalyst addition tank and injected into the reactor. Polymerization conditions were maintained for 15 minutes with ethylene as needed. The resulting solution was removed from the reactor and a hindered phenolic antioxidant (Irganox ^™ 1010, Ciba Geigy Corp.) was added to the resulting solution. The resulting polymer was dried in a vacuum oven fixed at 120 ° C. for about 20 hours.

Example F. Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl

Preparation of Dimethylsilyl (2,3,4,6-tetramethylindenyl) (isopropylamine):

Dimethylsilyl (2,3,4,6-tetramethylindenyl) Cl (22.29 g, 84.17 mmol) was stirred in THF with the addition of i-PrNH ₂ (28.68 mL, 336.7 mmol). The mixture was stirred for 16 hours. The volatiles were removed under reduced pressure. The residue was extracted with hexanes and filtered through a diatomaceous earth filter aid on a 10-15 mm glass frit. Hexane was removed under reduced pressure to give the product as a yellow oil (17.23 g, 71% yield).

Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride:

17.23 g (59.93 mmol) of dimethylsilyl (2,3,4,6-tetramethylindenyl) (isopropylamine) were dissolved in 350 ml of hexane in a 500 ml round bottom Schlenk flask in a dry box. Two equivalents (47.94 mL, 2.5 M in hexane) of n-BuLi were then added by syringe. The reaction was stirred for 12 hours. The solvent was removed under reduced pressure to give an orange powder. The powder was dissolved in 250 ml of THF. TiCl ₃ (THF) ₃ (22.2 g, 59.93 mmol) was added as a solid. After 15 minutes, CH ₂ Cl ₂ (2.48 mL, 29.97 mmol) was added. After 2 hours, the solvent was removed under reduced pressure. The residue was extracted with toluene and filtered through diatomaceous earth filter aid on 10-15 mm glass frit. Toluene was removed under reduced pressure. The residue was slurried in hexanes and filtered over 10-15 mm glass frit. The residue was dried under reduced pressure to give a red powder (12.3 g, 51% yield).

Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dimethyl:

In anhydrous box, 150 mL of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride (6.92 g, 17.12 mmol) in a 250 mL round bottom flask Suspended in Et ₂ O. Two equivalents of a 3.0M THF solution of MeMgCl (11.41 mL, 34.23 mmol) were added. The mixture was stirred for 1 hour. The volatiles were removed under reduced pressure. The residue was extracted with hexanes and filtered through a diatomaceous earth filter aid on a 10-15 mm glass frit. Hexane was removed under reduced pressure to give an orange powder (5.8 g, 93% yield).

Example G. Preparation of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium (1,4-diphenyl-1,3-butadiene)

0.50 g (1.24 mmol) of [(N-isopropylamido) (dimethyl) (2,3,4,6-tetramethylindenyl) silane] titanium dichloride in anhydrous box was added to a 60 mL 100 mL round bottom Schlenk flask. Slurry in ml of cyclohexane. 1,4-diphenyl-1,3-butadiene (0.255 g, 1.24 mmol) was added as a solid. 2 equivalents (0.989 mL, 2.5M in hexane) of n-BuLi were then added by syringe. The flask was equipped with a condenser and heated to reflux for 1 hour. Upon cooling, the reaction was filtered through diatomaceous earth filtration aid (Celite ^™ ) on 10-15 mm glass frits. Salt and filter aid were washed with 50 ml of pentane. The solvent was removed under reduced pressure to give a red / brown powder (300 mg, 45% yield).

Polymerization experiments were carried out using 3.8 L of a stirred reactor charged with 1440 g of Isopha E ^TM (mixed alkanes; commercially available from Exxon Chemical), 132 g of 1-octene and 10 mmoles of hydrogen. . The reactor was heated to 130 ° C. and saturated with ethylene to 450 psig (4.5 Mpa). 5.0 mmol (1.0 mL, 0.005M) metal complex, 15.0 mmol (1.0 mL, 0.015M) cocatalyst, trispentafluorophenylborane (TPFPB) and 50.0 mmol (1.0 mL, 0.05M) scavenger, further The catalyst was prepared in an anhydrous box by injecting together methylaluminoxane (liquid-nobel) modified with isofa E ^™ to give a total volume of 17 ml. The catalyst solution was then transferred to the catalyst addition loop by syringe and injected into the reactor for about 4 minutes using a high pressure solvent stream. The polymerization was allowed to proceed for 10 minutes while feeding ethylene as needed to maintain a pressure of 445 psig (4.5 Mpa). The polymer solution was then poured from the reactor into a nitrogen-purged glass kettle containing about 15 ml of isopropanol. A 20 ml aliquot of stabilizer solution prepared by dissolving 6.66 g of Irgaphos ^™ 168 and 3.33 g of Irganox ^™ 1010 in 500 ml of toluene was added. The polymer solution was poured into a tray, air dried overnight and then completely dried in a vacuum oven for 2 days.

Example H

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indacene-1- Synthesis of Il] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2-methyl-s-indasenyl) (cyclohexyl-amido) TiCl ₂ )

Preparation of Chlorodimethyl (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) silane

(1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) lithium (1c) (24.369 g, 0.13831 mol) in THF (100 mL) was added to Me in THF (150 mL). _To the solution of ₂ SiCl ₂ (89.252 g, 0.69155 mol) was added dropwise. The mixture was then stirred at 20-25 ° C. for 5 hours. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered with hexane. Hexane was removed to isolate the desired product as a gray crystalline solid (31.1451 g, 85.7%).

Preparation of N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) silaneamine

Chlorodimethyl (1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl) with addition of NEt ₃ (2.18 g, 0.0216 mol) and cyclohexylamine (2.13 g, 0.0216 mol) Silane (5.67 g, 0.0216 mol) was stirred in hexane (50 mL). The mixture was stirred for 16 hours. After the reaction time had elapsed, the mixture was filtered and the volatiles removed to isolate the desired product as a yellow oil (6.62 g, 94.3%).

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl ] Preparation of Silane Amine Earth (2-)-N] dilithium

N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-s with slow addition of nBuLi (0.04302 moles, 21.51 mL of a 2.0 M solution in cyclohexane) -Indasen-1-yl) silaneamine (6.67 g, 0.02048 mol) was stirred in hexane (100 mL). The mixture was then stirred for 16 hours. After the reaction time has elapsed, the desired product is isolated as a solid and used without further purification or analysis (7.23 g, the product still contains residual hexane).

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indacene-1- Production of silaneamineto (2-)-N] titanium

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indasen-1-yl ] Silaneamineto (2-)-N] dilithium (7.23 g, 0.0214 mol) was added slowly as a solid to a slurry of TiCl ₃ (THF) ₃ (7.93 g, 0.0214 mol) in THF (50 mL). The mixture was stirred for 30 minutes. Then PbCl ₂ (3.80 g, 0.0136 mol) was added and the mixture was further stirred for 1 hour. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was removed to isolate the dark residue. The residue was then slurried in hexane and the desired product was isolated by filtration as a solid (3.71 g, 39.2%).

Example H

Dimethyl [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indacene-1- Synthesis of Il] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2-methyl-s-indasenyl) (cyclohexyl-amido) TiMe ₂ )

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-s-indacene-1- Stirred in diethyl ether (50 mL) with slow addition of general silaneamineto (2-)-N] titanium (0.400 g, 0.00904 moles) to MeMgBr (0.181 moles, 0.60 mL of a 3.0 M solution in diethyl ether). It was. The mixture was then stirred for 1 hour. After the reaction time, the volatiles were removed and the residue was extracted and filtered using hexane. Hexane was removed to isolate the desired product as a solid (0.309 g, 85.1%).

Example I

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene- Synthesis of 1-yl] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2,3-dimethyl-s-indasenyl) (cyclohexylamido) TiCl ₂ )

Preparation of N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2,3-dimethyl-s-indasen-1-yl) silaneamine

Chlorodimethyl (1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene-1 with addition of NEt ₃ (3.29 g, 0.03251 mol) and t-butylamine (1.81 g, 0.01824 mol) -Yl) silane (5.00 g, 0.01806 moles) was stirred in hexane (80 mL). The mixture was stirred for 16 hours. After the reaction time has elapsed, the mixture is filtered and the volatiles are removed to isolate the desired product as a yellow oil (5.55 g, 90.9%).

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene-1 Preparation of -yl] silaneamineto (2-)-N] dilithium

n- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2,3-dimethyl- while slowly adding nBuLi (0.03454 mol, 13.8 mL of a 2.5M solution in hexane) s-indasen-1-yl) silaneamine (5.30 g, 0.01570 mol) was stirred in hexane (75 mL). The mixture was then stirred for 72 hours. After the reaction time had elapsed, the hexane was discarded and the volatiles removed to isolate the desired product as an orange glassy solid which was used without further purification or analysis (5.56 g, 99.9%).

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene- Preparation of 1-yl] silaneamineto (2-)-N] titanium

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene-1 -Yl] silaneamineto (2-)-N] dilithium (0.500 g, 0.01428 mol) was added slowly to a slurry of TiCl ₃ (THF) ₃ (0.529 g, 0.001428 mol) in THF (50 mL) as a solid. . The mixture was stirred for 2 hours. Then PbCl ₂ (0.317 g, 0.001142 mol) was added and the mixture was further stirred for 1 hour. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was removed to isolate the dark residue. The residue was then slurried in hexane and cooled in the refrigerator for 72 hours. Then, the desired product was isolated by filtration as a solid (0.259 g, 43.8%).

Example J

Dimethyl [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2,3-dimethyl-s-indacene- Synthesis of 1-yl] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2,3-dimethyl-s-indasenyl) (cyclohexylamido) TiMe ₂ )

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5 slowly adding MeMgBr (0.001447 mol, 0.48 mL of 3.0 M solution in diethyl ether) , 6,7-tetrahydro-2,3-dimethyl-s-indasen-1-yl] silaneamineto (2-)-N] titanium (0.300 g, 0.0006588 mol) in diethyl ether (50 mL) Stirred. The mixture was then stirred for 1 hour. After the reaction time, the volatiles were removed and the residue was extracted and filtered using hexane. Hexane was removed to isolate the desired product as an orange solid (0.249 g, 91.2%).

Example K

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-3-phenyl-s- Synthesis of sen-1-yl] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2-methyl-3-phenyl-s-indasenyl) (cyclohexylamido) TiCl ₂ )

Preparation of N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-3-phenyl-s-indasen-1-yl) silaneamine

Chlorodimethyl (1,5,6,7-tetrahydro-2-methyl-3-phenyl-s-indacene- while adding NEt ₃ (2.9673 g, 0.02932 mol) and cyclohexylamine (1.6373 g, 0.01651 mol) 1-yl) silane (9c) (5.5340 g, 0.01633 mol) was stirred in hexane (100 mL). The mixture was stirred for 24 hours. After the reaction time had elapsed, the mixture was filtered and the volatiles removed to isolate the desired product as a yellow oil (5.8969 g, 89.9%).

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-3-phenyl-s-indacene -1-yl] silaneamine earth (2-)-N] dilithium

N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-2-methyl-3 with slowly adding nBuLi (0.032 mol, 16.00 mL of a 2.0 M solution in cyclohexane) -Phenyl-s-indacene-1-yl) silaneamine (5.8969 g, 0.01468 mol) was stirred in hexane (100 mL). The mixture was then stirred for 16 hours, during which time a sticky precipitate formed. The volatiles were then removed and the resulting pale yellow solid slurried in cold hexanes. After the reaction time passed, the solid was collected as a yellow powder by suction filtration and used without further purification or analysis (5.3101 g, 87.5%).

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-3-phenyl-s- Preparation of sen-1-yl] silaneamineto (2-)-N] titanium

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-3- in THF (50 mL) Phenyl-s-indacene-1-yl] silaneamineto (2-)-N] dilithium (5.3103 g, 0.01284 mol) was added to TiCl ₃ (THF) ₃ (4.7570 g, 0.01284 mol) in THF (100 mL). Was added dropwise to the slurry of. The mixture was stirred for 2 hours. Then PbCl ₂ (1.8896 g, 0.006795 mol) was added and the mixture was further stirred for 1 hour. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was removed to isolate the dark residue. The residue was then slurried in hexane and cooled to -10 ° C. Then, the desired product was isolated by filtration as a red crystalline solid (3.0765 g, 46.2%).

Example L

Dimethyl [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-2-methyl-3-phenyl-s- Synthesis of sen-1-yl] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (2-methyl-3-phenyl-s-indasenyl) (cyclohexylamido) TiMe ₂ )

MeMgBr (0.002760 moles, 0.92 mL of 3.0 M solution in diethyl ether) was added slowly with dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5 , 6,7-tetrahydro-2-methyl-3-phenyl-s-indasen-1-yl] silaneamineto (2-)-N] titanium (0.7164 g, 0.001382 mol) was diluted with diethyl ether (50 mL). )). The mixture was then stirred for 1 hour. After the reaction time, the volatiles were removed and the residue was extracted and filtered using hexane. Hexane was removed to isolate the desired product as a sticky sulfur-red residue (0.5102 g, 77.3%).

Example M

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s-indacene-1- Synthesis of Il] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (3-phenyl-s-indasen-1-yl) (cyclohexylamido) TiCl ₂ )

Preparation of N- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-indasen-1-yl) silaneamine

Chlorodimethyl (1,5,6,7-tetrahydro-3-phenyl-s-indasen-1-yl) with NEt ₃ (1.5136 g, 0.01496 mol) and cyclohexylamine (1.2107 g, 0.01221 mol) Silane (3.8523 g, 0.01182 mol) was stirred in hexane (100 mL). The mixture was stirred for 24 hours. After the reaction time has elapsed, the mixture is filtered and the volatiles are removed to isolate the desired product as a yellow oil (4.3313 g, 94.5%).

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s-indasen-1-yl ] Preparation of Silane Amine Earth (2-)-N] dilithium

n- (cyclohexyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s, slowly adding nBuLi (0.024 mol, 12.00 mL of a 2.0 M solution in cyclohexane) -Indasen-1-yl) silaneamine (4.3313 g, 0.01117 mol) was stirred in hexane (100 mL). The mixture was then stirred for 16 hours, during which time a sticky precipitate formed. The volatiles were then removed and the resulting pale yellow solid slurried in cold hexanes. After the reaction time passed, the solid was collected as red crystalline powder by suction filtration and used without further purification or analysis (5.3101 g, 87.5%).

Dichloro [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s-indacene-1- Production of silaneamineto (2-)-N] titanium

[N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s- in THF (50 mL) Indasen-1-yl] silaneamineto (2-)-N] dilithium (4.2135 g, 0.01055 mol) was added dropwise to a slurry of TiCl ₃ (THF) ₃ (3.9085 g, 0.01055 mol) in THF (100 mL). It was. The mixture was stirred for 2 hours. Then PbCl ₂ (1.5373 g, 0.005529 mol) was added and the mixture was further stirred for 1 hour. After the reaction time had elapsed, the volatiles were removed and the residue was extracted and filtered using toluene. Toluene was removed to isolate the dark residue. The residue was then slurried in hexanes and cooled to 0 ° C. The desired product was then isolated by filtration as red-brown crystalline solid (2.7655 g, 52.0%).

Example N

Dimethyl [N- (cyclohexyl) -1,1-dimethyl- [1,2,3,4,5-η-1,5,6,7-tetrahydro-3-phenyl-s-indacene-1- Synthesis of Il] silaneamineto (2-)-N] titanium (also referred to as dimethylsilyl (3-phenyl-s-indasen-1-yl) (cyclohexylamido) TiMe ₂ )

Dichloro [N- (cyclohexyl) -1,1-dimethyl-1-[(1,2,3,4,5-η) while slowly adding MeMgBr (0.0022 mol, 0.74 mL of 3.0M solution in diethylether) -1,5,6,7-tetrahydro-3-phenyl-s-indasen-1-yl] silaneamineto (2-)-N] titanium (0.5581 g, 0.001106 mol) was diluted with diethyl ether (50 mL). )). The mixture was then stirred for 1 hour. After the reaction time, the volatiles were removed and the residue was extracted and filtered using hexane. Hexane was removed to isolate the desired product as a sulfur-red residue (0.2118 g, 41.3%).

2-ethylene / 1-octene copolymerization

A stirred 3.8 L reactor was charged with 1440 g of Isopha-E ^™ mixed alkane solvent (commercially available from Exxon Chemical) and 126 g of 1-octene comonomer. Hydrogen was added as molecular weight regulator by differential pressure expansion from a 75 ml addition tank at 25 psig (2070 kPa). The reactor was heated to a polymerization temperature of 130 ° C. and saturated with ethylene to 450 psig (3.1 MPa). About 2.0 μmol of the catalyst of Example H and the trispentafluorophenylborane cocatalyst, respectively, as a 0.005 M solution in toluene, were premixed in anhydrous boxes, transferred to a catalyst addition tank, and then injected into the reactor for about 4 minutes. Polymerization conditions were maintained for 10 minutes with as much ethylene as necessary. The resulting solution was removed from the reactor and a hindered phenolic antioxidant (Irganox ^™ 1010, Ciba Geigy Corporation) was added to the resulting solution. The resulting polymer was dried in a vacuum oven fixed at 120 ° C. for about 20 hours. Catalyst efficiency was 700 kg polymer / g Ti. The melt index (I ₂ ) of the polymer was 0.43 g / 10 min.

Claims (26)

An olefin polymer produced by polymerizing at least one α-olefin in the presence of a catalyst which also comprises a metal complex corresponding to formula (I): Formula 1 Where M is titanium, zirconium or hafnium in the +2, +3 or +4 type oxidation state; A ′ is at least 2 or 3 in a group selected from hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl, silyl, germanyl and mixtures thereof A substituted indenyl group containing up to 40 non-hydrogen atoms, wherein A 'is also covalently bonded to M by a divalent Z group; Z is a divalent moiety attached to both A 'and M by σ-bond and comprises a member of Group 14 of the boron or periodic table of elements, and also includes nitrogen or phosphorus, wherein the aliphatic or cycloaliphatic hydrocarbyl group is Covalently bound to nitrogen or phosphorus by primary or secondary carbon; X is an anionic or anionic ligand group having up to 60 atoms except for the ligand class which is a cyclic delocalized π-binding ligand group; X 'is each independently a neutral linking compound having up to 20 atoms; p is 0, 1 or 2, and 2 is less than the formal oxidation state of M, provided p is 1 when X is an anionic ligand; q is 0, 1 or 2. The method of claim 1, A polymer wherein the metal complex corresponds to formula (2): Formula 2 Where R ₁ and R ₂ are groups containing up to 20 non-hydrogen atoms independently selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germanyl and mixtures thereof, provided that R ₁ and At least one of R ₂ is not hydrogen; R ₃ , R ₄ , R ₅ and R ₆ are groups containing up to 20 non-hydrogen atoms independently selected from hydrogen, hydrocarbyl, perfluoro substituted hydrocarbyl, silyl, germanyl and mixtures thereof ; M is titanium, zirconium or hafnium; Z is a divalent moiety having up to 60 non-hydrogen atoms, including boron or group 14 members of the Periodic Table of the Elements, and also comprising nitrogen or phosphorus, wherein the aliphatic or cycloaliphatic hydrocarbyl group is a primary or secondary Covalently bonded to nitrogen or phosphorus by grade carbon; p is 0, 1 or 2; q is 0 or 1; only, When p is 2, q is 0, M is a +4 type oxidation state, X is a halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amido, di (hydrocarbyl) phosphido, hydrocarbyl sulfi Up to 20 non-hydrogen atoms selected from the group consisting of halo-, di (hydrocarbyl) amino-, hydrocarbyloxy- and di (hydrocarbyl) phosphino-substituted derivatives thereof Having an anionic ligand; When p is 1, q is 0, M is a +3 type oxidation state, X is allyl, 2- (N, N-dimethylaminomethyl) phenyl and 2- (N, N-dimethyl) -aminobenzyl A stabilizing anionic ligand group selected from the group consisting of: or M is a +4 type oxidation state, X is a divalent derivative of conjugated diene, and M and X together form a metal cyclocyclopentene group; When p is 0, q is 1, M is a +2 type oxidation state, X 'is a neutral conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, and has up to 40 carbon atoms Form M-pi complexes. The method of claim 1, An olefin polymer in which the metal complex corresponds to formula 3: Formula 3 Where R ₁ and R ₂ are independently hydrogen or C _1-6 alkyl, provided that both R ₁ and R ₂ are not hydrogen; R ₃ , R ₄ , R ₅ and R ₆ are independently hydrogen or C _1-6 alkyl; M is titanium; Y is -NR ^** -or -PR ^** -; Z ^* is SiR ^* ₂ , CR ^* ₂ , SiR ^* ₂ SiR ^* ₂ , CR ^* ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ ; R ^* in each occurrence is independently hydrogen or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl and mixtures thereof, having up to 20 non-hydrogen atoms, optionally from Z (when R ^* is not hydrogen), two R ^* group, or an R ^* group from one of the R ^* group from Z and Y is a form a ring system, and Y -NR ^* - or -PR ^* - When R ^* is covalently bonded to N or P via primary or secondary carbon; R ^** is an aliphatic or cycloaliphatic hydrocarbyl group covalently bonded to nitrogen or phosphorus of Y by primary or secondary carbon; p is 0, 1 or 2; q is 0 or 1; only, when p is 2, q is 0, M is a +4 type oxidation state and X is independently at each occurrence methyl or benzyl; When p is 1, q is 0, M is a +3 type oxidation state, X is 2- (N, N-dimethyl) aminobenzyl, or M is a +4 type oxidation state, and X is 1,4 -Butadienyl; When p is 0, q is 1, M is a +2 type oxidation state, and X 'is 1, 4- diphenyl- 1, 3- butadiene or 1, 3- pentadiene. (1) a metal complex corresponding to formula (Ia) below; And (2) the activating cocatalyst [the molar ratio of (1) :( 2) is 1: 10,000 to 100: 1], or (1) converting (1) to the active catalyst using an activation technique to sequentially An olefin polymer produced by a process comprising reacting at least one α-olefin in the presence of a catalyst comprising: Formula Ia Where M is titanium, zirconium or hafnium in the +2, +3 or +4 type oxidation state; R 'and R "are independently at each occurrence hydride, hydrocarbyl, silyl, germanyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbyl) amino, hydrocarbyleneamino, Di (hydrocarbyl) phosphino, hydrocarbylene-phosphino, hydrocarbyl sulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted Hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl, di (hydrocarbyl) amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di (hydrocarbyl) phosphino-substituted hydrocarbyl, hydrocar Bilylene-phosphino-substituted hydrocarbyl, or hydrocarbyl sulfido-substituted hydrocarbyl, wherein the R 'or R "group has a ratio of up to 40 -Have a hydrogen atom, and optionally two or more of the aforementioned groups can together form a divalent derivative; R ″ ′ is a divalent hydrocarbylene- or substituted hydrocarbylene group that forms a fusion system with the rest of the metal complex and contains 1 to 30 non-hydrogen atoms; Z is a divalent moiety or a moiety comprising one σ-bond and a neutral two electron pair capable of forming a co-covalent bond to M, wherein Z comprises a boron or group 14 member of the Periodic Table of the Elements And also include nitrogen or phosphorus, wherein the aliphatic or cycloaliphatic hydrocarbyl group is covalently bonded to nitrogen or phosphorus by primary or secondary carbon; X is a monovalent anionic ligand group having up to 60 atoms except for the ligand class which is a cyclic delocalized π-binding ligand group; X 'is each independently a neutral linking compound having up to 20 atoms; X ″ is a divalent anionic ligand group having up to 60 atoms; p is 0, 1, 2 or 3; q is 0, 1 or 2, r is 0 or 1; The method according to any one of claims 1 to 4, An olefin polymer in which an α-olefin is polymerized in the presence of a catalyst comprising a metal complex and an activating promoter. The method of claim 5, Olefin polymer wherein the activating promoter comprises trispentafluorophenyl-borane or a promoter corresponding to formula (4) Formula 4 (L ^* -H) _d ⁺ (A ^d- ) Where L ^* is a neutral Lewis base; (L ^* -H) ⁺ is Bronsted acid; A ^d- is an uncoordinated, compatible anion with a charge of d-; d is an integer of 1 to 3. The method of claim 6, An olefin polymer wherein the anion A ^d- is selected from the group consisting of (a) a stericly protected diboron anion corresponding to formula (5), and (b) an anion corresponding to formula (6): Formula 5 Formula 6 [M ' ^{k +} Q _n' ] ^d- Where S is alkyl, fluoroalkyl, aryl or fluoroaryl (also hydrogen if two S groups are present); Ar ^F is fluoroaryl; X ¹ is hydrogen or halide; k is an integer from 1 to 3; n 'is an integer from 2 to 6; n'-k is d; M 'is an element selected from Group 13 of the Periodic Table of the Elements; Q is independently at each occurrence selected from hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl and halosubstituted hydrocarbyl radicals, having up to 20 carbons, with only one time Q being a halide to be. The method of claim 6, The activating promoter consists of trispentafluorophenylborane, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) borate and di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate An olefin polymer comprising borane or borate selected from the group. The method of claim 6, The activating promoter may have a tri (hydrocarbyl) aluminum compound, oligomer or polymeric alumoxane compound having 1 to 10 carbons in each hydrocarbyl group, 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group. An olefin polymer also comprising an aluminum compound selected from the group consisting of a di (hydrocarbyl) (hydrocarbyloxy) aluminum compound having a compound or a mixture of the foregoing compounds. The method of claim 9, An olefin polymer corresponding to the aluminum compound of the formula T ¹ ₂ AlOT ² , wherein T ¹ is C _3-6 secondary or tertiary alkyl and T ² is a C _12-30 alkaryl radical or an aralkyl radical. The method of claim 10, The aluminum compound is 2,6-di (t-butyl) -4-methylphenyl, 2,6-di (t-butyl) -4-methyltolyl, 2,6-di (t-butyl) -4-methylphenyl or 4 An olefin polymer which is-(3 ', 5'-di (t-butyl) tolyl) -2,6-di (t-butyl) phenyl. Olefin interpolymers, which satisfy four or more of the following criteria: (a) I ₂ of 100 g / 10 min or less; (b) M _w / M _n between 1.5 and 3.0; (c) at least 0.03 vinyl / 1000 carbons, as measured by FTIR; (d) deconvoluted DSC melting curves showing two distinct first and second DSC melting points; And (e) Inequality: ATREF curve satisfying ATREF shape factor ≤ 0.90-0.00626 (average elution temperature). The method of claim 12, An olefin interpolymer where the ATREF curve satisfies the inequality: ATREF shape factor <0.75-0.00626 (average elution temperature). Olefin interpolymers, which satisfy four or more of the following criteria: (a) I ₂ of 100 g / 10 min or less; (b) M _w / M _n between 1.5 and 3.0; (c) at least 0.03 vinyl / 1000 carbons, as measured by FTIR; (d) delineated DSC melting curves showing two distinct first and second DSC melting points; And (e) Delineated gel permeation chromatogram showing two distinct first and second component fractions, wherein the first component fraction has a first density, a first I ₂ , and is provided in a first weight percent, second The component fraction has a second density, a second I ₂ and is provided at a second weight percent). The method of claim 14, First homogeneous the upper service temperature of the olefin cross polymer [UST (cross-polymer), to in accordance with the inequality, has an I ₂ comparable to the density, the first I ₂ comparable to the first density is provided to the first weight% an upper service temperature of the olefin polymer, and a second physical blend of a homogeneous olefin polymer is provided in the second weight percent having an I ₂ comparable to the density, the second I ₂ comparable to the second density [UST (blend) Larger Olefin Interpolymers: UST (homopolymer)-UST (blend) ≥ 256-275 (density of olefin interpolymer). The method according to any one of claims 12 to 15, An olefin interpolymer, further characterized as being an interpolymer of ethylene and at least one C ₃ -C ₂₀ α-olefin. The method according to any one of claims 12 to 16, Olefin interpolymers, which are also characterized as having at least 10 I ₁₀ / I ₂ . The method according to any one of claims 12 to 16, Olefin interpolymers, further characterized as having from 0.01 to 3 long chain branches / 1000 carbons. The method according to any one of claims 12 to 16, Olefin interpolymers, wherein the olefin interpolymers are characterized in that they also exhibit a critical shear rate at the start of the surface melt grinding at least 50% greater than the critical shear rate at the start of the surface melt grinding for the linear interpolymer. The linear interpolymer comprises the same comonomer or comonomers, the linear interpolymer has I ₂ and density within 10% of the olefin interpolymer, and the critical shear rate of each of the olefin and linear interpolymers is a gas extrusion rheometer. Measured at the same melt temperature). The method according to any one of claims 12 to 19, An olefin interpolymer further characterized by having a density of no greater than 0.915 g / cm ³ . (a) I ₂ of 100 g / 10 min or less; (b) M _w / M _n between 1.5 and 3.0; (c) at least 0.03 vinyl / 1000 carbons, as measured by FTIR; (d) at least two distinct DSC melting points; And (e) delineated gel permeation chromatogram showing two distinct first and second component fractions, wherein the first component fraction has a first density, a first I ₂ , and is provided in a first weight percent The two component fraction has a second density, a second I ₂ , and is provided at a second weight percent) of the upper service temperature of the product or formulation, including incorporating the olefin interpolymer into the product or formulation. How to improve. The method of claim 3, wherein The metal complex is (cyclohexyl amido) dimethyl (η ⁵ -2,3,4,6-tetramethylindenyl) silanetitanium (IV) dimethyl or (isopropylamido) dimethyl (η ⁵ -2,3,4 , 6-tetramethylindenyl) silane titanium (IV) dimethyl olefin polymer. The method according to any one of claims 12 to 16, An olefin polymer that is an interpolymer of ethylene, C ₃ -C ₂₀ α-olefins and optional dienes. The method of claim 23, Olefin polymers which are interpolymers of ethylene, propylene and dienes. The method of claim 12, Olefin polymers satisfying each of the criteria (a) to (e). The method of claim 14, Olefin polymers satisfying each of the criteria (a) to (e).