CN109790240A - Steric hindrance metallocene, synthesis and purposes - Google Patents

Abstract

In at least one embodiment, catalyst compounds are indicated by formula (I):Wherein M is group-4 metal.R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Each of be independently hydrogen or linear or branching C₁‑C₅₀Substituted or unsubstituted alkyl, halohydrocarbyl or silylhydrocarbyl.R¹And R³At least one of be not hydrogen.Each X is independently halogen or C₁‑C₅₀Substituted or unsubstituted alkyl, hydrogen-based, amino, alkoxy, sulfenyl, phosphorus base, halogen, diene, amine, phosphine, ether or their combination, or two X are bonded together to form becket compound ring or two X engagements to form cheland, diene ligand or alkylidene radical.

Description

Steric hindrance metallocene, synthesis and purposes

Inventor: Donna J.Crowther；Laughlin G.McCullough；Jacqueline A.Lovell

Prioity claim

It is submitted this application claims the USSN 62/404,570 submitted on October 5th, 2016 and on November 23rd, 2016 EP 16200207.5 priority and interests and by reference to the introducing of their full text.

Technical field

This disclosure relates to comprising wherein containing the new of the 4th race's catalyst compounds of non-bridging for replacing benzo [e] indenyl Type catalyst compounds and the catalyst system containing such catalyst compounds and application thereof.

Background technique

Due to their practical physical properties, polyolefin is commercially widely used.For example, various types of polyethylene packets High density, low-density and linear low density polyethylene are included, they are commercially more the most useful.Polyolefin is typically with making alkene The catalyst preparation of hydrocarbon monomer polymerization.In fact, olefin polymerization catalysis is in great demand in the industry.Therefore, it is desirable to look for To novel catalyst system, improves the commercial practicability of catalyst and provide to have compared to known polyolefin composition and improve The polyolefin of performance, such as the preparation of polyethylene.

Copolymer compositions have composition distribution, refer to the comonomer that short chain component is formed along copolymer chain Distribution.When the amount of short chain component changes in copolymer molecule, it is said that there is composition the composition of " width " to be distributed.Work as copolymerization When the amount of monomer/1000 carbon is similar in the copolymer molecule of different chain length, it is said that composition distribution " narrow ".

Composition distribution influences the performance of copolymer compositions, for example, stiffness, toughness, environmental stress crack resistance and heat-sealing Etc. performances.The composition distribution of copolymer compositions can be easily for example, by temperature rising elution classification (TREF) or crystal analysis It is classified (CRYSTAF) measurement.

The composition distribution of copolymer compositions is influenced by the person's character of the catalyst for the polyolefin for being used to be formed the composition. Ziegler-Natta catalyst and catalyst based on chromium typically prepare the composition with wide composition distribution (BCD), and golden Belong to cyclopentadienyl catalyst and typically prepares the composition with narrow composition distribution (NCD).

In addition, the polyolefin with high molecular weight, such as polyethylene have typically better than their low molecular weight counterpart Desirable mechanical performance.However, high molecular polyolefine is likely difficult to process and may prepare valuableness of getting up.Have The polyolefin composition of bimodal molecular weight distribution is desirable, because they can be in conjunction with the high molecular weight of the composition The improved processing performance of low molecular weight (" LMW ") fraction of the advantageous mechanical performance and composition of (" HMW ") fraction. " high molecular weight " used herein is defined as 200,000g/mol or higher number-average molecular weight (Mn) value." low molecular weight " is fixed Justice is the Mn value less than 200,000g/mol.

For example, useful bimodal polyolefin composition includes with low molecular weight and low co-monomer content (that is, being integrated to Comonomer in polyolefin backbone) the first polyolefin, while there is the second polyolefin high molecular weight and high comonomer to contain Amount.With this wherein comonomer mainly in combination with the wide orthogonal systems in high molecular weight chains at distribution (broad Orthogonal composition distribution, BOCD) composition improved physical property can be provided, such as Toughness properties and environmental stress crack resistance (ESCR).

Bimodal or wide molecular weight distribution polyolefin method is prepared there are a variety of, for example, melt blended, serial or parallel connection is matched Reactor is set, or the single reactor with bimetallic catalyst.However, these methods, for example, it is melt blended lock into due to It needs that polyolefin composition is made to be homogenized the shortcomings that bringing with high cost completely.In addition, synthesizing these in hybrid catalyst system Polyolefin composition will require to be catalyzed under conditions of essentially similar with the second catalyst for example, ethylene using the first catalyst Polymerization, while not interfering the polymerization catalyzed of the second catalyst.

Due to orthogonal systems at distribution composition for commercial desirable product improved physical property, So there is still a need for provide the catalyst and caltalyst of the linear low molecular weight, high density polyethylene (HDPE) with low co-monomer content System.It it is also required to provide the hybrid catalyst system of BOCD polyolefin composition.

Summary of the invention

Summary of the invention

In at least one embodiment, catalyst compounds are indicated by formula (I):

Wherein M is group-4 metal；R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Each of It is independently hydrogen, or linear or branching C₁-C₅₀Substituted or unsubstituted alkyl, halohydrocarbyl (halocarbyl) or silicyl Alkyl (silylcarbyl), wherein R¹And R³At least one of be not hydrogen；Each X is independently halogen (halide) or C₁- C₅₀Substituted or unsubstituted alkyl, hydrogen-based (hydride), amino (amide), alkoxy (alkoxide), sulfenyl (sulfide), phosphorus base (phosphide), halogen, diene, amine, phosphine, ether or their combination or two X be bonded together with Becket compound ring (a metallocycle ring) or two X engagements are formed to form cheland, diene ligand or alkane Pitch base.

In another embodiment, the preparation method of polyolefin composition includes making one or more alkene and catalyst System contact, the catalyst system includes: activator and the catalyst compounds indicated by formula (I).

In another embodiment, the preparation method of polyolefin composition includes making one or more alkene and catalyst System contact, the catalyst system includes: (a) catalyst compounds indicated by formula (I)；(b) it removes and is urged by what formula (I) was indicated Bridging or non-bridged metallocene catalyst compounds other than agent compound, and (c) activator.

Brief description

Fig. 1 is the drawing of the opposite hexene concentration based on total monomer concentration of activity.

Fig. 2 is the drawing of the opposite hexene concentration based on total monomer concentration of activity.

Fig. 3 is the drawing of the hexene concentration in the opposite charging of fusing point of ethylene-hexene co-polymers product.

Fig. 4 is the drawing of the hexene concentration in the opposite charging of fusing point of ethylene-hexene co-polymers product.

Fig. 5 is the drawing of the hexene concentration in the opposite charging of Mw of ethylene-hexene co-polymers product.

Fig. 6 is the drawing of the hexene concentration in the opposite charging of Mn of ethylene-hexene co-polymers product.

Detailed description of the invention

For the purpose of present disclosure, the numbering plan of each race of the periodic table of elements is according to Chemical and Engineering News, 63 (5), pg.27, description uses like that in (1985).Therefore, " group-4 metal " is selected from element The element of the 4th race of periodic table, such as Hf, Ti or Zr.

" catalyst productivity " is prepared in a period of T hours using the polymerization catalyst comprising W g catalyst (cat) The measurement of how many grams of polymer (P)；And can pass through formula: P/ (T × W) is indicated and with unit gPgcat^-1hr^-1It indicates." turn Rate " is to be converted to the amount of the monomer of polymer product, and be reported as mol% and be based on polymer output (weight) and feed anti- The amount of the monomer of device is answered to calculate.Catalyst activity is catalyst activity measurement how and the resulting polymer for being reported as preparation (P) quality (gP/g support type cat) of quality/loaded catalyst (cat).

" alkene ", or being known as " olefin(e) " is that carbon and hydrogen have the linear of at least one double bond, branching or a ring-typeization Close object.For present disclosure purpose, ethylene is considered as alpha-olefin.When polymer or copolymer are known as olefin-containing When, the alkene being present in this quasi polymer or copolymer is the polymerized form of the alkene.For example, when copolymer is said to be tool When having " ethylene " content of 35wt%-55wt%, it should be understood that the derivative auto polymerization of monomeric unit in the copolymer is anti- Ethylene and the derivative unit in answering are existed by 35wt%-55wt%, the weight based on the copolymer." polymer " With two or more identical or different monomeric units." homopolymer " is the polymer of the unit containing same monomer." copolymerization Object " is the polymer with two or more monomeric units different from each other." terpolymer " is that there are three types of each other not for tool The polymer of same monomeric unit.Term " difference " for being related to monomeric unit indicates that the monomeric unit differs each other and is At least one atom or isomery are different.Therefore, the definition of copolymer used herein includes terpolymer and similar Object.Oligomer is usually the polymer with low molecular weight, such as Mn less than 25,000g/mol, or less than 2,500g/mol, or Polymer with low monomeric unit number, such as 75 monomeric units or less or 50 monomeric units or less." vinyl polymerization Object " or " ethylene copolymer " are polymer or copolymer comprising at least unit of 50mol% ethylene derivative, " acrylic polymers " Or " propylene copolymer " is the polymer or copolymer for including at least unit of 50mol% propylene derived, it is such.

" catalyst system " is at least one activator, at least one catalyst compounds and Fei Bi indicated by formula (I) The second system component wanted, such as the combination of the second catalyst compounds.In addition catalyst system can have at least one carry Body material and/or at least one conactivator.When catalyst system is described as the neutral stable form comprising component, this field It should be understood to the one skilled in the art that the ionic species of the component is and monomer reaction is in the form of generating polymer.For in the disclosure For the purpose of appearance, " catalyst system " includes both neutrality and ionic species of the component of catalyst system.

Mn used herein is number-average molecular weight, and Mw is weight average molecular weight, and Mz is z average molecular weight, and wt% is weight hundred Divide rate, mol% is molar percentage.Molecular weight distribution (MWD) (also referred to as polydispersity index (PDI)) is defined as Mw divided by Mn. Unless otherwise mentioned, all molecular weight units (for example, Mw, Mn, Mz) are g/mol.

In this disclosure, catalyst can be described as catalyst precarsor, procatalyst compound, catalyst compounds Or transistion metal compound, and these terms are interchangeably used." anion ligand " be for metal ion contribute one or The negatively charged ligand of multiple electronics pair." neutral donor ligand " is the band that one or more electronics pair are contributed for metal ion The ligand of neutral charge.

For content related with catalyst compounds in the disclosure, term " substitution " refers to that hydrogen-based has replaced with Alkyl, hetero atom contain heteroatomic group.For example, methyl cyclopentadiene (MeCp) is to replace the Cp base for having methyl, ethyl alcohol It is to replace the ethyl for having-OH base.

For the purpose of present disclosure, " alkoxy (alkoxides) " is C including wherein alkyl₁-C₁₀Alkyl Those.Alkyl can be linear, branching or cyclic alkyl.Alkyl can be saturated or unsaturated.In at least one embodiment party In case, alkyl may include at least one aromatic group.Term " alkoxy (alkoxy) " or " alkoxy " preferably refer to alkyl ether Or aryl ether, wherein term alkyl is C₁-C₁₀Alkyl.The example of suitable alkylether radicals include, but are not limited to methoxyl group, Ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy group etc..

This disclosure has described transition metal complexes.Term complex compound is used to describe wherein assistant ligand and center mistake Cross the molecule of metallic atom coordination.The ligand and transition metal are huge and steadily bonded so that maintaining it in catalyst application Influence during (such as polymerization).The ligand can pass through covalent bond and/or supplied for electronic coordination or intermediate bond and transition metal Coordination.Generally make the activation of transition metal complex experience using activator and play their polymerizable functional, the activator is recognized To generate cation from the removal of transition metal due to anionic group (commonly referred to as leaving group).

Can hereinafter referred to as use in this disclosure: dme is 1,2- dimethoxy-ethane, and Me is methyl, and Et is second Base, Pr are propyl, and iPr is isopropyl, and n-Pr is n-propyl, and cPr is cyclopropyl, and Bu is butyl, and iBu is isobutyl group, and tBu is uncle Butyl, p-tBu are p- tert-butyls, and nBu is normal-butyl, and sBu is sec-butyl, and TMS is trimethyl silyl, and TIBAL is three different Butyl aluminium, TNOAL are three (n-octyl) aluminium, and MAO is methylaluminoxane, and sMAO is support type methylaluminoxane, and p-Me is to first Base, Ph are phenyl, and Bn is benzyl (that is, CH₂Ph), THF (also referred to as thf) is tetrahydrofuran, RT be room temperature (and be 23 DEG C, Unless otherwise indicated), tol is toluene, and EtOAc is ethyl acetate and Cy is cyclohexyl.

Term " alkyl (hydrocarbyl radical) ", " alkyl (hydrocarbyl) ", " alkyl (hydrocarbyl Group) ", " alkyl (alkyl radical) " and " alkyl (alkyl) " are interchangeably used in entire present disclosure.Together Sample, term " group ", " base " and " substituent group " are also interchangeably used in this disclosure.For present disclosure, " hydrocarbyl group " is defined as C₁-C₁₀₀Group can be linear, branching or cricoid, and when being ring-type, be aromatics or non- Aromatics.The example of such group includes, but are not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, tert-butyl, amyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl etc., including they Substituted analog.Substituted alkyl is at least one hydrogen atom of the wherein alkyl at least with non-hydrogen group, example Such as halogen (such as Br, Cl, F or I) or at least one functional group such as NR*₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、 SR*、BR*₂、SiR*₃、GeR*₃、SnR*₃、PbR*₃The base in alkyl ring is had been inserted at Deng substitution or in which at least one hetero atom Group.

Term " alkenyl " refers to straight chain, branch or cyclic hydrocarbon group with one or more carbon-to-carbon double bonds.These alkenyls can To be substituted.The example of suitable alkenyl includes, but are not limited to vinyl, acrylic, allyl, Isosorbide-5-Nitrae-butadienyl, cyclopropyl Alkenyl, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base etc., including their substitution analog.

Term " aryl " refer to carbon containing aromatic ring and its replace variant, including but not limited to, phenyl, 2- methylphenyl, The bromo- methylbenzyl of methylbenzyl, 4-.Similarly, heteroaryl refers to that wherein ring carbon atom (or two or three ring carbon atoms) has been used The aryl of hetero atom, preferably N, O or S replacement.Term as used herein " aromatics " also refers to quasi- aromatic heterocycle, they are and aromatics Miscellaneous ring ligand has similar performance and structure (almost plane), but is not belonging to define the miscellaneous cyclic substituent of aromatics；Together Sample, term aromatic also refers to substituted aromatic compounds.

(for example, normal-butyl, isobutyl group, Zhong Ding in the presence of the isomers of the alkyl of name, alkenyl, alkoxy or aryl Base and tert-butyl), to the group one of reference (for example, normal-butyl) should specially disclose in family remaining is different Structure body (for example, isobutyl group, sec-butyl and tert-butyl).Equally, to the reference of alkyl, alkenyl, alkoxy or aryl without advising Fixed specific isomers (for example, butyl) specially discloses all isomers (for example, normal-butyl, isobutyl group, sec-butyl and tertiary fourth Base).

Term " annular atom " refers to the atom for belonging to a part of cyclic annular ring structure.According to this definition, benzyl has 6 Annular atom, tetrahydrofuran have 5 annular atoms.Heterocycle is in ring structure with the hydrogen on heteroatomic ring, with wherein annular atom The ring replaced by the hetero atom that hetero atom substitutes is opposite.For example, tetrahydrofuran is heterocycle, 4-N, N- dimethyl-amino-phenyl is The ring that hetero atom replaces.

Term " co-catalyst " and " activator " are used interchangeably herein, and being defined as can be by urging neutrality Agent compound is converted to the catalyst compounds cation of catalytic activity and activates any one in above-mentioned catalyst compounds Any compound of kind.

Scavenger is can be added to the compound for promoting polymerization in catalyst system by removing impurity.Some removings Agent can also act as activator and be properly termed as conactivator.Conactivator (not being scavenger) can also be in conjunction with activator Using to form active catalyst system.It at least one embodiment, can be by conactivator and transistion metal compound Premixing is to form alkylated transition metallic compound.

In description herein, catalyst can be described as complex compound, catalyst precarsor, procatalyst compound, catalysis Immunomodulator compounds, transition metal complex or transistion metal compound, and these terms are interchangeably used.Polymerization catalyst body System is that monomer polymerization can be made at the catalyst system of polymer.

Term " continuous " refers to the system operated in the case where no one period of interrupting or stopping.For example, preparation is poly- The continuation method for closing object will be that wherein reactant is continuously imported one or more reactors and polymer product is continuous The method of taking-up.

" polymerisation in solution ", which refers to, is wherein aggregated in liquid polymerization medium, for example, atent solvent or monomer (one or more) or The polymerization carried out in their blend.Polymerisation in solution is usually homogeneous.Homogeneous polymerization is that wherein polymer product is molten Polymerization of the solution in polymerisation medium.Such system be not preferably it is muddy, such as J.Vladimir Oliveira, C.Dariva And J.C.Pinto, Ind.Eng.Chem.Res. (2000), described in 29,4627 like that.

Bulk polymerization refers to that the monomer wherein just polymerizeing and/or comonomer are used as solvent or diluent and hardly use Or without using atent solvent or the polymerization of diluent.Small part atent solvent possibly serves for the load of catalyst and scavenger Body.Bulk polymerization system contains atent solvent or diluent less than about 25wt%, such as less than about 10wt%, such as few In about 1wt%, such as 0wt%.

For the present invention and the appended claims, there is 0.86g/cm³Or the ethene polymers of lower density Referred to as ethylene elastomer or elastomer；With greater than 0.86 to less than 0.910g/cm³The ethene polymers of density be known as ethylene Plastic body or plastic body；With 0.910-0.940g/cm³The ethene polymers of density be known as low density polyethylene (LDPE)；With big In 0.940g/cm³The ethene polymers of density be known as high density polyethylene (HDPE) (HDPE).Density passes through according to ASTM D 1505 Density gradient column is to being slowly cooled to room temperature (that is, 10 minutes or more time) and aging is made persistently to be enough to make density permanent It is scheduled on +/- 0.001g/cm³Compression molding sample measurement in range.

In overlapping density range, that is, 0.890-0.930g/cm³, usual 0.915-0.930g/cm³In be it is linear not Polyethylene containing long chain branching be known as " linear low density polyethylene " (LLDPE) and can use Conventional Ziegler-Natta catalyst, Vanadium catalyst is made with metalloscene catalyst in gas-phase reactor and/or in slurry-phase reactor and/or in solution reactor It is standby." linear " refers to that polyethylene does not have long chain branches；Commonly referred to as branch index (g'_vis) be 0.97 or more, preferably 0.98 or More than.Branch index g'_visMeasurement as described below.

Catalyst compounds

Present disclosure provides novel non-the 4th race's catalyst compounds of bridging of benzo [e] indenyl comprising replacing.

In at least one embodiment, present disclosure provides the catalyst compounds indicated by formula (I), and includes this The catalyst system of kind compound:

M is group-4 metal.R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Each of it is independent Ground is hydrogen or linear or branching C₁-C₅₀Substituted or unsubstituted alkyl, halohydrocarbyl or silylhydrocarbyl.R¹And R³In at least One is not hydrogen.Alternatively, R¹And R³It is not hydrogen.Each X is independently halogen or C₁-C₅₀Substituted or unsubstituted alkyl, hydrogen Base, amino, alkoxy, sulfenyl, phosphorus base, halogen, diene, amine, phosphine, ether or their combination or two X are bonded together with shape At becket compound ring or two X engagements to form cheland, diene ligand or alkylidene radical.

In at least one embodiment, R¹It is linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl. R³It can be linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl.R¹And R³Each of can be independently It is linear or branching C₁-C₅Unsubstituted alkyl.Each X can be independently halogen or C₁-C₁₀(or C₁-C₅) replace or not Substituted alkyl.

In at least one embodiment of the invention, R¹And R³It is linear or branching C₁-C₁₀(or C₁-C₅) replace or Unsubstituted alkyl.

R¹And R³It can be identical or different.

In at least one embodiment of the invention, R¹And R³It is linear or branching C₁-C₁₀Substituted or unsubstituted alkane Base, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl.

In at least one embodiment of the invention, R²、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹It is hydrogen or linear or branching C₁-C₁₀ Substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl.

In at least one embodiment of the invention, R¹And R³It is linear or branching C₁-C₁₀Substituted or unsubstituted alkane Base, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl and R²、R⁴、R⁵、R⁶、R⁷、R⁸With R⁹It is hydrogen.

In at least one embodiment, R¹⁰It is hydrogen or C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably Linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, oneself Base, heptyl, octyl, nonyl or decyl.R¹¹、R¹²、R¹³And R¹⁴Each of can be independently C₁-C₁₀(or C₁-C₅) take Generation or unsubstituted alkyl, preferably linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, second Base, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl.

In at least one embodiment of the invention, each R¹And R³It is independently hydrogen, linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or the last of the ten Heavenly stems Base, wherein R¹And R³At least one of be not hydrogen (or not being H)；R²、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹It is hydrogen or linear or branch Change C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, pungent Base, nonyl or decyl；R¹⁰It is hydrogen or C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably linear or branching C₁-C₁₀ (or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl Or decyl；And R¹¹、R¹²、R¹³And R¹⁴Each of be independently C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, it is excellent Selected linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, oneself Base, heptyl, octyl, nonyl or decyl.

In at least one embodiment of the invention, R¹And R³It is linear or branching C₁-C₁₀(or C₁-C₅) replace or Unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl；R²、R⁴、R⁵、 R⁶、R⁷、R⁸And R⁹It is hydrogen or linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, third Base, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl；R¹⁰It is hydrogen or C₁-C₁₀Substituted or unsubstituted alkyl, preferably line Property or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, Heptyl, octyl, nonyl or decyl；And R¹¹、R¹²、R¹³And R¹⁴Each of be independently C₁-C₁₀(or C₁-C₅) replace or Unsubstituted alkyl, preferably linear or branching C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, third Base, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl.

In at least one embodiment of the invention, R¹And R³It is hydrogen, linear or branching C₁-C₁₀(or C₁-C₅) replace Or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl, wherein R¹ And R³In at least one or R¹And R³The two is not hydrogen；R²、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹And R¹⁰It is linear or branching C₁-C₁₀ (or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl Or decyl；R¹⁰It is hydrogen or C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably linear or branching C₁-C₁₀Replace or not Substituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl；And R¹¹、R¹²、R¹³ And R¹⁴Each of be independently C₁-C₁₀(or C₁-C₅) substituted or unsubstituted alkyl, preferably linear or branching C₁-C₁₀ (or C₁-C₅) substituted or unsubstituted alkyl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl Or decyl.

Non-limiting substance by formula (I) catalyst compounds indicated is:

In at least one embodiment, catalyst system further includes by formula (I) other than the second catalyst compounds The catalyst of expression, second catalyst compounds are bridgings in addition to the catalyst compounds indicated by formula (I) or not Bridged metallocene catalyst compounds.

Second metallocene catalyst compound can be by formula: Cp^ACp^BM'X'_nThe non-bridged metallocene catalyst indicated Close object.Each Cp^AAnd Cp^BIndependently selected from cyclopentadienyl ligands.Cp^AAnd Cp^BOne of or both can contain hetero atom. Cp^AAnd Cp^BOne of or both can be replaced by one or more R " bases.M' is selected from the 3rd to 12 race's atom and lanthanide atom.X' It is anion leaving group.N is the integer of 0 or 1-4.R " be selected from alkyl, low alkyl group, substituted alkyl, miscellaneous alkyl, alkenyl, Low-grade alkenyl, substituted alkenyl, miscellaneous thiazolinyl, alkynyl, low-grade alkynyl, substituted alkynyl, miscellaneous alkynyl, alkoxy, lower alkoxy, Aryloxy group, alkyl sulfide, low-grade alkyl sulphur, aryl sulphur, aryl, substituted aryl, heteroaryl, aralkyl, sub- aralkyl, alkane virtue Base, halogenated alkyl, halogenated alkenyl, halo alkynyl, miscellaneous alkyl, heterocycle, heteroaryl, contains heteroatom group, hydrocarbon at alkarylene Base, lower alkyl, substituted alkyl, miscellaneous alkyl, silicyl, monoborane base, phosphino- (phosphino), phosphine, amino, amine, ether And thioether.In at least one embodiment, by formula: Cp^ACp^BM'X'_nThe non-bridged metallocene catalyst preparation indicated has height The polyolefin of co-monomer content.

The non-limiting substance of second metallocene catalyst compound includes:

Dichloro bis- (n-propyl cyclopentadienyl groups) closes hafnium, dimethyl bis- (n-propyl cyclopentadienyl groups) closes hafnium, two Bis- (n-propyl cyclopentadienyl group) zirconiums of chlorine, bis- (n-propyl cyclopentadienyl group) zirconiums of dimethyl, the bis- (n-propyls of dichloro Cyclopentadienyl group) close titanium, dimethyl bis- (n-propyl cyclopentadienyl groups) conjunction titanium, dichloro (n-propyl cyclopentadienyl group, five first Cyclopentadienyl group) zirconium, dimethyl (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) zirconium, dichloro (positive third Cyclopentadienyl group, pentamethylcyclopentadiene base) close hafnium, dimethyl (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene Base) close hafnium, dichloro (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) conjunction titanium, dimethyl (n-propyl cyclopentadiene Base, pentamethylcyclopentadiene base) close titanium, dichloro (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) zirconium, diformazan Base (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) zirconium, dichloro (n-propyl cyclopentadienyl group, tetramethyl-ring Pentadienyl) close hafnium, dimethyl (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction hafnium, dichloro (n-propyl ring Pentadienyl, tetramethyl-ring pentadienyl) close titanium, dimethyl (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction Bis- (cyclopentadienyl group) zirconiums of titanium, dichloro, dichloro bis- (cyclopentadienyl groups) close titanium, dichloro bis- (cyclopentadienyl groups) closes Bis- (cyclopentadienyl group) zirconiums of hafnium, dimethyl, dimethyl bis- (cyclopentadienyl groups) close titanium, the bis- (cyclopentadiene of dimethyl Base) close hafnium, dichloro bis- (n-butyl cyclopentadienyls) conjunction hafnium, dimethyl bis- (n-butyl cyclopentadienyls) conjunction hafnium, two Bis- (n-butyl cyclopentadienyl) zirconiums of chlorine, bis- (n-butyl cyclopentadienyl) zirconiums of dimethyl, the bis- (normal-butyls of dichloro Cyclopentadienyl group) close titanium, dimethyl bis- (n-butyl cyclopentadienyls) conjunction titanium, dichloro bis- (pentamethylcyclopentadiene bases) conjunction It is double that hafnium, dimethyl bis- (pentamethylcyclopentadiene bases) close hafnium, bis- (pentamethylcyclopentadiene base) zirconiums of dichloro, dimethyl (pentamethylcyclopentadiene base) zirconium, dichloro bis- (pentamethylcyclopentadiene bases) close titanium, bis- (the pentamethyl rings penta 2 of dimethyl Alkenyl) close titanium, dichloro bis- (1- methyl -3- n-butyl cyclopentadienyls) conjunction hafnium, the bis- (1- methyl -3- normal-butyls of dimethyl Cyclopentadienyl group) close hafnium, bis- (1- methyl -3- n-butyl cyclopentadienyl) zirconiums of dichloro, the bis- (1- methyl -3- of dimethyl N-butyl cyclopentadienyl) zirconium, dichloro bis- (1- methyl -3- n-butyl cyclopentadienyls) conjunction titanium and the bis- (1- of dimethyl Methyl -3- n-butyl cyclopentadienyl) close titanium.

In at least one embodiment, the second catalyst is by formula: Cp^A(A)Cp^BM'X'_nThe bridged metallocene of expression is urged Agent compound.Each Cp^AAnd Cp^BIndependently selected from cyclopentadienyl ligands.Cp^AAnd Cp^BOne of or both can contain it is miscellaneous Atom.Cp^AAnd Cp^BOne of or both can be replaced by one or more R " bases.M' is selected from the 3rd to 12 race's atom and group of the lanthanides is former Son.X' is anion leaving group.N is the integer of 0 or 1-4.(A) divalent alkyl, bivalent lower alkyl, bivalent substituted alkane are selected from Base, divalent miscellaneous alkyl, divalent alkenyl, bivalent lower alkenyl, bivalent substituted alkenyl, divalent miscellaneous thiazolinyl, divalent alkynyl radical, bivalent lower Alkynyl, bivalent substituted alkynyl, the miscellaneous alkynyl of divalent, divalent alkoxy groups, bivalent lower alkoxy, divalent aryloxy group, divalent alkyl sulphur, Bivalent lower alkyl sulfide, divalent aryl sulphur, divalent aryl, bivalent substituted aryl, divalent heteroaryl radical, divalent aralkyl, divalent are sub- Aralkyl, divalent alkaryl, divalent alkylene aryl, divalent halogenated alkyl, divalent halogenated alkenyl, divalent halo alkynyl, divalent are miscellaneous Alkyl, divalent heterocycle, divalent heteroaryl radical, divalent contain heteroatom group, bivalent hydrocarbon radical, bivalent lower alkyl, bivalent substituted hydrocarbon Base, divalent miscellaneous alkyl, divalent silicyl, divalent monoborane base, divalent phosphino-, divalent phosphine, divalent amino, divalent amines, divalent Ether, divalent thioether；R " is selected from alkyl, low alkyl group, substituted alkyl, miscellaneous alkyl, alkenyl, low-grade alkenyl, substituted alkenyl, miscellaneous Alkenyl, alkynyl, low-grade alkynyl, substituted alkynyl, miscellaneous alkynyl, alkoxy, lower alkoxy, aryloxy group, alkyl sulfide, low alkyl group Sulphur, aryl sulphur, aryl, substituted aryl, heteroaryl, aralkyl, sub- aralkyl, alkaryl, alkarylene, halogenated alkyl, halogen For alkenyl, halo alkynyl, miscellaneous alkyl, heterocycle, heteroaryl, containing heteroatom group, alkyl, lower alkyl, substituted alkyl, miscellaneous Alkyl, silicyl, monoborane base, phosphino-, phosphine, amino, amine, ether and thioether.

In at least one embodiment, Cp^AAnd Cp^BIndependently selected from cyclopentadienyl group, n-propyl cyclopentadienyl group, five Methyl cyclopentadienyl, tetramethyl-ring pentadienyl and n-butyl cyclopentadienyl.

Present disclosure further provides for the method for making olefinic polymerization, including contacts alkene with catalyst system, described Catalyst system includes the catalyst compounds indicated by formula (I).The alkene can be ethylene, propylene, butylene, amylene, oneself Alkene, heptene, octene, nonene, decene, endecatylene, dodecylene or their mixture.Catalyst system can have above-mentioned Second catalyst, activator and/or carrier material.

The method can about 0 DEG C-about 300 DEG C at a temperature of, in the pressure of about 0.35MPa- about 10MPa The lower and/or time by up to about 300 minutes carries out.

Present disclosure further provides for comprising low molecular weight fraction and/or high molecular weight block being multimodal polyolefin group Close the polyolefin composition of object.In at least one embodiment, the low molecular weight fraction is urged by what is indicated by formula (I) The preparation of agent compound.The multimodal polyolefm composition can be prepared by the above method.

In at least one embodiment, in any method described herein, using a kind of catalyst compounds, such as Catalyst compounds are not different.For present disclosure, if a kind of catalyst compounds with another kind differ to A few atom, then it is assumed that they are different.For example, " bisindenyl's zirconium " is different from " dichloro (indenyl) (2- methyl indenes Base) zirconium ", the latter is different from " dichloro (indenyl) (2- methylindenyl) closes hafnium ".Only because isomers and different catalysis Immunomodulator compounds are considered identical for the object of the invention, such as dimethyl racemic-dimetylsilyl is double (2- methyl 4- phenyl) closes hafnium and thinks to close hafnium phase with dimethyl meso-dimetylsilyl bis- (2- methyl 4- phenyl) Together.

In at least one embodiment, two or more different catalyst compounds are present in used herein above In catalyst system.In at least one embodiment, two or more different catalyst compounds are present in reaction zone In, wherein carrying out method described herein (one or more).When two kinds of transition-metal catalysts are as hybrid catalyst system When for a reactor, both transistion metal compounds are preferably chosen such that both are compatible.It is any suitable Screening method (such as pass through¹H or¹³C NMR) to can be used for measuring which transistion metal compound be compatible.Preferably for transition Metallic compound uses identical activator, however, two different activators, such as non-coordinating anion activator and alumina Alkane can be applied in combination.If one or more transistion metal compounds contain be not hydrogen-based, alkyl or substituted alkyl X₁ Or X₂Ligand should then allow aikyiaiurnirsoxan beta to contact before adding non-coordinating anion activator with transistion metal compound.

(A:B) it can be made in any proportion by formula (I) catalyst compounds indicated and second catalyst compounds With.If the second catalyst compounds are (B), (A) can be by the catalyst compounds that formula (I) is indicated.Alternatively, if Two catalyst compounds are (A), then can be (B) by the catalyst compounds that formula (I) is indicated.(A) with (B) preferred molar ratio Belong to (A:B) about 1:1000- about 1000:1, such as about 1:100- about 500:1, such as about 1:10- about 200: 1, such as the range of about 1:1- about 100:1 perhaps 1:1-75:1 or 5:1-50:1.Selected specific ratio will take Certainly in selected accurate procatalyst, activation method and desired final product.In a specific embodiment, when When using described two catalyst compounds, under the occasion that the identical activator of the two activates, useful molar percentage (base In the molecular weight of catalyst compounds) (B) of (A) relatively about 0.1- about 90% for being about 10- about 99.9%, such as About 25- about 99% (A) relatively about 0.5- about 50% (B), such as about 1- is big relatively by about 50- about 99% (A) About 25% (B), such as about 75- about 99% (A) relatively about 1- about 10% (B).

The preparation method of catalyst compounds

Benzo [e] indenes is bought from Boulder Scientific.(CpPr)₂HfMe₂(1-EtC₉H₈)₂ZrMe₂From Albemarle purchase.Methylaluminoxane (MAO) is bought from Albemarle as the 30wt% solution in toluene.(CpMe₄H) ZrCl₃(CpMe₅)ZrCl₃All bought from Strem.

1,3Me₂The synthesis of benzo [e] indenyl lithium

Benzo [e] indenes (6.6g) is dissolved in Et₂In O (100mL) and with nBuLi (3.2g, 10M) deprotonation.True It is aerial to remove volatile matter and wash crude solid product with hexane (2 × 30mL).Make all to be dissolved in Et₂In O (100mL) and with MeI (30g) reacts 12hr at RT.Use H₂O (100mL) washs coarse reactants and is extracted with additional THF (50mL).To slightly it extract The merging of object group is taken to use MgSO₄It dries and is reduced into yellow liquid (6.9g).All mono- methyl benzo [e] indenes are dissolved in Et₂O In (100mL) and with nBuLi (3.1g, 10M) deprotonation.By remove volatile matter isolate Tan solid and with hexane (2 × 40mL) wash.Make all to react with MeI and as above post-process and generates 1,3- and 1,1- dimethylbiphenyl [e] indenes (5.4g) Mixture.Crude mixture is dissolved in Et₂In O (60mL) and with nBuLi (2.5g, 10M) deprotonation.Remove Et₂O simultaneously uses oneself Alkane (3 × 50mL) washs solid 1,3Me₂Simultaneously (4.6g) is dried in a vacuum in benzo [e] indenyl lithium.(referring to process 1).

1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂Synthesis

By 1,3Me₂Benzo [e] indenyl lithium (0.62g) is added to (CpMe₄)ZrCl₃(1.6g) is in Et₂Silt in O (60mL) In slurry.After 2 hours, reactant is reduced to dry in a vacuum and generates faint yellow solid (2.1g).At toluene (50mL) It is middle to be reacted by whole slurrying and with MeMgI (3g, 3M).(referring to process 1).Addition dimethoxy-ethane (2mL) simultaneously filters reaction Object.Filtrate is reduced to 20mL in terms of volume and adds pentane (30mL) to cause to precipitate.It is collected as faint yellow solid The product of (1.04g).

¹H NMR(400MHz,C₆D₆)ppm；8.12 (d), 7.55 (d), 7.35 to 7.13 (m ' s), 5.38 (s), 4.42 (s),2.17(s),2.01(s),1.73(s),1.71(s),1.52(s),1.33(s),-.75(s),-1.02(s)。

(1,3- dimethylbiphenyl [e] indenyl) (CpMe₅)ZrMe₂Synthesis

In Et₂By 1,3Me in O (60mL)₂Benzo [e] indenyl lithium (1.1g) slurrying simultaneously adds (CpMe₅)ZrCl₃(1.6g)。 After 2 hours, it filters reactant and reduces filtrate in a vacuum and generate yellow solid (1.4g).In Et₂By institute in O (40mL) It states 1.4g slurrying and is reacted 12 hours with MeMgI (2.2g, 3M).Remove Et₂Coarse fodder is simultaneously dissolved in toluene (50mL) by O.Add Add dimethoxy-ethane (2mL) and filters reactant.Filtrate is reduced to 20mL in terms of volume and add pentane (20mL) with Cause to precipitate.Coarse fodder is cooled to -35 DEG C.It is collected as the product of pale solid (0.6g).

¹H NMR(400MHz,C₆D₆)ppm；8.18 (d), 7.81 (d) 7.54 to 7.45 (m), 7.47 (s), 5.21 (s), 2.22(s),2.11(s),1.88(s),-1.20(s),-1.54(s).

The synthesis of loaded catalyst:

(CpPr)₂HfMe₂-MAO

MAO (6.3g, 30wt%Albemarle) is dissolved in 30mL toluene.It adds (CpPr)₂HfMe₂(108mg) simultaneously It is stirred to react mixture 30min.Add silica (4.25g, the ES roasted at 600 DEG C^TM757 (PQ Corporation, Conshohocken, Pennsylvania) and reaction stirred 2 hours.Volatile matter is removed in a vacuum until the stream that gains freedom Dynamic solid.

SMAO is by ES^TMThe preparation of 757 silica

Prepare solution of the methylaluminoxane (26g, in toluene, 30wt%, Albemarle) in toluene (125mL).To The ES that 20g is roasted at 600 DEG C is added in this agitating solution^TM757 (PQ Corporation, Conshohocken, Pennsylvania).Slurry is heated to 90 DEG C of holdings 3 hours and is cooled to RT.It filters and free flow is dried in a vacuum into Dynamic solid.

(1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂-SMAO

By (1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂(90mg) is added to SMAO-ES^TM757 (5g) exist In slurry in 30mL toluene.Reactant is stirred 3 hours and the catalyst is dried in a vacuum until flowing freely.

(1,3- dimethylbiphenyl [e] indenyl) (CpMe₅)ZrMe₂-SMAO

By (1,3- dimethylbiphenyl [e] indenyl) (CpMe₅)ZrMe₂(86mg) is added to SMAO-ES^TM757 (5g) exist In slurry in 30mL toluene.Reaction mixture is stirred for 3 hours at RT.Remove in a vacuum whole volatile matters until obtained from By flow solids.

(1-EtC₉H₈)₂ZrMe₂-SMAO

By (1-EtC₉H₈)₂ZrMe₂(83mg) is added to SMAO (5g) in the slurry in 30mL toluene.It is stirred at RT Reactant 3 hours simultaneously removes volatile matter until the flow solids that gain freedom in a vacuum.

(CpPr)₂HfMe₂-SMAO

By (CpPr)₂HfMe₂(200mg) is added to SMAO (10g) in the slurry in 50mL toluene.It is stirred at RT anti- It answers object 3 hours and removes volatile matter in a vacuum until the flow solids that gain freedom.

Fluorinated loaded catalyst

In N at 460 DEG C₂Purging is lower to roast Siral^TM- 40 (can be obtained from Sasol, Germany) 4 hours.Then make It and (NH₄)₂SiF₆It reacts and is roasted in air to 600 DEG C.For example, by the Siral of roasting^TM- 40 (50g) and (NH₄)₂SiF₆ (2.8g) is combined and is heated to 200 DEG C from RT in air and kept for 3 hours.Then it is heated to 600 DEG C of holdings 8 hours, so Afterwards in N₂It flows down and is cooled to RT and obtains fluorinated silica, F-Si.

(1,3- dimethylbiphenyl [e] indenyl) (CpMe₅)ZrMe₂-F-Si

Methylaluminoxane (430mg, in toluene, 30wt%) is mixed with toluene (10ml).Under stiring at RT to (1,3- dimethylbiphenyl [e] indenyl) (CpMe is added in this solution₅)ZrMe₂(17mg) continues 30min.Add fluorinated two Silica, simultaneously reaction mixture is stirred for 2 hours by F-Si, 40 (1g).Whole volatile matters are removed in a vacuum until the stream that gains freedom Dynamic solid.

(1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂-F-Si

Methylaluminoxane (430mg, in toluene, 30wt%) is mixed with toluene (10ml).Under stiring at RT to (1,3- dimethylbiphenyl [e] indenyl) (CpMe is added in this solution₄)ZrMe₂(18mg) continues 30min.Add fluorinated two Silica, simultaneously reaction mixture is stirred for 2 hours by F-Si, 40 (1g).Whole volatile matters are removed in a vacuum until the stream that gains freedom Dynamic solid.

(CpPr)₂HfMe₂-F-Si

Methylaluminoxane (2.2g, in toluene, 30wt%) is mixed with toluene (20ml).Under stiring to this at RT (CpPr) is added in one solution₂HfMe₂(80mg) continues 30min.Fluorinated silica is added, F-Si, 40 (5g) are simultaneously stirred anti- Answer mixture 2 hours.Whole volatile matters are removed in a vacuum until the solid for the flowing that gains freedom.

Activator

The catalyst system of present disclosure can have one or more activators.

After having synthesized above-mentioned complex compound, can by they are combined in any suitable manner with activator with Catalyst system is formed, including is used for slurry or gas-phase polymerization by loading them.Catalyst system can also be added to or produce It is born in polymerisation in solution or bulk polymerization (in monomer).Catalyst system generally comprises above-mentioned complex compound and activator such as aikyiaiurnirsoxan beta Or non-coordinating anion.

Can by by metallic catalyst constituents and activator and carrier (typically silica) by what is be known from literature that Any mode is combined to form load type catalyst system.Activator is defined as can be by the way that neutral metal compound to be converted to Catalytically-active metals compound cation and activate any compound any in above-mentioned catalyst compounds.It is unrestricted Activator is for example including aikyiaiurnirsoxan beta, alkyl aluminum, Ionizing activators (it can be neutral or ionic) and general type Co-catalyst.Preferred activator generally includes aluminium alkoxide compound, modified aluminium alkoxide compound and ionizing-anion Precursor compound, their abstraction reactions, σ-key metal ligand generate metal compound cation and provide balancing charge Noncoordinating or Weakly coordinating anions, such as non-coordinating anion.

Alumoxane activator

Alumoxane activator is used as the activator in catalyst system described herein.Aikyiaiurnirsoxan beta is usually containing-Al (R¹)- The oligomer compounds of O- subelement, wherein R¹It is alkyl.The example of aikyiaiurnirsoxan beta includes methylaluminoxane (MAO), modified methyl Aikyiaiurnirsoxan beta (MMAO), ethylaluminoxane and isobutyl aluminium alkoxide.Alkylaluminoxane and modified alkylaluminoxanes are properly as catalysis Agent activator, especially when seizable ligand is alkyl, halogen, alkoxy or amino.Different aikyiaiurnirsoxan betas can also be used With the mixture of modified alumoxane.It can it is preferable to use visually-clear methylaluminoxane.It can filter muddy or gelling Aikyiaiurnirsoxan beta is to prepare clear solution or can decant clarification aikyiaiurnirsoxan beta from the turbid solution.Useful aikyiaiurnirsoxan beta is United States Patent (USP) Modified methylaluminoxane (MMAO) co-catalyst 3A type that number US 5,041,584 is covered (from Akzo Chemicals, Inc. with Commercially available from trade name modified methylaluminoxane 3A type).

When activator is aikyiaiurnirsoxan beta (modified or unmodified), some embodiment selections are relative to catalyst compounds The maximum activation dosage of (each metal catalytic site) typically to be up to 5000 times of molar excess (Al/M).Minimum activator It is 1:1 molar ratio with catalyst compounds.Alternative preferred scope includes 1:1-500:1 perhaps 1:1-200:1 or 1:1- 100:1 or 1:1-50:1.

It is almost no or no in polymerization described here to use alumina in an optional embodiment Alkane.It is preferred that aikyiaiurnirsoxan beta exists by 0mol% or aikyiaiurnirsoxan beta presses and is less than 500:1, preferably smaller than 300:1, preferably smaller than 100:1, Preferably smaller than the aluminium of 1:1 and catalyst compounds transition metal mole ratio exist.

Ionization/non-coordinating anion activator

Term " non-coordinating anion " (NCA) refer to be unworthy of be located at it is described cation or be only weakly coordinated in it is described sun from Son, to keep the anion to be replaced by neutral Lewis base unstable enough." compatibility " non-coordinating anion is originally The complex compound that beginning is formed is non-degradable for those of neutrality when decomposing.In addition, the anion is not by anion substituent or segment It is transferred to cation, it is made to form neutral transition metal compound and the neutral by-product from the anion.It can be according to this Inventing the non-coordinating anion that uses is those of following anion: they be it is compatible, by the meaning of its charge balancing ion Stablize transition-metal cation in justice+1, keeps enough unstability still to allow to be replaced in the course of the polymerization process.Here Useful Ionizing activators typically comprise NCA, especially compatible NCA.

Within the scope of the invention using neutral or ionic Ionizing activators, such as four (pentafluorophenyl group) boric acid three (normal-butyl) ammonium, three perfluorophenyl boron metalloid precursors or three perfluoronapthyl boron metalloid precursors, more miscellaneous borane anions of halogenation (WO 98/43983), boric acid (US5,942,459) or their combination.Neutral or ion activation agent or and alumina is used alone Alkane or modified alumoxane activators are used in combination also within the scope of the present invention.

Description for useful activator refers to US 8,658,556 and US 6,211,105.

Preferred activator includes four (perfluoronapthyl) boric acid N, N- dimethyl puratized agricultural sprays, four (perfluorinated biphenyl) boric acid N, N- Dimethyl puratized agricultural spray, four (perfluorophenyl) boric acid N, N- dimethyl puratized agricultural sprays, four (3,5- bis- (trifluoromethyl) phenyl) boric acid N, N- bis- Methyl puratized agricultural spray, four (perfluoronapthyl) boratesFour (perfluorinated biphenyl) boratesFour (3,5- is bis- (trifluoromethyl) phenyl) borateFour (perfluorophenyl) borates[Me3NH+][B(C6F5) 4-]；1- (4- (three (pentafluorophenyl group) boric acid) -2,3,5,6- tetrafluoro phenyl) pyrrolidinesWith four (pentafluorophenyl group) borates, 4- (three (pentafluorophenyl group) boric acid) -2,3,5,6- ptfe pyridine.

In a preferred embodiment, activator includes triaryl carbon(such as tetraphenylboronic acid triphenylcarbeniumFour (pentafluorophenyl group) boratesFour (2,3,4,6- tetrafluoro phenyl) boratesFour (perfluor naphthalenes Base) borateFour (perfluorinated biphenyl) boratesFour (bis- (trifluoromethyl) phenyl of 3,5-) boric acid Triphenylcarbenium)。

In another embodiment, activator includes one of following substance or a variety of: four (pentafluorophenyl group) boric acid Trialkyl ammonium, four (pentafluorophenyl group) boric acid N, N- dialkyl group puratized agricultural sprays, four (pentafluorophenyl group) boric acid N, N- dimethyl-(2,4,6- tri- Methyl puratized agricultural spray), four (2,3,4,6- tetrafluoro phenyl) boric ammoniums, four (2,3,4,6- tetrafluoro phenyl) boric acid N, N- dialkyl group Puratized agricultural spray, four (perfluoronapthyl) boric ammoniums, four (perfluoronapthyl) boric acid N, N- dialkyl group puratized agricultural sprays, four (perfluorinated biphenyl) boron Sour trialkyl ammonium, four (perfluorinated biphenyl) boric acid N, N- dialkyl group puratized agricultural sprays, four (bis- (trifluoromethyl) phenyl of 3,5-) boric acid, three alkane Base ammonium, four (bis- (trifluoromethyl) phenyl of 3,5-) boric acid N, N- dialkyl group puratized agricultural sprays, four (bis- (trifluoromethyl) phenyl of 3,5-) boric acid N, N- dialkyl group-(2,4,6- trimethyl puratized agricultural spray), four (pentafluorophenyl group) boric acid two (isopropyl) ammoniums, (wherein alkyl is methyl, second Base, propyl, normal-butyl, sec-butyl or tert-butyl).

In one embodiment, activator is indicated by following formula:

(Z)_d ⁺(A^d-)

Wherein Z is (L-H) or reducible lewis acid, and L is neutral Lewis base；H is hydrogen；(L-H)+it is cloth Lanace platform Moral acid；A^d-It is the non-coordinating anion with charge d-；It is the integer of 1-3 with d, preferably Z is (Ar3C+), and wherein Ar is aryl Or substitution has heteroatomic aryl, C₁-C₄₀Alkyl or substituted C₁-C₄₀Alkyl.

Typical the ratio between activator and catalyst, such as the ratio between all NCA activators and catalyst are molar ratios about 1: 1.Alternative preferred scope includes 0.1:1-100:1 perhaps 0.5:1-200:1 perhaps 1:1-500:1 or 1:1-1000:1. The range being particularly useful is 0.5:1-10:1, preferably 1:1-5:1.

Catalyst compounds can be in conjunction with the combination of aikyiaiurnirsoxan beta and NCA also scope of the present disclosure interior (referring to example Such as, 5,153,157 US；US 5,453,410；EP 0 573 120 B1；WO 94/07928；With WO 95/14044 (they Disclosure full text is incorporated by reference herein), they, which are discussed, is used in combination aikyiaiurnirsoxan beta with Ionizing activators.

Non-essential scavenger or conactivator

Other than these activator compounds, the catalyst system of present disclosure may include scavenger or co-activating Agent.Scavenger or conactivator include alkyl aluminum or organo-aluminum compound, for example, trimethyl aluminium, triethyl aluminum, triisobutyl Aluminium, three-n-hexyl aluminium, three-octyl aluminums, diethyl zinc and diisobutylaluminium hydride (DIBAL-H).

Carrier material

In at least one embodiment, catalyst system includes inert support material.Carrier material can be porous load Body material, for example, talcum and inorganic oxide.Other carrier materials include zeolite, clay, organic clay or any other have Machine or inorganic carrier material etc. or their mixture.

In at least one embodiment, carrier material is the inorganic oxide of form fine crushing.Catalyst for this paper Suitable inorganic oxide material in system include the 2nd, 4,13 and 14 family metal oxide such as silica, aluminium oxide and Their mixture.The other inorganic oxides that can be used in combination individually or with silica or aluminium oxide be magnesia, Titanium oxide, zirconium oxide etc..However, it is possible to using other suitable carrier material, for example, functionalised polyolefin fine crushing is for example thin Broken polyethylene.The carrier being particularly useful includes magnesia, titanium oxide, zirconium oxide, montmorillonite, phyllosilicate, zeolite, cunning Stone, clay etc..In addition it is possible to use the combination of these carrier materials, for example, silica-chromium, silica-alumina, two Silica-titania etc..In at least one embodiment, carrier material is selected from Al₂O₃、ZrO₂、SiO₂、SiO₂/Al₂O₂Or it Mixture.The carrier material can be fluorinated.

Phrase " fluorinated support " used herein and " fluorinated support composition " refer to and are contained at least one is inorganic The carrier (hopefully, graininess and porous) of fluorine compounds processing.For example, fluorinated support composition can be silica load Body, wherein a part of silica hydroxyl has used fluorine or fluorochemical to replace.Suitable fluorochemical includes, but not It is limited to, inorganic fluorochemical and/or organic fluoride-containing compound.

It is well-suited for carrier the fluorine compounds of fluorine is provided can be organic or inorganic fluorine compounds and desirably inorganic contain Fluorine compounds.Such inorganic fluorochemical can be any compound containing fluorine atom, as long as its not carbon atoms.Especially It is it is desirable that inorganic fluorochemical selected from the following: NH₄BF₄、(NH₄)₂SiF₆、NH₄PF₆、NH₄F、(NH₄)₂TaF₇、 NH₄NbF₄、(NH₄)₂GeF₆、(NH₄)₂SmF₆、(NH₄)₂TiF₆、(NH₄)₂ZrF₆、MoF₆、ReF₆、GaF₃、SO₂ClF、F₂、SiF₄、 SF₆、ClF₃、ClF₅、BrF₅、IF₇、NF₃、HF、BF₃、NHF₂、NH₄HF₂And their combination.In at least one embodiment, Use ammonium hexafluorosilicate and ammonium tetrafluoroborate.

It is preferred that the carrier material, most preferably inorganic oxide have about 10- about 700m²The surface area of/g, about The pore volume and about 500 μm of about 5- of average particle size of 0.1- about 4.0cc/g.In at least one embodiment, it carries The surface area of body material is about 50- about 500m²/ g, pore volume is about 0.5- about 3.5cc/g and average particle size is About 200 μm of about 10-.The surface area of carrier material can be about 100- about 400m²/ g, pore volume are about 0.8- About 3.0cc/g, average particle size are about 100 μm of about 5-.The average pore size of carrier material can be about 10- aboutSuch as about 50- is aboutSuch as about 75- is aboutIn at least one embodiment, carrier Material is high surface area, unbodied silica (surface area=300m²/gm；Pore volume is 1.65cm³/gm).Titanium dioxide The non-limiting example of silicon is by Davison Chemical Division of W.R.Grace and Company with trade name Claim DAVISON 952, DAVISON 948 or DAVISON 955, by Sasol with product name Siral-40 and by PQ Corporation is with product name ES-757 sale.

Carrier material should be it is dry, i.e., without absorb water.The drying of carrier material can by about 100 DEG C- It heats or is roasted to carry out at about 1000 DEG C, for example, at least about 600 DEG C.When carrier material is silica, by it plus Heat arrives at least 200 DEG C, such as about 200 DEG C-about 850 DEG C, such as about 600 DEG C and keep about 1 minute-about 100 small When, about 12 hours-about 72 hours, or about 24 hours-about 60 hours time.The carrier material being fired should have There are at least some reactive hydroxyls (OH) to prepare the load type catalyst system of present disclosure.Then it is fired described in allowing Carrier material includes at least one, for example, the polymerisation catalyst system of at least one catalyst compounds and activator contacts.

It by the carrier material slurrying with reactive surfaces group (usual hydroxyl) and is allowed resulting in nonpolar solvent Slurry and at least one catalyst compounds, such as the solution contact of one or two kinds of catalyst compounds and activator.Extremely In a few embodiment, the slurry of carrier material is allowed to contact with activator first about 0.5 hour-about 24 hours, such as About 2 hours-about 16 hours, or about 4 hours-about 8 hours time.Then allow catalyst compounds solution with from The carrier of analysis/activator contact.In at least one embodiment, in situ to generate load type catalyst system.At at least one In embodiment, the slurry of carrier material is allowed to contact with catalyst compounds first about 0.5 hour-about 24 hours, such as About 2 hours-about 16 hours, or about 4 hours-about 8 hours time.Then the catalyst compounds (one of load are allowed Kind or it is a variety of) slurry contacted with activator solution.

The mixture of catalyst, activator and carrier can be heated approximately to 0 DEG C-about 70 DEG C, such as about 23 DEG C- About 60 DEG C, such as room temperature.Time of contact can be about 0.5 hour-about 24 hours, such as about 2 hours-about 16 small When, or about 4 hours-about 8 hours.

Suitable nonpolar solvent is that wherein all reactants used herein above, i.e. activator and catalyst compounds are Material that is at least partially soluble and being at the reaction temperatures liquid.The non-limiting example of nonpolar solvent is alkane, such as different Pentane, hexane, normal heptane, octane, nonane and decane, cycloalkane, such as hexamethylene, aromatic compounds, such as benzene, toluene and second Base benzene.

Polymerization

The embodiment of present disclosure includes polymerization, wherein making monomer (such as ethylene or propylene) and inessential Ground, comonomer are contacted with the catalyst system comprising at least one catalyst compounds and activator (as described above).It can be with At least one catalyst compounds and activator are combined in any order, and are usually combined before being contacted with monomer.

Here useful monomer includes substituted or unsubstituted C₂-C₄₀Alkene, preferably C₂-C₂₀Alpha-olefin, preferably C₂-C₁₂α- Alkene, optimal ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene and they Isomers.In a preferred embodiment, alkene include be propylene and one or more non-essential comonomers Monomer, the comonomer include one or more ethylene or C₄-C₄₀Alkene, preferably C₄-C₂₀Alkene or preferred C₆-C₁₂Alkene. C₄-C₄₀Olefinic monomer can be linear, branching or cricoid.C₄-C₄₀Cyclic olefin can be strain (strained) or not answer Become (unstrained), monocycle or polycyclic, and can optionally include one or more hetero atoms and/or one or more A functional group.In another preferred embodiment, alkene includes the monomer for being ethylene and non-essential comonomer, described Comonomer includes C₃-C₄₀Alkene, preferably C₄-C₂₀Alkene or preferred C₆-C₁₂One of alkene is a variety of.The C₃-C₄₀Alkene Hydrocarbon monomer can be linearly branching or cricoid.The C₃-C₄₀Cyclic olefin can be strain or unstrained, monocycle or more Ring, and may include hetero atom and/or one or more functional groups.

Illustrative C₂-C₄₀Olefinic monomer and non-essential comonomer include ethylene, propylene, butylene, amylene, hexene, Heptene, octene, nonene, decene, endecatylene, dodecylene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, Cycloheptene, cyclo-octene, cyclo-octadiene, cyclododecene, 7- oxanorbornene, 7- oxanorbornadiene, its derivative replaced Object and its isomers, preferably hexene, heptene, octene, nonene, decene, dodecylene, cyclo-octene, 1,5- cyclo-octadiene, 1- hydroxyl Base -4- cyclo-octene, 1- acetoxyl group -4- cyclo-octene, 5- methyl cyclopentene, cyclopentene, dicyclopentadiene, norbornene, drop ice The substitutive derivative of piece diene and they, preferably norbornene, norbornadiene and dicyclopentadiene.

In at least one embodiment, one or more diene press up to about 10wt%, such as about 0.00001- About 1.0wt%, such as about 0.002- about 0.5wt%, for example, about 0.003- about 0.2wt% be present in it is made here In standby polymer, the total weight based on the composition.It at least one embodiment, will about 500ppm or less Diene is added in polymerization, such as about 400ppm or less, such as about 300ppm or less.In at least one embodiment In, at least about diene of 50ppm is added in polymerization, or about 100ppm or more or 150ppm or more.

Diene monomers include any hydrocarbon structure at least two unsaturated bonds, preferably C₄-C₃₀, wherein the unsaturation At least two in key are easy to introduce polymer by stereospecificity or non-cubic specific catalyst (one or more) In.It may further be preferable that diene monomers are selected from α, ω-diene monomers (i.e. di-vinyl monomers).In at least one embodiment party In case, diene monomers are linear di-vinyl monomers, for example, containing those of 4-30 carbon atom.The non-limiting example of diene Including butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, ten Three carbon diene, 14 carbon diene, pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, two Ten carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two pentadecane diene, two 16 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, especially preferred diene packet Include 1,6- heptadiene, 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, 11 carbon diene of 1,10-, 12 carbon two of 1,11- Alkene, 1,12- oleatridecadiene, 14 carbon diene of 1,13- and low molecular weight polybutadiene (Mw is less than 1000g/mol).Ring-type two The non-limiting example of alkene includes cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinyl Base benzene, dicyclopentadiene or containing more advanced ring in each ring position with and without the diene of substituent group.

In at least one embodiment, when butylene is comonomer, butylene source can be various different comprising butylene The mixed butene stream of structure body.It is expected that the 1- butene monomers are preferentially consumed compared with other butene monomers by polymerization. The use of such mixed butene stream will provide economic benefit, because these mixture flows are usually the waste streams of refining process, Such as C₄Raffinate stream, and therefore can be than pure 1- butylene considerably cheaper.

The polymerization of present disclosure can be carried out by any suitable mode as known in the art.This can be used Known any suspension, homogeneous, ontology, solution, slurry or gas phase polymerization process in field.These methods can be by interval, half Intermittently or serially mode operation.Homogeneous polymerization method and slurry process are preferred.(homogeneous polymerization method is preferably wherein product At least about 90wt% method that dissolves in reaction medium).Particularly preferred ontology homogeneous process.(bulk process is preferably it Monomer concentration in all chargings of middle reactor is 70vol% or higher method.) alternatively, solvent or diluent are not present In or make an addition in reaction medium (in addition to be used as catalyst system or other additives carrier it is a small amount of, or usually and monomer The amount coexisted, such as the propane in propylene).In another embodiment, the method is slurry process.It is used herein Term " slurry phase polymerisation process " refer to and wherein make monomer using loaded catalyst and on the supported catalyst particle The polymerization of polymerization.At least 95wt% of polymer product from loaded catalyst is that solid particle is (insoluble in pelletized form Solution is in diluent).

Suitable diluent/solvent for polymerization includes noncoordinating inert fluid.Non-limiting example include it is linear and Branched hydrocarbon such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, 12 carbon alkane and their mixing Object；Cyclic annular and alicyclic such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and their mixture such as business Present on those (Isopar^TM)；For example perfluorinated C of perhalogenation hydrocarbon₄-C₁₀Alkane, chlorobenzene and aromatics and alkyl-substituted aromatics Compound such as benzene, toluene, mesitylene and dimethylbenzene.Suitable solvent further includes the liquid that can serve as monomer or comonomer State alkene, including but not limited to ethylene, propylene, 1- butylene, 1- hexene, 1- amylene, 3- Methyl-1-pentene, 4- methyl-1-pentene Alkene, 1- octene, 1- decene and its mixture.In a preferred embodiment, aliphatic hydrocarbon solvent is used as solvent, such as isobutyl Alkane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, 12 carbon alkane or their mixture；Cyclic annular or alicyclic ring Hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane or their mixture.In another embodiment, Solvent is not arsol, and aromatic compounds presses and is less than about 1wt%, such as less than about 0.5wt%, such as about 0wt% is present in solvent, solvent-based weight.

In at least one embodiment, the input concentration for the monomer of polymerization and comonomer is about 60vol% Solvent is lower, preferably approximately 40vol% or lower, preferably approximately 20vol% or lower, the total volume based on feed steam. It is preferred that polymerization is run with bulk process.

Preferred polymerization can be run under any temperature and/or pressure for being suitable for obtaining required polyolefin.Typically Temperature and/or pressure include about 0 DEG C-about 300 DEG C, such as about 20 DEG C-about 200 DEG C, such as about 35 DEG C-about 150 DEG C, such as about 40 DEG C-about 120 DEG C, such as about 45 DEG C-about 80 DEG C of temperature；About 0.35MPa- is about 10MPa, such as about 0.45MPa- about 6MPa, or the pressure of preferably approximately 0.5MPa- about 4MPa.

In typical polymerization, the duration of runs of reaction is up to about 300 minutes, such as about 5- about 250 minutes, Such as about 10- about 120 minutes.

In at least one embodiment, hydrogen presses about 0.001-50psig (0.007-345kPa), such as about 0.01- about 25psig (0.07-172kPa), such as the partial pressure of about 0.1-10psig (0.7-70kPa) are present in polymerization instead It answers in device.

Gas-phase polymerization

In the useful embodiment, catalyst system described herein is used for gas-phase polymerization.In general, for making In the gas fluidized bed process of standby polymer, make the gaseous stream caltalyst described here comprising one or more monomers Fluidized bed is continuously circulated through under reactive conditions in the presence of system.The gaseous stream is discharged from the fluidized bed and again It is recycled back to the reactor.Meanwhile polymer product being discharged from reactor and adds fresh monomer and substitutes the monomer having polymerize. (see, e.g., United States Patent (USP) 4,543,399；4,588,790；5,028,670；5,317,036；5,352,749；5,405, 922；5,436,304；5,453,471；5,462,999；5,616,661 and 5,668,228；They are all incorporated by reference into full Herein).

Slurry phase polymerisation

In the useful embodiment, catalyst system described herein is used for slurry phase polymerisation.Slurry phase polymerisation process one As it is with the range of about 50 atmospheric pressure (15psi-735psi, 103kPa-5068kPa) of 1- or even more big and 0 DEG C-about 120 DEG C of temperature operation.In slurry polymerization, solid-state, granulated polymer suspension be added to monomer and copolymerization wherein It is formed in the liquid polymerization diluent medium of monomer and catalyst system described here.It will be between the suspension including diluent It has a rest and ground or is continuously removed from reactor, in the reactor, volatile component is separated and recycled with polymer (non-must Strategic point, after the distillation) arrive reactor.Liquid diluent for polymerisation medium is usually the alkane containing 3-7 carbon atom, excellent Choosing is branched alkane.Used medium should be liquid and relatively inert under polymerization conditions.When a propane medium is used, it should The method is operated more than reaction diluent critical-temperature and pressure.It is preferred that using hexane or isobutane medium.

In an optional embodiment, the activity of catalyst system described herein is at least about 50g/mmol/ Hour, such as about 500 or more g/mmol/ hours, such as about 5,000 or more g/mmol/hr, such as about 50,000 Or more g/mmol/hr.In an optional embodiment, the conversion ratio of olefinic monomer is at least about 10%, based on poly- The weight of compound production (weight) and the monomer into reaction zone, such as about 20% or more, such as about 30% or more, Such as about 50% or more, such as about 80% or more.

In at least one embodiment, hardly with or without the use of aikyiaiurnirsoxan beta in the method for preparing polymer.It is excellent Selection of land, aikyiaiurnirsoxan beta are existed by zero mol%.Alternatively, mole of the aikyiaiurnirsoxan beta by aluminium and the transition metal of the catalyst indicated by formula (I) Than being less than about 500:1, it is, for example, less than about 300:1, is, for example, less than about 100:1, be, for example, less than that about 1:1 exists.

In a preferred embodiment, hardly with or without the use of clear in the method for preparing polyolefin composition Except agent.Preferably, scavenger (such as trialkylaluminium) is existed by zero mol%.Alternatively, scavenger is by scavenger metal and by formula (I) molar ratio of the transition metal of the catalyst indicated is less than about 100:1, is, for example, less than about 50:1, is, for example, less than about 15:1 is, for example, less than that about 10:1 exists.

In a preferred embodiment, polymerize: 1) 0-300 DEG C (preferably 25-150 DEG C, preferably 40-120 DEG C, it is excellent Select 45-80 DEG C) at a temperature of carry out；2) atmosphere be depressed into 10MPa (preferably 0.35-10MPa, preferably 0.45-6MPa, preferably It is carried out under pressure 0.5-4MPa)；3) aliphatic hydrocarbon solvent (such as iso-butane, butane, pentane, isopentane, hexane, isohexane, Heptane, octane, 12 carbon alkane or their mixture；Cyclic annular or alicyclic, such as hexamethylene, cycloheptane, hexahydrotoluene, first Basic ring heptane or their mixture；Aromatic compounds, which is pressed, preferably wherein is less than 1wt%, and preferably less than 0.5wt% is preferably pressed 0wt% is present in solvent, solvent-based weight) in carry out；4) wherein catalyst system used in polymerization includes to be less than 0.5mol% aikyiaiurnirsoxan beta, preferably 0mol% aikyiaiurnirsoxan beta.Alternatively, transition gold of the aikyiaiurnirsoxan beta by aluminium and the catalyst indicated by formula (I) The molar ratio of category is less than 500:1, and preferably smaller than 300:1, preferably smaller than 100:1, preferably smaller than 1:1 exist；5) polymerization preferably exists Occur in one reaction zone；6) productivity of catalyst system is at least 80,000g/mmol/hr (preferably at least 150,000g/ Mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000g/mmol/hr, preferably at least 300,000g/ mmol/hr)；7) optionally, there is no (for example, existing by zero mol% for scavenger (such as trialkyl aluminium compound).Alternatively, Scavenger is less than 100:1, preferably smaller than 50:1, preferably smaller than 15:1 by the molar ratio of scavenger metal and transition metal, preferably Less than 10:1 presence)；With 8) optionally, hydrogen presses 0.001-50psig (0.007-345kPa) (preferably 0.01-25psig (0.07-172kPa), more preferable 0.1-10psig (0.7-70kPa)) partial pressure be present in polymer reactor.Preferably at one Embodiment in, for the catalyst system in polymerizeing include at most a kind of catalyst compounds." reaction zone ", also referred to as " polymeric area " is the container for wherein polymerizeing generation, such as batch reactor.When multiple reactors are with the configuration of serial or parallel connection In use, each reactor is regarded as individual polymeric area.For in both batch reactor and flow reactor Multistage polymerization, each polymerization stage is regarded as individual polymeric area.In a preferred embodiment, it is aggregated in Occur in one reaction zone.Room temperature is about 23 DEG C, unless otherwise mentioned.

Other additives can also according to requiring for polymerizeing, such as one or more scavengers, promotor, modifying agent, Chain-transferring agent (such as diethyl zinc), reducing agent, oxidant, hydrogen, alkyl aluminum or silane.

Chain-transferring agent can be alkylaluminoxane, i.e., by formula AlR₃The compound of expression, ZnR₂(wherein each R is independently C₁-C₈Aliphatic group, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl or their isomers) or they Combination, such as diethyl zinc, methylaluminoxane, trimethyl aluminium, triisobutyl aluminium, trioctylaluminum or their combination.

Polyolefin product

Present disclosure further relates to the poly- of catalyst compounds by being indicated by formula (I) and method described herein preparation Compositions of olefines, such as resin.

In at least one embodiment, the method includes using the catalyst compounds preparation tool indicated by formula (I) Have and be greater than about 1, is greater than about 2, is greater than about 3, be greater than the Noblen or third of about 4 Mw/Mn Alkene copolymer, such as propylene-ethylene and/or propylene-alpha-olefin (preferably C₃-C₂₀) copolymer (for example, butene-hexene copolymer or Propylene-octene Copolymer).

In at least one embodiment, the method includes using the catalyst compounds indicated by formula (I) to prepare alkene Hydrocarbon polymer, preferably polyethylene and polypropylene homopolymer and copolymer.In one embodiment, the polymer prepared here is The homopolymer of ethylene preferably contains the about 0-25 moles one or more C of %₃-C₂₀Olefin comonomer (such as about 0.5-20 Mole %, such as about 15 moles of % of about 1-, such as about 10 moles of % of about 3-) ethylene copolymer.Olefin-copolymerization list Body can be C₃-C₁₂One of alpha-olefin, such as propylene, butylene, hexene, octene, decene, dodecylene are a variety of, preferably Propylene, butylene, hexene, octene.In one embodiment, the polymer prepared here is propylene copolymer, can be contained big (such as about 0.5-20 moles %, such as about 15 moles of % of about 1-, such as about 3- about 10 rub by about 0-25 moles % You are %) C₂Or C₄-C₂₀One of olefin comonomer is a variety of.Olefinic monomer can be ethylene or C₄-C₁₂Alpha-olefin, such as One of ethylene, butylene, hexene, octene, decene, dodecylene are a variety of, optimal ethylene, butylene, hexene, octene.

In a preferred embodiment, monomer is ethylene and comonomer is hexene, and preferably approximately 1- about 15 rubs That % hexene, such as about 10 moles of % of about 1-.

Here the polymer prepared can have about 5,000- about 1,000,000g/mol (such as about 25,000- About 750,000g/mol, such as about 50,000- about 500,000g/mol) Mw, and/or about 1- about 40 (such as About 1.2- about 20, such as about 1.3- about 10, such as about 1.4- about 5, such as about 1.5- about 4, such as greatly The Mw/Mn of about 1.5- about 3).

In a preferred embodiment, the polymer prepared here has to be measured by gel permeation chromatography (GPC) Unimodal or multimodal state molecular weight distribution.It is so-called it is " unimodal " refer to GPC trace have a peak or inflection point.So-called " multimodal " Refer to that GPC trace has at least two peaks or inflection point.Inflection point be wherein curve quadratic derivative symbols change where point (such as By bearing just, or vice versa).

In a preferred embodiment, the polymer prepared here has 0.90 or higher or 0.95 or higher, Or 0.98 or higher branch index (g').

Unless otherwise indicated, Mw, Mn, branch index (g') and MWD pass through the 24-25 pages of US 200,6/0,173,123 the [0334] measurement of GPC described in-[0341] section and references cited therein, and measured using polyethylene standard sample.

In a preferred embodiment, the polymer prepared here has 50% or bigger, preferably 60% or bigger, It is preferred that 70% or bigger composition Distribution Breadth Index (CDBI).CDBI is the amount of composition distribution of the monomer in polymer chain Degree, and PCT Publication WO 93/03093, especially the 7th and 8 columns as disclosed on 2 18th, 1993 and Wild etc. J.Poly.Sci., Poly.Phys.Ed., Vol.20, the p.441 measurement of program described in (1982) and US 5,008,204, packet It includes and ignores the fraction with the weight average molecular weight (Mw) less than 15,000 when measuring CDBI.

Blend

In at least one embodiment, by the polymer prepared here (such as polyethylene or polypropylene) formed film, Before molded parts or other products in conjunction with one or more additional polymer.Other useful polymer include poly- second Alkene, isotactic polypropylene, height isotactic polypropylene, syndiotactic polypropylenes, propylene and ethylene and/or butylene and/or The random copolymer of hexene, polybutene, ethane-acetic acid ethyenyl ester, LDPE, LLDPE, HDPE, ethane-acetic acid ethyenyl ester, ethylene Methyl acrylate, the copolymer of acrylic acid, polymethyl methacrylate or can be polymerize by high-pressure free radical method it is any its Its polymer, polyvinyl chloride, PB Polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR) vulcanize EPR, EPDM, block copolymer, styrene block copolymers, polyamide, polycarbonate, PET resin, the polyethylene of crosslinking, ethylene With the copolymer of vinyl alcohol (EVOH), the polymer of aromatic monomer such as polystyrene, poly- 1 ester, polyacetals gathers inclined difluoro second Alkene, polyethylene glycol and/or polyisobutene.

In at least one embodiment, polymer (such as polyethylene or polypropylene) presses about 10- about 99wt%, example Such as about 20- about 95wt%, such as about 30- about 90wt%, such as about 40- about 90wt%, such as about 50- is big About 90wt%, such as about 60- about 90wt%, such as about 70- about 90wt% are present in blends described above, are based on institute State the weight of total polymer in blend.

The blend of present disclosure can be prepared as follows: by the polymer of present disclosure and one or more polymer Mixing (as described above), reactor is connected in series to prepare reactor blend or use in the same reactor More than one catalyst is to prepare multiple polymer substance.Can before putting into extruder by mixed with polymers together or can To mix in an extruder.

Conventional equipment can be used in the blend of present disclosure and method is formed, such as by each component, such as polymer Dry blend and then melt mixed in a mixer, or by component directly mixing machine such as Banbury mixer, It is mixed in Haake mixing machine, Brabender mixer or single or double screw extruder, may include compounding extrusion Machine and the side arm extruder directly used in polymerization downstream may include at the loading hopper of film extruder by resin Powder or pellet are blended.In addition, as needed, additive may include in the blend, at one or more groups of blend In point, and/or in the product formed by blend, such as in film.Such additives are well known in the art, and be can wrap It includes, such as: filler；Antioxidant is (for example, the IRGANOX that hindered phenolic compound can for example be obtained from Ciba-Geigy^TM 1010 or IRGANOX^TM1076)；Phosphite ester is (for example, the IRGAFOS that can be obtained from Ciba-Geigy^TM168)；It is anti-stick Additive；Tackifier, such as polybutene, terpene resin, aliphatic series and aromatic hydrocarbon resin, alkali metal and stearine and hydrogen Change rosin；UV stabilizer；Heat stabilizer；Anti-blocking agent；Antitack agent；Antistatic agent；Pigment；Colorant；Dyestuff；Wax；Titanium dioxide Silicon；Filler；Talcum；Their mixture etc..

In at least one embodiment, the polyolefin composition for being multimodal polyolefm composition includes low molecular weight fraction And/or high molecular weight block.The low molecular weight fraction can be high density fraction (such as HDPE), preferably exist at least 10wt%, the weight based on the polyolefin.High molecular weight block can be low density fraction (such as LDPE, preferably LLDPE), It is preferred that there is at least 10wt%, the weight based on the polyolefin.In at least one embodiment, the low molecular weight fraction It is to be prepared by the catalyst compounds indicated by formula (I).High molecular weight block can pass through the second catalyst compounds system Standby, second catalyst compounds are the bridging or non-bridging gold in addition to the above-mentioned catalyst compounds indicated by formula (I) Belong to cyclopentadienyl catalyst compound.Low molecular weight fraction can be polypropylene or polyethylene.High molecular weight block can be polypropylene or Polyethylene, such as linear low density polyethylene.

In at least one embodiment, the low molecular weight fraction prepared by the catalyst compounds indicated by formula (I) With low co-monomer content." low co-monomer content " used herein is defined as containing 6wt% or less comonomer Polyolefin, the total weight based on the polyolefin.It can have by high molecular weight block prepared by the second catalyst compounds High comonomer content." high comonomer content " used herein is defined as containing the polyolefin greater than 6wt% comonomer, Total weight based on the polyolefin.

Film

Any of above polymer, such as above-mentioned polyethylene or its blend can be used for various terminals purposes application.These Using including, for example, the blow molding of single or multiple layer, squeezing out and/or shrink film.These films can pass through any suitable extrusion or co-extrusion Technology is formed out, such as blow molding vacuolar membrane processing technology, wherein composition can be extruded through annular die with molten condition, so After expand to be formed and be oriented either uniaxially or biaxially melt, be then cooled into tubulose, blown film then can axially cutting and expansion To form flat membrane.Film can subsequent No yield point, uniaxial orientation or biaxial orientation to identical or different degree.One in film layer It is a or it is multiple can by laterally and/or longitudinally orientation arrive identical or different degree.Typical cold drawing can be used in uniaxial orientation It stretches or hot-drawn stretching method carries out.Tenter apparatus can be used in biaxial orientation or double bubble methods are carried out and can be assembled at each layer Before or after carry out.For example, by polyethylene layer Extrusion Coating or can be laminated on oriented polypropylene layer or can be by poly- second Alkene and polypropylene are coextruded film forming together, are then orientated.Equally, oriented polypropylene can be laminated on oriented polyethylene or be orientated Polyethylene can be coated on polypropylene, then optionally so that the assembly is orientated.Typically, film (MD) presses at most 15, the preferably ratio of 5-7 along longitudinal direction, and transversely (TD) presses at most 15, and the ratio of preferably 7-9 is orientated.However, In another embodiment, film is orientated same degree along the direction MD and TD simultaneously.

Film can change in terms of thickness, this depends on expected application；However, the film of 1-50 μ m thick can be it is suitable 's.The usual thickness of film for being intended for packing is 10-50 μm.The thickness of sealant is typically 0.2-50 μm.In film and Can have sealant or sealant on outer surface can be only present on inner or outer surface.

In another embodiment, one or more layers can pass through sided corona treatment, electron beam irradiation, gamma-rays spoke It penetrates, flame treatment or microwave are modified.In a preferred embodiment, one or two of superficial layer passes through at corona Reason is modified.

Embodiment

Can hereinafter referred to as be used below: eq. refers to equivalent.

All reaction reagents obtain from Sigma Aldrich (St.Louis, MO) and to use like that when obtaining, unless separately It is described.All solvents are anhydrous.All reactions carry out under inert atmosphere of nitrogen, unless otherwise indicated.All deuterates are molten Agent is obtained from Cambridge Isotopes (Cambridge, MA) and the drying on 3 angstroms of molecular sieves before the use.

Underneath with SMAO be according to being described above " for ES^TMThe preparation of the SMAO of 757 silica " preparation.

Underneath with fluorinated silica F-Si according to be described above " fluorinated support type catalyst " preparation.

Following characterization product:

1H NMR

Unless otherwise indicated, it uses at room temperature in 5mm probe with 400 or 500MHz's¹The Bruker of H frequency operation Or Varian NMR spectrograph collects nonpolymer compound¹H NMR data.Using 30 ° of flip angle RF pulses, 8 are scanned, Between pulse there is delay in 5 seconds to record data.The chemical combination in the suitable deuterated solvents of about 1mL is dissolved in using about 5-10mg Object prepares sample, as listing in EXPERIMENTAL EXAMPLE.Respectively for D5- benzene, chloroform, D- methylene chloride, D-1,1,2,2- tetra- Chloroethanes and C₆D₅CD₂H with 7.15,7.24,5.32,5.98 and 2.10 by sample referring to solvent residual protium.Unless otherwise saying Bright, use is prepared by about 20mg polymer and 1mL solvent at 120 DEG C on Varian NMR spectrograph in 5mm probe D₂The NMR spectrum data of -1,1,2,2- tetrachloroethanes solution record polymer.Unless otherwise indicated, using 30 ° of flip angle RF Pulse, 120 scan, and between pulse there is delay in 5 seconds to record data.

High throughput-polymerization:

Solvent, polymer grade toluene and isohexane by ExxonMobil Chemical Company supply and before the use Thoroughly dry and degassing.Use the polymer grade ethylene (H containing 300ppm supplied by Air Liquide₂Ethylene conventional slot) And purify further below: allow it to pass through a series of columns: 500cc derives from the Oxyclear cylinder of Labclear (Oakland, CA) Body, then 500cc is filled with the drying bought from Aldrich Chemical CompanyThe column and 500cc of molecular sieve are filled out Filled with the drying bought from Aldrich Chemical CompanyThe column of molecular sieve.TnOAl (three-octyl aluminums, it is pure Only it is used) as the 2mmol/L solution in toluene.

Reactor description and preparation: in inert atmosphere (N₂) in use equipped with temperature control outer heating device, glass is slotting Enter object (inner volume=22.5mL of reactor), septum inlet, the adjusting supply source of nitrogen, ethylene and hexene is simultaneously equipped with once The autoclave of the PEEK mechanical agitator (800RPM) of property is polymerize.Prepare high pressure by being purged before the use with dry nitrogen Kettle.

Differential scanning calorimetry (DSC) measurement is carried out on TA-Q200 instrument to measure the fusing point of polymer.At 220 DEG C It is lower by sample preannealing 15 minutes (nitrogen purging), then allow to be cooled to ambient temperature overnight.Then with 100 DEG C/min of rate Sample is heated to 220 DEG C, it is then cooling with 50 DEG C/min of rate.Fusing point (second melting) is collected during the heating phase.

Ethylene/1- hervene copolymer

Prepare reactor as described above, is then purged with ethylene.At room temperature and atmospheric pressure via injection addition isohexane and 1- hexene.Then so that reactor is reached technological temperature (85 DEG C) and be packed into ethylene to operation pressure (130psig=896kPa), together When stirred with 800RPM.By 450 microlitres of load type catalyst systems (as above in " synthesis of the loaded catalyst " preparation) Put into hexene containing aequum (150 microlitres) at a temperature of reactor in.During polymerization allow ethylene enter (by using Computer-controlled solenoid valve) autoclave to be to maintain reactor gauge pressure (+/- 2psig).Monitoring temperature of reactor is simultaneously usually maintained in In +/- 1 DEG C.By adding about 300ppm CO₂It keeps stopping polymerization into autoclave.Added pre- Determine after the ethylene of cumulant or quenches polymerization after keeping 45 minutes maximum polymerization times.By reactor cooling and it is vented.True The aerial solvent that removes isolates polymer later.Data report is in figs. 1-6.Activity is reported as g/g'hr=grams in the drawing Polymer/gram loaded catalyst/hour.

Fig. 1 is the drawing 100 of the hexene concentration (mol/L) in the opposite charging of activity, based on total monomer concentration in charging.Such as Shown in Fig. 1, in SMAO supported catalyst compound (1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂(star) mentions The activity of about 3,800g/g'hr for the about 1,500g/g'hr under 0mol/L hexene and under about 0.22mol/L hexene. Catalyst compounds (1,3- dimethylbiphenyl [e] indenyl) (CpMe on fluorinated support₄)ZrMe₂(triangle) provides 1,900g/g'hr under 0mol/L hexene, under 0.12mol/L hexene about 3,050- about 3,250g/g'hr and The activity of about 1,000g/g'hr under 0.22mol/L hexene.In SMAO supported catalyst compound 1,3- dimethylbiphenyl [e] indenyl (CpMe₄)ZrCl₂(square) is provided about 1,950g/g'hr under 0mol/L hexene, under 0.12mol/L hexene About 2,700g/g'hr, and under about 0.22mol/L hexene about 3,050g/g'hr activity.These catalyst with SMAO supported catalyst compound (CpMe₄)(n-PrCp)ZrCl₂(hexagon), which is compared, has preferably activity.As right Than embodiment, at SMAO supported catalyst compound (1- ethyl-indenyl)₂ZrMe₂(circle) is provided under 0mol/L hexene About 900g/g'hr, about 1, the 000g/g'hr and about 1 under about 0.22mol/L hexene under 0.12mol/L hexene, The activity of 200g/g'hr.

Fig. 2 is the drawing 200 of the hexene concentration (mol/L) in the opposite charging of activity, based on total monomer concentration in charging.Such as Shown in Fig. 2, catalyst compounds (1,3- dimethylbiphenyl [e] the indenyl) (CpMe on fluorinated support₅)ZrMe₂(triangle) mentions For the about 200g/g'hr under 0mol/L hexene, the about 200g/g'hr under 0.12mol/L hexene, in 0.22mol/L hexene Under about 300g/g'hr and under 0.35mol/L hexene about 400g/g'hr activity.In SMAO supported catalyst Close object (1,3- dimethylbiphenyl [e] indenyl) (CpMe₅)ZrMe₂(star) provides the about 400g/g'hr under 0mol/L hexene, About 1,500g/g'hr under 0.12mol/L hexene, about 1, the 800g/g'hr and in 0.35mol/ under 0.22mol/L hexene The activity of about 1,900g/g'hr under L hexene.These catalyst respectively provide and in SMAO supported catalyst compounds (n-PrCp)₂HfMe₂(diamond shape) compares higher activity.Embodiment as a comparison, (3- n-propyl Cp) on fluorinated support₂HfMe₂(square) provides about 10,000g/g'hr about 8,000- under 0mol/L hexene, big under 0.12mol/L hexene About 6,500- about 7,500g/g'hr, under 0.22mol/L hexene about 2,400- about 2,800g/g'hr and The activity of about 2,200g/g'hr under 0.35mol/L hexene.(3- n-propyl Cp) on SMAO carrier₂HfMe₂(hexagon) It provides about 7,800g/g'hr under 0mol/L hexene, about 7,700g/g'hr under 0.12mol/L hexene, in 0.22mol/ About 7,700g/g'hr about 4,200- under L hexene, and about 4,500g/g'hr about 2,000- under 0.35mol/L hexene Activity.At SMAO supported catalyst compound (1- ethyl-indenyl)₂ZrMe₂(circle) provides big under 0mol/L hexene About 900g/g'hr, about 1,000g/g'hr under 0.12mol/L hexene, about 1,200g/g'hr under 0.22mol/L hexene With the activity of the about 1,400g/g'hr under 0.35mol/L hexene.

Fig. 3 is the drawing 300 of the hexene concentration (mol/L) in the opposite charging of fusing point of ethylene-hexene co-polymers product, base The total monomer concentration in charging.As shown in figure 3, the fusing point of the copolymer formed by the catalyst all is urged for tested Reduce for agent system as hexene concentration increases: (1,3- dimethylbiphenyl [e] indenyl) on SMAO carrier (CpMe₄)ZrMe₂(star)；(1,3- dimethylbiphenyl [e] indenyl) (CpMe on fluorinated support₄)ZrMe₂(triangle)； (1- ethyl-indenyl) on SMAO carrier₂ZrMe₂(circle)；With (1,3- dimethylbiphenyl [e] indenyl) on SMAO carrier (CpMe₄)ZrCl₂(square).

Fig. 4 is the drawing 400 of the hexene concentration (mol/L) in the opposite charging of fusing point of ethylene-hexene co-polymers product, base The total monomer concentration in charging.As shown in figure 4, the fusing point of the polymer formed by the catalyst all is urged for tested Reduce for agent system as hexene concentration increases: (1,3- dimethylbiphenyl [e] indenyl) on fluorinated support (CpMe₅)ZrMe₂(triangle)；(1,3- dimethylbiphenyl [e] indenyl) (CpMe on SMAO carrier₅)ZrMe₂(star)； (1- ethyl-indenyl) on SMAO carrier₂ZrMe₂(circle)；(3- n-propyl Cp) on fluorinated support₂HfMe₂It is (square Shape)；With (the 3- n-propyl Cp) on SMAO carrier₂HfMe₂(hexagon).

Fig. 5 is drawing for hexene concentration (mol/L) in the opposite charging of weight average molecular weight Mw of ethylene-hexene co-polymers product Figure 50 0, based on the total monomer concentration in charging.As shown in figure 5, in SMAO supported catalyst compound (1,3- dimethyl Benzo [e] indenyl) (CpMe₄)ZrMe₂(star) provide about 125,000g/mol under 0mol/L hexene, 0.12mol/L oneself Under alkene about 120,000g/mol and under 0.22mol/L hexene about 110,000g/mol MW value.On fluorinated support Catalyst compounds (1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrMe₂(triangle) provides under 0mol/L hexene about 150,000g/mol, about 140, the 000g/mol and about 115 under 0.22mol/L hexene under 0.12mol/L hexene, The MW value of 000g/mol.In SMAO supported catalyst compound (1,3- dimethylbiphenyl [e] indenyl) (CpMe₄)ZrCl₂ (square) is provided about 160,000g/mol under 0mol/L hexene, about 160,000g/mol under 0.12mol/L hexene With the MW value of the about 160,000g/mol under about 0.22mol/L hexene.These catalyst respectively with urging on SMAO carrier Agent compound (CpMe₄)(n-PrCp)ZrCl₂(hexagon) and (n-PrCp) on SMAO carrier₂HfMe₂(diamond shape) is compared Low-molecular weight polymer is provided.In addition, at SMAO supported catalyst compound (1- ethyl-indenyl)₂ZrMe₂(circle) provides About 125,000g/mol under 0mol/L hexene, about 110, the 000g/mol and about under 0.12mol/L hexene The MW value of about 100,000g/mol under 0.22mol/L hexene.

Fig. 6 is the hexene concentration (mol/L) in the opposite charging of number-average molecular weight (Mn) of ethylene-hexene co-polymers product Drawing 600, based on total monomer concentration in charging.As shown in fig. 6, catalyst compounds (1, the 3- dimethyl on fluorinated support Benzo [e] indenyl) (CpMe₅)ZrMe₂(triangle) is provided about 90,000g/mol under 0mol/L hexene, in 0.12mol/L About 95,000g/mol under hexene, under 0.22mol/L hexene about 90,000g/mol and under 0.35mol/L hexene about The Mn value of 90,000g/mol.In SMAO supported catalyst compound (1,3- dimethylbiphenyl [e] indenyl) (CpMe₅) ZrMe₂(star) is provided about 105,000g/mol under 0mol/L hexene, about 110,000g/ under 0.12mol/L hexene Mol, under 0.22mol/L hexene about 100,000g/mol and under 0.35mol/L hexene about 98,000g/mol Mn Value.These catalyst are respectively and in SMAO supported catalyst compound (n-PrCp)₂HfMe₂(diamond shape) has compared to offer The polymer of lower Mn value.In addition, at SMAO supported catalyst compound (1- ethyl-indenyl)₂ZrMe₂(circle) provides About 115,000g/mol under 0mol/L hexene, about 120,000g/mol under 0.12mol/L hexene, 0.22mol/L oneself Under alkene about 95,000g/mol- about 105,000g/mol and under 0.35mol/L hexene about 100,000g/mol Mn Value.(3- n-propyl Cp) on fluorinated support₂HfMe₂(square) is provided about 390,000g/mol under 0mol/L hexene, About 395,000g/mol under 0.12mol/L hexene, under 0.22mol/L hexene about 375,000g/mol and The Mn value of about 375,000g/mol under 0.35mol/L hexene.(3- n-propyl Cp) on SMAO carrier₂HfMe₂(hexagon) It provides about 330,000g/mol under 0mol/L hexene, about 390,000g/mol under 0.12mol/L hexene, About 415,000g/mol about 395,000g/mol- under 0.22mol/L hexene, and about 390 under 0.35mol/L hexene, The Mn value of 000g/mol.

For example, these data are illustrated provides linear low molecular weight by the catalyst that formula (I) is indicated under polymerization conditions Ethene polymers.By formula (I) indicate catalyst can be used for include one or more second catalyst catalyst system, it is described Second catalyst provides less linear, low-density, high molecular polyolefine and corresponding copolymer.These data are indicated by formula (I) catalyst indicated one or more second catalyst can provide less linear, low-density, High molecular weight polyethylene and Linear low molecular weight polyethylene is provided under the essentially similar polymerizing condition of corresponding copolymers and linear low molecular weight polyethylene is total Polymers.In at least one embodiment, such orthogonality (orthogonality) is advantageous, because what is indicated by formula (I) Catalyst does not interfere the polymerization of one of hybrid catalyst system or a variety of second catalyst.Such catalyst system provides tool There are the BOCD composition of improved physical property, such as resin.The BOCD composition can be provided with improved stiffness/tough Property, improved mechanical balance and the film being more easily manufactured.In addition, such catalyst system is for manufacture polyolefin composition and often Manufacturing method is advised compared to offer cost savings.

All documents described herein, including any priority documents and/or test procedure all with the present invention not contradiction All permissions under be incorporated by reference.Although from above-mentioned general introduction and specific embodiment it is readily apparent that having been described above and retouching Some embodiments have been stated, but without departing from the spirit and scope of the disclosure can be with various modification can be adapted.Therefore, It is not intended to present disclosure to be so limited.Similarly, term " include (comprising) " think " include with term (including) " synonymous.Equally, when composition, element or element group are before transitional term " including ", it should manage Solution be also consider with transitional term " substantially by ... form ", " by ... form ", " being selected from " or " being " exist The same combination or element group before composition, element or each element enumerated, vice versa.

Claims (24)

1. the catalyst compounds indicated by following formula (I):

Wherein M is group-4 metal,

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³And R¹⁴Each of be independently hydrogen, or linear or branching C₁-C₅₀Substituted or unsubstituted alkyl, halohydrocarbyl or silylhydrocarbyl, wherein R¹And R³At least one of be not hydrogen, and

Each X is independently halogen or C₁-C₅₀Substituted or unsubstituted alkyl, hydrogen-based, amino, alkoxy, sulfenyl, phosphorus base, halogen Base, diene, amine, phosphine, ether or their combination or two X are bonded together to form becket compound ring or two X engagements To form cheland, diene ligand or alkylidene radical.

2. the catalyst compounds of claim 1, wherein R¹It is linear or branching C₁-C₁₀Substituted or unsubstituted alkyl.

3. the catalyst compounds of claims 1 or 2, wherein R³It is linear or branching C₁-C₁₀Substituted or unsubstituted alkyl.

4. the catalyst compounds of claim 1, wherein R¹And R³Each of be independently linear or branching C₁-C₅It is unsubstituted Alkyl.

5. the catalyst compounds of any one of claim 1-4, wherein each X is independently halogen or C₁-C₁₀Replace or not Substituted alkyl.

6. the catalyst compounds of any one of claim 1-5, wherein R¹⁰It is hydrogen or C₁-C₁₀Substituted or unsubstituted alkyl, Wherein R¹¹、R¹²、R¹³And R¹⁴Each of be independently C₁-C₁₀Substituted or unsubstituted alkyl.

7. the catalyst compounds of claim 1, wherein including one in following substance by the catalyst compounds that formula (I) is indicated Kind is a variety of:

8. catalyst system includes:

(a) catalyst compounds of any one of claim 1-7；

(b) optionally, the bridging in addition to the catalyst compounds indicated by formula (I) or non-bridged metallocene catalyst compounds Object；With

(c) activator.

9. the catalyst system of claim 8, wherein metallocene catalyst compound (b) is by formula: Cp^ACp^BM'X'_nIt indicates Non- bridged metallocene catalyst compounds, wherein each Cp^AAnd Cp^BIndependently selected from cyclopentadienyl ligands, Cp^AAnd Cp^BIn One or both of can contain hetero atom, Cp^AAnd Cp^BOne of or both can be replaced by one or more R " bases, wherein M' select From the 3rd to 12 race's atom and lanthanide atom, wherein X' is anion leaving group, and wherein n is the integer of 0 or 1-4, and wherein R " is selected From alkyl, low alkyl group, substituted alkyl, miscellaneous alkyl, alkenyl, low-grade alkenyl, substituted alkenyl, miscellaneous thiazolinyl, alkynyl, rudimentary alkynes Base, substituted alkynyl, miscellaneous alkynyl, alkoxy, lower alkoxy, aryloxy group, alkyl sulfide, low-grade alkyl sulphur, aryl sulphur, aryl, Substituted aryl, heteroaryl, aralkyl, sub- aralkyl, alkaryl, alkarylene, halogenated alkyl, halogenated alkenyl, halo alkynyl, Miscellaneous alkyl, heterocycle, heteroaryl, containing heteroatom group, alkyl, lower alkyl, substituted alkyl, miscellaneous alkyl, silicyl, first Boryl, phosphino-, phosphine, amino, amine, ether and thioether.

10. the catalyst system of claim 8, wherein metallocene catalyst compound (b) includes one of following substance Or it is a variety of:

Dichloro bis- (n-propyl cyclopentadienyl groups) conjunction hafnium,

Dimethyl bis- (n-propyl cyclopentadienyl groups) conjunction hafnium,

Bis- (n-propyl cyclopentadienyl group) zirconiums of dichloro,

Bis- (n-propyl cyclopentadienyl group) zirconiums of dimethyl,

Dichloro bis- (n-propyl cyclopentadienyl groups) conjunction titanium,

Dimethyl bis- (n-propyl cyclopentadienyl groups) conjunction titanium,

Dichloro (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) zirconium,

Dimethyl (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) zirconium,

Dichloro (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) conjunction hafnium,

Dimethyl (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) conjunction hafnium,

Dichloro (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) conjunction titanium,

Dimethyl (n-propyl cyclopentadienyl group, pentamethylcyclopentadiene base) conjunction titanium,

Dichloro (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) zirconium,

Dimethyl (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) zirconium,

Dichloro (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction hafnium,

Dimethyl (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction hafnium,

Dichloro (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction titanium,

Dimethyl (n-propyl cyclopentadienyl group, tetramethyl-ring pentadienyl) conjunction titanium,

Bis- (cyclopentadienyl group) zirconiums of dichloro,

Dichloro bis- (cyclopentadienyl groups) conjunction titanium,

Dichloro bis- (cyclopentadienyl groups) conjunction hafnium,

Bis- (cyclopentadienyl group) zirconiums of dimethyl,

Dimethyl bis- (cyclopentadienyl groups) conjunction titanium,

Dimethyl bis- (cyclopentadienyl groups) conjunction hafnium,

Dichloro bis- (n-butyl cyclopentadienyls) conjunction hafnium,

Dimethyl bis- (n-butyl cyclopentadienyls) conjunction hafnium,

Bis- (n-butyl cyclopentadienyl) zirconiums of dichloro,

Bis- (n-butyl cyclopentadienyl) zirconiums of dimethyl,

Dichloro bis- (n-butyl cyclopentadienyls) conjunction titanium,

Dimethyl bis- (n-butyl cyclopentadienyls) conjunction titanium,

Dichloro bis- (pentamethylcyclopentadiene bases) conjunction hafnium,

Dimethyl bis- (pentamethylcyclopentadiene bases) conjunction hafnium,

Bis- (pentamethylcyclopentadiene base) zirconiums of dichloro,

Bis- (pentamethylcyclopentadiene base) zirconiums of dimethyl,

Dichloro bis- (pentamethylcyclopentadiene bases) conjunction titanium,

Dimethyl bis- (pentamethylcyclopentadiene bases) conjunction titanium,

Dichloro bis- (1- methyl -3- n-butyl cyclopentadienyls) conjunction hafnium,

Dimethyl bis- (1- methyl -3- n-butyl cyclopentadienyls) conjunction hafnium,

Bis- (1- methyl -3- n-butyl cyclopentadienyl) zirconiums of dichloro,

Bis- (1- methyl -3- n-butyl cyclopentadienyl) zirconiums of dimethyl,

Dichloro bis- (1- methyl -3- n-butyl cyclopentadienyls) closes titanium, and

Dimethyl bis- (1- methyl -3- n-butyl cyclopentadienyls) closes titanium.

11. the catalyst system of claim 8, wherein metallocene catalyst compound (b) is bis- (the n-propyl rings of dimethyl Pentadienyl) close hafnium.

12. the catalyst system of claim 8, wherein metallocene catalyst compound (b) is by formula: Cp^A(A)Cp^BM'X'_n The bridged metallocene catalyst compounds of expression, wherein each Cp^AAnd Cp^BIndependently selected from cyclopentadienyl ligands, Cp^AAnd Cp^B One of or both can contain hetero atom, Cp^AAnd Cp^BOne of or both can be replaced by one or more R " bases, wherein M' Selected from the 3rd to 12 race's atom and lanthanide atom, wherein X' is anion leaving group, and wherein n is the integer of 0 or 1-4, wherein (A) divalent alkyl, bivalent lower alkyl, bivalent substituted alkyl, divalent miscellaneous alkyl, divalent alkenyl, bivalent lower alkenyl, two are selected from Valence substituted alkenyl, divalent miscellaneous thiazolinyl, divalent alkynyl radical, bivalent lower alkynyl, bivalent substituted alkynyl, the miscellaneous alkynyl of divalent, divalent alcoxyl Base, bivalent lower alkoxy, divalent aryloxy group, divalent alkyl sulphur, bivalent lower alkyl sulfide, divalent aryl sulphur, divalent aryl, two Valence substituted aryl, divalent heteroaryl radical, divalent aralkyl, divalent Asia aralkyl, divalent alkaryl, divalent alkylene aryl, divalent halogen Substituted alkyl, divalent halogenated alkenyl, divalent halo alkynyl, divalent miscellaneous alkyl, divalent heterocycle, divalent heteroaryl radical, divalent contain miscellaneous original Subbase group, bivalent hydrocarbon radical, bivalent lower alkyl, bivalent substituted alkyl, divalent miscellaneous alkyl, divalent silicyl, divalent monoborane Base, divalent phosphino-, divalent phosphine, divalent amino, divalent amines, divalent ether, divalent thioether；Wherein R " is selected from alkyl, low alkyl group, takes Alkyl, miscellaneous alkyl, alkenyl, low-grade alkenyl, substituted alkenyl, miscellaneous thiazolinyl, alkynyl, low-grade alkynyl, substituted alkynyl, the miscellaneous alkynes in generation Base, alkoxy, lower alkoxy, aryloxy group, alkyl sulfide, low-grade alkyl sulphur, aryl sulphur, aryl, substituted aryl, heteroaryl, Aralkyl, sub- aralkyl, alkaryl, alkarylene, halogenated alkyl, halogenated alkenyl, halo alkynyl, miscellaneous alkyl, heterocycle, heteroaryl Base, containing heteroatom group, alkyl, lower alkyl, substituted alkyl, miscellaneous alkyl, silicyl, monoborane base, phosphino-, phosphine, ammonia Base, amine, ether and thioether.

13. the catalyst system of claim 9 or 12, wherein Cp^AAnd Cp^BEach of independently selected from: cyclopentadienyl group, N-propyl cyclopentadienyl group, pentamethylcyclopentadiene base, tetramethyl-ring pentadienyl and n-butyl cyclopentadienyl.

14. the catalyst system of any one of claim 8-13 also includes carrier material.

15. the catalyst system of any one of claim 8-14, wherein the activator include one of following substance or It is a variety of:

Four (perfluorophenyl) boric acid N, N- dimethyl puratized agricultural sprays,

Four (perfluoronapthyl) boric acid N, N- dimethyl puratized agricultural sprays,

Four (perfluorinated biphenyl) boric acid N, N- dimethyl puratized agricultural sprays,

Four (bis- (trifluoromethyl) phenyl of 3,5-) boric acid N, N- dimethyl puratized agricultural sprays,

Four (perfluoronapthyl) borates

Four (perfluorinated biphenyl) borates

Four (bis- (trifluoromethyl) phenyl of 3,5-) borates

Four (perfluorophenyl) borates

Four (perfluoronapthyl) boric acid trimethyl ammoniums,

Four (perfluoronapthyl) boric acid triethyl ammoniums,

Four (perfluoronapthyl) boric acid tripropyl ammoniums,

Four (perfluoronapthyl) boric acid three (normal-butyl) ammoniums,

Four (perfluoronapthyl) boric acid three (tert-butyl) ammoniums,

Four (perfluoronapthyl) boric acid N, N- diethyl puratized agricultural sprays,

Four (perfluoronapthyl) boric acid N, N- dimethyl-(2,4,6- trimethyl puratized agricultural spray) and

Four (perfluoronapthyl) boric acid(tropillium)。

16. the catalyst system of any one of claim 8-15, wherein the activator includes aikyiaiurnirsoxan beta.

17. the catalyst system of claim 14,15 or 16, wherein the carrier material is selected from Al₂O₃、ZrO₂、SiO₂Or SiO₂/ Al₂O₂。

18. the catalyst system of any one of claim 14-17, wherein the carrier material is fluorinated.

19. the preparation method of polyolefin composition, the catalysis including making any one of at least one alkene and claim 8-18 The contact of agent system and acquisition polyolefin.

20. the method for claim 19, wherein the polyolefin composition is the multimodal polyolefin group comprising low molecular weight fraction Object is closed, wherein the low molecular weight fraction is prepared by the catalyst compounds indicated by formula (I).

21. the method for claim 19 or 20, wherein the activator includes aikyiaiurnirsoxan beta, non-coordinating anion or their mixing Object.

22. the method for any one of claim 19-21, wherein the method about 0 DEG C-about 300 DEG C at a temperature of, It is carried out under the pressure of about 0.35MPa- about 10MPa and by up to about 300 minutes time.

23. the multimodal polyolefin with low molecular weight fraction of the method preparation by any one of claim 19-22, wherein The low molecular weight fraction is prepared by the catalyst compounds indicated by formula (I).

24. the method for any one of claim 19-23, wherein at least one alkene includes ethylene, propylene, butylene, penta Alkene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene or their mixture.