Catalyst system and method of making and using same

Abstract

This application relates to catalyst systems and methods of making and using the same. Methods of making a catalyst system are provided that include contacting at least one aromatic hydrocarbon, at least one activator, at least one catalyst having a Group 3 to Group 12 metal atom or a lanthanide metal atom, and at least one catalyst support to form a first mixture. The methods include reducing the amount of aromatic hydrocarbon in the first mixture to form a second mixture having 1.5 wt% or less of aromatic hydrocarbon, based on the total weight of the second mixture. The methods can further include adding a saturated hydrocarbon to the second mixture to form a third mixture.

Description

[0001] This application is a divisional application of Chinese patent application No. 201880029087.1, filed on February 28, 2018, entitled "Catalyst System and Preparation and Use Method Thereof".

[0002] Cross-references to related applications

[0003] This application claims the benefit of Provisional Application No. 62 / 475282, filed on March 23, 2017, the disclosure of which is hereby incorporated in its entirety by reference. Technical Field

[0004] This invention relates to catalyst systems for olefin polymerization, methods for preparing said catalyst systems, and methods for polymerizing olefins to produce polyolefin compositions. Background Technology

[0005] Polyolefin polymers have a wide range of commercial applications due to their robust physical properties. For example, various types of polyethylene polymers, including high-density, low-density, and linear low-density polyethylene polymers, are among the most commercially useful. Polyolefin polymers are typically produced using catalysts (one or more) (which are mixed with one or more other components to form a catalyst system) that facilitate the polymerization of olefin monomers in a reactor such as a gas-phase fluidized bed reactor.

[0006] Improvements to the operability of methods for polyolefin formation (e.g., sheeting, fouling, etc.) include modifying the catalyst system by preparing it in different ways. For example, improvements to operability include: combining catalyst system components in a specific order; manipulating the ratios of various catalyst system components; varying the contact time and / or temperature when combining catalyst system components; or simply adding various compounds, such as carboxylic acids or other additives, to the catalyst system. However, such improvements to the operability have resulted in catalyst systems that are increasingly difficult to supply to the reactor. For example, the catalyst system becomes sticky or generates static electricity, thus preventing the catalyst system from flowing continuously and smoothly into the reactor.

[0007] The ability of a catalyst system to flow into a reactor is called flowability, and it can be improved by preparing the catalyst system in the presence of a solvent such as toluene, because toluene generally readily dissolves one or more components used in commercial catalyst systems. For example, toluene typically interacts with the cyclopentadiene ring of a metallocene catalyst to promote dissolution through the interaction of the ring's π orbitals (i.e., π stacking). As a result, toluene is believed to be essential in the preparation of metallocene catalyst systems. Thus, it is commonly used in the preparation of metallocene catalyst systems and also for transferring the catalyst system into the polymerization reactor. However, articles made from polyolefin polymers, such as films, are frequently used as plastic packaging for food, and the presence of non-polyolefin materials in these articles is becoming increasingly subject to stricter controls in various jurisdictions worldwide.

[0008] Therefore, a catalyst system with good flowability to be transferred to the polymerization reactor is needed, which also reduces or eliminates the amount of toluene used in the preparation of the catalyst system. Summary of the Invention

[0009] In one embodiment, the present invention provides a method for preparing a catalyst system comprising contacting at least one aromatic hydrocarbon, such as toluene, at least one activator, at least one catalyst having a group 3 to group 12 metal atom or a lanthanide metal atom, and at least one catalyst support to form a first mixture. The method includes reducing the amount of toluene in the first mixture to form a second mixture having 1.5 wt% or less of aromatic hydrocarbon based on the total weight of the second mixture. The method may further include adding saturated hydrocarbons to the second mixture to form a third mixture.

[0010] In another embodiment, the present invention provides a catalyst system comprising a catalyst having group 3 to group 12 metal atoms or lanthanide metal atoms. The catalyst system further comprises at least one activator, at least one support material, 1.5 wt% or less of aromatic hydrocarbons and saturated hydrocarbons based on the total weight of the catalyst system.

[0011] In yet another embodiment, the present invention provides a method for producing a polyolefin composition by polymerizing olefins, the method comprising contacting at least one olefin with the catalyst system described above.

[0012] Other embodiments of the invention are described and claimed herein, and will be apparent from the following disclosure. Detailed Implementation

[0013] Before disclosing and describing the compounds, components, compositions, and / or methods of the present invention, it should be understood that, unless otherwise indicated, the invention is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, metallocene structures, etc., as these can be varied unless otherwise specified. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0014] This invention relates to catalyst systems for olefin polymerization, methods for producing such catalyst systems, and polyolefins formed from such catalyst systems. Embodiments of the invention include a method for preparing a catalyst system comprising contacting at least one aromatic hydrocarbon, such as toluene, at least one activator, at least one catalyst having Group 3 to Group 12 metal atoms or lanthanide metal atoms, and at least one catalyst support to form a first mixture; reducing the amount of aromatic hydrocarbon to form a second mixture having 1.5 wt% or less of aromatic hydrocarbon based on the total weight of the second mixture; and adding saturated hydrocarbons to the second mixture to form a third mixture, which is the catalyst system of the invention. The catalyst having Group 3 to Group 12 metal atoms or lanthanide metal atoms may be a metallocene catalyst containing a Group 4 metal. Aromatic hydrocarbons include toluene, benzene, o-xylene, m-xylene, p-xylene, naphthalene, anthracene, phenanthrene, and mixtures thereof.

[0015] In at least one embodiment, reducing the amount of aromatics includes applying heat to the first and / or second mixture at a temperature of about 70°C or lower, such as about 60°C, 50°C, or 40°C or lower. After reducing the amount of aromatics, the second mixture may have 0.5 wt% or less of aromatics based on the total weight of the second mixture, for example, about 0 wt% based on the total weight of the second mixture.

[0016] Embodiments of the present invention also include a catalyst system comprising a Group 4 metal catalyst selected from metallocene catalysts or bis(phenolate) catalysts. The catalyst system may further comprise at least one activator, at least one support material, at least one saturated hydrocarbon, and 1.5 wt% or less of an aromatic hydrocarbon, based on the total weight of the catalyst system. The activator of the catalyst system may be an alkylaluminoxane, such as methylaluminoxane.

[0017] The addition of saturated hydrocarbons provides a reduced aromatic content to the catalyst system while allowing it to provide sufficient flowability for transport and / or introduction into the reactor. Providing sufficient flowability is unexpected because catalyst system components, such as activators like methylaluminoxanes, precipitate in the presence of saturated hydrocarbons. Not limited by theory, it is believed that saturated hydrocarbons are generally substantially insoluble in inorganic materials such as aluminoxanes due to the difference in polarity; saturated hydrocarbons are nonpolar, while aluminoxanes are typically polar. Furthermore, drying the catalyst system to such a low wt% aromatic content would be expected to alter the surface properties of the catalyst system (e.g., the formation of cracks / fissures), reducing the productivity of the catalyst system for polymerization methods. It has been found that neither drying nor adding saturated hydrocarbons to the catalyst system of the present invention reduces the productivity of the catalyst system for polymerization.

[0018] The reduced aromatic content in the catalyst system provides a polyolefin product with a lower aromatic content. This polyolefin product can be used as plastic packaging for food. Furthermore, many saturated hydrocarbons have lower boiling points than aromatic hydrocarbons such as toluene (110°C), making them easier to remove from the polyolefin product.

[0019] As used herein, the term "saturated hydrocarbon" includes hydrocarbons containing zero carbon-carbon double bonds. The saturated hydrocarbon can be linear or cyclic. The saturated hydrocarbon can be C4-C6. 40 Hydrocarbons and mixtures thereof, such as C4-C7 hydrocarbons and mixtures thereof. In at least one embodiment, the C4-C7 hydrocarbons... 40 The hydrocarbon is cyclohexane, isopentane, isohexane, hexane, heptane, or a mixture thereof. The catalyst system of the present invention may have 1.5 wt% or less, 0.5 wt% or less, or about 0 wt% aromatic hydrocarbons, based on the total weight of the catalyst system.

[0020] In at least one embodiment, a method for producing a polyolefin composition by polymerizing olefins includes contacting at least one olefin with a catalyst system and obtaining a concentration of 0.01 mg / m³. 2 Or a polyolefin with a lower aromatic content. Polymerization can be carried out at a temperature of about 0°C to about 300°C and a pressure of about 0.35 MPa to about 10 MPa for up to about 300 minutes. The at least one olefin may be ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, or a mixture thereof.

[0021] For the purposes of this invention, the periodic table group numbering scheme described in Chemical and Engineering News, 63(5), page 27 (1985) is used. Therefore, “Group 4 metal” refers to elements from Group 4 of the periodic table, such as Hf, Ti, or Zr.

[0022] "Catalyst productivity" is a measure of how many grams of polymer (P) are produced using a polymer catalyst containing W grams of catalyst (cat) over a time period of T hours; and can be expressed as: P / (T x W), in gP / gcat. -1 hr -1 The conversion rate is the amount of monomer converted into the polymer product and is reported as mol% and is calculated based on the polymer yield (by weight) and the amount of monomer fed into the reactor. Catalyst activity is a measure of the activity level of the catalyst and is reported as the mass of the product polymer (P) produced per unit mass of loaded catalyst (cat) (gP / g loaded catalyst). In at least one embodiment, the catalyst activity is at least 800 g polymer / g loaded catalyst / hour, for example, about 1000 or more g polymer / g loaded catalyst / hour, for example, about 2000 or more g polymer / g loaded catalyst / hour, for example, about 3000 or more g polymer / g loaded catalyst / hour, for example, about 4000 or more g polymer / g loaded catalyst / hour, for example, about 5000 or more g polymer / g loaded catalyst / hour.

[0023] "Olefin" optionally refers to "alkene," which is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. When a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is an olefin in polymeric form. For example, when a copolymer is said to contain 35 wt%-55 wt% "ethylene," it should be understood that the monomer (mer) units in the copolymer are derived from ethylene in the polymerization reaction, and that the derived units are present in 35 wt%-55 wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more different monomer units. A "terpolymer" is a polymer having three different monomer units. The use of "different" to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of "copolymer" includes terpolymers, etc. Oligomers typically have low molecular weights, such as Mn less than 25000 g / mol or less than 2500 g / mol, or low monomer unit numbers, such as 75 monomer units or less or 50 monomer units or less. "Ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% ethylene-derived units, and "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% propylene-derived units, etc.

[0024] A "catalyst system" is a combination of at least one catalyst and a support material. A catalyst system may contain at least one activator and / or at least one co-activator. When a catalyst system is described as comprising a neutral, stable form of a component, it is known that the ionic form of that component is the form in which it reacts with the monomer to produce a polymer. For the purposes of this invention, a "catalyst system" includes both the neutral and ionic forms of the catalyst system components.

[0025] As used in this article, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight; wt% is the weight percentage, and mol% is the molar percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are in g / mol.

[0026] In this invention, a catalyst may be described as a catalyst precursor, precatalyst, catalyst, or transition metal compound, and these terms are used interchangeably. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is an electrically neutral ligand that donates one or more pairs of electrons to a metal ion.

[0027] For the purposes of this invention relating to catalysts, the term "substituted" means that the hydrogen group has been replaced by a hydrocarbon group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (MeCp) is a methyl-substituted Cp group, and ethyl alcohols are -OH-substituted ethyl groups.

[0028] For the purposes of this invention, "alkoxide" includes those alkyl groups that are C1-C. 10 A hydrocarbon group. This hydrocarbon group can be straight-chain, branched, or cyclic. The hydrocarbon group can be saturated or unsaturated. In some embodiments, the hydrocarbon group may contain at least one aryl group. The term "alkoxy" or "alkoxide" preferably refers to a hydrocarbon ether or aryl ether group, wherein the term hydrocarbon group is C1-C. 10 Hydrocarbon group. Examples of suitable hydrocarbon ether groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, etc.

[0029] This invention describes transition metal complexes. The term complex is used to describe molecules in which an auxiliary ligand is coordinated to a central transition metal atom. This ligand is stably bound to the transition metal to maintain its influence during catalyst use, such as in polymerization. The ligand can be coordinated to the transition metal via covalent bonds and / or electron-donating coordination or intermediate bonds. Transition metal complexes typically undergo activation with an activator to exert their polymerization function, which is believed to produce cations resulting from the removal of anionic groups (often referred to as leaving groups) from the transition metal.

[0030] When used in this invention, the following abbreviations represent: dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylaluminoxane, sMAO is supported methylaluminoxane, p-Me is p-methyl, Bn is benzyl (i.e., CH2Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (and 23°C, unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0031] The terms "hydrocabyl radical," "hydrocarbyl," "hydrocarbyl group," "alkyl radical," and "alkyl" are used interchangeably throughout this invention. Similarly, the terms "group," "radical," and "substituent" are also used interchangeably in this invention. For the purposes of this invention, "hydrocabyl" is defined as C1-C... 100 The group can be linear, branched, or cyclic, and when cyclic, it can be aromatic or non-aromatic. Examples of such groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc., including their substituted analogs. A substituted hydrocarbon group is a group in which at least one hydrogen atom of the hydrocarbon group has been substituted with at least one non-hydrogen group such as a halogen (e.g., 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*3, etc., or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0032] The term "alkenyl" refers to a straight-chain, branched-chain, or cyclic hydrocarbon group having one or more carbon-carbon double bonds. These alkenyl groups can be substituted. Suitable examples of alkenyl groups include, but are not limited to, vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogues.

[0033] The term “aryl” or “aryl group” refers to a carbon-containing aromatic ring and its substituted variants, including but not limited to phenyl, 2-methyl-phenyl, xylyl, and 4-bromo-xylyl. Similarly, “heteroaryl” refers to an aryl group in which the ring carbon atom (or two or three ring carbon atoms) has been substituted with a heteroatom, preferably N, O, or S. As used herein, the term “aromatic” also refers to a pseudoaromatic heterocycle, which is a heterocyclic substituent with properties and structure similar to aromatic heterocyclic ligands (nearly planar), but not within the definition of an aromatic group; similarly, the term “aromatic” also refers to substituted aromatic groups.

[0034] In cases where the alkyl, alkenyl, alkyloxy, or aryl group has isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), reference to one member of the group (e.g., n-butyl) clearly discloses the remaining isomers in the group (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, reference to the alkyl, alkenyl, alkyloxy, or aryl group without specifying a particular isomer (e.g., butyl) clearly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0035] The term "ring atom" refers to an atom that is part of a cyclic structure. By this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms. A heterocyclic ring is a ring structure containing heteroatoms, which is the opposite of a heteroatom-substituted ring (where hydrogen atoms on ring atoms are replaced by heteroatoms). For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring.

[0036] As used herein, "complex" often also refers to catalyst precursors, precatalysts, catalysts, catalysts, transition metal compounds, or transition metal complexes. These terms are used interchangeably. Activators and cocatalysts are also used interchangeably.

[0037] In this invention, a catalyst may be described as a catalyst precursor, precatalyst, catalyst, or transition metal compound, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers.

[0038] The term "continuously" refers to a system that operates for a period of time without interruption or stoppage. For example, a continuous process for producing polymers would be a method in which reactants are continuously introduced into one or more reactors and polymer products are continuously extracted.

[0039] catalyst

[0040] In at least one embodiment, the present invention provides a catalyst system comprising a catalyst having metal atoms. The catalyst may be a metallocene catalyst. The metal may be a Group 3 to Group 12 metal atom, such as a Group 3 to Group 10 metal atom, or a lanthanide atom. The catalyst having Group 3 to Group 12 metal atoms may be monodentate or multidentate, such as bindentate, tripentate, or tetradentate, wherein heteroatoms of the catalyst, such as phosphorus, oxygen, nitrogen, or sulfur, are chelated to the metal atoms of the catalyst. Non-limiting examples include bis(phenolates). In at least one embodiment, the Group 3 to Group 12 metal atoms are selected from Group 5, Group 6, Group 8, or Group 10 metal atoms. In at least one embodiment, the Group 3 to Group 10 metal atoms are selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni. In at least one embodiment, the metal atoms are selected from Group 4, 5, and 6 metal atoms. In at least one embodiment, the metal atom is a Group 4 metal atom selected from Ti, Zr, or Hf. The oxidation state of the metal atom can be from 0 to +7, for example +1, +2, +3, +4, or +5, for example +2, +3, or +4.

[0041] The catalyst of this invention can be chromium or a chromium-based catalyst. Chromium-based catalysts include chromium oxide (CrO3) and silyl chromate catalysts. Chromium catalysts have been the subject of much development in the field of continuous fluidized bed gas-phase polymerization for the production of polyethylene polymers. Such catalysts and polymerization methods are described, for example, in U.S. Publication No. 2011 / 0010938 and U.S. Patent Nos. 7915357; 8129484; 7202313; 6833417; 6841630; 6989344; 7504463; 7563851; 8420754; and 8101691.

[0042] As used herein, metallocene catalysts comprise metallocenes containing group 3 to group 12 metal complexes (preferably group 4 to group 6 metal complexes, such as group 4 metal complexes). The metallocene catalyst of the catalyst system of the present invention can be an unbridged metallocene catalyst as shown in the following formula: Cp A Cp B M'X' n , where each Cp A and Cp B Independently selected from cyclopentadienyl ligands and ligands isovalve to cyclopentadienyl, Cp A and Cp B One or both may contain heteroatoms and Cp A and Cp BOne or both can be substituted with one or more R'' groups. M' is selected from Groups 3 to 12 and lanthanides. X' is an anion leaving group. n is 0 or an integer from 1 to 4. R'' is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, ynyl, lower ynyl, substituted ynyl, heteroynyl, alkoxy, lower alkoxy, aryloxy, alkyl sulfide, lower alkyl sulfide, aryl sulfide, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, alkylene aryl, haloalkyl, haloalkenyl, haloynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing group, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphin, phosphine, amino, amine, ether, and thioether.

[0043] In at least one implementation, each Cp A and Cp B Independently selected from cyclopentadienyl, indole, fluorenyl, cyclopentadienylphenanthrene, benzo[a]indole, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentadienylcyclododecene, phenanthrene, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopentadienyl[a]acenaphthyl, 7-H-dibenzofluorenyl, indole[1,2-9]anthraene, thieno[a]indole, thieno[a]fluorenyl and their hydrogenated forms.

[0044] The metallocene catalyst can be a bridged metallocene catalyst as shown in the following formula: Cp A (A)Cp B M'X' n Cp A and Cp B Each of the ligands is independently selected from cyclopentadienyl ligands and isovalenced ligands of cyclopentadienyl. Cp A and Cp B One or both may contain heteroatoms and Cp A and Cp BOne or both can be substituted with one or more R'' groups. M' is selected from group 3-12 atoms and lanthanides. X' is an anion leaving group. n is 0 or an integer 1-4. (A) is selected from divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent ynyl, divalent lower ynyl, divalent substituted ynyl, divalent heteroynyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkyl sulfide, divalent lower alkyl sulfide, divalent aryl sulfide, divalent aryl, divalent substituted aryl, divalent heteroaryl. Divalent aryl, divalent arylene, divalent alkylaryl, divalent alkylenearyl, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl, divalent heteroatom-containing group, divalent hydrocarbon, divalent lower hydrocarbon, divalent substituted hydrocarbon, divalent heterohydrocarbon, divalent silyl, divalent boryl, divalent phosphin, divalent phosphine, divalent amino, divalent amine, divalent ether, divalent sulfide. R'' is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkyl sulfide, lower alkyl sulfide, aryl sulfide, aryl, substituted aryl, heteroaryl, aralkyl, arylene alkyl, alkylaryl, alkylene aryl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, group containing heteroatoms, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphin, phosphine, amino, amine, germanium, ether and thioether.

[0045] In at least one embodiment, Cp A and Cp B Each of them is independently selected from cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl and n-butylcyclopentadienyl.

[0046] (A) can be O, S, NR', or SiR'2, where each R' is independently hydrogen or C1-C. 20 Hydrocarbon group.

[0047] In another embodiment, the metallocene catalyst is as shown in the following formula:

[0048] T y Cp m MG n X q ,

[0049] Where Cp is independently a substituted or unsubstituted cyclopentadienyl ligand or a substituted or unsubstituted isovalenced ligand with cyclopentadienyl. M is a group 4 transition metal. G is a ligand of formula JR*. zThe heteroatomic groups shown are N, P, O, or S, and R* are linear, branched, or cyclic C1-C groups. 20 Hydrocarbon group. z is 1 or 2. T is a bridging group. y is 0 or 1. X is a leaving group. m=1, n=1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q equals the oxidation state of the transition metal.

[0050] In at least one embodiment, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or an isomer thereof.

[0051] The metallocene catalyst can be selected from:

[0052] Bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dichloride;

[0053] Dimethylsilylbis(tetrahydroindene)zirconium dichloride;

[0054] bis(n-propylcyclopentadienyl)dimethylhafnium;

[0055] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium;

[0056] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride;

[0057] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium;

[0058] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride;

[0059] µ-(CH3)2Si(cyclopentadienyl)(l-adamantylamino)M(R)2;

[0060] µ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0061] µ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0062] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0063] µ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0064] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2;

[0065] µ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2;

[0066] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0067] µ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0068] µ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indargen-1-yl)(tert-butylamino)M(R)2;

[0069] M is selected from Ti, Zr, and Hf; and R is selected from halogens or C1-C5 alkyl groups.

[0070] In at least one embodiment, the catalyst is a bis(phenolic salt) catalyst as shown in formula (I):

[0071] (I).

[0072] M is a Group 4 metal. X 1 and X 2 Independently, the unit price is C1-C 20 Hydrocarbon group, C1-C 20 Substituted hydrocarbon group, heteroatom or heteroatom-containing group, or X 1 and X 2 To combine together to form C4-C 62 Ring-shaped or multi-ringed structures. R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 It is hydrogen on its own, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R9 Or R 10 Two or more of them combine to form C4-C 62 Cyclic or polycyclic ring structures, or combinations thereof. Q is a neutral donor group. J is a heterocyclic, substituted or unsubstituted C7-C. 60 A fused polycyclic group, wherein at least one ring is aromatic, and wherein at least one ring, which may or may not be aromatic, has at least 5 ring atoms. G is as defined for J or may be hydrogen, C2-C. 60 Hydrocarbon group, C1-C 60 Substituted hydrocarbon groups, or those that can independently react with R 6 R 7 Or R 8 Or their combination forms C4-C 60 Ring-shaped or multi-ringed structures. Y is divalent C1-C. 20 Hydrocarbon group or divalent C1-C 20 The substituted hydrocarbon group or (-Q*-Y-) together form a heterocycle. The heterocycle can be aromatic and / or can have multiple fused rings.

[0073] In at least one embodiment, the catalyst shown in formula (I) is:

[0074] or

[0075] .

[0076] M is Hf, Zr, or Ti. X 1 X 2 R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Y is as defined for equation (I). R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R26 R 27 and R 28 It is hydrogen on its own, C1-C 40 Hydrocarbon group, C1-C 40 Substituted hydrocarbon groups, containing functional groups from elements of groups 13-17, or R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 R 21 R 22 R 23 R 24 R 25 R 26 R 27 and R 28 Two or more of them can independently combine to form C4-C 62 Ring-shaped or multi-ringed ring structures, or combinations thereof. R 11 and R 12 They can combine to form 5-8 membered heterocycles. Q* is a group 15 or 16 atom. z is 0 or 1. J* is CR” or N, and G* is CR” or N, where R” is C1-C. 20 Hydrocarbon group or C1-C containing carbonyl group 20 Hydrocarbon group. If Q* is a group 16 atom, then z=0, and if Q* is a group 15 atom, then z=1.

[0077] In at least one embodiment, the first catalyst represented by formula (I) is:

[0078] .

[0079] Y is a divalent C1-C3 hydrocarbon group. Q * It is NR2, OR, SR, PR2, where R is as shown for equation (I). 1 As defined. M is Zr, Hf, or Ti. X 1 and X 2Independently, it is as defined for equation (I). R 29 and R 30 Independently, it is C1-C 40 Hydrocarbon group. R 31 and R 32 Independently linear C1-C 20 Hydrocarbon group, benzyl or toluene group.

[0080] The catalyst system of the present invention may include a second catalyst having group 3 to group 12 metal atoms or lanthanide metal atoms and having a chemical structure different from that of the first catalyst in the catalyst system. For the purposes of the present invention, a catalyst is considered different from another if they differ by at least one atom. For example, “bisindenylzirconium chloride” is different from “(indenyl)(2-methylindenyl)zirconium chloride”, which is different from “(indenyl)(2-methylindenyl)hafnium chloride”. Catalysts that differ only in isomerism are considered identical for the purposes of the present invention; for example, racemic-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium is considered identical to meso-dimethylsilylbis(2-methyl-4-phenyl)dimethylhafnium.

[0081] In at least one embodiment, two or more different catalysts are present in the catalyst system used herein. In at least one embodiment, two or more different catalysts are present in the reaction zone in which the methods (one or more) described herein are performed. When two transition metal catalysts are used as a mixed catalyst system in a reactor, the two transition metal compounds are preferably selected such that they are compatible. Any suitable screening method (e.g., by...) 1 H or 13 C NMR can be used to determine which transition metal compounds are compatible. It is preferred to use the same activator for all transition metal compounds; however, two different activators, such as a noncoordinate anion activator and an aluminoxane, can be used in combination. If one or more transition metal compounds contain an X1 or X2 ligand (which is not hydrogen-based, hydrocarbon-based, or substituted hydrocarbon-based), the aluminoxane should be contacted with the transition metal compound before the addition of the noncoordinate anion activator.

[0082] The first and second catalysts can be used in any ratio (A:B). If the second catalyst is (B), then the first catalyst can be (A). Alternatively, if the second catalyst is (A), then the first catalyst can be (B). The preferred molar ratio of the (A) transition metal compound to the (B) transition metal compound falls within the range (A:B) of about 1:1000 to about 1000:1, for example about 1:100 to about 500:1, for example about 1:10 to about 200:1, for example about 1:1 to about 100:1, and alternatively 1:1 to 75:1, and alternatively 5:1 to 50:1. The specific ratio chosen will depend on the exact catalyst selected, the activation method, and the desired end product. In one specific embodiment, when two catalysts are used, both of which are activated by the same activator, the useful molar percentage (based on the molecular weight of the catalyst) is about 10 to about 99.9% (A) to about 0.1 to about 90% (B), for example about 25 to about 99% (A) to about 0.5 to about 50% (B), for example about 50 to about 99% (A) to about 1 to about 25% (B), for example about 75 to about 99% (A) to about 1 to about 10% (B).

[0083] Activator

[0084] The catalyst system of the present invention can be formed by combining the above-described catalysts with activators in any manner known from the literature, including by loading them for use in slurry or gas-phase polymerization. An activator is defined as any compound that can activate any of the above-described catalysts by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators include, for example, aluminoxanes, alkylaluminums, ionized activators, which can be neutral or ionic, and conventional types of co-catalysts. Preferred activators typically include aluminoxane compounds, modified aluminoxane compounds, and ionized anionic precursor compounds that abstract reactive, β-bonded metal ligands, thereby cationizing the metal compound and providing a charge-balanced, uncoordinated or weakly coordinated anion.

[0085] Non-limiting species of non-coordinated or weakly coordinated anionic activators include N,N-dimethylphenylamine tetra(perfluorophenyl)borate, N,N-dimethylphenylamine tetra(perfluoronaphthyl)borate, N,N-dimethylphenylamine tetra(perfluorobiphenyl)borate, N,N-dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbocation tetra(perfluoronaphthyl)borate, triphenylcarbocation tetra(perfluorobiphenyl)borate, and triphenylcarbocation tetra(3,5-bis(trifluoromethyl)phenyl)borate. (trifluoromethyl)phenyl)borate, triphenylcarbocation tetra(perfluorophenyl)borate, trimethylammonium tetra(perfluoronaphthyl)borate, triethylammonium tetra(perfluoronaphthyl)borate, tripropylammonium tetra(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetra(perfluoronaphthyl)borate, tri(tert-butyl)ammonium tetra(perfluoronaphthyl)borate, N,N-diethylphenylammonium tetra(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylphenylammonium)tetra(perfluoronaphthyl)borate, and Tetra(perfluoronaphthyl)borate.

[0086] Aluminoxane activator

[0087] Aluminoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are typically oligomers containing an -Al(R1)-O- subunit, where R1 is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the abstractable ligand is alkyl, halogenated, alkyl, or amino. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually clear methylaluminoxane is preferred. The turbid or gelled aluminoxane can be filtered to produce a clear solution, or the clear aluminoxane can be decanted from the turbid solution. The useful aluminoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available under the trade name Modified Methylalumoxane type 3A from Akzo Chemicals, Inc., and included in U.S. Patent No. 5041584).

[0088] Optional cleaning agents or activators

[0089] In addition to these activator compounds, the catalyst system of the present invention may include scavengers or co-activators. Scavengers or co-activators include alkyl aluminum or organoaluminum compounds, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc.

[0090] carrier material

[0091] In at least one embodiment, the catalyst system comprises an inert support material. The supported material may be a porous support material such as talc, and inorganic oxides. Other support materials include zeolites, clay, organoclay, or any other organic or inorganic support material, or mixtures thereof.

[0092] In at least one embodiment, the support material is a finely divided inorganic oxide. Suitable inorganic oxide materials for the catalyst systems used herein include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, silica-alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina are magnesium oxide, titanium dioxide, zirconium oxide, etc. However, other suitable support materials can be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, succinate, zeolite, talc, clay, silica clay, silica clay, etc. Furthermore, combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium dioxide, etc. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O2, silica clay, silica / clay, or mixtures thereof. The support material may be fluorinated.

[0093] As used herein, the terms "fluorinated support" and "fluorinated support composition" refer to a support that is ideally particulate and porous and has been treated with at least one inorganic fluorinated compound. For example, the fluorinated support composition may be a silica support in which a portion of the silica hydroxyl groups has been replaced with fluorine or a fluorinated compound. Suitable fluorinated compounds include, but are not limited to, inorganic and / or organic fluorinated compounds.

[0094] The fluorine compound suitable for providing fluorine to the support can be an organic or inorganic fluorine compound, and ideally an inorganic fluorine-containing compound. Such an inorganic fluorine-containing compound can be any compound containing fluorine atoms, as long as it does not contain carbon atoms. Particularly desirable inorganic fluorine-containing compounds are selected from 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, NH4HF2, and combinations thereof. In at least one embodiment, ammonium hexafluorosilicate and ammonium tetrafluoroborate are used.

[0095] Preferably, the carrier material, and most preferably, the inorganic oxide, has a surface area of ​​approximately 10 to approximately 700 m². 2 The pore volume is approximately 0.1–4.0 cc / g, and the average particle size is approximately 5–500 μm. In at least one embodiment, the surface area of ​​the carrier material is approximately 50–500 m². 2 The pore volume is approximately 0.5–3.5 cc / g, and the average particle size is approximately 10–200 μm. The surface area of ​​the support material can be approximately 100–400 m². 2 The pore volume is approximately 0.8 to approximately 3.0 cc / g, and the average particle size is approximately 5 to approximately 100 μm. The average pore size of the support material is approximately 10 to approximately 1000 Å, preferably approximately 50 to approximately 500 Å, and most preferably approximately 75 to approximately 350 Å. In at least one embodiment, the support material is high surface area, amorphous silica (surface area = 300 m² / g). 2 / gm; pore volume is 1.65cm³. 3 / gm). Non-limiting silica is marketed under the trademarks DAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments, DAVISON 948 is used.

[0096] The support material should be dry, i.e., free from absorbed water. Drying of the support material can be achieved by heating or calcining at approximately 100°C to approximately 1000°C, preferably at least approximately 600°C. When the support material is silica, it is heated to at least 200°C, for example, approximately 200°C to approximately 850°C, for example, approximately 600°C; and carried out for approximately 1 minute to approximately 100 hours, 5 minutes to approximately 12 hours, for example, approximately 1 hour to approximately 72 hours. The calcined support material should have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst system comprising, for example, at least one catalyst and an activator.

[0097] Catalyst system formation:

[0098] Embodiments of the present invention include a method for preparing a catalyst system comprising contacting at least one aromatic hydrocarbon, at least one activator, at least one catalyst having Group 3 to Group 12 metal atoms or lanthanide metal atoms, and at least one catalyst support to form a first mixture, reducing the amount of the aromatic hydrocarbon to form a second mixture having 1.5 wt% or less of the aromatic hydrocarbon based on the total weight of the second mixture, and adding saturated hydrocarbons to the second mixture to form a third mixture, which is the catalyst system of the present invention. The catalyst having Group 3 to Group 12 metal atoms or lanthanide metal atoms may be a metallocene catalyst containing a Group 4 metal.

[0099] In at least one embodiment, reducing the amount of aromatics includes applying heat to the first and / or second mixture at a temperature of about 80°C or lower, such as about 70°C or lower, about 65°C or lower, about 60°C or lower, or about 55°C or lower. After reducing the amount of aromatics, the second mixture may have 0.5 wt% or less of aromatics based on the total weight of the second mixture, for example, about 0 wt% based on the total weight of the second mixture.

[0100] The support material can be slurried in a nonpolar solvent, and the resulting slurry is contacted with a solution of at least one catalyst and activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for approximately 0.5 hours to approximately 24 hours, for example, approximately 2 hours to approximately 16 hours, or approximately 4 hours to approximately 8 hours. The catalyst solution is then contacted with the support / activator. In at least one embodiment, the supported catalyst system is generated in situ. In at least one embodiment, the slurry of the support material is first contacted with the catalyst for approximately 0.5 hours to approximately 24 hours, for example, approximately 2 hours to approximately 16 hours, or approximately 4 hours to approximately 8 hours. The slurry of the supported catalyst (one or more) is then contacted with the activator solution.

[0101] The mixture of catalyst, activator, and support can be heated to approximately 0°C to approximately 70°C, for example, approximately 23°C to approximately 60°C, such as room temperature. The contact time can be approximately 0.5 hours to approximately 24 hours, for example, approximately 2 hours to approximately 16 hours, or approximately 4 hours to approximately 8 hours.

[0102] A suitable nonpolar solvent is a material in which all reactants used herein, such as activators and catalysts, are at least partially soluble and are liquid at the reaction temperature. Non-limiting examples of nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane; cycloalkanes, such as cyclohexane; and aromatics, such as benzene, toluene, xylene, and ethylbenzene.

[0103] Toluene can be added to the reactor, followed by an activator, such as an activator solution dissolved in toluene. A catalyst can then be added to the reactor, such as a toluene solution of the catalyst. The mixture can be stirred at a certain temperature, such as room temperature. A support material can then be added to the mixture under stirring. Additional toluene can be added to the mixture to form a slurry with a desired consistency, such as about 2 cc / g silica to about 6 cc / g silica, such as about 4 cc / g. Toluene is then removed. Toluene removal involves drying the mixture and can be carried out under a vacuum atmosphere, purging with an inert atmosphere, heating the mixture, or a combination thereof. For heating the mixture, any suitable temperature can be used, which evaporates the toluene. It should be understood that reducing pressure under vacuum will lower the boiling point of toluene, depending on the pressure of the reactor. The toluene removal temperature can be about 10°C to about 200°C, such as about 40°C to about 140°C, such as about 60°C to about 120°C, such as about 80°C or lower, such as about 70°C or lower. In at least one embodiment, toluene removal includes applying heat, applying a vacuum, and applying nitrogen purging from the bottom of the container by bubbling nitrogen through the mixture. The mixture is dried (i.e., toluene removed) until it contains less than 1.5 wt% toluene, based on the total weight of the dried mixture. The dried mixture can then be allowed to return to room temperature. Saturated hydrocarbons can then be added to the dried mixture (and may be stirred) to form a catalyst system. The catalyst system regains the fluidity lost due to the removal of toluene from the catalyst system component mixture. The amount of saturated hydrocarbons in the catalyst system can be (based on the total weight of the catalyst system) about 0.1 wt% to about 20 wt%, for example about 0.3 wt% to about 15 wt%, for example about 0.4 wt% to about 10 wt%, for example about 0.5 wt% to about 5 wt%, for example about 1 wt% to about 3 wt%.

[0104] The saturated hydrocarbon can be linear or cyclic. Saturated hydrocarbons include propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and their "isomers," or mixtures thereof. Cyclic hydrocarbons include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and cyclononane.

[0105] Aggregation methods

[0106] In at least one embodiment of the invention, the method comprises polymerizing an olefin to produce a polyolefin composition by contacting at least one olefin with the catalyst system of the invention and obtaining the polyolefin composition. The polymerization can be carried out at a temperature of about 0°C to about 300°C, a pressure of about 0.35 MPa to about 10 MPa, and / or for a time of up to about 300 minutes.

[0107] Embodiments of the present invention include a polymerization method in which a monomer (e.g., ethylene or propylene) and optionally a comonomer are contacted with a catalyst system comprising at least one catalyst and an activator. The at least one catalyst and activator may be combined in any order and are typically combined prior to contact with the monomer.

[0108] The monomers useful in this article include substituted or unsubstituted C2-C. 40 α-olefins, preferably C2-C 20 α-olefins, preferably C2-C 12 α-olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, their isomers, or mixtures thereof. In a preferred embodiment, the olefin comprises a monomer (which is ethylene) and one or more optional comonomers containing one or more ethylene or C4-C... 40 Olefins, preferably C4-C 20 Olefins, or preferably C6-C 12 Olefins. The olefin monomer may be linear, branched, or cyclic. The olefin monomer may be tensioned or untensioned, monocyclic or polycyclic, and may include one or more heteroatoms and / or one or more functional groups.

[0109] Exemplary olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, their substituted derivatives and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their substituted derivatives thereof, preferably norbornene, norbornadiene, dicyclopentadiene and mixtures thereof.

[0110] In at least one embodiment, the amount of one or more dienes in the polymer produced herein is at most about 10 wt%, for example, about 0.00001 to about 1.0 wt%, for example, about 0.002 to about 0.5 wt%, for example, about 0.003 to about 0.2 wt%, based on the total weight of the composition. In at least one embodiment, about 500 ppm or less of dienes are added to the polymer, for example, about 400 ppm or less, for example, about 300 ppm or less. In at least one embodiment, at least about 50 ppm of dienes are added to the polymer, or about 100 ppm or more, or 150 ppm or more.

[0111] Diene monomers include any hydrocarbon structure, preferably C4-C. 30 It has at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily introduced into the polymer by a stereoregular or atactic catalyst (one or more). More preferably, the diene monomer is selected from α,ω-diene monomers (i.e., divinyl monomers). In at least one embodiment, the diene monomer is a linear divinyl monomer, for example, those containing 4-30 carbon atoms. Non-limiting examples of dienes include butadiene, pentadiene, hexadiene, heptadecadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, heptadecanadiene, octadecadiene, nonadecadiene, icosadecanadiene, icosadecanadiene, icosadecanadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecanadiene, octadecadiene, nonadecadiene, triadecadiene, and particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and low molecular weight polybutadiene (Mw less than 1000 g / mol). Non-limiting examples of cyclic dienes include cyclopentadiene, vinylnorbornene, norbornene, ethimidenorbornene, divinylbenzene, dicyclopentadiene, or dienes containing higher rings, with or without substituents at various ring positions.

[0112] The polymerization method of the present invention can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, and / or gas-phase polymerization method can be used. Such methods can be carried out in batch, semi-batch, or continuous modes. Homogeneous polymerization and slurry methods are preferred. (A homogeneous polymerization method is defined as a method in which at least about 90 wt% of the product is soluble in the reaction medium). Bulk homogeneous methods are particularly preferred. (A bulk method is defined as a method in which the monomer concentration in the total feed to the reactor is 70 vol% or greater). Alternatively, no solvent or diluent is present or added to the reaction medium (except for small amounts used as a carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). In another embodiment, the method is a slurry method. As used herein, the term "slurry polymerization method" refers to a polymerization method in which a supported catalyst is used and the monomer is polymerized on supported catalyst particles. At least 95 wt% of the polymer product derived from the supported catalyst is in pellet form as solid particles (not dissolved in the diluent). The method of the present invention may include introducing the catalyst system as a slurry into the reactor.

[0113] Suitable diluents / solvents for polymerization include noncoordinate inert liquids. Non-limiting examples include straight-chain and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, for example, commercially available (Isopar) TM ); fully halogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins, which can act as monomers or comonomers, including but not limited to ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, or mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, or mixtures thereof. In another embodiment, the solvent is not aromatic, and the amount of the aromatic compound in the solvent is less than about 1 wt%, for example less than about 0.5 wt%, for example about 0 wt%, based on the weight of the solvent.

[0114] In at least one embodiment, the feed concentration of the monomers and comonomers used for polymerization is about 60 vol% solvent or less, preferably about 40 vol% or less, or about 20 vol% or less, based on the total volume of the feed stream. Preferably, the polymerization is carried out using a bulk method.

[0115] Preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired polyolefin. Typical temperatures and / or pressures include temperatures of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 150°C, such as about 40°C to about 120°C, such as about 45°C to about 80°C; and pressures of about 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa, or preferably about 0.5 MPa to about 4 MPa.

[0116] In a typical polymerization, the reaction runs for at most about 300 minutes, for example about 5 to about 250 minutes, or for example about 10 to about 120 minutes.

[0117] Hydrogen can be added to the reactor for molecular weight control of polyolefins. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of approximately 0.001-50 psig (0.007-345 kPa), for example, approximately 0.01-approximately 25 psig (0.07-172 kPa), for example, approximately 0.1-10 psig (0.7-70 kPa). In one embodiment, 600 ppm or less of hydrogen is added, or 500 ppm or less, or 400 ppm or less, or 300 ppm or less. In other embodiments, at least 50 ppm of hydrogen is added, or 100 ppm or more, or 150 ppm or more.

[0118] In one alternative embodiment, the catalyst activity is at least about 50 g / mmol / h, for example about 500 or greater g / mmol / h, for example about 5000 or greater g / mmol / h, for example about 50000 or greater g / mmol / h. In one alternative embodiment, the conversion of the olefin monomer is at least about 10%, based on the polymer yield (by weight) and the weight of the monomer entering the reaction zone, for example about 20% or greater, for example about 30% or greater, for example about 50% or greater, for example about 80% or greater.

[0119] In a preferred embodiment, the polymerization is carried out at a temperature of 0-300°C (preferably 25-150°C, more preferably 40-120°C, more preferably 45-80°C); 2) at a pressure of atmospheric pressure to 10 MPa (preferably 0.35-10 MPa, more preferably 0.45-6 MPa, more preferably 0.5-4 MPa) in an aliphatic hydrocarbon solvent (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic or alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, or mixtures thereof; preferably wherein the aromatic compound is present in the solvent in an amount of less than 1 wt%, more preferably less than 0.5 wt%, more preferably 0 wt%, based on the weight of the solvent); 4) wherein the catalyst system used for the polymerization contains less than 0.5 mol% of aluminum oxane, preferably 0 mol% of aluminum oxane. Alternatively, the aluminoxane is present in a molar ratio of aluminum to the transition metal of the catalyst of less than 500:1, preferably less than 300:1, more preferably less than 100:1, and more preferably less than 1:1; 5) the polymerization is preferably carried out in a reaction zone; 6) the productivity of the catalyst is at least 80,000 g / mmol / h (preferably at least 150,000 g / mmol / h, more preferably at least 200,000 g / mmol / h, more preferably at least 250,000 g / mmol / h, and more preferably at least 300,000 g / mmol / h); and 7) optionally, a scavenger (e.g., a trialkylaluminum compound) is absent (e.g., present at 0 mol%). Alternatively, the scavenger is present in a scavenger metal to transition metal molar ratio of less than 100:1, preferably less than 50:1, more preferably less than 15:1, and more preferably less than 10:1; and 8) optionally, hydrogen is present in the polymerization reactor at a partial pressure of 0.001-50 psig (0.007-345 kPa) (preferably 0.01-25 psig (0.07-172 kPa), more preferably 0.1-10 psig (0.7-70 kPa)). In a preferred embodiment, the catalyst system used for polymerization comprises no more than one catalyst. A “reaction zone,” also called a “polymerization zone,” is a vessel in which polymerization occurs, such as a batch reactor. When multiple reactors are used in series or parallel configurations, each reactor is considered a separate polymerization zone. For multi-stage polymerization in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, polymerization occurs in one reaction zone.

[0120] Other additives may also be used in the polymerization as needed, such as one or more scavengers, accelerators, modifiers, chain transfer agents (e.g., diethylzinc), reducing agents, oxidizing agents, hydrogen, alkylaluminum or silanes.

[0121] The chain transfer agent can be an alkylaluminoxane, a compound of the formula AlR3, ZnR2 (where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or its isomers) or a combination thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or a combination thereof.

[0122] Polyolefin products

[0123] The present invention also relates to polyolefin compositions, such as resins, produced by the catalyst system and polymerization method of the present invention. The polyolefins of the present invention can have a content of 0.01 mg / m³. 2 Or even lower concentrations of toluene.

[0124] In at least one embodiment, the method includes using the catalyst system of the present invention to produce propylene homopolymers or propylene copolymers, such as propylene-ethylene and / or propylene-α-olefins (preferably C3-C4). 20 A copolymer (e.g., propylene-hexene copolymer or propylene-octene copolymer) having a Mw / Mn greater than about 1, for example greater than about 2, for example greater than about 3, for example greater than about 4.

[0125] In at least one embodiment, the method includes producing olefin polymers, preferably polyethylene and polypropylene homopolymers and copolymers, using the catalyst system of the present invention. In at least one embodiment, the polymer produced herein is an ethylene homopolymer or ethylene copolymer, preferably having about 0-25 mol% of one or more C3-C4 groups. 20 Olefin comonomers (e.g., about 0.5-20 mol%, e.g., about 1-15 mol%, e.g., about 3-10 mol%).

[0126] The Mw of the polymers produced in this article can be about 5,000 to about 1,000,000 g / mol (e.g., about 25,000 to about 750,000 g / mol, e.g., about 50,000 to about 500,000 g / mol), and / or Mw / Mn is about 1 to about 40 (e.g., about 1.2 to about 20, e.g., about 1.3 to about 10, e.g., about 1.4 to about 5, e.g., about 1.5 to about 4, e.g., about 1.5 to about 3).

[0127] blends

[0128] In at least one embodiment, the polymer produced herein (e.g., polyethylene or polypropylene) is combined with one or more additional polymers prior to forming a film, molded part, or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymers of propylene and ethylene, and / or butene, and / or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, acrylic copolymers, polymethyl methacrylate, or any other polymer polymerizable by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymers, styrene-based block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 ester, polyacetal, polyvinylidene fluoride, polyethylene glycol, and / or polyisobutylene.

[0129] In at least one embodiment, the amount of the polymer (e.g., polyethylene or polypropylene) in the blend is about 10 to about 99 wt%, based on the weight of the total polymer in the blend, for example, about 20 to about 95 wt%, for example, about 30 to about 90 wt%, for example, about 40 to about 90 wt%, for example, about 50 to about 90 wt%, for example, about 60 to about 90 wt%, for example, about 70 to about 90 wt%.

[0130] The blends of the present invention can be produced by mixing the polymers of the present invention with one or more polymers (as described above), by producing reactor blends by connecting reactors in series, or by producing multiple polymer species by using more than one catalyst in the same reactor. The polymers can be mixed together before being placed in an extruder or can be mixed in the extruder.

[0131] The blends of the present invention can be formed using conventional equipment and methods, such as by dry mixing the individual components, such as polymers, and subsequently melt-mixing them in a mixer, or by mixing the components directly together in a mixer such as a Banbury mixer, Haake mixer, Brabender internal mixer, or single or twin-screw extruder. This can include the direct use of compounding extruders and side-arm extruders downstream of the polymerization process, or the blending of resin powder or granules at the hopper of a film extruder. Furthermore, additives may be included, as needed, in the blends, in one or more components of the blends, and / or in the product (e.g., a film) formed from the blends. Such additives may include, for example: fillers; antioxidants (e.g., hindered phenols such as IRGANOX). TM1010 or IRGANOX TM 1076, which is available from Ciba-Geigy; phosphites (e.g., IRGAFOS) TM 168, which may be obtained from Ciba-Geigy; anti-sticking additives; tackifiers such as polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and glyceryl stearate, and hydrogenated rosin; UV stabilizers; heat stabilizers; antiblocking agents; release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc; mixtures thereof, etc.

[0132] In at least one embodiment, the polyolefin composition, such as a resin (which is a multimodal polyolefin composition), comprises a low molecular weight portion and / or a high molecular weight portion. In at least one embodiment, the high molecular weight portion is produced using a catalyst represented by formula (I). The low molecular weight portion can be produced using a second catalyst, which is a bridged or unbridged metallocene catalyst, as described above. The high molecular weight portion can be polypropylene, polyethylene, or copolymers thereof. The low molecular weight portion can be polypropylene, polyethylene, or copolymers thereof.

[0133] In at least one embodiment, the comonomer content of the polyolefin composition produced by the catalyst system of the present invention is about 3 wt% to about 15 wt%, for example, about 4 wt% to about 10 wt%, for example, about 5 wt% to about 8 wt%. In at least one embodiment, the polydispersity index of the polyolefin composition produced by the catalyst system of the present invention is about 2 to about 6, for example, about 2 to about 5.

[0134] membrane

[0135] Any of the aforementioned polymers, such as the aforementioned ethylene copolymers or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, single-layer or multi-layer blow molding, extrusion, and / or shrink films. These films can be manufactured using any suitable extrusion or co-extrusion technology, such as blown bubble film processing technology, in which the composition can be extruded in a molten state through an annular die, then expanded to form a uniaxially or biaxially oriented melt, and then cooled to form a tubular blown film, which can then be axially cut and unfolded to form a flat film. The film can subsequently be unoriented, uniaxially oriented, or biaxially oriented to the same or different degrees. One or more layers of the film can be oriented to the same or different degrees in the transverse and / or longitudinal directions. Uniaxial orientation can be accomplished using typical cold-drawing or hot-drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a twin-bubble method, and can be performed before or after the individual layers are placed together. For example, a polyethylene layer can be extruded over or laminated onto an oriented polypropylene layer, or polyethylene and polypropylene can be co-extruded into a film and then oriented. Similarly, oriented polypropylene can be laminated onto oriented polyethylene, or oriented polyethylene can be coated onto polypropylene, and then optionally the composition can be even further oriented. Typically, the film is oriented in the longitudinal (MD) direction at a ratio of up to 15, preferably 5-7, and in the transverse (TD) direction at a ratio of up to 15, preferably 7-9. However, in another embodiment, the film is oriented to the same degree in both the MD and TD directions.

[0136] The thickness of the film can vary depending on the target application; however, a film thickness of 1m-50m may be suitable. Films intended for packaging are typically 10m-50m thick. The thickness of the sealing layer is typically 0.2m-50m. The sealing layer may be present on both the inner and outer surfaces of the film, or it may be present only on the inner or outer surface.

[0137] In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave treatment. In a preferred embodiment, one or two of the surface layers are modified by corona treatment.

[0138] Example

[0139] It will be understood that while the invention has been described in conjunction with its specific embodiments, the foregoing description is illustrative and not intended to limit the scope of the invention. Other aspects, advantages, and modifications will be apparent to those skilled in the art to which this invention pertains.

[0140] Therefore, the following embodiments are presented to provide a complete disclosure and description to those skilled in the art, and are not intended to limit the scope of what the inventors consider to be their invention.

[0141] All reagents are available from Sigma Aldrich (St. Louis, MO) and can be used directly unless otherwise specified. All solvents are anhydrous. All reactions are carried out under an inert nitrogen atmosphere unless otherwise specified. All deuterated solvents are available from Cambridge Isotopes (Cambridge, MA) and dried on a 3 Å molecular sieve before use.

[0142] Funnel test for measuring flow properties

[0143] The following procedure outlines the steps for a funnel test used to measure catalyst flowability. These steps are performed under anaerobic conditions in a nitrogen atmosphere. Each funnel has a narrow opening at a first end and a wide opening at a second end opposite the first end. The diameter of the narrow opening of the funnel is 14 mm, 12 mm, 10 mm, or 7 mm. The steps are as follows:

[0144] 1) Weigh the 20g sample of the catalyst system to be measured into the funnel, and cover the narrow opening with a lid to prevent the catalyst system from flowing.

[0145] 2) Start the stopwatch when the cover is removed;

[0146] 3) Stop the stopwatch once the entire sample has flowed through the narrow opening;

[0147] 4) Record the stopwatch time in a lab notebook and repeat the procedure using funnels with narrow openings of different sizes. If the catalyst does not flow through a funnel of a certain size, do not conduct further testing using a smaller funnel.

[0148] Preparation of catalyst system

[0149] Comparative Example 1: Dimethylsilylbis(tetrahydroindene)zirconia and toluene 1.5 wt%: 2.0 L of toluene was first added to a 2-gallon (7.57 L) reactor, followed by 1060 g of a 30 wt% toluene solution of methylaluminoxane (available from Albemarle, Baton Rouge, La.), and then 19.0 g of a 10% toluene solution of dimethylsilylbis(tetrahydroindene)zirconia. The mixture was stirred at approximately 23 °C for 60 minutes, after which 850 g of silica (ES70 silica, dehydrated at 600 °C, available from PQ Corp, PA) was added to the liquid with stirring. The stirring speed was increased for approximately 10 minutes to ensure the silica was dispersed in the liquid, and then toluene was added to bring the slurry of the liquid to a solid consistency of 4 cc / g silica. 250 g of Irgastat was added. TMA 10 wt% toluene solution of AS 990 additive was prepared. The mixture was stirred for 30 minutes. It was then dried under vacuum and purged with nitrogen at 160°F (71.1°C) until the mixture contained ~1.5 wt% toluene, based on the total weight of the dried mixture, to form the catalyst system. The dried mixture was then cooled to approximately 23°C.

[0150] Comparative Example 2: Dimethylsilylbis(tetrahydroindene)zirconium dichloride and toluene 0wt%: 60g of the catalyst system of Comparative Example 1 was placed in a round-bottom flask and connected to a rotary evaporator. The catalyst system was dried at 70°C under complete vacuum for about 6 hours until the residual toluene in the catalyst system was less than 1000ppm.

[0151] Example 1: Dimethylsilylbis(tetrahydroindene)zirconium dichloride and isopentane 3.0 wt%: 25 g of the catalyst system of Comparative Example 2 was placed in a round-bottom flask. Then anhydrous isopentane (0.75 g) was added, and the mixture was stirred at 45 °C for 1 hour.

[0152] Example 2: Dimethylsilyl bis(tetrahydroindene)zirconium dichloride and hexane 1.5 wt%: 60 g of the catalyst system from Comparative Example 1 was placed in a round-bottom flask and connected to a rotary evaporator. The catalyst system was dried at 70 °C under complete vacuum for approximately 6 hours until the residual toluene in the catalyst system was less than 1000 ppm. 25 g of this catalyst system was placed in a new round-bottom flask. Anhydrous n-hexane (0.375 g) was added. The flask was sealed, and the catalyst system was mixed at 70 °C for 1 hour.

[0153] Table 1 shows the flowability data for the catalyst systems: Example 1, Example 2, Comparative Example 1, and Comparative Example 2. As shown in Table 1, the catalyst systems with 3 wt% isopentane (Example 1) or 1.5 wt% hexane (Example 2) provided flowable catalyst systems through, for example, the narrow end of a 10 mm funnel, which were considered sufficiently flowable for injecting the catalyst systems into polyolefin gas-phase reactors.

[0154] Table 1

[0155]

[0156] Comparative Example 3: Bis(1-methyl,3-n-butylcyclopentadienyl)zirconia and toluene 1.5 wt%: 2.0 L of toluene was first added to a 2-gallon (7.57 L) reactor, followed by 1060 g of a 30 wt% toluene solution of methylaluminoxane (available from Albemarle, Baton Rouge, La.), and then 23.1 g of a 10% toluene solution of bis(1-methyl,3-n-butylcyclopentadienyl)zirconia. The mixture was stirred at approximately 23 °C for 60 minutes, after which 850 g of silica (Davison 948 silica, dehydrated at 600 °C, available from WRGrace, Davison Chemical Division, Baltimore, Md.) was added to the liquid with stirring. The stirring speed was increased for approximately 10 minutes to ensure the silica was dispersed in the liquid, and then toluene was added to bring the slurry of the liquid to a solid consistency of 4 cc / g silica. Add 62.5g of Irgastat TM A 10 wt% toluene solution of AS990 additive was prepared. The mixture was stirred for 30 minutes. It was then dried under vacuum and purged with nitrogen at 160°F (71.1°C) until the mixture contained ~1.5 wt% toluene, based on the total weight of the dried mixture, to form the catalyst system. The dried mixture was then cooled to approximately 23°C.

[0157] Comparative Example 4: Bis(1-methyl,3-n-butylcyclopentadienyl)zirconia and toluene 0wt%: 60 g of the catalyst system of Comparative Example 3 was placed in a round-bottom flask and connected to a rotary evaporator. The catalyst system was dried at 70 °C under complete vacuum for about 6 hours until the residual toluene in the catalyst system was less than 1000 ppm.

[0158] Example 3: Bis(1-methyl,3-n-butylcyclopentadienyl)zirconia dichloride and hexane 1.5wt%: 25g of the catalyst system from Comparative Example 4 was placed in a round-bottom flask and connected to a rotary evaporator. Anhydrous n-hexane (0.375g) was added. The flask was sealed, and the catalyst system was mixed at 70°C for 1 hour.

[0159] Table 2 shows the flowability data for the catalyst systems: Example 3, Comparative Example 3, and Comparative Example 4. As shown in Table 2, the catalyst system with 1.5 wt% hexane (Example 3) provides a flowable catalyst system through, for example, the narrow end of a 10 mm funnel, which is considered to be sufficiently flowable for injecting the catalyst system into a polyolefin gas-phase reactor.

[0160] Table 2

[0161]

[0162] Comparative Example 5: 1.5 wt% bis(n-propylcyclopentadienyl)dimethylhafnium and toluene: 2.0 L of toluene was first added to a 2-gallon (7.57 L) reactor, followed by 1060 g of a 30 wt% toluene solution of methylaluminoxane (available from Albemarle, Baton Rouge, La.), and then 23.0 g of a 25% toluene solution of bis(n-propylcyclopentadienyl)dimethylhafnium. The mixture was stirred at approximately 23°C for 60 minutes, after which 850 g of silica (ES70 silica, dehydrated at 600°C, available from PQ Corp, PA) was added to the liquid with stirring. The stirring speed was increased for approximately 10 minutes to ensure the silica was dispersed in the liquid, and then toluene was added to bring the slurry of the liquid to a solid consistency of 4 cc / g silica. The mixture was then dried under vacuum and purged with nitrogen at 160°F (71.1°C) until it contained ~1.5 wt% toluene, based on the total weight of the dried mixture, to form the catalyst system. The dried mixture was then cooled to approximately 23°C.

[0163] Comparative Example 6: Bis(n-propylcyclopentadienyl)dimethylhafnium and toluene 0wt%: 60 g of the catalyst system of Comparative Example 5 was placed in a round-bottom flask and connected to a rotary evaporator. The catalyst system was dried at 70 °C under complete vacuum for about 6 hours until the toluene present in the catalyst system was 1000 ppm or lower.

[0164] Example 4: bis(n-propylcyclopentadienyl)dimethylhafnium and isopentane 3.0 wt%: 25 g of the catalyst system of Comparative Example 6 was placed in a round-bottom flask. Anhydrous isopentane (0.75 g) was added. The flask was sealed, and the catalyst system was mixed at 45°C for 1 hour.

[0165] Example 5: bis(n-propylcyclopentadienyl)dimethylhafnium and isopentane 1.5wt%: 25g of the catalyst system of Comparative Example 6 was placed in a round-bottom flask. Anhydrous isopentane (0.375g) was added. The flask was sealed, and the catalyst system was mixed at 45°C for 1 hour.

[0166] Table 3 shows the flowability data for the catalyst systems of Examples 4, 5, Comparative Examples 5, and 6. As shown in Table 3, the catalyst systems with 3 wt% isopentane (Example 4) or 1.5 wt% hexane (Example 5) provided flowability through, for example, the narrow end of a 10 mm funnel, which was considered sufficiently flowable for injecting the catalyst system into a polyolefin gas-phase reactor. Furthermore, the catalyst systems with 3 wt% isopentane (Example 4) or 1.5 wt% isopentane (Example 5) provided increased flowability at the narrow end of a 7 mm funnel compared to the catalyst systems with 1.5 wt% toluene (Comparative Example 5) and 0 wt% toluene (Comparative Example 6).

[0167] Table 3

[0168]

[0169] Comparative Example 7: Before removing toluene, saturated hydrocarbon mineral oil (which is >C) 40 Hydrocarbon materials are added to various catalyst systems containing an activator, methyl alumina. Toluene is then removed as described above. Precipitation of methyl alumina after toluene removal has been observed. Due to the precipitation of the activator, such catalyst systems present numerous challenges for commercial operation, thus limiting their usefulness.

[0170] In summary, it has been found that the combination of saturated hydrocarbons (e.g., isopentane and / or hexane) with a reduced amount of toluene in the catalyst system can provide such a catalyst system with an acceptable level of flowability for transport and / or injection into the polymerization reactor.

[0171] Unless otherwise specified, the phrases “consistently composed of…” and “consistently composed of…” do not exclude the presence of other steps, elements or materials, whether or not they are expressly mentioned in this specification, provided that such steps, elements or materials do not affect the essential and novel characteristics of the invention. Furthermore, they do not exclude impurities and variations that are generally associated with the elements and materials used.

[0172] For brevity, only certain ranges are explicitly disclosed here. However, a range from any lower limit can be combined with any upper limit to describe an unspecified range, and a range from any lower limit can be combined with any other lower limit to describe an unspecified range; similarly, a range from any upper limit can be combined with any other upper limit to describe an unspecified range. Furthermore, a range includes every point or individual value between its endpoints, even if not explicitly stated. Therefore, each point or individual value can be used as its lower or upper limit, combined with any other point or individual value or any other lower or upper limit, to describe an unspecified range.

[0173] For jurisdictions where such incorporation is permitted, all priority documents are fully incorporated herein by reference, provided that such disclosure is consistent with the description of the invention. Furthermore, for jurisdictions where such incorporation is permitted, all documents and references cited therein, including test procedures, disclosures, patents, journal articles, etc., are fully incorporated herein by reference, provided that such disclosure is consistent with the description of the invention.

[0174] Although the invention has been described with reference to many embodiments and examples, those skilled in the art who benefit from the invention will understand that other embodiments can be made without departing from the scope and spirit of the invention disclosed herein.

[0175] This application also relates to the following implementation schemes:

[0176] 1. A method for preparing a catalyst system, comprising:

[0177] A first mixture is formed by contacting at least one aromatic hydrocarbon, at least one activator, at least one catalyst having metal atoms from Group 3 to Group 12 or lanthanide metal atoms, and at least one catalyst support.

[0178] To form a second mixture by reducing the amount of aromatics in the first mixture, the second mixture having 1.5 wt% or less of the at least one aromatic hydrocarbon, based on the total weight of the second mixture; and

[0179] At least one saturated hydrocarbon is added to the second mixture to form a third mixture.

[0180] 2. The method of implementation scheme 1, wherein the activator is an alkylaluminoxane.

[0181] 3. The method of implementation scheme 1 or implementation scheme 2, wherein the saturated hydrocarbon is C4-C 40 Hydrocarbons or mixtures thereof.

[0182] 4. The method of implementation scheme 3, wherein C4-C 40 The hydrocarbons are selected from isopentane, isohexane, hexane, heptane, and mixtures thereof.

[0183] 5. The method of any one of embodiments 1-4, wherein reducing aromatics includes applying heat to the first mixture at a temperature of about 40°C or lower.

[0184] 6. The method of any one of embodiments 1-5, wherein the second mixture has 0.5 wt% or less of aromatics, based on the total weight of the second mixture.

[0185] 7. The method of any one of embodiments 1-6, wherein after reduction, the catalyst system contains approximately 0 wt% aromatics based on the total weight of the second mixture.

[0186] 8. The method of any one of embodiments 1-7, wherein the catalyst having group 3 to group 12 metal atoms or lanthanide metal atoms is a metallocene catalyst containing group 4 metals.

[0187] 9. A catalyst system comprising products of a combination of the following substances:

[0188] Catalysts containing metal atoms from Group 3 to Group 12 or lanthanide metal atoms;

[0189] At least one activator;

[0190] At least one carrier material;

[0191] 1.5 wt% or less of aromatics, based on the total weight of the catalyst system; and

[0192] Saturated hydrocarbons.

[0193] 10. The catalyst system of embodiment 9, wherein the metal atom is a group 4 metal atom, and the catalyst is selected from metallocene catalysts and bis(phenolic) catalysts.

[0194] 11. The catalyst system of embodiment 9 or embodiment 10, wherein the saturated hydrocarbon is C4-C 40 Hydrocarbons or mixtures thereof.

[0195] 12. The catalyst system of embodiment 11, wherein the C4-C 40 The hydrocarbons are selected from cyclohexane, isopentane, isohexane, hexane, heptane, and mixtures thereof.

[0196] 13. The catalyst system of any one of embodiments 9-12, wherein the catalyst system contains 0.5 wt% or less of aromatics, based on the total weight of the catalyst system.

[0197] 14. The catalyst system of any one of embodiments 9-13, wherein the catalyst system comprises approximately 0 wt% aromatic hydrocarbons based on the total weight of the catalyst system.

[0198] 15. The catalyst system of any one of embodiments 9-14, wherein the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, alumina-silica, silica clay, silica / clay, SiO2 / TiO2, and combinations thereof.

[0199] 16. The catalyst system of any one of embodiments 9-15, wherein the activator is an alkylaluminoxane.

[0200] 17. The catalyst system of any one of embodiments 9-16, wherein the alkylaluminoxane is methylaluminoxane.

[0201] 18. The catalyst system of any one of embodiments 9-17, wherein the catalyst is a metallocene catalyst of the following formula: Cp A Cp B M'X' n : Cp A and Cp B Each of the ligands in Cp is independently selected from cyclopentadienyl ligands and isovalenced ligands of cyclopentadienyl ligands. A and Cp B One or both may contain heteroatoms and Cp A and Cp B One or both can be substituted with one or more R'' groups: where M' is an element selected from Groups 3-12 and the lanthanides; where X' is an anionic ligand; where n is 0 or an integer 1-4; where R'' is selected from alkyl, lower alkyl, substituted alkyl, heteroalkyl, alkenyl, lower alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, lower alkenyl, substituted alkenyl, heteroalkynyl, alkoxy, lower alkoxy, aryloxy, alkyl sulfide, lower alkyl sulfide, aryl sulfide, aryl, substituted aryl, heteroaryl, arylalkyl, arylenealkyl, alkylaryl, alkylenearyl, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, groups containing heteroatoms, hydrocarbon, lower hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphonyl, phosphine, amino, amine, ether, and thioether.

[0202] 19. The catalyst system of any one of embodiments 9-17, wherein the metallocene catalyst is a metallocene catalyst of the following formula: Cp A (A)Cp B M'X' n : Cp A and Cp B Each of the ligands in Cp is independently selected from cyclopentadienyl ligands and isovalenced ligands of cyclopentadienyl ligands. A and Cp B One or both may contain heteroatoms and Cp A and Cp BOne or both of them may be substituted with one or more R'' groups; wherein M' is an element selected from Groups 3-12 and the lanthanides; wherein X' is an anionic ligand; wherein n is 0 or an integer 1-4; wherein (A) is selected from divalent alkyl, divalent lower alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent lower alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkoxy, divalent lower alkoxy, divalent aryloxy, divalent alkyl sulfide, divalent lower alkyl sulfide, divalent aryl sulfide, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent arylalkylene, divalent alkylene aryl, divalent alkylene aryl, divalent alkyl halogen, divalent alkylene halogen, divalent alkyl halogen, divalent alkyl halogen, divalent heteroalkyl, divalent heterocyclic, divalent heteroaryl. The following are divalent groups containing heteroatoms: divalent hydrocarbon groups, divalent lower hydrocarbon groups, divalent substituted hydrocarbon groups, divalent heterohydrocarbon groups, divalent silyl groups, divalent borosyl groups, divalent phosphin groups, divalent phosphine groups, divalent amino groups, divalent amine groups, divalent ether groups, and divalent thioether groups; wherein R'' is selected from alkyl groups, lower alkyl groups, substituted alkyl groups, heteroalkyl groups, alkenyl groups, lower alkenyl groups, substituted alkenyl groups, heteroalkenyl groups, alkynyl groups, lower alkenyl groups, arylyl groups, alkyl sulfides, lower alkyl sulfides, aryl sulfides, aryl groups, substituted aryl groups, heteroaryl groups, arylalkyl groups, arylene alkyl groups, alkylaryl groups, alkylene aryl groups, alkylene aryl groups, halogenated alkyl groups, halogenated alkenyl groups, halogenated alkynyl groups, heteroalkyl groups, heterocyclic groups, heteroaryl groups, groups containing heteroatoms, hydrocarbon groups, lower hydrocarbon groups, substituted hydrocarbon groups, heterohydrocarbon groups, silyl groups, borosyl groups, phosphin groups, phosphine groups, amino groups, amine groups, ether groups, and thioether groups.

[0203] 20. The catalyst system of any one of embodiments 9-17, wherein the catalyst is a metallocene catalyst as shown in the following formula:

[0204] T y Cp m MG n X q ,

[0205] Where Cp is independently a cyclopentadienyl ligand or a ligand with a structure similar to cyclopentadienyl, M is a group 4 transition metal, and G is a ligand of formula JR*. z The heteroatomic groups shown are J, which is N, P, O, or S, and R*, which are linear, branched, or cyclic C1-C groups. 20 The hydrocarbon group and z are 1 or 2, T is a bridging group, and y is 0 or 1, X is an anionic ligand, and m=1, n=1, 2 or 3, q=0, 1, 2 or 3, and the sum of m+n+q equals the oxidation state of the transition metal.

[0206] 21. The catalyst system of any one of embodiments 9-17, wherein the catalyst is selected from the following metallocene catalysts:

[0207] Bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dichloride;

[0208] Dimethylsilylbis(tetrahydroindene)zirconium dichloride;

[0209] bis(n-propylcyclopentadienyl)dimethylhafnium;

[0210] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)dimethyltitanium;

[0211] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)titanium dichloride;

[0212] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium;

[0213] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)titanium dichloride;

[0214] µ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)M(R)2;

[0215] µ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0216] µ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0217] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0218] µ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2;

[0219] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2;

[0220] µ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2;

[0221] µ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2;

[0222] µ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2; and

[0223] µ-(CH3)2Si(η 5-2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indarin-1-yl)(tert-butylamino)M(R)2; and combinations thereof; wherein M is selected from Ti, Zr and Hf; and R is selected from halogens or C1-C5 alkyl groups.

[0224] 22. The catalyst system according to any one of embodiments 9-21, further comprising a second catalyst having group 3 to group 12 metal atoms or lanthanide metal atoms and having a chemical structure different from that of the first catalyst.

[0225] 23. A method for producing a polyolefin composition by polymerizing olefins, the method comprising contacting at least one olefin with a catalyst system of any one of embodiments 9-22 and obtaining a composition having a content of 0.01 mg / m³. 2 Or polyolefin compositions with lower aromatic hydrocarbon content.

[0226] 24. The method of embodiment 23, wherein the polymerization is carried out at a temperature of about 0°C to about 300°C and a pressure of about 0.35 MPa to about 10 MPa for a period of up to about 300 minutes.

[0227] 25. The method of embodiment 23 or embodiment 24, wherein the at least one olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and mixtures thereof.

[0228] 26. The method or catalyst system of any of the foregoing embodiments, wherein the aromatic hydrocarbon is toluene.

Claims

1. A method for preparing a catalyst system, comprising: At least one aromatic hydrocarbon, preferably toluene, at least one activator, at least one catalyst having a Group 4 metal atom and selected from metallocene catalysts and bis(phenolate) catalysts, and at least one catalyst support are contacted to form a first mixture, wherein the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, alumina-silica, silica clay, silica / clay, SiO2 / TiO2, and combinations thereof; The amount of aromatics in the first mixture is reduced to form a second mixture having 1.5 wt% or less of the at least one aromatic hydrocarbon, based on the total weight of the second mixture; and At least one saturated hydrocarbon is added to the second mixture to form a third mixture, which is a catalyst system, wherein the saturated hydrocarbon is C4-C. 40 The amount of hydrocarbons or mixtures thereof in the catalyst system is from 0.1 wt% to 20 wt%, based on the total weight of the catalyst system.

2. The method according to claim 1, wherein the activator is an alkylaluminoxane.

3. The method according to claim 1 or 2, wherein the C4-C 40 The hydrocarbons are selected from isopentane, isohexane, hexane, heptane, and mixtures thereof.

4. The method according to any one of claims 1-3, wherein reducing aromatics comprises applying heat to the first mixture at a temperature of about 40°C or lower.

5. The method according to any one of claims 1-4, wherein the second mixture has 0.5 wt% or less of aromatics, based on the total weight of the second mixture.

6. The method according to any one of claims 1-5, wherein after reduction, the catalyst system contains approximately 0 wt% aromatics based on the total weight of the second mixture.

7. A catalyst system prepared by any one of claims 1-3 or 6.

8. The catalyst system according to claim 7, wherein the activator is methylaluminoxane.

9. A method for producing a polyolefin composition by polymerizing olefins, the method comprising contacting at least one olefin with a catalyst system according to any one of claims 7 or 8 and obtaining a composition having a concentration of 0.01 mg / m³. 2 Or polyolefin compositions with lower aromatic hydrocarbon content.

10. The method of claim 9, wherein the polymerization is carried out at a temperature of 0°C to 300°C and a pressure of 0.35 MPa to 10 MPa for a period of up to 300 minutes.

11. The method according to claim 9 or claim 10, wherein the at least one olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and mixtures thereof.

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