CN111587257B

CN111587257B - Mixed catalyst system with four metallocenes on a single support

Info

Publication number: CN111587257B
Application number: CN201880076911.9A
Authority: CN
Inventors: M·W·赫尔特卡普; D·F·森德斯; M·S·贝多雅; 吕清泰
Original assignee: ExxonMobil Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2017-10-31
Filing date: 2018-09-20
Publication date: 2023-02-10
Anticipated expiration: 2038-09-20
Also published as: WO2019089153A1; CN111587257A

Abstract

The present invention provides supported catalyst systems and methods of use thereof. Specifically, the catalyst system includes four different catalysts, a support material, and an activator. The catalyst system can be used to prepare polyolefins such as polyethylene.

Description

Mixed catalyst system with four metallocenes on a single support

The inventor: matthew.Holtcamp, david F.Sanders, matthew S.Bedoya and Ching-Tai Lue

Priority requirement

The present application claims priority and benefit of USSN62/579566 filed on day 31, 10, 2017 and EP17209428.6 filed on day 21, 12, 2017, both of which are incorporated by reference in their entirety.

Technical Field

The present invention provides multi-catalyst systems and methods of use thereof. Specifically, the catalyst system comprises four group 4 metallocene compounds, a support material, and an activator. The catalyst system can be used in olefin polymerization processes.

Background

Polyolefins are widely used commercially due to their robust physical properties. For example, various types of polyethylene, including high density, low density and linear low density polyethylenes, are some of the most commercially useful. Polyolefins are typically prepared using catalysts for polymerizing olefin monomers.

Low density polyethylene is typically produced at high pressure using free radical initiators or in a gas phase process using ziegler-natta or vanadium catalysts. Low density polyethylene typically has a density of about 0.916g/cm ³ . The usual low density polyethylene produced using free radical initiators is known in the industry as "LDPE". LDPE is also referred to as "branched" or "heterogeneously branched" polyethylene due to a relatively high number of long chain branches extending from the main polymer backbone. Polyethylenes of similar density which do not contain branching are known as "linear low density polyethylenes" ("LLDPE") and are usually produced with conventional ziegler-natta catalysts or with metallocene catalysts. By "linear" is meant that the polyethylene has few, if any, long chain branches, and typically has a g' vis value of 0.97 or higher, for example 0.98 or higher. The polyethylene having a density of still greater is a high density polyethylene ("HDPE"), e.g., a density greater than 0.940g/cm ³ And is typically prepared with a ziegler-natta or chromium catalyst. Very low density polyethylene ("VLDPE") can be produced by several different processes, which result in a typical density of 0.890 to 0.915g/cm ³ The polyethylene of (3).

Copolymers of polyolefins such as polyethylene have a comonomer, such as hexene, incorporated into the polyethylene backbone. These copolymers provide different physical properties compared to polyethylene alone and are typically produced in low pressure reactors using, for example, solution, slurry or gas phase polymerization processes. The polymerization can be carried out in the presence of catalyst systems such as those using ziegler-natta catalysts, chromium-based catalysts or metallocene catalysts.

Copolymer compositions such as resins have a compositional distribution, which refers to the distribution of comonomers that form short chain branches along the copolymer backbone. When the amount of short chain branching varies between copolymer molecules, the composition is said to have a "broad" composition distribution. The composition distribution is said to be "narrow" when the comonomer amount/1000 carbons is similar between copolymer molecules of different chain lengths.

The composition distribution affects the properties of the copolymer composition, such as stiffness, toughness, environmental stress crack resistance, and heat sealing, among other properties. The composition distribution of the polyolefin composition can be easily measured by e.g. Temperature Rising Elution Fractionation (TREF) or crystallization analysis fractionation (CRYSTAF).

The composition distribution of the copolymer composition is influenced by the nature of the catalyst(s) used to form the polyolefin of the composition. Ziegler-natta catalysts and chromium-based catalysts tend to produce compositions with a broad composition distribution, while metallocene catalysts generally produce compositions with a narrow composition distribution.

In addition, polyolefins such as polyethylene having high molecular weights typically have desirable mechanical properties compared to their lower molecular weight counterparts. However, high molecular weight polyolefins can be difficult to process and can be expensive to produce. Polyolefin compositions having a bimodal molecular weight distribution are desirable because they can combine the advantageous mechanical properties of the high molecular weight portion of the composition with improved processability of the low molecular weight portion of the composition.

For example, useful bimodal polyolefin compositions include a first polyolefin having a low molecular weight and a high comonomer content (i.e., comonomer incorporated into the polyolefin backbone), while a second polyolefin has a high molecular weight and a low comonomer content. As used herein, "low comonomer content" is defined as a polyolefin having 6wt% or less comonomer based on the total weight of the polyolefin. The high molecular weight fraction produced by the second catalyst may have a high comonomer content. As used herein, "high comonomer content" is defined as a polyolefin having greater than 6wt% comonomer, based on the total weight of the polyolefin.

There are several methods of producing bimodal or broad molecular weight distribution polyolefins, such as melt blending, polymerization in reactors configured in series or parallel, or polymerization in a single reactor using a bimetallic catalyst. However, these methods, such as melt blending, are difficult to fully homogenize the polyolefin composition and have high costs.

In addition, the synthesis of these bimodal polyolefin compositions using a mixed catalyst system will include a first catalyst to catalyze the polymerization of, for example, ethylene under conditions substantially similar to a second catalyst, while not interfering with the polymerization catalysis of the second catalyst.

There is a need for catalyst systems that provide polyolefin compositions having a new combination of comonomer content fraction and molecular weight. There is a further need for new multi-catalyst systems in which one catalyst does not inhibit the polymerization catalysis of any other catalyst, and vice versa.

Catalysts for olefin polymerization are typically based on cyclopentadienyl transition metal catalyst compounds as catalyst precursors, in combination with an activator (typically an alumoxane) or with an activator containing a non-coordinating anion. Typical metallocene catalyst systems include a metallocene catalyst, an activator, and an optional support. Supported catalyst systems are used in many polymerization processes, often in slurry or gas phase polymerization processes.

For example, U.S. Pat. No.7829495 discloses Me ₂ Si (fluorenyl) (3-nPr-Cp) ZrCl ₂ And U.S. Pat. No.7179876 discloses loaded (nPrCp) ₂ HfMe ₂ 。

Furthermore, stadelhofer, j.; weidlein, j.; haaland, A.J.organomet.chem.1975, 84, C1-C4 discloses the preparation of potassium cyclopentadienide.

Furthermore, me has already been synthesized ₂ C(Cp)(Me ₃ SiCH ₂ -Ind)MCl ₂ And Me ₂ C(Cp)(Me，Me ₃ SiCH ₂ -Ind)MCl ₂ (wherein M is Zr or Hf) and screened for syndiotactic polymerization of propylene; see Leino, r., gomez, f.; cole, a.; waymouth, r. macromolecules2001, 34, 2072-2082.

Metallocenes are often combined with other catalysts, or even other metallocenes, to attempt to alter polymer properties. See, for example, U.S. Pat. Nos. 8088867 and 5516848 (which disclose the use of two different cyclopentadienyl-based transition metal catalyst compounds activated with alumoxane or a non-coordinating anion). See also PCT/US2016/021748, filed 3, 10, 2016, which discloses two metallocenes for the preparation of ethylene copolymers.

Also, me has been synthesized ₂ C(Cp)(Me ₃ SiCH ₂ -Ind)MCl ₂ And Me ₂ C(Cp)(Me，Me ₃ SiCH ₂ -Ind)MCl ₂ (wherein M is Zr or Hf), and screened for syndiotactic polymerization of propylene; see Leino, r., gomez, f.; cole, a.; waymouth, r. macromolecules2001, 34, 2072-2082.

Additional references of interest include: immobilized Me of Hong et al ₂ Si(C ₅ Me ₄ )(N-t-Bu)TiCl ₂ /(nBuCp) ₂ ZrCl ₂ Hybrid Metallocene Catalyst System for the Production of Poly (ethylene-co-hexene) with Psuedo-bimodule Molecular Weight and invente Commomer Distribution, (Polymer Engineering and Science-2007, DOI10.1002/pen, pp. 131-139, published on-line in Wiley Interscience (www.interscience.wiley.com) 2007Society of Plastics Engineers); kim, j.d. et al, j.polym.sci.part a: polyo chem.,38, 1427 (2000); iedema, p.d. et al, ind.eng.chem.res.,43, 36 (2004); U.S. Pat. No.4701432;5032562;5077255;5135526;5183867;5382630;5382631;5525678;6069213;6207606;6656866;6828394;6964937;6956094;6964937;6995109;7041617;7119153;7129302;7141632;7172987;7179876;7192902;7199072;7199073;7226886;7285608;7312283;7355058;7385015;7396888;7595364;7619047;7662894;7829495;7855253;8110518;8138113;8268944;8288487;8329834;8378029;8575284;8598061;8680218;8785551;8815357;8940842;8957168;9079993;9163098;9181370;9303099; U.S. publication No.2004/259722;2006/275571;2007/043176;2010/331505;2012/0130032;2014/0031504;2014/0127427;2015/299352;2016/0032027;2016/075803; PCT publication No. WO97/35891; WO98/49209; WO00/12565; WO2001/09200; WO02/060957; WO2004/046214; WO2006/080817; WO2007/067259; WO2007/080365; WO2009/146167; WO2012/006272; WO2012/158260; WO2014/0242314; WO2015/123168; WO2016/172099; PCT application No. PCT/US2016/021757, filed 3/10/2016; EP2374822; EP2003166; EP0729387; EP0676418; EP0705851; KR20150058020; KR101132180; sheu, S.,2006, "Enhanced Bimodal PE masks the allowable payload", http:// www.tappi.org/content/06as iaplace/pdfs-english/Enhanced. Pdf; and Chen et al, "Modeling and Simulation of Borstar Bimodal Polyethylene Process Based on Rigorous PC-SAFT evaluation of State Model", industrial&Engineering Chemical Research,53, pages 19905-19915, (2014). Other references of interest include: U.S. publication No.2015/0322184 and "Polymer Chemistry" of A.Calhoun et al, chapter 5, pages 77-87.

There remains a need in the art for new and improved catalyst systems for olefin polymerization to achieve increased activity or enhanced polymer properties, to increase conversion or comonomer incorporation, or to alter comonomer distribution. There is also a need for supported catalyst systems and methods of using such catalyst systems to polymerize olefins (e.g., ethylene) to provide ethylene polymers having unique properties of high stiffness, high toughness, and good processability.

Summary of The Invention

The present invention provides a supported catalyst system comprising four group 4 metallocene compounds; a carrier material; and an activator, wherein the catalyst system comprises:

a) At least two different catalysts represented by formula (A):

wherein:

m is Hf or Zr;

each R ¹ ，R ² And R ⁴ Independently is hydrogen, alkoxy or C ₁ -C ₄₀ A substituted or unsubstituted hydrocarbyl group;

R ³ independently is hydrogen, alkoxy or C ₁ -C ₄₀ Substituted or unsubstituted hydrocarbyl or is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ And each R' is independently C ₁ -C ₂₀ A substituted or unsubstituted hydrocarbyl group;

each R ⁷ ，R ⁸ ，R ⁹ And R ¹⁰ Independently of one another is hydrogen, alkoxy, C ₁ -C ₄₀ Substituted or unsubstituted hydrocarbyl, -CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ Wherein each R' is independently C ₁ -C ₂₀ A substituted or unsubstituted hydrocarbyl group, provided that R ⁷ ，R ⁸ ，R ⁹ And R ¹⁰ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ Preferably R ⁸ And/or R ⁹ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ (ii) a Preferably R ⁹ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ ；

T ¹ Is a bridging group; and

each X is independently a monovalent anionic ligand, or two xs are joined and bound to a metal atom to form a metallocyclic ring, or two xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand;

b) At least two different catalysts represented by formula (B):

T ² _y Cp _m M ¹ X _q (B)

wherein:

each Cp is independently a cyclopentadienyl, indenyl, or fluorenyl, which may be independently substituted or unsubstituted;

M ¹ is zirconium or hafnium;

T ² is a bridging group;

y is 0 or 1, which means that T is absent or present ² ；

X is halo, hydrido, alkyl, alkenyl or arylalkyl;

m =2 or 3,q =0,1,2 or 3, and the sum of m + q is equal to the oxidation state of the transition metal, typically 2,3 or 4; and

each Cp and X is bound to M ¹ The above step (1);

c) A carrier material; and

d) An activator.

The invention also provides a process for polymerizing monomers (e.g., olefin monomers) comprising contacting one or more monomers with the supported catalyst system described above.

The present invention also provides a process for producing an ethylene polymer composition comprising: i) In a single reaction zone, in gas or slurry phase, ethylene and C ₃ -C ₂₀ Contacting the comonomer with a catalyst system comprising a support, an activator, and the catalyst system described above, and ii) obtaining an in situ ethylene polymer composition having at least 50 mole percent ethylene and a density of 0.890g/cc or greater, alternatively 0.910g/cc or greater, alternatively 0.935g/cc or greater.

The present invention also provides a process for producing an ethylene polymer composition comprising: i) In a single reaction zone, in gas or slurry phase, ethylene and C ₃ -C ₂₀ The comonomer is contacted with a catalyst system comprising a support, an activator and the above catalyst system, and an ethylene polymer is obtained having: a) A density of 0.890g/cc or greater, b) a melt flow index (ASTM 1238,190 ℃,2.16 kg) is 0.1 to 80dg/min, c) the Mw/Mn is 2.5 to 12.5.

The invention also provides polymer compositions produced by the methods and catalyst systems described herein.

Brief description of the drawings

FIG. 1 is a 4D-gel permeation chromatography/spectrum of a polyethylene resin according to at least one embodiment.

Fig. 2A is a graph showing normalized Mw versus normalized Tw (deg.c) for a polyethylene resin, according to at least one embodiment.

Fig. 2B is a graph showing normalized Mw versus normalized Tw (deg.c) for a polyethylene resin, according to at least one embodiment.

Fig. 2C is a graph showing normalized Mw versus normalized Tw (deg.c) for a polyethylene resin, according to at least one embodiment.

Detailed description of the invention

The present invention provides multi-catalyst systems and methods of use thereof. Specifically, the catalyst system includes four different group 4 metallocene compounds, a support material, and an activator. The catalyst system can be used in olefin polymerization processes. The catalyst system of the present invention may provide increased activity or enhanced polymer properties to increase conversion or comonomer incorporation, or to alter comonomer distribution. The catalyst system and process of the present invention can provide ethylene polymers with unique properties of high stiffness, high toughness and good processability.

For the purposes of the present invention, a "catalyst system" is a combination of at least four catalyst compounds, an activator and a support material. The catalyst system may further comprise one or more additional catalyst compounds. The terms "mixed catalyst system", "mixed catalyst" and "supported catalyst system" are used interchangeably herein with "catalyst system". For purposes of the present invention, when the catalyst system is described as comprising a neutral stable form of the component, it is well understood by those skilled in the art that the ionic form of the component is the form that reacts with the monomer to produce the polymer.

The term "complex" is used to describe a molecule in which an ancillary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably binds to the transition metal to preserve its effect during catalyst use, e.g., in polymerization. The ligand may coordinate to the transition metal through a covalent bond and/or an electron donating coordination or an intermediate bond. The transition metal complexes are typically activated to perform their polymerization function using an activator that is believed to generate a cation as a result of the removal of an anionic group (often referred to as a leaving group) from the transition metal. As used herein, "complex" is also often referred to as a "catalyst precursor," procatalyst, "" catalyst compound, "" metal catalyst compound, "" transition metal compound, "or" transition metal complex. These terms are used interchangeably. "activators" and "cocatalysts" may also be used interchangeably.

The terms "hydrocarbyl radical", "hydrocarbyl", and "hydrocarbyl group" are used interchangeably throughout this document. Likewise, the terms "group", "radical" and "substituent" are also used interchangeably herein. For the purposes of the present invention, a "hydrocarbyl group" is defined as being C ₁ -C ₁₀₀ A group, which may be linear, branched or cyclic, and when cyclic, aromatic or non-aromatic.

For the purposes of the present invention, the term "substituted" means that a hydrogen group has been replaced by a heteroatom or heteroatom-containing group, unless otherwise indicated. For example, a substituted hydrocarbyl group is one in which at least one hydrogen atom of the hydrocarbyl group has been replaced by at least one functional group such as Cl, br, F, I, NR ₂ ，OR*，SeR*，TeR*，PR* ₂ ，AsR* ₂ ，SbR* ₂ ，SR*，BR* ₂ ，SiR* ₃ ，GeR* ₃ ，SnR* ₃ ，PbR* ₃ Isosubstitution (wherein R is H or C) ₁ -C ₂₀ Hydrocarbyl), or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

The term "ring atom" denotes an atom that is part of a cyclic ring structure. By this definition, benzyl has six ring atoms and tetrahydrofuran has 5 ring atoms.

A "ring carbon atom" is a carbon atom that is part of a cyclic ring structure. By this definition, benzyl has six ring carbon atoms and para-methylstyrene also has six ring carbon atoms.

The term "aryl" or "aryl group" denotes six carbon aromatic rings and substituted variants thereof, including but not limited to phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl represents an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom (preferably N, O or S).

A "heterocyclic ring" is a ring having a heteroatom in the ring structure, as opposed to a heteroatom-substituted ring in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocyclic ring, and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring.

As used herein, the term "aromatic" also refers to a pseudo-aromatic heterocycle, which is a substituent of a heterocycle that has similar properties and structure (close to planar) as the ligand of an aromatic heterocycle, but by definition is not aromatic; likewise, the term aromatic also refers to substituted aromatic compounds.

The term "continuous" means a system that operates without interruption or cessation. For example, a continuous process for producing a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

As used herein, the numbering scheme for groups of the periodic Table is a novel notation as described in Chemical and Engineering News,63 (5), 27, (1985).

An "olefin" is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For the purposes of this specification and the claims appended hereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt.% to 55 wt.%, it is understood that the monomer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are present at 35 wt.% to 55 wt.% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. "different" as used in reference to a monomeric unit means that the monomeric units differ from each other by at least one atom or are isomerically different. Thus, as used herein, the definition of copolymer includes terpolymers and the like. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50mol% of ethylene derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50mol% of propylene derived units, and the like.

For the purposes of the present invention, ethylene polymers having a density of 0.86g/cm3 or less are referred to as ethylene elastomers or elastomers; ethylene polymers having a density of greater than 0.86 to less than 0.910g/cm3 are referred to as ethylene plastomers or plastomers; ethylene polymers having a density of from 0.910 to 0.940g/cm3 are known as low density polyethylene; and ethylene polymers having a density greater than 0.940g/cm3 are known as High Density Polyethylene (HDPE). The density was measured according to ASTM D1505 using a density gradient column on compression molded test specimens that had been slowly cooled to room temperature (i.e., over a period of 10 minutes or more) and allowed to age for a sufficient time to allow the density to be constant within +/-0.001g/cm 3.

Polyethylenes that are linear and do not contain long chain branching within the overlapping density range (i.e., 0.890-0.930g/cm3, typically 0.915-0.930g/cm 3) are referred to as "linear low density polyethylenes" (LLDPE) and have been produced with conventional ziegler-natta, vanadium or metallocene catalysts in gas phase reactors and/or in slurry reactors and/or in solution reactors. By "linear" is meant that the polyethylene has no long chain branches, commonly referred to as a branching index (g' vis) of 0.97 or higher, preferably 0.98 or higher. Branching index g' _vis Was measured by GPC-4D as described below.

For the purposes of the present invention, ethylene should be considered an alpha-olefin.

As used herein, M _n Is the number average molecular weight, M _w Is the weight average molecular weight, and M _z Is the z average molecular weight, wt% is weight percent, and mol% is mole percent. Unless otherwise indicated, all molecular weights (e.g., mw, mn, mz) are reported in units of g/mol. The Molecular Weight Distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. The following abbreviations may be used herein: me is methyl, et is ethyl, t-Bu and ^t bu is tert-butyl, iPr and ⁱ pr is isopropyl, cy is cyclohexyl, THF (also known as THF) is tetrahydrofuran, bn is benzyl, ph is phenyl, cp is cyclopentadienyl, cp is pentamethylcyclopentadienyl, ind is indenyl, flu is fluorenyl, and MAO is methylaluminoxane.

As used herein, the term "metallocene compound" includes compounds having two or three Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Zr or Hf metal atom, and one or more leaving groups bound to at least one metal atom.

For the purposes of the present invention, the term "substituted" with respect to the entire metallocene catalyst compound means that the hydrogen group has been replaced by a hydrocarbyl group, a heteroatom or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is Cp substituted with a methyl group.

For the purposes of the present invention, "alkoxy" includes those in which the alkyl group is a C1-C10 hydrocarbyl group. The alkyl group may be linear, branched or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may include at least one aromatic group.

The present invention provides a supported catalyst system comprising: (i) Two different bridged metallocene compounds, both of which are good comonomer incorporating agents (incorporators); (ii) Two additional metallocene compounds, both of which are poor comonomer incorporators; (iii) a support material; and (iv) an activator; wherein the two bridged metallocene compounds, both of which are good comonomer incorporating agents, are different and both are represented by formula (a):

wherein:

m is Hf or Zr;

each R ⁷ ，R ⁸ And R ¹⁰ Independently is hydrogen, alkoxy or C ₁ -C ₄₀ A substituted or unsubstituted hydrocarbyl group;

R ⁹ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ And each R' is independently C ₁ -C ₂₀ A substituted or unsubstituted hydrocarbyl group;

T ¹ is a bridging group; and

each X is independently a monovalent anionic ligand, or two xs are joined and bound to a metal atom to form a metallocyclic ring, or two xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and

the at least two different catalysts, both of which are poor comonomer incorporators, are represented by formula (B):

T ² _y Cp _m M ¹ X _q (B)

wherein:

M ¹ is zirconium or hafnium;

T ² is a bridging group;

y is 0 or 1, which indicates the absence or presence of T;

x is halo, hydrido, alkyl, alkenyl or arylalkyl;

m =2 or 3,q =0,1,2 or 3, and the sum m + q is equal to 2,3 or 4; and

each Cp and X is bound to M ¹ The above.

In one embodiment, the supported catalyst system of the present invention comprises:

a) At least two different catalysts represented by formula (A):

wherein:

m is Hf or Zr;

T ¹ Is a bridging group; and

b) At least one catalyst represented by formula (C) and at least one catalyst represented by formula (D):

Cp _m M ¹ X _q (C)

T ³ Cp _m M ² X _q (D)

wherein:

M ¹ is zirconium or hafnium;

M ² is zirconium or hafnium;

T ³ is a bridging group;

x is halo, hydrido, alkyl, alkenyl or arylalkyl;

m =2 or 3,q =0,1,2 or 3, and the sum of m + q is 2,3 or 4; and

each Cp and X is bound to M ¹ Or M ² The above step (1);

c) A carrier material; and

d) An activator.

The four catalyst compounds may have different hydrogen responses (each having a different reactivity with hydrogen) in the polymerization process. Hydrogen is often used in olefin polymerization to control the final properties of polyolefins. The first catalyst may exhibit a greater negative response to changes in the hydrogen concentration in the reactor than the second catalyst. If the catalyst has a different hydrogen response in the supported catalyst system, the properties of the polymer formed can be influenced. When such a combination of two catalyst compounds is used, variations in the hydrogen concentration in the reactor can affect the molecular weight, molecular weight distribution and other properties of the polyolefin formed. Accordingly, the present invention further provides a multimodal polyolefin obtained from a polymerization using the above-described supported catalyst system.

In at least one embodiment, the catalyst of formula (a) is a good comonomer (e.g., hexene) incorporation agent (e.g., providing a comonomer content of 6% or greater) and produces polyethylene having a higher molecular weight than the catalysts of formulae (B), (C), and (D) (which under similar conditions produces a lower molecular weight than the catalyst of formula (a)). The catalysts of formulae (B), (C) and (D) may also incorporate less comonomer (e.g. hexene) under similar reaction conditions. When two catalysts represented by formula (a) and at least two catalysts represented by formula catalyst (B) are combined on one support, an in-reactor blend of polyethylene is produced having a mixture of low and high density resins in which the higher density resin (or higher melting point) is combined with the lower density higher molecular weight resin. The catalysts of formulae (A), (B), (C) and (D) may independently be a single isomer or a combination of isomers, for example 2,3,4,5 or 6 isomers, typically 2 isomers.

The four transition metal catalyst compounds may be used in any ratio. Preferred molar ratios of the catalyst of formula (a) (two bridged transition metal catalysts) to the catalyst of formula (B), (C) or (D) (at least two additional transition metal catalysts), for example (a: B), (a: C) or (a: D) may independently be 1:1000-1000:1, alternatively 1:100-500:1, alternatively 1:10-200:1, alternatively 1:1-100:1, and alternatively 1:1-75:1, and alternatively 5:1-50:1. the particular ratio selected will depend on the exact catalyst compound selected, the method of activation and the desired end product. In one embodiment, useful mole percentages of the catalysts represented by formulas (A) and (B), based on the molecular weight of the catalyst compound, are (10-99.9% (A)): (0.1-90% (B)), alternatively (25-99% (A)): (0.5-50% (B)), optionally (50-99% (A)): (1-25% (B)), and alternatively (75-99% (A)): (1-10% (B)). In one embodiment, useful mole percentages of the catalysts represented by formulas (a) and (C), based on the molecular weight of the catalyst compound, are (10-99.9% (a)): (0.1-90% (C)), alternatively (25-99% (A)): (0.5-50% (C)), alternatively (50-99% (A)): (1-25% (C)), and alternatively (75-99% (A)): (1-10% (C)). In one embodiment, useful mole percentages of the catalysts represented by formulas (a) and (D), based on the molecular weight of the catalyst compound, are (10-99.9% (a)): (0.1-90% (D)), alternatively (25-99% (A)): (0.5-50% (D)), alternatively (50-99% (A)): (1-25% (D)), and alternatively (75-99% (A)): (1-10% (D)).

For the purposes of the present invention, a metallocene catalyst compound is considered to be different from another if one catalyst compound differs from another by at least one atom. For example, "bisindenyl zirconium dichloride" is different from "(indenyl) (2-methylindenyl) zirconium dichloride", which is different from "(indenyl) (2-methylindenyl) hafnium dichloride". Catalyst compounds differing only in isomer are considered to be the same for the purposes of the present invention, for example rac-bis (1-methylindenyl) hafnium dimethyl is considered to be the same as meso-bis (1-methylindenyl) hafnium dimethyl. Thus, as used herein, a single metallocene catalyst compound having a racemic and/or meso isomer does not itself constitute two different metallocene catalyst compounds.

In a useful embodiment of the catalyst system, for both catalysts represented by formula (A), M is Hf.

In a useful embodiment of the catalyst system, for both catalysts of formula (B), M ¹ Is Zr.

In a useful embodiment of the catalyst system, M is Hf for both catalysts of formula (A) and M is Hf for both catalysts of formula (B) ¹ Is Zr.

In a useful embodiment of the catalyst system, for both catalysts of formula (A), M is Hf, and M ¹ Is Hf and M ² Is Zr.

In a useful embodiment of the catalyst system, for the catalyst of formula (A), M is Hf, and M ¹ And M ² Is Zr.

In a useful embodiment of the catalyst system, R ⁹ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ Wherein each R' is independently C ₁ -C ₂₀ Substituted or unsubstituted hydrocarbyl.

Two bridged metallocenes of formula (A)

In at least one embodiment, the supported catalyst system comprises at least two different catalysts represented by formula (a):

wherein:

m is Hf or Zr, preferably Hf;

T ¹ Is a bridging group; and

each X is independently a monovalent anionic ligand, or two xs are joined and bound to a metal atom to form a metallocyclic ring, or two xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

In any of the embodiments of the invention, T ¹ Is a bridging group containing at least one group 13, 14, 15 or 16 element, in particular boron or a group 14, 15 or 16 element. Examples of suitable bridging groups include P (= S) R, P (= Se) R, P (= O) R, R · ₂ C，R* ₂ Si，R* ₂ Ge，R* ₂ CCR* ₂ ，R* ₂ CCR* ₂ CR* ₂ ，R* ₂ CCR* ₂ CR* ₂ CR* ₂ ，R*C＝CR*，R*C＝CR*CR* ₂ ，R* ₂ CCR*＝CR*CR* ₂ ，R*C＝CR*CR*＝CR*，R*C＝CR*CR* ₂ CR* ₂ ，R* ₂ CSiR* ₂ ，R* ₂ SiSiR* ₂ ，R* ₂ SiOSiR* ₂ ，R* ₂ CSiR* ₂ CR* ₂ ，R* ₂ SiCR* ₂ SiR* ₂ ，R*C＝CR*SiR* ₂ ，R* ₂ CGeR* ₂ ，R* ₂ GeGeR* ₂ ，R* ₂ CGeR* ₂ CR* ₂ ，R* ₂ GeCR* ₂ GeR* ₂ ，R* ₂ SiGeR* ₂ ，R*C＝CR*GeR* ₂ ，R*B，R* ₂ C–BR*，R* ₂ C–BR*–CR* ₂ ，R* ₂ C–O–CR* ₂ ，R* ₂ CR* ₂ C–O–CR* ₂ CR* ₂ ，R* ₂ C–O–CR* ₂ CR* ₂ ，R* ₂ C–O–CR*＝CR*，R* ₂ C–S–CR* ₂ ，R* ₂ CR* ₂ C–S–CR* ₂ CR* ₂ ，R* ₂ C–S–CR* ₂ CR* ₂ ，R* ₂ C–S–CR*＝CR*，R* ₂ C–Se–CR* ₂ ，R* ₂ CR* ₂ C–Se–CR* ₂ CR* ₂ ，R* ₂ C–Se–CR* ₂ CR* ₂ ，R* ₂ C–Se–CR*＝CR*，R* ₂ C–N＝CR*，R* ₂ C–NR*–CR* ₂ ，R* ₂ C–NR*–CR* ₂ CR* ₂ ，R* ₂ C–NR*–CR*＝CR*，R* ₂ CR* ₂ C–NR*–CR* ₂ CR* ₂ ，R* ₂ C–P＝CR*，R* ₂ C–PR*–CR* ₂ O, S, se, te, NR, PR, asR, sbR, O-O, S-S, R N-NR, R P-PR, O-S, O-NR, O-PR, S-NR, S-PR and R N-PR, where R is hydrogen or contains C ₁ -C ₂₀ And optionally two or more adjacent R may be joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. For the bridging group T ¹ Preferred examples of (2) include CH ₂ ，CH ₂ CH ₂ ，SiMe ₂ ，SiPh ₂ ，SiMePh，Si(CH ₂ ) ₃ ，Si(CH ₂ ) ₄ ，O，S，NPh，PPh，NMe，PMe，NEt，NPr，NBu，PEt，PPr，Me ₂ SiOSiMe ₂ And PBu. In a preferred embodiment of the present invention, in any embodiment of any formula described herein, T is ¹ Is of the formula ER ^d ₂ Or (ER) ^d ₂ ) ₂ Wherein E is C, si or Ge, and each R ^d Independently hydrogen, halogen, C1-C20 hydrocarbyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) or C1-C20 substituted hydrocarbyl, and two R ^d Cyclic structures, including aromatic, partially saturated or saturated cyclic or fused ring systems, may be formed. Preferably, T ¹ Is a bridging group containing carbon or silicon, e.g. dialkylsilyl, preferably T ¹ Is selected from CH ₂ ，CH ₂ CH ₂ ，C(CH ₃ ) ₂ ，SiMe ₂ Cyclotrimethylenesilylene (Si (CH) ₂ ) ₃ ) Cyclopentamethylenesilylene radical (Si (CH) ₂ ) ₅ ) And cyclotetramethylenesilylene (Si (CH) ₂ ) ₄ )。

In a preferred embodiment, each R is ¹ ，R ² And R ⁴ Independently is hydrogen, alkoxy or substituted C ₁ -C ₂₀ Hydrocarbyl or unsubstituted C ₁ -C ₂₀ Hydrocarbyl, preferably each R ¹ ，R ² And R ⁴ Independently is C ₁ -C ₁₂ Alkyl, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof, preferably hydrogen or methyl.

In a preferred embodiment, R ³ Is hydrogen, alkoxy or substituted C ₁ -C ₁₂ Hydrocarbyl or unsubstituted C ₁ -C ₁₂ Hydrocarbyl, preferably R ³ Is C ₁ -C ₂₀ Alkyl, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof, preferably hydrogen or methyl, or R ³ is-R ²⁰ -SiR' ₃ Or is-R ²⁰ -CR' ₃ Wherein R is ²⁰ Is hydrogen or C ₁ -C ₄ Hydrocarbyl (preferably-CH) ₂ -；-CH ₂ CH ₂ -，-(Me)CHCH ₂ -， _- (Me) CH-, and each R' is independently hydrogen or C ₁ -C ₂₀ Substituted or unsubstituted hydrocarbyl, preferably substituted C ₁ -C ₁₂ Hydrocarbyl or unsubstituted C ₁ -C ₁₂ A hydrocarbon radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl or isomers thereof, R' is C ₁ -C ₂₀ Alkyl or aryl, such as methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl, with the proviso that at least one R ' is not H, alternatively 2R's are not H, alternatively 3R's are not H.

Alternatively, R ³ is-CH ₂ -SiMe ₃ ，-CH ₂ -SiEt ₃ ，-CH ₂ -SiPr ₃ ，-CH ₂ -SiBu ₃ ，-CH ₂ -SiCy ₃ ，-CH ₂ -C(CH ₃ ) ₃ ，-CH ₂ -CH(CH ₃ ) ₂ ，-CH ₂ CPh ₃ ，-CH ₂ (C ₆ Me ₅ )，-CH ₂ -C(CH ₃ ) ₂ Ph，-CH ₂ -C(Cy)Ph ₂ ， _- CH ₂ -SiH(CH ₃ ) ₂ ，-CH ₂ SiPh ₃ ，-CH ₂ -Si(CH ₃ ) ₂ Ph，-CH ₂ -Si(CH ₃ ) ₂ Ph，-CH ₂ -Si(CH ₃ )Ph ₂ ，-CH ₂ -Si(Et) ₂ Ph，-CH ₂ -Si(Et)Ph ₂ ，-CH ₂ -Si(CH ₂ ) ₃ Ph，-CH ₂ -Si(CH ₂ ) ₄ Ph，-CH ₂ -Si(Cy)Ph ₂ or-CH ₂ -Si(Cy) ₂ Ph。

Alternatively, R ¹ ，R ² ，R ³ And R ⁴ Is not H.

In a preferred embodiment, each R is ⁷ ，R ⁸ And R ¹⁰ Independently is hydrogen, alkoxy or substituted C ₁ -C ₁₂ Hydrocarbyl or unsubstituted C ₁ -C ₁₂ Hydrocarbyl, preferably C ₁ -C ₂₀ Alkyl, preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof, preferably hydrogen or methyl.

In a preferred embodiment, R ⁹ is-R ²⁰ -SiR' ₃ Or is-R ²⁰ -CR' ₃ Wherein R is ²⁰ Is C ₁ -C ₄ Hydrocarbyl (preferably-CH) ₂ -，-CH ₂ CH ₂ -，-(Me)CHCH ₂ -， _- (Me) CH-, and each R' is independently hydrogen or C ₁ -C ₂₀ Substituted or unsubstituted hydrocarbyl, preferably substituted C ₁ -C ₁₂ Hydrocarbyl or unsubstituted C ₁ -C ₁₂ A hydrocarbon radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl or isomers thereof, R' is C ₁ -C ₂₀ Alkyl or aryl groups such as methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl, provided that at least one R ' is not H, alternatively 2R ' are not H, alternatively 3R ' are not H;

alternatively, R ⁹ is-CH ₂ -SiMe ₃ ，-CH ₂ -SiEt ₃ ，-CH ₂ -SiPr ₃ ，-CH ₂ -SiBu ₃ ，-CH ₂ -SiCy ₃ ，-CH ₂ (C ₆ Me ₅ )，-CH ₂ -C(CH ₃ ) ₂ Ph，-CH ₂ -C(Cy)Ph ₂ ， _- CH ₂ -SiH(CH ₃ ) ₂ ，-CH ₂ SiPh ₃ ，-CH ₂ -Si(CH ₃ ) ₂ Ph，-CH ₂ -Si(CH ₃ )Ph ₂ ，-CH ₂ -Si(Et) ₂ Ph，-CH ₂ -Si(Et)Ph ₂ ，-CH ₂ -Si(CH ₂ ) ₃ Ph，-CH ₂ -Si(CH ₂ ) ₄ Ph，-CH ₂ -Si(Cy)Ph ₂ or-CH ₂ -Si(Cy) ₂ Ph。

Alternatively, R ³ And R ⁹ Independently is-R ²⁰ -SiR' ₃ Or is-R ²⁰ -CR' ₃ Wherein R is ²⁰ Is C ₁ -C ₄ Hydrocarbyl (preferably-CH) ₂ -，-CH ₂ CH ₂ -，-(Me)CHCH ₂ -， _- (Me) CH-, and each R' is independently hydrogen, or C ₁ -C ₂₀ Substituted or unsubstituted hydrocarbyl, preferably substituted C ₁ -C ₁₂ Hydrocarbyl or unsubstituted C ₁ -C ₁₂ A hydrocarbon radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl or isomers thereof, R' is C ₁ -C ₂₀ Alkyl or aryl radicals, such as the methyl, methylphenyl, phenyl, biphenyl, pentamethylphenyl, tetramethylphenyl or di-tert-butylphenyl radical; alternatively R ³ And R ⁹ Selected from: -CH ₂ -SiMe ₃ ，-CH ₂ -SiEt ₃ ，-CH ₂ -SiPr ₃ ，-CH ₂ -SiBu ₃ ，-CH ₂ -SiCy ₃ ，-CH ₂ -C(CH ₃ ) ₃ ，-CH ₂ -CH(CH ₃ ) ₂ ，-CH ₂ CPh ₃ ，-CH ₂ (C ₆ Me ₅ )，-CH ₂ -C(CH ₃ ) ₂ Ph，-CH ₂ -C(Cy)Ph _2.- CH ₂ -SiH(CH ₃ ) ₂ ，-CH ₂ SiPh ₃ ，-CH ₂ -Si(CH ₃ ) ₂ Ph，-CH ₂ -Si(CH ₃ )Ph ₂ ，-CH ₂ -Si(Et) ₂ Ph，-CH ₂ -Si(Et)Ph ₂ ，-CH ₂ -Si(CH ₂ ) ₃ Ph，-CH ₂ -Si(CH ₂ ) ₄ Ph，-CH ₂ -Si(Cy)Ph ₂ or-CH ₂ -Si(Cy) ₂ Ph。

Alternatively, R ³ And R ⁹ Is not hydrogen.

Alternatively, R ³ And R ⁹ Independently not C ₁ -C ₄₀ Substituted or unsubstituted hydrocarbyl.

Alternatively, each X may independently be a halo, hydride, alkyl, alkenyl, or arylalkyl group.

Alternatively, each X is independently selected from hydrocarbyl groups having 1 to 20 carbon atoms, aryl groups, hydride groups, amino groups, alkoxy groups, thio groups, phosphido groups, halo groups, dienes, amines, phosphines, ethers, and combinations thereof, (two X's may form part of a fused ring or ring system), preferably each X is independently selected from halo groups, aryl groups, and C ₁ -C ₅ Alkyl, preferably each X is phenyl, methyl, ethyl, propyl, butyl, pentyl or chloro.

Useful asymmetric catalysts are preferably such that the mirror plane cannot be drawn through the metal center and the cyclopentadienyl moieties bridging to the metal center are structurally different.

In a useful embodiment, M is Hf or Zr, each R ¹ ，R ² ，R ³ And R ⁴ Is H or C ₁ -C ₂₀ Alkyl, and R ⁹ is-R ²⁰ -SiR' ₃ or-R ²⁰ -CR' ₃ Wherein R is ²⁰ Is CH ₂ And R' is C ₁ -C ₂₀ Alkyl or aryl.

In a useful embodiment, M is Hf or Zr, each R ¹ ，R ² ，R ³ And R ⁴ Is hydrogen or C ₁ -C ₂₀ Alkyl, and R ⁹ is-R ²⁰ -SiR' ₃ or-R ²⁰ -CR' ₃ Wherein R is ²⁰ Is CH ₂ And R' is C ₁ -C ₂₀ Alkyl or aryl, and R ³ is-R ²⁰ -SiR' ₃ or-R ₂₀ -CR' ₃ Wherein R is ₂₀ Is CH ₂ And R' is C ₁ -C ₂₀ Alkyl or aryl.

The catalyst compound represented by formula (a) may be one or more of the following:

rac/meso-Me ₂ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a racemic-Me ₂ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a rac/meso-Ph ₂ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a rac/meso-PhMeSi (3-Me) ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a Rac/meso- (CH) ₂ ) ₄ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a Rac/meso- (CH) ₂ ) ₃ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ ；Me(H)Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ ；Ph(H)Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a Rac/meso- (biphenyl) ₂ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a Rac/meso- (F-C) ₆ H ₄ ) ₂ Si(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a rac/meso-Me ₂ Ge(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a racemic-Me ₂ Ge(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ (ii) a Racemic/endorac-Ph ₂ Ge(3-Me ₃ Si-CH ₂ -Cp) ₂ HfMe ₂ ；Me ₂ Si(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；Ph ₂ Si(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；Me ₂ Ge(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；Ph ₂ Ge(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；PhMeSi(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；(CH ₂ ) ₃ Si(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；(CH ₂ ) ₄ Si(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ ；Et ₂ Si(Me ₄ Cp)(3-Me ₃ Si-CH ₂ -Cp)HfMe ₂ (ii) a And halide forms thereof, wherein Me ₂ Is made from Et ₂ ，Cl ₂ ，Br ₂ ，I ₂ Or Ph ₂ And (3) substitution.

Two different metallocenes of the formula B

One or both of the at least two metallocenes useful herein as poor comonomer incorporating agents are represented by formula (B):

T ² _y Cp _m M ¹ X _q (B)

wherein:

M ¹ is zirconium or hafnium;

T ² is a bridging group;

y is 0 or 1, which indicates the absence or presence of T;

x is halo, hydrido, alkyl, alkenyl or arylalkyl;

m =2 or 3,q =0,1,2 or 3, and the sum of m + q is equal to the oxidation state of the transition metal; and

each Cp and X is bound to M ¹ The above.

In one embodiment, one or both of the at least two metallocenes useful herein as poor comonomer incorporating agents is represented by formula (C):

Cp _m M ² X _q (C)

wherein:

M ² is zirconium or hafnium;

x is halo, hydrido, alkyl, alkenyl or arylalkyl;

each Cp and X is bound to M ¹ The above.

One or both of the at least two metallocenes useful herein as poor comonomer incorporating agents may be represented by formula (D):

T ³ Cp _m M ³ X _q (D)

wherein:

M ³ is zirconium or hafnium;

T ³ is a bridging group;

x is halo, hydrido, alkyl, alkenyl or arylalkyl;

each Cp and X is bound to M ² The above.

The following description applies to the formulae described herein, including formulae (B), (C) and (D).

In one embodiment, each X may be independently a halo, hydride, alkyl, alkenyl, or arylalkyl group.

In any of the embodiments of the invention, T ² And T ³ Independently a bridging group containing at least one group 13, 14, 15 or 16 elementIn particular boron or a group 14, 15 or 16 element. Examples of suitable bridging groups include P (= S) R, P (= Se) R, P (= O) R, R · ₂ C，R* ₂ Si，R* ₂ Ge，R* ₂ CCR* ₂ ，R* ₂ CCR* ₂ CR* ₂ ，R* ₂ CCR* ₂ CR* ₂ CR* ₂ ，R*C＝CR*，R*C＝CR*CR* ₂ ，R* ₂ CCR*＝CR*CR* ₂ ，R*C＝CR*CR*＝CR*，R*C＝CR*CR* ₂ CR* ₂ ，R* ₂ CSiR* ₂ ，R* ₂ SiSiR* ₂ ，R* ₂ SiOSiR* ₂ ，R* ₂ CSiR* ₂ CR* ₂ ，R* ₂ SiCR* ₂ SiR* ₂ ，R*C＝CR*SiR* ₂ ，R* ₂ CGeR* ₂ ，R* ₂ GeGeR* ₂ ，R* ₂ CGeR* ₂ CR* ₂ ，R* ₂ GeCR* ₂ GeR* ₂ ，R* ₂ SiGeR* ₂ ，R*C＝CR*GeR* ₂ ，R*B，R* ₂ C–BR*，R* ₂ C–BR*–CR* ₂ ，R* ₂ C–O–CR* ₂ ，R* ₂ CR* ₂ C–O–CR* ₂ CR* ₂ ，R* ₂ C–O–CR* ₂ CR* ₂ ，R* ₂ C–O–CR*＝CR*，R* ₂ C–S–CR* ₂ ，R* ₂ CR* ₂ C–S–CR* ₂ CR* ₂ ，R* ₂ C–S–CR* ₂ CR* ₂ ，R* ₂ C–S–CR*＝CR*，R* ₂ C–Se–CR* ₂ ，R* ₂ CR* ₂ C–Se–CR* ₂ CR* ₂ ，R* ₂ C–Se–CR* ₂ CR* ₂ ，R* ₂ C–Se–CR*＝CR*，R* ₂ C–N＝CR*，R* ₂ C–NR*–CR* ₂ ，R* ₂ C–NR*–CR* ₂ CR* ₂ ，R* ₂ C–NR*–CR*＝CR*，R* ₂ CR* ₂ C–NR*–CR* ₂ CR* ₂ ，R* ₂ C–P＝CR*，R* ₂ C–PR*–CR* ₂ O, S, se, te, NR, PR, asR, sbR, O-O, S-S, R N-NR, R P-PR, O-S, O-NR, O-PR, S-NR, S-PR and R N-PR, wherein R is hydrogen orContaining C ₁ -C ₂₀ And optionally two or more adjacent R may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. For bridging radicals T ² And T ³ Preferred examples of (2) include CH ₂ ，CH ₂ CH ₂ ，SiMe ₂ ，SiPh ₂ ，SiMePh，Si(CH ₂ ) ₃ ，Si(CH ₂ ) ₄ ，O，S，NPh，PPh，NMe，PMe，NEt，NPr，NBu，PEt，PPr，Me ₂ SiOSiMe ₂ And PBu. In a preferred embodiment of the present invention, in any embodiment of any formula described herein, T is ² And T ³ Independently is of the formula ER ^d ₂ Or (ER) ^d ₂ ) ₂ Wherein E is C, si or Ge, and each R ^d Independently of one another is hydrogen, halogen, C ₁ -C ₂₀ A hydrocarbyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) or a C1-C20 substituted hydrocarbyl group, and two R' s ^d Cyclic structures, including aromatic, partially saturated or saturated cyclic or fused ring systems, may be formed. Preferably, T ² And T ³ Independently a bridging group containing carbon or silicon, e.g. dialkylsilyl, preferably T ² And T ³ Independently selected from CH ₂ ，CH ₂ CH ₂ ，C(CH ₃ ) ₂ ，SiMe ₂ Cyclotrimethylenesilylene (Si (CH) ₂ ) ₃ ) Cyclopentamethylenesilylene radical (Si (CH) ₂ ) ₅ ) And cyclotetramethylenesilylene (Si (CH) ₂ ) ₄ )。

Alternatively, each X is independently selected from hydrocarbyl groups having 1 to 20 carbon atoms, aryl groups, hydride groups, amino groups, alkoxy groups, thio groups, phosphido groups, halo groups, dienes, amines, phosphines, ethers, and combinations thereof, (two X's may form part of a fused ring or ring system), preferably each X is independently selected from halo groups,aryl and C ₁ -C ₅ Alkyl, preferably each X is phenyl, methyl, ethyl, propyl, butyl, pentyl or chloro.

Typically, each Cp is independently a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, or a substituted or unsubstituted fluorene.

Independently, each Cp may be substituted with one or more substituents R. Non-limiting examples of substituents R include one or more of the following: hydrogen, or a linear, branched alkyl, or alkenyl, alkynyl, cycloalkyl or aryl group, an acyl group, an alkoxy group, an aryloxy group, an alkylthio group, a dialkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl-or dialkyl-carbamoyl group, an acyloxy group, an acylamino group, an aroylamino group, a linear, branched or cyclic alkylene group, or a combination thereof. In a preferred embodiment, the substituent R has up to 50 non-hydrogen atoms, preferably 1 to 30 carbons, which may also be substituted with halogens or heteroatoms or the like. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, e.g., t-butyl, isopropyl, and the like. Other hydrocarbyl groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl-substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halohydrocarbyl-substituted organometalloid radicals including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and disubstituted boron groups including, for example, dimethylboron; and disubstituted chalcogen groups including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen groups including methoxy, ethoxy, propoxy, phenoxy, methylthio and ethylthio. Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium, and the like, including olefins such as, but not limited to, ethylenically unsaturated substituents, including vinyl terminated ligands, such as but-3-enyl, prop-2-enyl, hex-5-enyl, and the like. Further, at least two R groups, preferably two adjacent R groups, can be joined to form a ring structure having 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, or combinations thereof.

In one embodiment of Cp, the substituent (S) R are independently a hydrocarbyl group, a heteroatom or heteroatom containing group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or isomers thereof, N, O, S, P or C ₁ -C ₂₀ Hydrocarbyl groups substituted with N, O, S or P heteroatoms or heteroatom containing groups (typically having up to 12 atoms, including N, O, S and P heteroatoms).

Non-limiting examples of Cp include (substituted or unsubstituted) cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, nitrenyl (azenyl), azulene, pentalene, phosphoryl (phosphoryl), phosphoimine (WO 99/40125), pyrrolyl, pyrazolyl, carbazolyl, borabenzophenones (borabezene), and the like, including hydrogenated versions thereof, such as tetrahydroindenyl. In another embodiment, each Cp may independently comprise one or more heteroatoms, such as nitrogen, silicon, boron, germanium, sulfur and phosphorus, which in combination with carbon atoms form an open, pentacyclic or preferably fused ring or ring system, such as a heterocyclopentadienyl ancillary ligand. Other Cp ligands include, but are not limited to, porphyrins, phthalocyanines, corrins, and other polyazamacrocycles.

Independently, each Cp of formulas (B), (C) and (D) may be unsubstituted or substituted with any one or combination of substituent groups R. Non-limiting examples of substituents R used in the structure include hydrogen groups, hydrocarbyl groups, lower hydrocarbyl groups, substituted hydrocarbyl groups, heterohydrocarbyl groups, alkyl groups, lower alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, lower alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, lower alkynyl groups, substituted alkynyl groups, heteroalkynyl groups, alkoxy groups, lower alkoxy groups, aryloxy groups, hydroxy groups, alkylthio groups, lower alkylthio groups, arylthio groups, sulfoxy groups, aryl groups, substituted aryl groups, heteroaryl groups, arylalkyl groups, aralkylene groups, alkylaryl groups, alkarylyl groups, halo groups, haloalkyl groups, haloalkenyl groups, haloalkynyl groups, heteroalkyl groups, heterocycles, heteroaryl groups, heteroatom-containing groups, silyl groups, boranyl groups, phosphino groups, phosphine groups, amino groups, amine groups, cycloalkyl groups, acyl groups, alkylthio groups, dialkylamine groups, alkylamido groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkyl-and dialkyl-carbamoyl groups, acyloxy groups, acylamino groups, aroylamino groups, and combinations thereof.

Preferred examples of the alkyl substituent R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, such as tert-butyl, isopropyl and the like. Other possible groups include substituted alkyl and aryl groups such as fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid groups including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halohydrocarbyl-substituted organometalloid radicals including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and disubstituted boron groups, including, for example, dimethylboron; and disubstituted group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylthio and ethylthio. Other substituents R include olefins such as, but not limited to, ethylenically unsaturated substituents including vinyl terminated ligands such as 3-butenyl, 2-propenyl, 5-hexenyl and the like. In one embodiment, at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of: carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof. Furthermore, substituents R, such as 1-butyl, can form a bonding link to the element M.

The Cp ligands are, in one embodiment, different from each other and, in another embodiment, the same.

The metallocene catalyst compounds described above are expected to include their structural or optical or enantiomeric (racemic mixture), and may be pure enantiomers in one embodiment.

In a useful embodiment, M ¹ And M ² Are all zirconium, preferably M ¹ And M ² Both zirconium and M is hafnium.

In one useful embodiment, M ¹ And M ² Both are zirconium and wherein T ³ The bridge containing at least 2 or more carbon, silicon, oxygen, nitrogen atoms, preferably T ³ Is Si (Me) ₂ OSi(Me) ₂ -，-Si(Me) ₂ Si(Me) ₂ -or-CH ₂ CH ₂ -。

In one useful embodiment, M in formula B ¹ Is Zr and Cp is indenyl.

Suitable unbridged metallocenes useful herein include, but are not limited to, the metallocenes disclosed and mentioned in the above-referenced U.S. patents, as well as those disclosed and mentioned in the following: U.S. Pat. No.7179876;7169864;7157531;7129302;6995109;6958306;6884748;6689847; U.S. patent publication No.2007/0055028 and PCT published application No. WO97/22635; WO00/699/22; WO01/30860; WO01/30861; WO02/46246; WO02/50088; WO04/026921; and WO06/019494, all incorporated herein by reference in their entirety. Additional catalysts suitable for use herein include U.S. Pat. Nos. 6309997;6265338; U.S. publication No.2006/019925 and the following articles: chem Rev 2000, 100, 1253; resconi; chem Rev 2003, 103, 283; chem eur.j.2006, 12, 7546Mitsui; j Mol Catal a 2004, 213, 141; macromol Chem Phys,2005, 206, 1847; and those mentioned in J Am Chem Soc 2001, 123, 6847.

Exemplary compounds of formula (B) include: bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) hafnium dichlorideAlkenyl) zirconium dimethyl, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-phenylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-n-butylcyclopentadienyl) hafnium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, bis (tetrahydro-1-indenyl) zirconium dichloride, bis (tetrahydro-1-indenyl) zirconium dimethyl, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dimethyl, rac/meso-bis (1-ethylindenyl) zirconium dichloride, rac/meso-bis (1-ethylindenyl) zirconium dimethyl, rac/meso-bis (1-methylindenyl) zirconium dichloride, rac/meso-bis (1-methylindenyl) zirconium dimethyl, rac/meso-bis (1-butylindenyl) zirconium dichloride, rac/meso-bis (1-butylindenyl) zirconium dimethyl, meso-bis (1-ethylindenyl) zirconium dichloride, meso-bis (1-ethylindenyl) zirconium dimethyl, (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, and (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dimethyl, and dimethylsilyl-bis (indenyl) zirconium dichloride, rac/meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-Et Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-Et Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-Et Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (NpPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (NpPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ 。

Exemplary compounds of formula (C) include: bis (cyclopentadienyl) zirconium dichloride; bis (cyclopentadienyl) zirconium dimethyl; bis (n-butylcyclopentadienyl) zirconium dichloride; bis (n-butylcyclopentadienyl) zirconium dimethyl; bis (pentamethylcyclopentadienyl) zirconium dichloride; bis (pentamethylcyclopentadienyl) zirconium dimethyl; bis (pentamethylcyclopentadienyl) hafnium dichloride; bis (pentamethylcyclopentadienyl) zirconium dimethyl; bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride; bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl; bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride; bis (1-methyl-3-phenylcyclopentadienyl) zirconium dimethyl; bis (1-methyl-3-n-butylcyclopentadienyl) hafnium dichloride; bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl; bis (indenyl) zirconium dichloride; bis (indenyl) zirconium dimethyl; bis (tetrahydro-1-indenyl) zirconium dichloride; bis (tetrahydro-1-indenyl) zirconium dimethyl; (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride; (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dimethyl; rac/meso-bis (1-ethylindenyl) zirconium dichloride; rac/meso-bis (1-ethylindenyl) zirconium dimethyl; rac/meso-bis (1-methylindenyl) zirconium dichloride; rac/meso-bis (1-methylindenyl) zirconium dimethyl; rac/meso-bis (1-propylindenyl) zirconium dichloride; rac/meso-bis (1-propylindenyl) zirconium dimethyl; rac/meso-bis (1-butylindenyl) zirconium dichloride; rac/meso-bis (1-butylindenyl) zirconium dimethyl; meso-bis (1-ethyl indenyl) zirconium dichloride; meso-bis (1-ethyl indenyl) dimethyl zirconium; (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride; and (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dimethyl.

Exemplary compounds represented by formula (D) include:

rac/meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (NpPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (NpPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ .

Carrier material

In an embodiment of the invention, the catalyst system may comprise a support material. Preferably, the support material is a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organoclays or any other organic or inorganic support material, or mixtures thereof. As used herein, "support" and "support material" are used interchangeably.

PreferablyThe support material is an inorganic oxide in finely divided form. Suitable inorganic oxide materials for use in the supported catalyst systems herein include group 2,4, group 13 and 14 metal oxides such as silica, alumina and mixtures thereof. Other inorganic oxides that may be used alone or in combination with the silica or alumina are magnesia, titania, zirconia, and the like. However, other suitable support materials may be used, such as finely divided functionalised polyolefins, for example finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay, and the like. In addition, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include Al ₂ O ₃ ，ZrO ₂ ，SiO ₂ And combinations thereof, more preferably SiO ₂ ，Al ₂ O ₃ Or SiO ₂ /Al ₂ O ₃ 。

It is preferred that the support material (most preferably the inorganic oxide) have a surface area of from about 10m2/g to about 700m2/g, a pore volume of from about 0.1cc/g to about 4.0cc/g, and an average particle size of from about 5 μm to about 500. Mu.m. More preferably, the support material has a surface area of from about 50m2/g to about 500m2/g, a pore volume of from about 0.5cc/g to about 3.5cc/g, and an average particle size of from about 10 μm to about 200 μm. Most preferably, the support material has a surface area of from about 100m2/g to about 400m2/g, a pore volume of from about 0.8cc/g to about 3.0cc/g, and an average particle size of from about 5 μm to about 100 μm. The average pore size of the support material may be

Preferably 50 to about

And most preferably from 75 to about

In some embodiments, the support material is a high surface area, amorphous silica (surface area ≧ 300m2/gm, pore volume ≧ 300m 2/gm)1.65cm3/gm) and sold under the trade name DAVISON Chemical Division of w.r.grace and Company under the trade name DAVISON 952 or DAVISON 955, which is particularly useful. In other embodiments, DAVIDSON 948 is used.

In some embodiments of the invention, the support material may be dry, i.e., without absorbed water. Drying of the support material may be accomplished by heating or calcining at a temperature of from about 100 c to about 1000 c, preferably at least about 600 c. When the support material is silica, it is typically heated to at least 200 ℃, preferably from about 200 ℃ to about 850 ℃, and most preferably about 600 ℃; and for a period of time of from about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material preferably has at least some reactive hydroxyl (OH) groups.

In a particularly useful embodiment, the support material is fluorinated. The compound containing a fluorinating agent may be any compound containing a fluorine atom. Particularly desirable are inorganic fluorine-containing compounds selected from the group consisting of NH ₄ BF ₄ ，(NH ₄ ) ₂ SiF ₆ ，NH ₄ PF ₆ ，NH ₄ F，(NH ₄ ) ₂ TaF ₇ ，NH ₄ NbF ₄ ，(NH ₄ ) ₂ GeF ₆ ，(NH ₄ ) ₂ SmF ₆ ，(NH ₄ ) ₂ TiF ₆ ，(NH ₄ ) ₂ ZrF ₆ ，MoF ₆ ，ReF ₆ ，GaF ₃ ，SO ₂ ClF，F ₂ ，SiF ₄ ，SF ₆ ，ClF ₃ ，ClF ₅ ，BrF ₅ ，IF ₇ ，NF ₃ ，HF，BF ₃ ，NHF ₂ And NH ₄ HF ₂ . Among these, ammonium hexafluorosilicate and ammonium tetrafluoroborate are useful. Combinations of these compounds may also be used.

Ammonium hexafluorosilicate and ammonium tetrafluoroborate fluoride compounds are generally solid particles, as are silica supports. Desirably, the support is treated with the fluorine compound by dry blending the two components by simple blending at a concentration of 0.01 to 10.0 millimoles F/g of support, desirably 0.05 to 6.0 millimoles F/g of support, and most desirably 0.1 to 3.0 millimoles F/g of support. The fluorine compound may be dry mixed with the support either before or after addition to the vessel to dehydrate or calcine the support. Thus, the fluorine concentration present on the support is from 0.1 to 25wt%, alternatively from 0.19 to 19wt%, alternatively from 0.6 to 3.5wt%, based on the weight of the support.

The above two metal catalysts described herein are typically used at 10 to 100 micromoles of metal per gram of solid support; alternatively 20 to 80 micromoles of metal per gram of solid support; or at a loading level of 40-60 micromoles of metal per gram of support. However, larger or smaller values may be used, provided that the total amount of solid complex does not exceed the pore volume of the support.

In at least one embodiment, the support material comprises a support material treated with an electron-withdrawing anion. The support material may be silica, alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstates, titania, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron-withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, hydrogen sulfate, or any combination thereof.

The electron-withdrawing component used to treat the support material may be any component which, after treatment, increases the lewis or bronsted acidity of the support material (as compared to a support material which has not been treated with at least one electron-withdrawing anion). In at least one embodiment, the electron-withdrawing component is an electron-withdrawing anion derived from a salt, acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for the anion. The electron-withdrawing anion can be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phosphotungstic acid, or mixtures thereof, or combinations thereof. In at least one embodiment of the present invention, the electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or the like, or any combination thereof. In at least one embodiment, the electron-withdrawing anion is sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate, fluorozirconate, fluorotitanate, or a combination thereof.

Thus, for example, a support material suitable for use in the catalyst system of the present invention may be one or more of the following: fluorinated alumina, chlorinated alumina, brominated alumina, sulfated alumina, fluorinated silica-alumina, chlorinated silica-alumina, brominated silica-alumina, sulfated silica-alumina, fluorinated silica-zirconia, chlorinated silica-zirconia, brominated silica-zirconia, sulfated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, and the like, or combinations thereof. In at least one embodiment, the activator-support can be or can include fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or a combination thereof. In another embodiment, the support material comprises hexafluorotitanic acid treated alumina, hexafluorotitanic acid treated silica coated alumina, hexafluorozirconic acid treated silica-alumina, trifluoroacetic acid treated silica-alumina, fluorided boria-alumina, tetrafluoroboric acid treated silica, tetrafluoroboric acid treated alumina, hexafluorophosphoric acid treated alumina, or a combination thereof. In addition, any of these activator-supports optionally can be treated with metal ions.

Non-limiting examples of cations in salt form suitable for use in the present invention as electron-withdrawing anions include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H +, [ H (OEt) ₂ ) ₂ ]+ or combinations thereof。

Furthermore, combinations of one or more different electron-withdrawing anions in different proportions may be used to adjust the specific acidity of the support material to a desired level. The combination of electron withdrawing components may be contacted with the support material simultaneously or separately and in any order to provide the desired acidity of the chemically treated support material. For example, in at least one embodiment, two or more electron-withdrawing anion source compounds are in two or more separate contacting steps.

In one embodiment of the present invention, an example of a method of preparing a chemically-treated support material is as follows: the selected support material or combination of support materials may be contacted with a first electron-withdrawing anion source compound to form a first mixture; such a first mixture may be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture may then be calcined to form a treated support material. In such a method, the first and second electron-withdrawing anion source compounds may be the same or different compounds.

Methods of contacting the oxide with an electron-withdrawing component (typically a salt or acid of an electron-withdrawing anion) may include but are not limited to gelation, cogelling, dipping one compound into another, the like, or combinations thereof. After the contacting process, the contacted support material, electron-withdrawing anion, and optional metal ion mixture may be calcined.

According to another embodiment of the invention, the support material may be treated by a method comprising: (i) Contacting a support material with a first electron-withdrawing anion source compound to form a first mixture; (ii) Calcining the first mixture to produce a calcined first mixture; (iii) Contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture; and (iv) calcining the second mixture to form a treated support material.

Activating agent

The supported catalyst system may be formed by combining the two metal catalysts described above with an activator in any manner known in the literature, including supporting them for slurry or gas phase polymerization. An activator is defined as any compound that can activate any of the above catalysts by converting a neutral metal catalyst compound into a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and cocatalysts of conventional type. Preferred activators generally include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive, sigma-bonded metal ligands, render the metal compounds cationic, and provide charge-balanced non-coordinating or weakly coordinating anions.

Alumoxane activators

Alumoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally oligomeric compounds containing-Al (R) ¹ ) -O-subunit wherein R ¹ Is an alkyl group. Examples of the aluminoxane include Methylaluminoxane (MAO), modified Methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halo, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes may also be used. Visually clear methylaluminoxane may preferably be used. The cloudy or gelled aluminoxane can be filtered to produce a clear solution or the clear aluminoxane can be decanted from the cloudy solution. A useful aluminoxane is Modified Methylaluminoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, inc. Under the trade name modified methylaluminoxane type 3A, which is encompassed in U.S. patent No. 5041584).

Another useful aluminoxane is solid polymethylaluminoxane such as disclosed in U.S. Pat. Nos. 9340630;8404880; and 8975209.

When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator, which is typically up to 5000 times the molar excess of Al/M relative to the catalyst (per metal catalytic center). The minimum activator to catalyst compound molar ratio is 1:1. alternative preferred ranges include 1:1-500:1, alternatively 1:1-200:1, alternatively 1:1-100:1, or alternatively 1:1-50:1.

in an alternative embodiment, little or no aluminoxane is used in the polymerization process described herein. Preferably, the aluminoxane is present in 0mol%, alternatively the aluminoxane is present in a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1:1 is present.

Non-coordinating anion activators

The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to a cation, or which is only weakly coordinated to a cation, thereby remaining sufficiently labile to be displaced by a neutral lewis base. "compatible" noncoordinating anions are those which do not degrade to neutrality upon decomposition of the initially formed complex. Furthermore, the anion does not transfer an anionic substituent or moiety to the cation such that it forms a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful according to embodiments of the present invention are those that are compatible with the transition metal cation and stabilize the transition metal cation in the sense of balancing its ionic charge by +1, and yet retain sufficient instability to allow displacement during polymerization.

The use of ionizing activators (neutral or ionic) such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a trisperfluorophenylboron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, a polyhalogenated heteroborane anion (WO 98/43983), boric acid (U.S. Pat. No. 5942459), or combinations thereof is within the scope of the present invention. It is also within the scope of the present invention to use neutral or ionic activators, either alone or in combination with alumoxane or modified alumoxane activators.

For a description of useful activators, see U.S. Pat. Nos. 8658556 and 6211105.

Preferred activators include N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluorophenyl) borate, [ Me3NH + ] [ B (C6F 5) 4- ],1- (4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium; and [ Me3NH + ] [ B (C6F 5) 4- ],1- (4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium; and sodium tetrakis (pentafluorophenyl) borate, potassium tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluoropyridinium, sodium tetrakis (perfluorophenyl) aluminate, potassium tetrakis (pentafluorophenyl and N, N-dimethylanilinium tetrakis (perfluorophenyl) aluminate.

In a preferred embodiment, the activator comprises a triarylcarbonium (e.g., triphenylcarbonium tetraphenylborate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triphenylcarbonium tetrakis (perfluoronaphthyl) borate, triphenylcarbonium tetrakis (perfluorobiphenyl) borate, triphenylcarbonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate).

In another embodiment, the activator comprises one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dialkylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N, N-dialkylanilinium tetrakis (perfluoronaphthyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N, N-dialkylanilinium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dialkylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dialkyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, (where alkyl is methyl, ethyl, propyl, N-butyl, sec-butyl, or tert-butyl).

Typical activator to catalyst ratios, for example the total NCA activator to catalyst ratio is about 1:1 molar ratio. Alternative preferred ranges include 0.1:1-100:1, alternatively 0.5:1-200:1, alternatively 1:1-500:1, alternatively 1:1-1000:1. particularly useful ranges are 0.5:1-10:1, preferably 1:1-5:1.

optional scavenger or co-activator

In addition to the activator compound, a scavenger, chain transfer agent or co-activator may be used. Aluminum alkyls or organoaluminum compounds that can be used as co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc.

In some embodiments, the catalyst system will additionally comprise one or more scavenging compounds. Here, the term "scavenger" means a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. Typically, the scavenging compound will be an organometallic compound such as U.S. Pat. No.5153157;5241025; and PCT publication No. WO91/09882; WO 94/03506; WO 93/14132; and group 13 organometallic compounds of WO 95/07941. Exemplary compounds include triethylaluminum, triethylborane, triisobutylaluminum, methylaluminoxane, isobutylaluminoxane and tri-n-octylaluminum. With a large volume or C attached to a metallic or metalloid center ₆ -C ₂₀ Those scavenging compounds for linear hydrocarbyl substituents typically minimize adverse interactions with the active catalyst. Examples include triethylaluminum, but bulky compounds such as triisobutylaluminum, triisobutylaluminum isoamyl (tri-iso-prenylaluminum), and long-chain linear alkyl-substituted aluminum compounds such as tri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum are more preferred. When alumoxanes are used as activators, any excess above that required for activation will be scavengedImpurities, and additional scavenging compounds may not be necessary. Alumoxane can also be added in scavenging amounts with other activators, such as methylalumoxane, [ Me ] ₂ HNPh]+[B(pfp) ₄ ]-or B (pfp) ₃ (perfluorophenyl = pfp = C) ₆ F ₅ )。

Preferred aluminum scavengers include those in which oxygen is present. I.e. the material itself or the aluminium mixture used as scavenger, comprises an aluminium/oxygen species, such as an aluminoxane or an alkylaluminium oxide, such as a dialkylaluminium oxide, for example bis (diisobutylaluminium) oxide. In one aspect, the aluminum-containing scavenger can be of the formula ((R) _z -Al-) _y O-) _x Wherein z is 1-2,y is 1-2,x is 1-100, and R is C ₁ -C ₁₂ A hydrocarbyl group. In another aspect, the oxygen to aluminum (O/Al) molar ratio of the scavenger is from about 0.25 to about 1.5, more particularly from about 0.5 to about 1.

Preparation of Mixed catalyst systems

The four or more metal catalyst compounds described above can be combined to form a mixed catalyst system.

When combined, the four or more metal catalyst compounds may be added together in the desired ratio, contacted with the activator or contacted with the support material or supported activator. The metal catalyst compounds may be added to the mixture sequentially or simultaneously.

Alternative preparations may include adding a first metal catalyst compound to a slurry comprising a support or supported activator mixture for a specified reaction time, followed by adding a second metal catalyst compound solution, mixing for another specified time, followed by adding a third metal catalyst compound, followed by a fourth metal catalyst compound, after which the mixture may be recovered for use in a polymerization reactor, e.g., spray dried for recovery. Finally, additional additives such as about 10vol% 1-hexene may be present in the mixture prior to addition of the first metal catalyst compound.

The first metal catalyst compound may be supported via contact with a support material for a reaction time. The formed supported catalyst composition may then be mixed with a diluent (e.g., mineral oil) to form a slurry, which may or may not include an activator. The slurry may then be mixed with the second, third, and fourth metal catalyst compounds prior to introducing the formed mixed catalyst system into the polymerization reactor. The second, third and fourth metal catalyst compounds may be mixed at any point prior to introduction into the reactor, for example in the polymerization feed vessel or in-line in the catalyst delivery system.

The mixed catalyst system may be formed by combining a first metal catalyst compound (e.g., a metal catalyst compound useful for producing a first polymer property, such as a high molecular weight polymer fraction and/or high comonomer content) with a support and an activator, desirably in a first diluent, such as an alkane or toluene, to produce a supported, activated catalyst compound. The supported activated catalyst compound (which may or may not be separated from the first diluent) is then combined in one embodiment with a second diluent, such as a high viscosity diluent, for example mineral oil or silicone oil, or an alkane diluent containing 5 to 99wt% mineral oil or silicone oil, for example toluene, to form a slurry of the supported metal catalyst compound, and subsequently or simultaneously combined with a similar polymer property, such as a high molecular weight polymer fraction or high comonomer content, or a second metal catalyst compound (such as a metal catalyst compound that can be used to produce a second polymer property, such as a low molecular weight polymer fraction or low comonomer content), in the diluent or as a dry solid compound to form a supported activated mixed catalyst system ("mixed catalyst system"). Other alkane diluents include isopentane, hexane, n-heptane, octane, nonane and decane, cycloalkanes such as cyclohexane, aromatics such as benzene, toluene, xylene and ethylbenzene. The third metal catalyst compound and then the fourth metal catalyst compound are added in a similar manner. The resulting mixed catalyst system may be the supported and activated first metal catalyst compound in a slurry comprising mineral oil or silicone oil, and the second, third and fourth metal catalyst compounds are not supported and are not combined with additional activators, wherein the second, third and fourth metal catalyst compounds may or may not be partially or fully soluble in the slurry. In one embodiment, the diluent is comprised of mineral oil.

As used herein, mineral oil or "high viscosity diluent" refers to a mixture of petroleum hydrocarbons and hydrocarbons, which may include aliphatic, aromatic and/or paraffinic components, which are liquid at temperatures above 23 ℃ and typically have a molecular weight of at least 300 atomic mass units (amu) to 500amu or greater, and a viscosity of 40 to 300 centistokes (cSt) or greater at 40 ℃, or in one embodiment 50 to 200cSt. The term "mineral oil" includes synthetic oils or liquid polymers known in the art, polybutenes, refined naphthenes AND refined paraffins, as disclosed, FOR example, in BLUE BOOK 2001, MATERIALS, COMPOUNDING INCIDENTS, MACHINERY AND SERVICES FOR RUBBER 189 (J.H.Lippincott, D.R.Smith, K.Kish & B.Gordon eds., lippincott & Peto Inc.2001). Preferred mineral oils and silicone oils are those that do not include a moiety reactive with the metallocene catalyst (examples of which include hydroxyl and carboxyl groups).

The diluent may comprise a mineral oil, a silicone oil and/or a blend of hydrocarbons selected from: c ₁ -C ₁₀ Alkane, C ₆ -C ₂₀ Aromatic hydrocarbons, C ₇ -C ₂₁ Alkyl substituted hydrocarbons and mixtures thereof. When the diluent is a blend comprising mineral oil, the diluent may comprise 5 to 99wt% mineral oil. In some embodiments, the diluent may consist essentially of mineral oil.

In one embodiment, the first metal catalyst compound is combined with an activator and a first diluent to form a catalyst slurry, which is then combined with a support material. Until such contact is made, the carrier particles are optionally not previously activated. The first metal catalyst compound may be in any desired form such as a dry powder, a suspension in a diluent, a solution in a diluent, a liquid, and the like. The catalyst slurry and support particles are then thoroughly mixed, in one embodiment, at an elevated temperature such that both the first metal catalyst compound and the activator are deposited on the support particles to form the support slurry.

Alternatively, the four catalyst compounds are dissolved together in toluene and added to the MAO silica after dissolution. Alternatively, the catalysts may be added in any order, either in steps or together, to form a slurry, which optionally may be filtered and dried under vacuum. Optionally, the catalyst may be added to the heated slurry at room temperature to 150 ℃, more preferably 80 ℃.

Alternatively, after the first metal catalyst compound and activator are deposited on the support, the second metal catalyst compound may then be combined with the supported first metal catalyst compound, wherein the second metal catalyst is combined with a diluent comprising an alkane, mineral oil, and/or silicone oil by any suitable means prior to, simultaneously with, or after the second metal catalyst compound is contacted with the supported first metal catalyst compound. The third and then fourth metal catalyst compounds are then added in a manner similar to the second metal catalyst. In one embodiment, the first metal catalyst compound is separated from the first diluent in a dry state and then combined with the second metal catalyst compound. Preferably, the second, third and fourth metal catalyst compounds are not activated, i.e., not combined with any activator, prior to being combined with the supported first metal catalyst compound. The resulting solid slurry (comprising the supported first, second, third and fourth metal catalyst compounds) is then preferably thoroughly mixed at elevated temperature.

A wide range of mixing temperatures is possible for the various stages in the preparation of the mixed catalyst system. For example, when the first metal catalyst compound and at least one activator, such as methylalumoxane, are combined with the first diluent to form a mixture, the mixture is preferably heated to a first temperature of 25 ℃ to 150 ℃, preferably 50 ℃ to 125 ℃, more preferably 75 ℃ to 100 ℃, most preferably 80 ℃ to 100 ℃ and stirred for a period of time of 30 seconds to 12 hours, preferably 1 minute to 6 hours, more preferably 10 minutes to 4 hours, and most preferably 30 minutes to 3 hours.

The mixture is then combined with a support material to provide a first support slurry. The support material may be heated or dehydrated (if desired) prior to combination. In one or more embodiments, the first support slurry is mixed at a temperature greater than 50 ℃, preferably greater than 70 ℃, more preferably greater than 80 ℃ and most preferably greater than 85 ℃ for a period of time ranging from 30 seconds to 12 hours, preferably from 1 minute to 6 hours, more preferably from 10 minutes to 4 hours and most preferably from 30 minutes to 3 hours. Preferably, the mixing time of the support slurry is sufficient to provide an assemblage of activated support particles having the first metal catalyst compound deposited thereon. The first diluent may then be removed from the first support slurry to provide a dried supported first catalyst compound. For example, the first diluent may be removed under vacuum or by nitrogen purge.

Next, the second metal catalyst compound is combined with the activated first metal catalyst compound in the presence of a diluent (e.g., an alkane, mineral oil, or silicone oil). Preferably, the second metal catalyst compound is present in a molar ratio to the first metal catalyst compound of 1:4-4:1 depending on whether the second metal catalyst compound produces similar or different polymer properties as previously discussed. Most preferably, the molar ratio is about 1:1, wherein the metal catalyst compound produces similar attributes, and is 2:1 wherein the metal catalyst compound produces different polymer properties. The third and fourth metal catalyst compounds are then added in a similar manner. The slurry formed (or the first support slurry) is preferably heated to a first temperature of from 25 ℃ to 150 ℃, preferably from 50 ℃ to 125 ℃, more preferably from 75 ℃ to 100 ℃, most preferably from 80 ℃ to 100 ℃ and stirred for a period of time of from 30 seconds to 12 hours, preferably from 1 minute to 6 hours, more preferably from 10 minutes to 4 hours and most preferably from 30 minutes to 3 hours. The resulting mixed catalyst system will have a 4:4:1:1 (first high molecular weight metal catalyst compound: second high molecular weight metal catalyst compound: first low molecular weight metal catalyst compound: second low molecular weight catalyst compound).

The first diluent being an aromatic compound or an alkaneA hydrocarbon, preferably a hydrocarbon diluent having a boiling point of less than 200 ℃, such as toluene, xylene, hexane, and the like, which can be removed from the supported first metal catalyst compound under vacuum or by nitrogen purge, provides a supported mixed catalyst system. Even after the addition of oil and/or a second (or other) catalyst compound, it may be desirable to treat the slurry to further remove any remaining solvent, such as toluene. This may be by way of example N ₂ Purging or vacuum. Depending on the level of mineral oil addition, the resulting mixed catalyst system may remain a slurry or may be a free-flowing powder, which contains a certain amount of mineral oil. Thus, while in one embodiment in the form of a slurry of solids in mineral oil, the mixed catalyst system may take any physical form such as a free-flowing solid. For example, in one embodiment the mixed catalyst system may be 1 to 99wt% solids content based on the weight of the mixed catalyst system (mineral oil, support, total catalyst compound and activator (s)).

Polymerization process

The present invention provides a process for producing an ethylene polymer composition comprising: i) In a single reaction zone, in gas or slurry phase, ethylene and C ₃ -C ₂₀ The comonomer is contacted with a catalyst system comprising a support, an activator and the above catalyst system, and an ethylene polymer composition is obtained having: 1) at least 50mol% ethylene, 2) a density of 0.890g/cc or greater, alternatively 0.910g/cc or greater, alternatively 0.935g/cc or greater, 3) a melt flow index of 0.1 to 80dg.min, and 4) a Mw/Mn of 2.5 to 21.5. Without wishing to be bound by theory, it is believed that the ethylene polymers produced herein (i.e., the in situ ethylene polymer compositions) have at least four polymer components, wherein the first and second components are derived from the catalyst shown in formula a, and have more comonomer (e.g., hexene) and higher Mw than the third and fourth components derived from the catalyst shown in formula (B), preferably (C) and (D), which have less comonomer (e.g., hexene) and lower Mw than the first component.

In at least one embodiment, the polymerization process comprises contacting a monomer (e.g., ethylene) and optionally a comonomer (e.g., hexene) with a supported catalyst system comprising two group 4 metallocene compounds (e.g., two catalysts according to formula (a)), two different group 4 (e.g., zr) metallocene compounds (e.g., two catalysts according to formula (B) or one catalyst according to formula (C) and one catalyst according to formula (D)), an activator, and a support material, as described above.

The monomer comprises substituted or unsubstituted C ₂ -C _40α Olefins, preferably C ₂ -C _20α Olefins, preferably C ₂ -C ₁₂ Alpha-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In a preferred embodiment, the monomers comprise ethylene and optionally comonomers comprising one or more C ₃ -C ₄₀ Olefins, preferably C ₄ -C ₂₀ Olefins, or preferably C ₆ -C ₁₂ An olefin. C ₃ -C ₄₀ The olefin monomers may be linear, branched or cyclic. C ₃ -C ₄₀ The cyclic olefin may be strained (strained) or unstrained (unstrained), monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

Exemplary C ₃ -C ₄₀ Comonomers include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologs and derivatives.

In a preferred embodiment, the one or more dienes are present in the polymer produced herein in an amount of up to 10 weight percent, preferably from 0.00001 to 1.0 weight percent, preferably from 0.002 to 0.5 weight percent, even more preferably from 0.003 to 0.2 weight percent, based on the total weight of the composition. In some embodiments, 500ppm or less of diene is added to the polymerization, preferably 400ppm or less, preferably 300ppm or less. In other embodiments, at least 50ppm of diene is added to the polymerization, alternatively 100ppm or more, alternatively 150ppm or more.

Preferred diene monomers include any hydrocarbon structure having at least two unsaturated bonds, preferably C ₄ -C ₃₀ Wherein at least two of the unsaturated bonds are readily incorporated into the polymer by the stereospecific or non-stereospecific catalyst(s). It is further preferred that the diene monomer is selected from α, ω -diene monomers (i.e., divinyl monomers). More preferably, the diolefin monomers are linear divinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, 1, 13-tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing dienes with or without substituents at various ring positions.

In a particularly preferred embodiment, the process provides for the polymerization of ethylene and at least one comonomer having from 3 to 8 carbon atoms, preferably from 4 to 8 carbon atoms. Specifically, the comonomers are propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene and 1-octene, with 1-hexene, 1-butene and 1-octene being most preferred.

In a particularly preferred embodiment, the process provides for the polymerization of one or more monomers selected from the group consisting of: propylene, 1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and combinations thereof.

The polymerization process of the present invention may be carried out in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art may be used. Such processes may be carried out in batch, semi-batch, or continuous mode. Gas phase polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is one in which at least 90% by weight of the product is soluble in the reaction medium). The bulk homogeneous process is particularly preferred. (the bulk method is a method in which the monomer concentration in the entire feed to the reactor is 70vol% or more). Alternatively, no solvent or diluent is present or added to the reaction medium (other than a small amount of a carrier used as a catalyst system or other additive, or an amount commonly found with monomers; e.g., propane in propylene).

In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" refers to a polymerization process wherein a supported catalyst is used and monomer is polymerized on the supported catalyst particles. At least 95wt% of the polymer product derived from the supported catalyst is in the form of pellets such as solid particles (not dissolved in the diluent).

In another embodiment, the process is a gas phase process.

Suitable diluents/solvents for the polymerization include non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, such as are commercially available (Isopar) ^TM ) (ii) a Perhalogenated hydrocarbons, e.g. perfluorinated C _4-10 Alkanes, chlorobenzene, and aromatic and alkyl-substituted aromatics such as benzene, toluene, mesitylene, and xylenes. Suitable solvents also include liquid olefins that may serve as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably the aromatic compound is present in the solvent in an amount less than 1 weight percent, preferably less than 0.5 weight percent, preferably less than 0 weight percent, based on the weight of the solvent.

Gas phase polymerization

Generally, in a fluidized gas bed process for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. A gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor. At the same time, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (see, e.g., U.S. Pat. Nos. 4543399;4588790, 5317036, 5352749, 5405922, 5453304. In a preferred embodiment, the present invention relates to a process for producing an ethylene alpha-olefin copolymer comprising: ethylene and at least one alpha-olefin are polymerized by contacting ethylene and at least one alpha-olefin with the catalyst system described herein in at least one gas phase reactor at a reactor pressure of 0.7 to 70bar and a reactor temperature of 20 ℃ to 150 ℃ to form an ethylene alpha-olefin copolymer, preferably the copolymer has a density of 0.890g/cc (preferably 0.900 to 0.940 g/cc) or greater, a melt flow index of 0.1 to 80g/10min, and an Mw/Mn of 2.5 to 12.5, and optionally an Mw/Mz of 2 to 3, and/or an Mw value of 50000 to 250000g/mol.

Slurry phase polymerisation

Slurry polymerization processes are typically operated at pressures in the range of from 1 to about 50 atmospheres (15 psi to 735psi,103kpa to 5068 kPa) or even higher and temperatures of from 0 ℃ to about 120 ℃. In slurry polymerisation, a suspension of solid particulate polymer is formed in a liquid polymerisation diluent medium to which the monomer and comonomer and catalyst are added. The suspension comprising diluent is intermittently or continuously removed from the reactor, wherein volatile components are separated from the polymer and recycled (optionally after distillation) to the reactor. The liquid diluent used in the polymerization medium is generally an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium used should be liquid and relatively inert under the polymerization conditions. When a propane medium is used, the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or isobutane medium is used.

In a preferred embodiment, the present invention relates to a process for producing an ethylene alpha-olefin copolymer comprising: ethylene and at least one alpha-olefin are polymerized by contacting ethylene and at least one alpha-olefin with the catalyst system described herein in at least one slurry phase reactor at a reactor pressure of 0.7 to 70bar and a reactor temperature of 60 ℃ to 130 ℃ to form an ethylene alpha-olefin copolymer, said copolymer preferably having a density of 0.890g/cc or greater, a melt flow index of 0.1 to 80g/10min, and a Mw/Mn of 2.5 to 12.5.

Polyolefin products

The invention further provides compositions of matter produced by the methods described herein.

As used herein, "high molecular weight" is defined as a number average molecular weight (Mn) value of 150000g/mol or greater. "Low molecular weight" is defined as Mn values of less than 150000g/mol.

As used herein, "low comonomer content" is defined as a polyolefin having 6wt% or less comonomer based on the total weight of the polyolefin. As used herein, "high comonomer content" is defined as a polyolefin having greater than 6 weight percent comonomer, based on the total weight of the polyolefin.

In a preferred embodiment, the process described herein produces an ethylene homopolymer or ethylene copolymer, such as an ethylene-alpha-olefin (preferably C) ₃ -C ₂₀ ) Copolymers (e.g., ethylene-butene copolymers, ethylene-hexene and/or ethylene-octene copolymers having a Mw/Mn of greater than 1 to 20 (preferably greater than 1 to 12).

In a preferred embodiment, the polymer produced herein comprises ethylene and 0 to 25mol% (alternatively 0.5 to 20mol%, alternatively 1 to 15mol%, preferably 3 to 10 mol%) of one or more C ₃ -C ₂₀ Olefin comonomer (preferably C) ₃ -C ₁₂ Alpha-olefins, preferably propene, butene, hexene, octene, decene, dodecene, preferably propene, butene, hexene, octene).

In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably 1 to 15mol% hexene, alternatively 1 to 10mol%.

In a preferred embodiment, the polymer formed has: a) RCI, m is more than 30 and Mw/Mn is more than 3; or b) RCI, m is greater than 50 and Mw/Mn is greater than 5.

In a preferred embodiment, the instant invention provides a polyethylene composition comprising:

ethylene derived units and 0.5-20wt% of C ₃ -C ₁₂ Alpha-olefin derived units (alternatively 99-85wt% ethylene derived units and 1-15wt% C) ₃ -C ₁₂ Alpha-olefin derived units), based on the weight of the polymer;

MI is 0.1-6g/10min (alternatively 0.5-5g/10min, alternatively 0.75-4g/10 min);

a density of 0.890-0.940g/ml (alternatively 0.90-0.935g/ml, alternatively 0.91-0.930 g/ml);

HLMI is 5-40g/10min (alternatively 10-37g/ml, alternatively 15-35 g/ml);

Tw ₁ -Tw ₂ a value less than-30 ℃ (alternatively less than-34 ℃, alternatively less than-38 ℃);

Mw ₁ /Mw ₂ a value of 0.9-4 (alternatively 1.4-3.5, alternatively 1.9-3.0);

Mw/Mn is from 5 to 30 (alternatively from 4 to 20, alternatively from 5 to 10);

Mz/Mw is from 2.5 to 10 (alternatively from 2.5 to 8, alternatively from 2.5 to 4);

Mz/Mn is 15-40 (alternatively 15-30, alternatively 15-25); and

g' (vis) is greater than 0.90 (alternatively greater than 0.93, alternatively greater than 0.95).

ethylene derived units and 0.5-20wt% of C ₃ -C ₁₂ An alpha-olefin derived unit;

MI is 0.1-6g/10min;

a density of 0.890 to 0.940g/cc;

HLMI is 5-40g/10min;

Tw ₁ -Tw ₂ the value is greater than-36 ℃;

Mw ₁ /Mw ₂ the value is 0.9 to 4;

Mw/Mn is from 5 to 10;

Mz/Mw is from 2.5 to 3.5;

Mz/Mn is 15-25; and

g' (vis) is greater than 0.90.

MI is 0.1-20g/10min;

a density of 0.890 to 0.940g/cc;

the melt index ratio I21/I2 is 25-45g/10min;

Tw ₁ -Tw ₂ the value is less than-30 ℃;

Mw ₁ /Mw ₂ the value is 0.9 to 4;

Mw/Mn is from 5 to 10;

Mz/Mw is from 2.5 to 3.5;

Mz/Mn is 15-25; and

g' (vis) is greater than 0.90.

In particular, the present invention provides an in situ ethylene polymer composition having: 1) At least 50mol% of ethylene; and 2) a density of 0.89g/cc or greater, preferably 0.910g/cc or greater (ASTM 1505). Preferably, the comonomer (e.g. hexene) content in the higher molecular weight (Mn greater than 150000 g/mol) component of the resin of the copolymer is higher, preferably at least 10% higher, preferably at least 20% higher, preferably at least 30% higher, than in the lower molecular weight component.

The copolymers produced herein generally have a composition distribution breadth T as measured by TREF ₇₅ -T ₂₅ Is greater than 20 deg.C, preferably greater than 30 deg.C, preferably greater than 40 deg.C. T is ₇₅ -T ₂₅ Values represent the uniformity of the composition distribution as determined by temperature rising elution fractionation. The TREF curve was generated as follows. The temperature at which 25% of the polymer was eluted was then subtracted from the temperature at which 75% of the polymer was eluted, as determined by the integration of the area under the reref curve. T is ₇₅ -T ₂₅ The values represent differences. The closer these temperatures are to each other, the narrower the composition distribution.

Typically, the Mw of the polymers produced herein is from 5000 to 1000000g/mol (preferably from 25000 to 750000g/mol, preferably from 50000 to 500000 g/mol) and/or the Mw/Mn is greater than 1 to 40 (alternatively from 1.2 to 20, alternatively from 1.3 to 10, alternatively from 1.4 to 12,2-10, alternatively from 2.5 to 10) as determined by GPC-4D.

The typical Mz/Mw of the polymers produced herein (as determined by GPC-4D) is from about 1 to about 10, such as from about 2 to about 6, such as from about 2 to about 4, such as from about 2 to about 3. The ratio of Mz/Mw is a measure of the width of the high molecular weight portion of the polymer molecular weight distribution, which is an indication of the tear strength of the polymer. Furthermore, mz/Mn indicates the viscosity of the polymer. For example, a high Mz/Mn value indicates a low viscosity, while a low Mz/Mn value indicates a high viscosity. Thus, a polymer with a larger Mz/Mn ratio would be expected to have a lower viscosity at high shear rates than a polymer with a similar weight average molecular weight, but a smaller Mz/Mn ratio.

Typical Mz/Mn of the polymers produced herein is from about 1 to about 10, such as from about 2 to about 6, for example from about 3 to about 5.

The polymers produced herein may have a monomodal or multimodal molecular weight distribution as determined by gel permeation chromatography (GPC-4D). By "multimodal" is meant that the GPC trace has at least two peaks or more than 2 inflection points. An inflection point is a point at which the second derivative of the curve changes sign (e.g., from negative to positive or vice versa).

Usefully, in a preferred embodiment, the polymers produced herein have a monomodal molecular weight distribution, as determined by gel permeation chromatography (GPC-4D), and Mw/Mn is 5 or greater, preferably 7 or greater.

In another embodiment, the polymer produced herein has more than two peaks in a TREF measurement (see below). As used in this specification and the appended claims, greater than two peaks in a TREF measurement means that, using the following TREF method, there are greater than two distinct normalized IR response peaks in a plot of normalized IR response (vertical or y-axis) versus elution temperature (horizontal or x-axis, and temperature increasing from left to right). "Peak" means in this context where the overall slope of the plot changes from positive to negative as the temperature increases. There is a local minimum between the two peaks where the overall slope of the plot changes from negative to positive with increasing temperature. The "general trend" of the graph is intended to exclude a plurality of local minima and maxima, which may occur in intervals of 2 ℃ or less. Preferably, the different peaks are spaced at least 3 ℃ apart, more preferably at least 4 ℃ apart, even more preferably at least 5 ℃ apart. In addition, different peaks appear on the graph at temperatures above 20 ℃ and below 120 ℃, with the rinse temperature running to 0 ℃ or lower. This limitation avoids confusion with the distinct peaks on the graph at low temperatures due to materials that remain soluble at the lowest elution temperature. More than two peaks on such a plot indicate a multimodal Composition Distribution (CD). An alternative method for TREF measurement can be used if the following method does not show more than two peaks, i.e. see b. Monrabal, "Crystallization Analysis Fractionation: a New Technique for the Analysis of branched Distribution in Polyolefins ", journal of Applied Polymer Science, vol.52, 491-499 (1994).

TREF method

Temperature Rising Elution Fractionation (TREF) analysis was performed using a Crystallization Elution Fractionation (CEF) instrument from Polymer Char, s.a. of valencia, spain. A summary of the principles of CEF analysis and the specific instruments to be used is found in the article Monrabal, B. et al Crystallization analysis.A New Separation Process for Polyolefin Resins. Macromol. Symp.2007, 257, 71. Specifically, a method following the "TREF separation method" shown in fig. 1a of this article is used, where Fc =0. The details of the analysis method and the characteristics of the apparatus used are as follows.

The solvent used to prepare the sample solution and for the elution was 1,2-dichlorobenzene (ODCB) that was stabilized by dissolving 1.6g of 2,6-bis (1,1-dimethylethyl) -4-methylphenol (butylated hydroxytoluene) in 4L bottles of fresh solvent at ambient temperature. The stable solvent was then filtered using a 0.1 μm teflon filter (Millipore). The sample to be analyzed (6-10 mg) was dissolved in 8ml of ODCB dosed at ambient temperature by stirring (medium setting) for 90min at 150 ℃. The small-volume composition solution was first filtered through an in-line filter (stainless steel, 10 μm) which was backwashed after each filtration. The filtrate was then used to completely fill a 200 μ l injection valve loop. The volume in the loop was then introduced at 140 ℃ near the center of a CEF column (15 cm long stainless steel tube, 3/8 "outer diameter, 7.8mm inner diameter, packed with inert support (stainless steel balls)) and the column temperature stabilized at 125 ℃ for 20min. The sample volume was then crystallized in the column by cooling to 0 ℃ at a cooling rate of 1 ℃/min. The column was kept at 0 ℃ for 10min, and then an ODCB flow (1 ml/min) was injected into the column for 10min to rinse and measure the polymer without crystallization (soluble fraction). The broadband channel of the infrared detector used (Polymer Char IR 5) produced an absorbance signal that was proportional to the Polymer concentration in the rinse stream. The complete TREF curve is then generated as follows: the column temperature was raised from 0 ℃ to 140 ℃ at a rate of 2 ℃/min while the ODCB flow was maintained at 1ml/min to rinse and measure the concentration of the dissolved polymer.

GPC4D procedure: determination of molecular weight, comonomer composition and Long chain branching by GPC-IR coupled with multiple detectors

Moment (moment) and distribution of molecular weights (Mw, mn, mw/Mn, etc.), comonomer content (C), unless otherwise indicated ₂ ，C ₃ ，C ₆ Etc.) and branching index (g' vis) were determined by high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5, 18-angle light scattering detector based on a multichannel bandpass filter and a viscometer. Three Agilent PLgel 10 μm mix-B LS columns were used to provide polymer separation. Aldrich reagent grade 1,2,4-Trichlorobenzene (TCB) containing 300ppm of the antioxidant Butylated Hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm teflon filter and degassed with an in-line degasser before entering the GPC instrument. The nominal flow rate was 1.0mL/min and the nominal injection volume was 200. Mu.L. The entire system, including transfer lines, columns and detectors, was contained in an oven maintained at 145 ℃. The polymer sample was weighed and sealed in a conventional vial to which 80 μ L of flow marker (heptane) was added. After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument with 8mL of TCB solvent added. The polymer was dissolved at 160 ℃ and shaken continuously for a majority of the PE samples for approximately 1 hour, or for a PP sample for 2 hours. The density of TCB used in the concentration calculation was 1.463g/ml at room temperature and 1.284g/ml at 145 ℃. The sample solution concentration is 0.2-2.0mg/ml, and lower concentrations are used for higher molecular weight samples. The concentration (c) at each point of the chromatogram was calculated from the baseline-subtracted IR5 broadband signal intensity (I) using the following equation: c = β I, where β is the mass constant. Mass recovery is calculated from the ratio of the integrated area of the concentration chromatography within the elution volume to the injection mass (which is equal to the predetermined concentration multiplied by the injection loop volume). Conventional molecular weights (IR MW) were determined by combining the general calibration relationship with volume calibration using monodisperse Polystyrene (PS) standards of 700-10 Mg/mol. The MW at each elution volume is calculated using the following equation:

where the variables with subscript "PS" represent polystyrene and those without subscript represent test samples. In this method, α _PS =0.67 and K _PS 0.000175 and alpha and K for other materials are calculated and disclosed as in the literature (Sun, t. Et al Macromolecules,2001, 34, 6812), except for the purpose of the present invention for linear ethylene polymers α =0.695 and K =0.000579, for linear propylene polymers α =0.705 and K =0.0002288, for linear butene polymers α =0.695 and K = 28 zxft 3528, for ethylene-butene copolymers α is 0.695 and K is 0.000579 ^ for ethylene-butene copolymers (1-0.0087 w2b 0.000018 ^ w2 b), where w2b is the bulk weight percentage of butene comonomer, α is 0.39695 and K is 24 zxft 24 ^ 24 (w 2 b) ^ 351.0075, where w2b is the weight percentage of bulk comonomer, and K is 3534 wt% of bulk comonomer, wherein w2b is 3534 wt% of ethylene-octene comonomer, wherein w 3 b is 0.0075 wt% of bulk comonomer, and K is 3534 wt% of bulk comonomer, wherein w 3-octene copolymer, wherein 2b is 0.3 wt% of ethylene-octene copolymer, and wherein 2b is comonomer. The concentration is in g/cm ³ Expressed, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g, unless otherwise indicated.

The comonomer composition is determined by the corresponding CH ₂ And CH ₃ The IR5 detector intensity ratio of the channel (which was calibrated with a series of PE and PP homopolymer/copolymer standards, the nominal values of which were predetermined by NMR or FTIR). Specifically, this provides methyl groups per 1000 total Carbons (CH) as a function of molecular weight ₃ /1000 TC). Short Chain Branching (SCB) content/1000 TC (SCB/1000 TC) is then corrected to CH by applying chain ends as a function of molecular weight ₃ Calculated as the/1000 TC function, assuming each chain is linear and terminated at each end by a methyl group. The weight% comonomer is then obtained from the following expression, where for C ₃ ，C ₄ ，C ₆ ，C ₈ And the like, f is 0.3,0.4 respectively,0.6,0.8, etc.:

w2＝f*SCB/1000TC。

the bulk composition of the polymer from GPC-IR and GPC-4D analysis was determined by considering the CH between the integration limits of the concentration chromatograms ₃ And CH ₂ The entire signal of the channel. First, the following ratios were obtained:

the CH was then applied as described previously in obtaining CH3/1000TC as a function of molecular weight ₃ And CH ₂ The same correction of the signal ratio is made to obtain the bulk CH3/1000TC. Bulk methyl chain ends/1000 TC (bulk CH3 ends/1000 TC) were obtained by weight averaging the chain end corrections over the molecular weight range. Then

w2b = f body CH3/1000TC

Body SCB/1000TC = body CH3/1000 TC-body CH3 end/1000 TC

And the body SCB/1000TC is converted into the body w2 in the same manner as described above.

The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point of the chromatogram was determined by analyzing the LS output using a Zimm model for static Light Scattering (Light Scattering from Polymer Solutions; huglin, M.B. editor; academic Press, 1972):

here, Δ R (θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined from IR5 analysis, A ₂ Is the second dimensional coefficient, P (theta) is the form factor of the monodisperse random coil, and K _o Is the optical constant of the system:

wherein N is _A Is the Afugardo constant, and (dn/dc) is the refractive index increment of the system. The refractive index n =1.500 at 145 ℃ and λ =665nm for TCB. For analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers, dn/dc =0.1048ml/mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn/dc =0.1048 (1-0.00126 w 2) ml/mg and A2=0.0015, where w2 is the weight percentage of butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a wheatstone bridge configuration, and two pressure sensors, was used to measure the specific viscosity. One sensor measures the total pressure drop across the detector and the other (which is located between the two sides of the bridge) measures the pressure difference. The specific viscosity, η s, of the solution flowing through the viscometer is calculated from their outputs. Intrinsic viscosity [ eta ] at each point of the chromatogram]Is calculated by the following equation: [ eta ]]= η s/c, where c is concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is taken as

Calculated of wherein a _ps Is 0.67 and K _ps Is 0.000175.

The branching index (g' VIS) is calculated using the GPC-IR5-LS-VIS method output as follows. The average intrinsic viscosity [. Eta. ] avg of the sample is calculated by the following formula:

where the sum is taken from all chromatographic sections i between the integration limits. The branching index g' vis is defined as

Wherein M is _v Is the viscosity average molecular weight based on the molecular weight determined by LS analysis, and K and a are for reference linear polymers, which for the purposes of the present invention, for linear ethylene polymers, a =0.695 and K =0000579, α =0.705 and K =0.0002288 for linear propylene polymers, α =0.695 and K =0.000181 for linear butene polymers, α is 0.695 and K is 0.000579 (1-0.0087 w2b 0.000018 (w 2 b) ^ 2) for ethylene-butene copolymers, where w2b is the bulk weight percent of butene comonomer, α is 0.695 and K is 0.000579 (1-0.0075 w2b) for ethylene-hexene copolymers, where w2b is the bulk weight percent of hexene comonomer, and α is 0.695 and K is 0.000579 (1-0.0072b) for ethylene-octene copolymers, where 2b is the bulk weight percent of octene comonomer. The concentration is in g/cm ³ Expressed, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g, unless otherwise indicated. The calculation of the w2b value is as described above.

The reversed comonomer index (RCI, m) is determined from x2 (mol% comonomer C) as a function of the molecular weight ₃ ，C ₄ ，C ₆ ，C ₈ Etc.), where x2 is obtained from the following expression, where n is the number of carbon atoms in the comonomer (for C) ₃ Is 3 for C ₄ Is 4 for C ₆ Is 6, etc.):

the molecular weight distribution W (z) (where z = log) was then determined ₁₀ M) is changed to W' (z) by setting a point of W smaller than 5% of the maximum value of W to 0; this effectively removes points where the S/N in the constituent signals is low. Further, the point at which W' having a molecular weight of less than 2000gm/mol was set to 0.

Then W' is re-corrected so that

And the changed weight average molecular weight (M) is calculated as follows within the range of effectively reduced molecular weight _w ′)：

RCI, m is then calculated as:

the inverse comonomer index (RCI, w) is also defined based on the weight fraction comonomer signal (w 2/100) and is calculated as follows:

note that in the above fixed integration, the integration limit is the widest possible for generality; however, in practice the function integrates only over a limited range of acquired data, which considers the function in the range of the remaining unacquired data to be 0. Furthermore, the method is simple. By way of obtaining W ', it is possible that W' is a discontinuous function and the above integration needs to be done piecewise.

The three comonomer distribution ratios (expressed as CDR-1, w, CDR-2,w, and CDR-3,w) are also defined as follows based on% by weight (w 2) comonomer signal:

wherein w2 (Mw) is the% weight comonomer signal corresponding to molecular weight Mw, w2 (Mz) is the% weight comonomer signal corresponding to molecular weight Mz, w2[ (Mw + Mn)/2) ] is the% weight comonomer signal corresponding to molecular weight (Mw + Mn)/2, and w2[ (Mz + Mw)/2 ] is the% weight comonomer signal corresponding to molecular weight Mz + Mw/2, wherein Mw is the weight average molecular weight, mn is the number average molecular weight, and Mz is the z average molecular weight.

Thus, the comonomer distribution ratio (CDR-1, m, CDR-2, m, CDR-3,m) can also be defined using the% mol comonomer signal as follows:

wherein x2 (Mw) is the% mol comonomer signal corresponding to molecular weight Mw, x2 (Mz) is the% mol comonomer signal corresponding to molecular weight Mz, x2[ (Mw + Mn)/2) ] is the% mol comonomer signal corresponding to molecular weight (Mw + Mn)/2, and x2[ (Mz + Mw)/2 ] is the% mol comonomer signal corresponding to molecular weight Mz + Mw/2, wherein Mw is the weight average molecular weight, mn is the number average molecular weight, and Mz is the z average molecular weight.

An "in situ polymer composition" (also referred to as an "in situ blend" or "reactor blend") is a composition that is the product of polymerization using two catalysts in the same reactor as described herein. Without wishing to be bound by theory, it is believed that the two catalysts produce a reactor blend (i.e., an interpenetrating network) of two (or more) components made using the two catalysts in the same reactor (or reaction zone). These kinds of compositions may be referred to as reactor blends, although the term may not be strictly precise, as there may be polymer species that comprise components produced by each catalyst compound that are not technically blends.

An "ex situ blend" is a blend that is a physical blend of two or more polymers that are separately synthesized and then subsequently blended together, typically using a melt mixing process (e.g., an extruder). Ex situ blends are characterized by the collection of the polymer components after they exit the respective synthesis processes and then combined to form a blend; whereas for the in situ polymer composition, the polymer components are prepared in a common synthesis process and the composition is collected upon exiting the polymerization process.

In any of the embodiments described herein, the polymer composition produced is an in situ polymer composition.

In at least one embodiment of the invention, the polymer produced is an in situ polymer composition having an ethylene content of 70wt% or greater, preferably 80wt% or greater, preferably 90wt% or greater and/or a density of 0.910 or greater, alternatively 0.93g/cc or greater; alternatively 0.935g/cc or greater, alternatively 0.938g/cc or greater.

In at least one embodiment of the invention, the polymer produced is an in situ polymer composition having a density of 0.890g/cc or greater, alternatively 0.935 to 0.960g/cc.

In at least one embodiment of the present invention, the polymer produced by the process described herein comprises ethylene and one or more comonomers, and the polymer has: 1) RCI, m is greater than 30 (alternatively greater than 30 to 50), mw/Mn is greater than 1, e.g., 1 to 15, or 2.3 to 15, or 3 to 15, and optionally T ₇₅ -T ₂₅ Is 15 to 20 ℃; or 2) RCI, m is greater than 50 (alternatively greater than 80), mw/Mn is greater than 5 (alternatively 5 to 10), and optionally T ₇₅ -T ₂₅ Is 25-45 ℃.

End use

The multimodal polyolefins produced by the processes disclosed herein and blends thereof may be used in forming operations such as sheet and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotational molding. Fibers include melt spinning, solution spinning, and melt blown fiber operations for use in woven or nonwoven forms in the manufacture of filters, diaper fabrics, medical wraps, geotextiles, and the like. Extruded articles include medical tubing, wire cable coatings, pipes, geomembranes, and pond liners. Molded articles include single and multi-layer constructions in the form of bottles, cans, large hollow articles, rigid food containers and toys, and the like.

The polyolefins produced by the processes disclosed herein and blends thereof are useful in film applications. Such applications include, for example, single or multilayer blown, extruded and/or shrink films. These films may be formed by any number of well known extrusion or coextrusion techniques, such as blown film (blown film) processing techniques in which the composition may be extruded in a molten state through an annular die and then expanded to form a uniaxially or biaxially oriented melt, then cooled to form a tubular blown film, which may then be axially slit and unrolled to form a flat film. The film may then be unoriented, uniaxially oriented, biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented to the same or different degrees in the cross direction and/or machine direction. Uniaxial orientation can be accomplished using conventional cold-drawing or hot-drawing processes. Biaxial orientation may be accomplished using a tenter frame apparatus or a double bubble process, and may be performed before or after the layers are brought together. For example, a polyethylene layer may be extrusion coated or laminated onto an oriented polypropylene layer, or the polyethylene and polypropylene may be coextruded together into a film and then oriented. Also, oriented polypropylene may be laminated to oriented polyethylene, or oriented polyethylene may be coated onto polypropylene, then optionally the composition may be even further oriented. Typically the film is oriented in the Machine Direction (MD) at a ratio of at most 15, preferably 5 to 7, and in the Transverse Direction (TD) at a ratio of at most 15, preferably 7 to 9. However, in another embodiment, the film is oriented to the same extent in both the MD and TD directions.

The thickness of the film may vary depending on the intended application; however, films of 1-50 μm thickness are generally suitable. Films intended for packaging are typically 10-50 μm thick. The thickness of the sealing layer is usually 0.2 to 50 μm. The sealing layer may be present on both the inner and outer surfaces of the film, or the sealing layer may be present only on the inner or outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

Blends

The polymers produced herein can be further blended with additional ethylene polymers (referred to as "second ethylene polymers" or "second ethylene copolymers") and used in molded parts and other common polyethylene applications.

In one aspect of the invention, the second ethylene polymer is selected from the group consisting of ethylene homopolymers, ethylene copolymers, and blends thereof. Useful second ethylene copolymers may comprise one or more comonomers in addition to ethylene, and may be random copolymers, statistical copolymers, block copolymers and/or blends thereof. The method of making the second ethylene polymer is not critical as it can be made by slurry, solution, gas phase, high pressure or other suitable method, and by using a catalyst system suitable for polymerizing polyethylene, such as a ziegler-natta type catalyst, a chromium catalyst, a metallocene type catalyst, other suitable catalyst system or combinations thereof, or by free radical polymerization. In a preferred embodiment, the second ethylene polymer is prepared by the methods of U.S. Pat. Nos. 6342566;6384142;5741563; PCT publication No. WO03/040201; and catalysts, activators and methods as described in WO 97/19991. Such catalysts are well known in the art and are described, for example, in Z _IEGLER C _ATALYSTS (Gerhard Fink, rolf Mulhaupt and Hans H. Brintzinger, eds., springer-Verlag 1995); resconi et al; and I, II M _{ETALLOCENE-BASED} P _OLYOLEFINS (Wiley&Sons 2000). Additional useful second ethylene polymers and copolymers are described in PCT/US2016/028271, pages 30-34 [00118 ] filed on 18/19/4/2016]-[00126]In a section.

Experiment of

Test method

1H NMR

1H NMR data were obtained at 120 ℃ using a 10mm CryoProbe and Bruker spectrophotometer ¹ H frequency 400MHz was collected (from Bruker Corporation, UK). Data were recorded using a maximum pulse width of 45 °, a pulse interval of 5 seconds and an average of 512 transients. The sample was prepared by dissolving 80mg of the sample in 3mL of a solvent heated at 140 ℃. The peak identification is that of reference solvent tetrachloroethane-1,2D ₂ Determined at 5.98 ppm.

GPC4D program

Distribution and moment of molecular weight (Mw, mn, mz, mw/Mn, etc.), comonomer content (C), unless otherwise indicated ₂ ，C ₃ ，C ₆ Etc.) and the branching index (g') were determined by using high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with an infrared detector IR5, 18-angle light scattering detector based on a multichannel bandpass filter and a viscometer. Three Agilent PLGel 10 μm mix-B LS columns were used to provide polymer separation. Aldrich reagent grade 1,2,4-Trichlorobenzene (TCB) with 300ppm antioxidant Butylated Hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm teflon filter and degassed with an in-line degasser before entering the GPC instrument. The nominal flow rate was 1.0mL/min and the nominal injection volume was 200. Mu.L. The entire system including the transfer line, column and detector were contained in an oven maintained at 145 ℃. A given amount of polymer sample was weighed and sealed in a conventional vial to which was added 80 μ L of flow marker (heptane). After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument with 8mL of TCB solvent added. The polymer was dissolved at 160 ℃ and shaken continuously for approximately 1 hour for most of the polyethylene sample, or 2 hours for the polypropylene sample. The density of TCB used in the concentration calculation was 1.463g/ml at room temperature and 1.284g/ml at 145 ℃. The sample solution concentration is 0.2-2.0mg/ml, and lower concentrations are used for higher molecular weight samples. The concentration (c) at each point of the chromatogram was calculated from the baseline-subtracted IR5 broadband signal intensity (I) using the following equation: c = β I, where β is the mass constant. Mass recovery is determined by concentration chromatography in the elution volumeIs calculated as the ratio of the integrated area of (a) to the injection mass (which is equal to the predetermined concentration times the injection circuit volume). Conventional molecular weights (IR MW) were determined by combining the general calibration relationship with volume calibration using monodisperse Polystyrene (PS) standards of 700-10 Mg/mol. The MW at each elution volume is calculated using the following equation:

where the variables with subscript "PS" represent polystyrene and those without subscript represent test samples. In this method, α _PS =0.67 and K _PS 0.000175 and alpha and K for other materials as calculated and disclosed in the literature (Sun, t. Et al Macromolecules,2001, 34, 6812), except for the purposes of the present invention for linear ethylene polymers α =0.695 and K =0.000579, for linear propylene polymers α =0.705 and K =0.0002288, for linear butene polymers α =0.695 and K =0.000181, for ethylene-butene copolymers α is 0.695 and K is 0.000579 ^ for ethylene-butene copolymers (1-0.0087 w2b 0.000018 ^ 3528 (w 2 b) ^ 2), where w2b is the bulk weight percentage of butene comonomer, for ethylene-hexene copolymers α is 0.695 and K is 24 zxft 3924 (1-3524 w2 b) ^ 2), where w2b is the bulk weight percentage of butene comonomer, and K is 24 zxft 2b 3534 and wherein w2b is the bulk weight percentage of ethylene-octene comonomer, where w 3-0071 is 0.0071 and 0.00734 wt% of ethylene-octene copolymer. The concentration is in g/cm ³ Expressed, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g, unless otherwise indicated.

The comonomer composition is determined by the corresponding CH ₂ And CH ₃ The IR5 detector intensity ratio of the channel (which was calibrated with a series of PE and PP homopolymer/copolymer standards, the nominal values of which were predetermined by NMR or FTIR). Specifically, this provides methyl groups per 1000 total Carbons (CH) as a function of molecular weight ₃ /1000 TC). Short Chain Branching (SCB) content/1000 TC (SCB/1000 TC)) Then corrected to CH by applying chain ends as a function of molecular weight ₃ Calculated as the/1000 TC function, assuming each chain is linear and terminated at each end by a methyl group. The weight% comonomer is then obtained from the following expression, where for C ₃ ，C ₄ ，C ₆ ，C ₈ Etc., f is 0.3,0.4,0.6,0.8, etc.:

w2＝f*SCB/1000TC。

the bulk composition of the polymer from GPC-IR and GPC-4D analysis was determined by considering the CH between the integration limits of the concentration chromatograms ₃ And CH ₂ The entire signal of the channel is obtained. First, the following ratios were obtained:

CH as a function of molecular weight is then obtained as before ₃ Application of CH as described in/1000 TC ₃ And CH ₂ The same correction of the signal ratio is applied to obtain the body CH ₃ And/1000 TC. Bulk methyl chain end/1000 TC (bulk CH) ₃ End/1000 TC) is obtained by weight averaging the chain end corrections over the molecular weight range. Then the

w2b = f body CH3/1000TC

Bulk SCB/1000TC = bulk CH3/1000 TC-bulk CH3 end/1000 TC

And the body SCB/1000TC is converted into a body w2 in the same manner as described above.

here, Δ R (θ) is measured at the scattering angle θAmount of excess Rayleigh scattering intensity, c is the polymer concentration determined from IR5 analysis, A ₂ Is the second virial coefficient, P (theta) is the form factor of the monodisperse random coil, and K _o Is the optical constant of the system:

wherein N is _A Is the Afugardo constant, and (dn/dc) is the refractive index increment of the system. The refractive index n =1.500 at 145 ℃ and λ =665nm for TCB. For analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers, dn/dc =0.1048ml/mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn/dc =0.1048 (1-0.00126 w 2) ml/mg and A2=0.0015, where w2 is the weight percent of butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a wheatstone bridge configuration, and two pressure sensors, was used to measure the specific viscosity. One sensor measures the total pressure drop across the detector and the other (which is located between the two sides of the bridge) measures the pressure difference. The specific viscosity η s of the solution flowing through the viscometer is calculated from their outputs. Intrinsic viscosity [ eta ] at each point of the chromatogram]Is calculated by the following equation: [ eta ]]= η s/c, where c is concentration and is determined by the IR5 broadband channel output. The viscosity MW at each point is taken as

Calculated of wherein a _ps Is 0.67 and K _ps Is 0.000175.

where the sum is taken from all chromatographic sections i between the integration limits.

The branching index g' vis is defined as

Where Mv is the viscosity average molecular weight based on molecular weight determined by LS analysis and K and α are for reference linear polymers, which for the purposes of the present invention α =0.695 and K =0.000579 for linear ethylene polymers, α =0.705 and K =0.0002288 for linear propylene polymers, α =0.695 and K =0.000181 for linear butene polymers, α is 0.695 and K is 0.000579 (1-0.0087 w2b 0.000018 (w 2 b) ^ 2) for ethylene-butene copolymers, where w2b is the bulk weight percentage of butene comonomer, α is 0.695 and K is 0.000579 (1-0.0075 wwb) for ethylene-hexene copolymers, where α is 0.695 and K is 0.000579 (1-0.0075 ww 2 b) where α is the bulk weight percentage of hexene comonomer and K is 0.00726 wt% for ethylene-octene copolymers, where α is 2w 2b and 2w 2b is the bulk weight percentage of octene copolymer, where 2K is 3926 and 2w 2b, where 2K is the bulk weight percentage of octene copolymer. The concentration is in g/cm ³ Expressed, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g, unless otherwise indicated. The calculation of the w2b value is as described above.

The inverse comonomer index (RCI, m) is determined from x2 (mol% comonomer C) as a function of the molecular weight ₃ ，C ₄ ，C ₆ ，C ₈ Etc.) where x2 is obtained from the following expression, where n is the number of carbon atoms in the comonomer (for C) ₃ Is 3 for C ₄ Is 4 for C ₆ Is 6, etc.):

the molecular weight distribution W (z) (where z = log) was then determined ₁₀ M) is changed to W' (z) by setting a point of W smaller than 5% of the maximum value of W to 0; this effectively removes points where the S/N in the constituent signals is low. Further, the point of W' having a molecular weight of less than 2000gm/mol was set to 0. Then W' is re-corrected so that

RCI, m is then calculated as:

where w2 (Mw) is the% weight comonomer signal corresponding to molecular weight Mw, w2 (Mz) is the% weight comonomer signal corresponding to molecular weight Mz, w2[ (Mw + Mn)/2) ] is the% weight comonomer signal corresponding to molecular weight (Mw + Mn)/2, and w2[ (Mz + Mw)/2 ] is the% weight comonomer signal corresponding to molecular weight Mz + Mw/2, where Mw is the weight average molecular weight, mn is the number average molecular weight, and Mz is the z average molecular weight.

All molecular weights are weight average molecular weights (Mw) unless otherwise indicated. All molecular weights are reported in g/mol unless otherwise indicated.

Melt Index (MI), also known as I2, is reported in g/10min and is determined according to ASTM D1238, 190 ℃,2.16kg load.

The High Load Melt Index (HLMI), also known as I21, is reported in g/10min and is determined according to ASTM D1238, 190 ℃,21.6kg load.

Melt Index Ratio (MIR) is MI divided by HLMI, as determined by ASTM D1238.

Density is determined according to ASTM D1505.

The bulk density was determined as follows; the resin was poured into a 400cc fixed volume cylinder via a 7/8 "diameter funnel; bulk density is the weight of the resin in the cylinder divided by 400cc to yield the value in g/cc.

Catalyst compound

Experiment of

All operations are carried out under inert N ₂ Purging in a glove box, unless otherwise specified. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried on molecular sieves prior to use. N-butyllithium (2.5M in hexane), dimethylsilyl dichloride (Me) ₂ SiCl ₂ ) And methyl magnesium bromide (3.0M in diethyl ether) was purchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl) ₄ ) 99+% and (trimethylsilyl) methyltrifluoromethane sulfonate were purchased from Strem Chemicals and TCI America, respectively, and used as received. Potassium cyclopentadienide (KCp) was prepared according to literature procedures. (Stadelhofer, J.; weidlein, J.; haaland, A.J. organomet.chem.1975, 84, C1-C4); n-butyllithium (2.5M in hexane), methyl iodide, indene and methyllithium (1.6M in diethyl ether) were purchased from Sigma-Aldrich. 1-Ethyl-indene and lithium-1-ethyl-indene were prepared according to literature procedures. ¹ H NMR measurements were recorded on a 400MHz Bruker spectrophotometer.

Synthesis of Complex 1

Synthesis of (trimethylsilyl) methylcyclopentadiene, (Me) ₃ Si)CH ₂ CpH. Pure (trimethylsilyl) methyltrifluoromethanesulfonate (10.57g, 44.7 mmol) was dissolved at 150mL diethyl ether and cooled to-25 ℃ to which solid potassium cyclopentadienide (4.66g, 44.7 mmol) was slowly added over a period of 5-10 minutes. The resulting mixture was stirred at room temperature for 5 hours. Careful removal of volatiles from the reaction mixture under dynamic vacuum to avoid volatile (trimethylsilyl) methylcyclopentadienes, (Me) ₃ Si)CH ₂ CpH evaporates. The reaction flask (250 mL round bottom flask) and the frit (frit) with diatomaceous earth (celite) were weighed to calculate the yield of the product after extraction. The crude material was extracted into pentane (3 x10 mL) and used without any further purging. Based on the above mathematical procedure, the yield was calculated to be 5.55g (81.6%). Recording of coarse material ¹ H NMR spectroscopy to ensure product formation. ¹ H NMR(400MHz，C ₆ D ₆ )：δ-0.05(9H，s，Si-CH ₃ )，1.77(2H，d，J _HH ＝1.2Hz，Me ₃ Si-CH ₂ )，2.83(1H，sex，J _HH ＝1.5Hz，Cp-CH)，5.80-6.49(4H，m，Cp-CH)ppm。

Synthesis of (trimethylsilyl) methylcyclopentadienyl lithium, (Me) ₃ Si)CH ₂ CpLi. A hexane solution of n-butyllithium (14.6 mL,36.5 mmol) was added dropwise over a period of 15-20 minutes at-25 deg.C (Me) ₃ Si)CH ₂ CpH (5.55g, 36.5 mmol) in pre-cooled solution (pentane and diethyl ether, 50/50 mL). The resulting mixture was gradually brought to room temperature and then continuously stirred overnight. Volatiles were removed in vacuo and the remaining crude material was washed thoroughly with pentane. The final material was dried under vacuum to obtain (Me) ₃ Si)CH ₂ CpLi was a colorless crystalline solid with a yield of 5.75g (99.7%). ¹ H NMR(400MHz，THF-d ₈ )：δ-0.09(9H，s，Si-CH ₃ )，1.84(2H，s，Me ₃ Si-CH ₂ )，5.36(2H，t，J _HH ＝2.6Hz，Cp-H)，5.47(2H，t，J _HH ＝2.6Hz，Cp-H)ppm。

Synthesis of dimethylsilyl-bis ((trimethylsilyl) methylcyclopentadiene), me ₂ Si((Me ₃ Si)CH ₂ CpH) ₂ . Mixing pure Me ₂ SiCl ₂ (340mg, 2.6 mmol) was dissolved in 10mL of THF, andcooled to-25 ℃. Solid (trimethylsilyl) methylcyclopentadienyl lithium was added to the above mixture and the resulting mixture was stirred at room temperature overnight to ensure completion of the reaction. The reaction mixture was freed of volatiles under vacuum and subsequently triturated with pentane to remove traces of THF. The crude material was extracted into pentane and the solvent was subsequently removed under vacuum to give Me ₂ Si((Me ₃ Si)CH ₂ CpH) ₂ In the form of a thick yellow viscous oil, yield 750mg (80%). ¹ H NMR(400MHz，C ₆ D ₆ )：δ-0.15(6H，bs，SiMe ₂ -CH ₃ )，0.05(18H，s，SiMe ₃ -CH ₃ )，1.81-1.87(4H，m，Me ₃ Si-CH ₂ )，3.26(1H，s，Cp-H)，3.37(1H，s，Cp-H)，5.99-6.82(6H，m，Cp-H)ppm。

Synthesis of dimethylsilyl-bis ((trimethylsilyl) methylcyclopentadienyl lithium) dimethoxyethane Complex, me ₂ Si((Me ₃ Si)CH ₂ Cp) ₂ Li ₂ Dme. A solution of n-butyllithium in hexane (1.7mL, 4.2mmol,2.5M solution) was added dropwise to Me at-25 ℃ over a period of 5-10 minutes ₂ Si((Me ₃ Si)CH ₂ CpH) ₂ (750 mg, 2.1mmol) in 10mL of dimethoxyethane. The resulting mixture was gradually warmed to room temperature and then continuously stirred overnight. The volatiles were removed from the reaction mixture under vacuum and DME was removed by trituration with pentane. The crude material was washed thoroughly with pentane to remove any soluble impurities and dried under vacuum to give Me ₂ Si((Me ₃ Si)CH ₂ Cp) ₂ Li ₂ Dme as a colorless crystalline solid in a yield of 830mg (93%). ¹ H NMR(400MHz，THF-d ₈ )：δ0.2(18H，s，SiMe ₃ -CH ₃ )，0.93(6H，bs，SiMe ₂ -CH ₃ )，2.26(4H，s，Me ₃ Si-CH ₂ )，2.57(4H，s，dme-CH ₂ )，2.77(6H，s，dme-OCH ₃ )，5.94-6.15(6H，m，Cp-H)ppm。

Synthesis of rac-meso-dimethylsilyl-bis ((trimethylsilyl) methylcyclopentadieneCo) hafnium dichloride, me ₂ Si((Me ₃ Si)CH ₂ Cp) ₂ HfCl ₂ . Solid HfCl was added at-25 deg.C ₄ (570mg, 1.8mmol) was added to Me ₂ Si((Me ₃ Si)CH ₂ Cp) ₂ Li ₂ Dme (830 mg,1.8 mmol) in pre-cooled diethyl ether (20 mL). The resulting mixture was stirred at room temperature overnight. The volatiles were removed from the reaction mixture under vacuum and then extracted into dichloromethane. Removal of solvent under vacuum to yield Me ₂ Si((Me ₃ Si)CH ₂ -Cp) ₂ HfCl ₂ Was obtained in a yield of 1.02g (94%). Of the final material ¹ The H NMR spectra integrated (integral) to 1:1 ratio of rac/meso isomer. ¹ H NMR(400MHz，CD ₂ Cl ₂ )：δ-0.05(18H，s，SiMe ₃ -CH ₃ )，-0.04(18H，s，SiMe ₃ -CH ₃ )，-0.64(3H，s，SiMe ₂ -CH ₃ Meso), -0.65 (6H, s, siMe) ₂ -CH ₃ Racemic), -0.68 (3H, s, siMe) ₂ -CH ₃ Meso), 2.08-2.18 (8H, m, me) ₃ Si-CH ₂ )，5.14(2H，t，J _HH ＝2.6Hz，Cp-H)，5.28(2H，t，J _HH ＝2.6Hz，Cp-H)，5.64(2H，t，J _HH ＝2.7Hz，Cp-H)，5.77(2H，t，J _HH ＝2.7Hz，Cp-H)，6.19(2H，t，J _HH ＝2.7Hz，Cp-H)，6.34(2H，t，J _HH ＝2.7Hz，Cp-H)ppm。

Synthesis of rac-meso-dimethylsilyl-bis ((trimethylsilyl) methylcyclopentadienyl) hafnium dimethyl, me ₂ Si((Me ₃ Si)CH ₂ Cp) ₂ HfMe ₂ . A solution of MeMgBr (1.12mL, 3.34mmol) in ether (ethereal) was added dropwise to Me over a period of 3-5 minutes at-25 deg.C ₂ Si((Me ₃ Si)CH ₂ -Cp) ₂ HfCl ₂ (1.01g, 1.65mmol) in pre-cooled diethyl ether. The resulting mixture was stirred at room temperature overnight to ensure completion of the reaction. The insoluble material was filtered through a pad of celite. Removing the volatiles from the filtrate under vacuum, and then extracting the crude materialTo pentane. Removal of the solvent in vacuo to yield Me ₂ Si((Me ₃ Si)CH ₂ -Cp) ₂ HfMe ₂ Yield was 660g (71%). Of the final material ¹ The H NMR spectrum integrated 1:1 ratio of rac/meso isomer. ¹ H NMR(400MHz，C ₆ D ₆ )：δ-0.25(3H，s，Hf-CH ₃ Meso), delta-0.24 (6H, s, hf-CH) ₃ Racemic), delta-0.20 (3H, s, hf-CH ₃ Meso), 0.03 (18H, s, siMe) ₃ -CH ₃ )，0.04(18H，s，SiMe ₃ -CH ₃ )，0.19(3H，s，SiMe ₂ -CH ₃ Meso), 0.20 (6H, s, siMe) ₂ -CH ₃ Racemic), 0.22 (3H, s, siMe) ₂ -CH ₃ Meso), 2.06 (4h,s ₃ Si-CH ₂ Rac), 2.09 (4h, d, j) _HH ＝3.1Hz，Me ₃ Si-CH ₂ Meso), 5.03 (2H, t, J) _HH ＝2.2Hz，Cp-H)，5.10(2H，t，J _HH ＝2.2Hz，Cp-H)，5.34(2H，t，J _HH ＝2.6Hz，Cp-H)，5.44(2H，t，J _HH ＝2.6Hz，Cp-H)，6.26(2H，t，J _HH ＝2.6Hz，Cp-H)，6.31(2H，t，J _HH ＝2.6Hz，Cp-H)ppm。

Synthesis of Complex 2

Synthesis of Diphenylsilyl-bis (trifluoromethanesulfonate), ph ₂ Si(OTf) ₂

Will be pure Ph ₂ SiCl ₂ (1.0 g,4.0 mmol) was dissolved in 100mL of DCM, and cooled to-25 ℃ and solid silver trifluoromethanesulfonate (2.1 g,4.0 mmol) was added thereto over a period of 2-3 minutes. The resulting mixture was covered with aluminum foil and stirred at room temperature overnight. The insoluble by-product, agCl, was filtered off and the volatiles were removed from the filtrate under vacuum to give Ph ₂ Si(OTf) ₂ Was obtained in a yield of 1.9g (98.0%). ¹ H NMR(400MHz，CD ₂ Cl ₂ )：δ7.50-7.55(4H，m，Ar-CH)，7.65-7.70(2H，m，Ar-CH)，7.73-7.75(4H，m，Ar-CH)ppm。

Synthesis of Diphenylsilyl-bis- (trimethylsilylmethylcyclopentadiene), ph ₂ Si(Me ₃ SiCH ₂ CpH) ₂ .

The solid Ph ₂ Si(OTf) ₂ (900mg, 1.8 mmol) was slurried in 15mL of diethyl ether and cooled to-25 deg.C, and solid Me was added thereto over a period of 3-5 minutes ₃ SiCH ₂ CpLi (580 mg,3.6 mmol). The resulting mixture was stirred at room temperature overnight to ensure completion of the reaction. All volatiles were removed from the reaction mixture under vacuum and triturated with hexane. The crude material was then extracted into hexane and the solvent subsequently removed to give Ph ₂ Si((Me ₃ Si)CH ₂ CpH) ₂ Yield was 870mg (99.6%) of a pale yellow oil. ¹ H NMR(400MHz，C ₆ D ₆ )：δ0.01-0.06(18H，m，SiMe ₃ -CH ₃ )，1.79-1.88(4H，m，Me ₃ Si-CH ₂ )，3.92(1H，bs，Cp-CH)，4.06(1H，bs，Cp-CH)，6.13-6.92(6H，m，Cp-CH)，7.24-7.30(6H，m，Ar-CH)，7.71-7.80(4H，m，Ar-CH)ppm。

Synthesis of Diphenylsilyl-bis- (trimethylsilylmethylcyclopentadienyl) lithium, ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ Li ₂ 。

Will be pure Ph ₂ Si(Me ₃ SiCH ₂ CpH) ₂ (870mg, 1.8mmol) was dissolved in 15mL of THF, and cooled to-25 ℃ and a hexane solution of n-butyllithium (1.5mL, 3.62mmol,2.5M diethyl ether solution) was added thereto over a period of 3 to 5 minutesAnd (4) liquid. The resulting mixture was gradually warmed to room temperature and then stirred continuously overnight. The reaction mixture was freed of volatiles under vacuum and triturated with pentane. The crude material was washed thoroughly with hexane to remove soluble impurities, and dried under vacuum to give Ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ Li ₂ Was obtained as an off-white solid in a yield of 890mg (99.5%). ¹ H NMR(400MHz，THF-d ₈ )：δ0.13(18H，s，SiMe ₃ -CH ₃ )，2.92(4H，m，Me ₃ Si-CH ₂ )，5.57-6.80(6H，m，Cp-CH)，7.29(6H，bs，Ar-CH)，7.98(4H，bs，Ar-CH)ppm。

Synthesis of rac-meso-diphenylsilyl-bis- (trimethylsilylmethyl cyclopentadienyl) hafnium dichloride, ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ HfCl ₂ . Mixing solid HfCl ₄ (573mg, 1.8 mmol) was slurried in 15mL of diethyl ether and cooled to-25 deg.C, and solid Ph was added thereto ₂ Si(Me ₃ SiCH ₂ Cp) ₂ Li ₂ (890mg, 1.8mmol). The resulting mixture was stirred at room temperature overnight. Insoluble material was removed by filtration and volatiles were removed from the filtrate in vacuo to give Ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ HfCl ₂ The yield of the pale yellow oil material was 1.18g (89.5%). ¹ H NMR(400MHz，CD ₂ Cl ₂ )：δ0.01(9H，s，SiMe ₃ -CH ₃ )，0.02(9H，s，SiMe ₃ -CH ₃ )，2.07-2.24(4H，m，Me ₃ Si-CH ₂ )，5.25(1H，t，J _HH ＝2.4Hz，Cp-CH)，5.42(1H，t，J _HH ＝2.4Hz，Cp-CH)，5.78(1H，t，J _HH ＝2.4Hz，Cp-CH)，5.94(1H，t，J _HH ＝2.4Hz，Cp-CH)，6.29(1H，t，J _HH ＝2.4Hz，Cp-CH)，6.44(1H，t，J _HH ＝2.4Hz，Cp-CH)，7.48-7.55(6H，m，Ar-CH)，7.90-7.98(4H，m，Ar-CH)ppm。

Synthesis of rac-meso-diphenylsilyl-bis- (trimethylsilylmethyl-cyclopentadienyl) hafnium dimethyl, ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ HfMe ₂ .

Will be pure Ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ HfCl ₂ (1.18g, 1.6 mmol) was dissolved in 20mL of diethyl ether and cooled to-25 ℃ and a solution of MeMgBr in ether (1.1mL, 3.26mmol) was added thereto over a period of 3-5 minutes. The resulting mixture was gradually warmed to room temperature and stirred continuously for 2 hours. Volatiles were removed under reduced pressure and triturated with hexanes. The crude material was then extracted into hexane and the solvent was removed to give Ph ₂ Si(Me ₃ SiCH ₂ Cp) ₂ HfMe ₂ The yield of the light, thick viscous oil of (2) was 720mg (79.3%). Of purified compounds ¹ The H NMR spectrum integrated 1:1 ratio of rac/meso isomer. ¹ H NMR(400MHz，C ₆ D ₆ )：δ-0.26(3H，s，Hf-CH ₃ Meso), -0.25 (6H, s, hf-CH) ₃ Rac), -0.22 (3H, s, hf-CH ₃ Meso), 0.05 (18H, s, siMe) ₃ -CH ₃ )，0.06(18H，s，SiMe ₃ -CH ₃ )，1.97-2.10(4H，m，Me ₃ Si-CH ₂ )，5.24(2H，t，J _HH ＝2.2Hz，Cp-CH)，5.33(2H，t，J _HH ＝2.2Hz，Cp-CH)，5.59(2H，t，J _HH ＝2.6Hz，Cp-CH)，5.71(2H，t，J _HH ＝2.6Hz，Cp-CH)，6.23(2H，dd，J _HH ＝2.2Hz，2.6Hz，Cp-CH)，6.34(2H，dd，J _HH ＝2.2Hz，2.6Hz，Cp-CH)，7.16-7.21(12H，m，Ar-CH)，7.84-7.95(8H，m，Ar-CH)ppm。

Synthesis of Complex 3 racemic, meso (1-EthInd) ₂ ZrMe ₂

Synthesis of rac-meso-bis (1-ethyl-indenyl) zirconium dimethyl, (1)-EtInd) ₂ ZrMe ₂ . In a 500mL round bottom flask, solid ZrCl ₄ (9.42g, 40.4 mmol) was slurried with 250mL of Dimethoxyethane (DME) and cooled to-25 ℃. Solid lithium-1-ethyl-indenyl (12.13g, 80.8mmol) was added over a period of 5-10 minutes, and the reaction mixture was gradually warmed to room temperature. The resulting orange-yellow mixture was heated at 80 ℃ for 1 hour to ensure the formation of bis (1-ethyl-indenyl) zirconium dichloride. The mixture was initially clear and then a by-product (LiCl) precipitated out during the reaction indicating the formation of the product. Without further purification, the reaction mixture of bis (1-ethyl-indenyl) zirconium dichloride was cooled to-25 ℃ and an ether solution of methylmagnesium bromide (27.0 mL,80.8mmol,3.0M diethyl ether solution) was added thereto over a period of 10-15 minutes. The resulting mixture slowly turned yellowish and then brownish red during the reaction and was continuously stirred at room temperature overnight. Volatiles were removed in vacuo. The crude material was then extracted with hexane (50 mLx 5) and the solvent was subsequently removed to form an off-white solid (1-EtInd) ₂ ZrMe ₂ The yield was 13.0g (78.9%). Of the final material ¹ The H NMR spectrum integrates 1:1 ratio of rac/meso isomer. ¹ H NMR(400MHz，C ₆ D ₆ )：δ-1.38(3H，s，Zr-CH ₃ Meso), -0.88 (6H, s, zr-CH) ₃ Racemic), -0.30 (3H, s, zr-CH ₃ Meso), 1.10-1.04 (12H, m, et-CH) ₃ )，2.41-2.52(4H，m，Et-CH ₂ )，2.67-2.79(4H，m，Et-CH ₂ )，5.46-5.52(8H，m，Ind-CH)，6.90-6.96(8H，m，Ar-CH)，7.08-7.15(4H，m，Ar-CH)，7.28-7.22(4H，m，Ar-CH)ppm。

Synthesis of Complex 4 meso-O (Me) ₂ Si Ind) ₂ ZrCl ₂ :4 meso-O (Me) ₂ SiInd) ₂ ZrCl ₂ Prepared as described in U.S. patent No. 7060765.

Supported catalysts

SMAO-ES70-875: methylalumoxane treated silica was prepared in a manner similar to that described below:

4L stirred vessel in drying cabinetMethylaluminoxane (MAO, 30wt% in toluene, about 1000 g) and about 2000g toluene were added. The solution was then stirred at 60RPM for 5 minutes. Next, approximately 800g of ES-70 which had been calcined at 875 ℃ (see below) was added ^TM Silica (PQ Corporation, conshahecen, pa.) was added to the vessel. The slurry was then heated at 100 ℃ and stirred at 120RPM for 3 hours. Then cooled to 25 ℃ and cooled to temperature over 2 hours. After cooling, the vessel was set to 8RPM and placed under vacuum for 72 hours. After emptying the vessel and screening the loaded MAO, about 1100g of the loaded MAO will be collected.

ES70 which has been calcined at 875 deg.C ^TM The silica is such ES70 ^TM Silica, which has been calcined at 880 ℃ for 4 hours after warming to 880 ℃ according to the following ramp rate.

℃	℃/h	℃
			Environment(s)	100	200
200	50	300
			300	133	400
400	200	800
			800	50	880

An amount of 60.0g of SMAO-ES70-875C was charged to a Celestir vessel along with 150mL of toluene. Racemic/meso-dimethylsilylbis (trimethylsilylmethylene-cyclopentadienylhafnium) dimethyl (0.545g, 0.961mmol), meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (0.125g, 0.239mmol), rac, meso-diphenylsilylbis (trimethylsilylmethylene-cyclopentadienyl) hafnium dimethyl (0.664g, 0.961mmol) and rac/meso-bis (1-ethylindenyl) zirconium dimethyl (0.098g, 0.239mmol) were dissolved in 20mL of toluene and charged to a Celestir vessel. After stirring for 3 hours, the slurry was then filtered and washed with 20mL of toluene and several portions of 30mL of hexane. The supported catalyst was then dried under vacuum to obtain 60.5g of pale yellow silica.

C1: the comparative polymer product (C1) was formed as described below in a gas phase pilot plant using the catalyst shown below.

Comparative polymer products (C2-C8) were obtained from commercial sources and used without further modification. The comparative polymer products are as follows:

c2: LL3001 polyethylene was obtained from ExxonMobil Chemical Company (Baytown, tex.) and reported to have a density of 0.918g/cc, a melt index of 1.1dg/min and a melt index ratio of 28.

C3：Dowlex ^TM 2045 is polyethylene available from Dow Chemical Company (Midland, mich.) and is reported to have a density of 0.920g/cc, a melt index of 1.0dg/min and a melt index ratioIs 29.

C4：Exceed ^TM 1018 is polyethylene available from ExxonMobil Chemical Company (Baytown, tex.) and is reported to have a density of 0.919g/cc, a melt index of 1.0dg/min and a melt index ratio of 16.

C5：Enable ^TM 2010 is polyethylene available from ExxonMobil Chemical Company (Baytown, tex.) and is reported to have a density of 0.920g/cc, a melt index of 1.1dg/min and a melt index ratio of 34.

C6：Borstar ^TM FB 2230 is a polyethylene obtained from Borealis AG (Austria) and reported to have a density of 0.923g/cc, a melt index of 0.2dg/min and a melt index ratio of 110.

C7：Evolue ^TM 3010 is a polyethylene available from Mitsui Chemical Company (Japan) and is reported to have a density of 0.926g/cc and a melt index of 0.8dg/min.

C8：Elite ^TM 5400 is polyethylene available from The Dow Chemical Company (Midland, mich.) and is reported to have a density of 0.918g/cc, a melt index of 1.1dg/min and a melt index ratio of 32.

C9: polyethylene prepared in a metallocene gas phase process as described in part 8A of PCT/US2015/015119 (polymers 1-10, table 1) has a density of 0.918g/cc, a melt index of 0.9dg/min and a melt index ratio of 28.

Gas phase pilot test for supported catalysts

The polymerization was carried out in an 18.5 foot high gas phase fluidized bed reactor having a 10 foot body and an 8.5 foot expansion section. Recycle and feed gas was fed to the reactor body through a perforated distributor plate and the reactor was controlled at 300psi and 70mol% ethylene. The reactor temperature was maintained at 185 ° F throughout the polymerization by controlling the temperature of the recycle gas loop.

TABLE 1

The supported catalyst system showed good activity and 26lbs of PE resin was obtained for membrane analysis.

Cross Fractional Chromatography (CFC)

Cross-fractionation chromatography (CFC), which combines TREF with conventional GPC (TREF/GPC), as disclosed in WO2015/123164A1, was performed on the bimodal polypropylene produced in Table 1 above on a CFC-2 instrument from Polymer Char in Balansia, spain. Instrument operation and subsequent data processing (e.g., smoothing parameters, setting baselines and defining integration limits) is performed according to the instrument's CFC user manual in the manner described or as is conventional in the art. The instrument was equipped with a TREF column of a first size (stainless steel; outer diameter 3/8'; length 15cm; packed, non-porous stainless steel microspheres) and a set of GPC columns of a second size (a 3 XPLgel 10 μm hybrid B column from Polymer Labs, UK). Downstream of the GPC column is an infrared detector (IR 4 from Polymer Char) capable of generating an absorbance signal proportional to the concentration of Polymer in solution.

The sample to be analyzed was dissolved in o-dichlorobenzene at a concentration of about 5mg/ml by stirring at 150 ℃ for 75 min. A volume of 0.5ml of the solution containing 2.5mg of polymer was then loaded into the center of the TREF column and the column temperature was lowered and stabilized at about 120 ℃ for 30min. The column was then slowly cooled (0.2 ℃/min) to 30 ℃ (for ambient temperature testing) or-15 ℃ (for low temperature testing) to crystallize the polymer on the inert support. The temperature was kept at low temperature for 10min, and then the soluble fraction was injected into the GPC column. All GPC analyses were carried out using ortho-dichlorobenzene as a solvent at 1ml/min, a column temperature of 140 ℃ and in "Overlap GPC entries" mode. The subsequent higher temperature fractions were then analyzed as follows: the TREF column temperature was increased in a stepwise manner to the set point of the fractions, the polymer was dissolved for 16min ("analysis time"), and the dissolved polymer was injected into the GPC column for 3min ("elution time"). The polymer sample was not analyzed for soluble fractions or "purge", only for "insoluble" fractions, i.e., fractions that were insoluble at-15 ℃ or lower.

The molecular weight of the eluted polymer was determined using a universal calibration method. Thirteen narrow molecular weight distribution polystyrene standards (obtained from Polymer Labs, UK) ranging from 1.5 to 8200Kg/mol were used to generate a universal calibration curve. The Mark-Houwink parameters were obtained from appendix I of Size Exclusion Chromatography (Size Exclusion Chromatography) of s.mori and h.g.barth (Springer, 1999). For polystyrene K =1.38x10 was used ^-4 dl/g and α =0.7; and for polyethylene K =5.05x10 ^-4 dl/g and α =0.693. Fractions with weight% recovery (as reported by the instrument software) less than 0.5% were not processed for calculation of average molecular weight (Mn, mw, etc.) of individual fractions or aggregates of fractions.

A GPC-4D spectrum of the PE resin of the resin produced above was obtained and is shown in fig. 1.

Measurement of T by CFC _w1 ，T _w2 ，M _w1 And M _w2

Low temperature cross-fractionation (CFC) is used herein to determine both Molecular Weight Distribution (MWD) and Short Chain Branching Distribution (SCBD) compositional information using one or more temperature gradient gel permeation chromatography columns to compare the polymers of the present invention with other products commercially available. The procedures used to interpret the data obtained from CFCs are discussed in more detail below. This technique helps explain, among other information, the comonomer levels of the high to low molecular weight fractions of polyethylene.

From the CFC data obtained, each fraction is listed by its fractionation temperature (Ti) and its normalized weight percent (wt%) value (Wi), cumulative weight percent and moment of various molecular weight averages (moment) including weight average molecular weight Mwi.

The molecular weight fraction of the polyethylene was then determined as follows: the elution temperature (in degrees celsius) is first plotted on the x-axis of the graph, while the integral of the weight of polymer that has eluted up to the elution temperature is plotted on the right y-axis. The closest point at which 50% of the polymer has been rinsed is determined by the integration, which is then used to divide each graph into half 1 and half 2.

Qualitatively, from at least one temperature ladderElution of a gradient of molecular weight fractions of polyethylene (gradient based on both the molecular weight of the individual polymer chains and the branching level on each chain) with a temperature gradient by a gel chromatography column, wherein 50wt% or less of the cumulative molecular weight polyethylene fraction is at a temperature T _w1 Rinsing, and more than 50wt% of the cumulative molecular weight polyethylene fraction at a temperature T _w2 Leaching at T _w1 The eluted molecular weight fraction is the high molecular weight component M _w1 And at T _w2 The eluted fraction is the low molecular weight component M _w2 。

Quantitatively, to calculate T _w1 ，T _w2 ，M _w1 And M _w2 The data obtained from the fractionated CFC are divided into two approximately equal halves. The weight average of each half of Ti and Mwi is calculated according to the conventional definition of weight average. From T _w1 ，T _w2 ，M _w1 And M _w2 The calculation excludes the lack of sufficient quantities in the initial data file to be processed for the average molecular weight value<0.5 wt.%).

From the CFC data, the fraction with the cumulative weight percentage (sum of weights) closest to 50% was determined. The staged CFC data is divided in half, e.g., ti ≦ 84 ℃ as half 1 and Ti >84 ℃ as half 2. Fractions without the average molecular weight reported in the initial data file were excluded. The left hand y-axis represents the weight percent (wt%) of the eluted fraction. The curve was divided in half using the procedure described above and these values were used to calculate the weight average elution temperature for each half using the formula shown in equation 1:

in equation 1, ti represents the elution temperature of each eluted fraction, and Wi represents the normalized weight% (polymer amount) of each eluted fraction. The left hand axis represents the weight average molecular weight of each elution fraction (Mwj). These values are used to calculate the weight average molecular weight of each half using the formula shown in equation 2:

in equation 2, mw represents the weight average molecular weight of each eluted fraction, and Wj represents the normalized weight% (polymer amount) of each eluted fraction. The values calculated using the above technique are shown in fig. 2 and can be used to classify the MWD x SCBD of the experimental and control polymers.

In the graphs of FIG. 2A, FIG. 2B and FIG. 2C, the x-axis represents the difference (T) between the first and second weight average elution temperatures as indicated by "normalized Tw (. Degree. C.)" _w1 -T _w2 ). The y-axis on the logarithmic scale represents the ratio of the first weight average molecular weight to the second weight average molecular weight (M) as indicated by "normalized Mw _w1 /M _w2 ). The various types of polymer compositions as represented in the figures can be described as follows:

at the point X =0/Y = 0: absolute narrow MWD and absolute narrow SCBD. X =0 is practically impossible due to the forced halving along the temperature axis, as shown in fig. 2A, 2B and 2C.

Line X = 0: broadening the MWD while maintaining the ideal case of an absolutely narrow SCBD. At X =0, there is no difference in the Y value moving up or down direction, i.e., the MWD is widened while the SCBD is kept absolutely narrow.

Line Y = 0: broadening the SCBD while keeping the MWD unchanged and narrow.

Angle with X <0/Y < 1: a product, wherein the polymer composition is characterized by a combination of low Mwi/low Ti (high SCB) molecules and high Mwi/high Ti (low SCB) molecules; it is exemplified by a conventional LLDPE prepared with ZN catalyst.

Corners with X <0/Y > 1: a product, wherein the polymer composition is characterized by a combination of low Mwi/high Ti (low SCB) molecules and high Mwi/low Ti (high SCB) molecules; it is exemplified by the so-called BOCD (wide orthogonal composition distribution) or inverted composition distribution product.

Fig. 2A, 2B and 2C show the density distribution (split) of the very broad CD from the polymer produced above. The MWD was reasonably good (e.g., 7.75PDI for 35 MIR), probably due to the high component PDI.

In summary, the catalyst system of the present invention can provide increased activity or enhanced polymer performance, increased conversion or comonomer incorporation, and can alter comonomer distribution. The catalyst system and process of the present invention can also provide ethylene polymers with unique properties of high stiffness, high toughness and good processability as well as improved film properties.

All documents described herein are incorporated by reference herein, including any priority documents and/or test procedures, as long as they are not inconsistent herewith. While forms of embodiments have been illustrated and described, as would be apparent from the foregoing general description and the specific embodiments, various changes may be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including". Also whenever a component, element or group of elements is preceded by the conjunction "comprising," it is to be understood that we also contemplate the group of identical components and elements preceded by the conjunction "consisting essentially of … …," "consisting of … …," "selected from the group consisting of … …," or "is" in the recitation of said component, element or elements, and vice versa, for example, the terms "comprising," "consisting essentially of … …," "consisting of … …," also include the product of combinations of elements enumerated after that term.

Claims

1. A catalyst system comprising:

at least two different catalysts represented by formula a:

wherein:

m is Hf or Zr;

each R ¹ 、R ² And R ⁴ Independently is hydrogen, alkoxy or C ₁ -C ₄₀ A substituted or unsubstituted hydrocarbyl group;

each R ⁷ 、R ⁸ 、R ⁹ And R ¹⁰ Independently of one another is hydrogen, alkoxy, C ₁ -C ₄₀ Substituted or unsubstituted hydrocarbyl, -CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ And each R' is independently C ₁ -C ₂₀ A substituted or unsubstituted hydrocarbon group, wherein R ⁷ 、R ⁸ 、R ⁹ And R ¹⁰ is-CH ₂ -SiR' ₃ or-CH ₂ -CR' ₃ ；

T ¹ Is a bridging group; and

at least one catalyst represented by formula C and at least one catalyst represented by formula D:

Cp _m M ¹ X _q C

T ³ Cp _m M ² X _q D

wherein:

each Cp is independently a cyclopentadienyl or indenyl group;

M ¹ is zirconium or hafnium;

M ² is zirconium or hafnium;

T ³ is a bridging group containing at least three atoms;

x is halo, hydrogen, alkyl, alkenyl, or arylalkyl;

m =2, q =2, and the sum of m + q is equal to the oxidation state of the transition metal;

each Cp and X is bound to M ¹ Or M ² C, removing;

a carrier material; and

an activator.

2. The catalyst system of claim 1, wherein M is ¹ And M ² Both are zirconium.

3. The catalyst system of claim 1, wherein M ¹ And M ² Both are zirconium and wherein T ³ Containing at least 3 or more carbon, silicon, oxygen or nitrogen atoms.

4. The catalyst system of claim 1, wherein M is ¹ And M ² Both zirconium and M is hafnium.

5. The catalyst system of claim 1, wherein each of the catalysts represented by formula C is selected from the group consisting of:

bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-phenylcyclopentadienyl) zirconium dimethyl, bis (1-methyl-3-n-butylcyclopentadienyl) hafnium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, bis (tetrahydro-1-indenyl) zirconium dichloride, bis (tetrahydro-1-indenyl) zirconium dimethyl, (n-propylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, (n-propylcyclopentadienyl) (rac-ethylcyclopentadienyl) (rac-1-ethylcyclopentadienyl) zirconium diethyl (rac-1-ethylmeso-ethylcyclopentadienyl), rac/meso-bis (1-ethylindenyl) zirconium dimethyl, rac/meso-bis (1-methylindenyl) zirconium dichloride, rac/meso-bis (1-methylindenyl) zirconium dimethyl, rac/meso-bis (1-propylindenyl) zirconium dichloride, rac/meso-bis (1-propylindenyl) zirconium dimethyl, rac/meso-bis (1-butylindenyl) zirconium dichloride, rac/meso-bis (1-butylindenyl) zirconium dimethyl, meso-bis (1-ethylindenyl) zirconium dichloride, meso-bis (1-ethylindenyl) zirconium dimethyl, (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dichloride, and (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium dimethyl, or dimethylsilyl-bis (indenyl) zirconium dichloride.

6. The catalyst system of claim 1, wherein each of the catalysts represented by formula D is selected from the group consisting of: rac/meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Meso- (Me) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-EtInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBu) ₂ Si-O-SiPh ₂ )O(1-PrInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (NpPhSi) ₂ (Ind) ₂ ZrCl ₂ (ii) a Rac/meso- (Me) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (Ph) ₂ Si) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (MePhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Rac/meso- (tBuPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ (ii) a Or rac/meso- (NpPhSi) ₂ (1-MeInd) ₂ ZrCl ₂ 。

7. The catalyst system of claim 1, wherein the activator comprises an alumoxane or a non-coordinating anion.

8. The catalyst system of claim 1, wherein the activator is methylalumoxane.

9. The catalyst system of claim 1, wherein the support is a silica aluminate comprising an electron-withdrawing anion, optionally a fluoride or sulfate.

10. The catalyst system of claim 1, wherein the support is treated with an aluminum alkyl.

11. The catalyst system of claim 9, wherein the support is free of methylaluminoxane and/or a non-coordinating anion.

12. The catalyst system of claim 1, wherein saidThe activator comprises one or more of the following: n, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluorophenyl) borate, [ Me ₃ NH ⁺ ][B(C ₆ F ₅ ) ^4- ]1- (4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium and [ Me ₃ NH ⁺ ][B(C ₆ F ₅ ) ^4- ]1- (4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium, sodium tetrakis (pentafluorophenyl) borate, potassium tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluoropyridinium, sodium tetrakis (perfluorophenyl) aluminate, potassium tetrakis (pentafluorophenyl) and N, N-dimethylanilinium tetrakis (perfluorophenyl) aluminate.

13. A process for polymerizing olefin monomers comprising contacting one or more olefin monomers with the catalyst system of claim 1.

14. The process of claim 13, wherein the olefin monomer comprises ethylene and the olefin monomer polymerizes to form linear low density polyethylene.

15. A process for producing an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one alpha-olefin by contacting the ethylene and the at least one alpha-olefin with the catalyst system of claim 1 in at least one gas phase reactor at a reactor pressure of from 0.7 to 70bar and a reactor temperature of from 20 ℃ to 150 ℃ to form an ethylene alpha-olefin copolymer.

16. A process for producing an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one alpha-olefin by contacting the ethylene and the at least one alpha-olefin with the catalyst system of claim 1 in at least one slurry phase reactor at a reactor pressure of from 0.7 to 70bar and a reactor temperature of from 60 ℃ to 130 ℃ to form an ethylene alpha-olefin copolymer.

17. The catalyst system of claim 1, wherein T ³ Is a bridging group containing only three atoms.