method for forming a catalyst composition

专利摘要:
PRODUCTION OF POLYOLEFINES PRODUCTS Methods and systems of catalysts for their preparation and use. A method of methylating a catalyst composition by substantially normalizing the enantiomeric distribution is provided. The method includes forming a slurry of the organometallic compound in dimethoxyethane (DME), and adding a solution of RMgBr in DME, where R is a methyl group or a benzyl group, and where RMgBr is greater than about 2 , 3 equivalents in relation to the organometallic compound. After adding RMgBr, the slurry is mixed for at least about four hours. An alkylated organometallic is isolated, in which the methylated species has a meso / rac ratio that is between about 0.9 and about 1.2.
公开号:BR112016019334B1
申请号:R112016019334-2
申请日:2015-02-10
公开日:2021-03-09
发明作者:Francis C. Rix；Alexander D. Todd；C. Jeff Harlan
申请人:Univation Technologies, Llc；
IPC主号:

专利说明:

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[0001] This application claims the benefit of provisional North American patent applications with the following serial numbers: serial number 61 / 938,466, by Ching-Tai Lue et al, filed on February 11, 2014 (2014U002.PRV); serial number 61 / 938,472, by Ching-Tai Lue et al, filed on February 11, 2014 (2014U003.PRV.); serial number 61 / 981.291, by Francis C. Rix et al, filed on April 18, 2014 (2014U010.PRV.); serial number 61 / 985.151, by Francis C. Rix et al, filed on April 28, 2014 (2014U012.PRV.); serial number 62 / 032.383, by Sun-Chueh Kao et al, filed on August 1, 2014 (2014U018.PRV.); serial number 62 / 087,905, by Francis C. Rix et al, filed on December 5, 2014 (2014U035.PRV.); serial number 62 / 088,196, by Daniel P. Zilker, Jr. et al., deposited on December 5, 2014 (2014U036.PRV), serial number 62 / 087,911, by Ching-Tai Lue et al., deposited on December 5, 2014 (2014U037.PRV), and serial number 62 / 087,914, by Francis C. Rix et al., Filed on December 5, 2014 (2014U038.PRV), whose disclosures are incorporated by reference in their entirety. Background
[0002] Alpha-olefin ethylene (polyethylene) copolymers are typically produced in a low pressure reactor, using, for example, solution, slurry, or gas phase polymerization processes. Polymerization occurs in the presence of catalytic systems, such as those using, for example, a Ziegler-Natta catalyst, a chromium-based catalyst, a metallocene catalyst, or combinations thereof.
[0003] Various catalyst compositions containing a single site, for example, metallocene catalysts, were used to prepare polyethylene copolymers, producing relatively homogeneous copolymers at good polymerization rates. In contrast to traditional Ziegler-Natta compositions, catalysts of single site catalyst compositions, such as metallocene catalysts, are catalytic compounds in which each catalyst molecule contains one or only a few polymerization sites. Single-site catalysts often produce polyethylene copolymers that have a narrow molecular weight distribution. Although there are single-site catalysts that can produce broader molecular weight distributions, these catalysts often show a narrowing of the molecular weight distribution as the reaction temperature is increased, for example, to increase production rates. In addition, a single-site catalyst will often incorporate a comonomer between the polyethylene copolymer molecules at a relatively uniform rate. The molecular weight distribution and the amount of comonomer incorporation can be used to determine a composition distribution.
[0004] The distribution of the composition of an ethylene alpha-olefin copolymer refers to the distribution of the comonomer, which forms short chain branches between the molecules comprising the polyethylene polymer. When the amount of short chain branches varies between polyethylene molecules, the resin is said to have a "wide" composition distribution. When the amount of comonomer per 1000 carbons is similar between polyethylene molecules of different chain lengths, the composition distribution is said to be "narrow".
[0005] The composition distribution is known to influence the properties of copolymers, for example, stiffness, hardness, extractable content, resistance to failure under environmental stress, and heat sealing, among other properties. The distribution of the composition of a polyolefin can be easily measured using methods known in the art, for example, fractionation by elution with temperature gradient (TREF) or fractionation of crystallization analysis (CRYSTAF).
[0006] It is generally known in the prior art that the distribution of the composition of a polyolefin is largely dictated by the type of catalyst used and is typically invariable for a given catalyst system. Ziegler-Natta catalysts and chromium-based catalysts produce resins with broad-composition distributions (BCD), while metallocene catalysts typically produce resins with narrow-composition distributions (NCD).
[0007] Resins having a wide distribution of the orthogonal composition (BOCD) in which the comonomer is incorporated predominantly in the high molecular weight chains can lead to improved physical properties, for example, toughness properties and resistance to environmental stress failure (ESCR ). Because of the better physical properties of resins with the required orthogonal composition distribution for commercially desirable products, there is a need for controlled techniques to form polyethylene copolymers with a wide distribution of the orthogonal composition. summary
[0008] An exemplary embodiment described here provides a method of alkylating an organometallic compound, substantially normalizing the stereochemical configuration. The method includes forming slurry of an organometallic compound in dimethoxyethane (DME) and adding a solution of RMgBr in DME, where R is a methyl group or a benzyl group, and where RMgBr is greater than about 2.3 equivalents in relation to the organometallic compound. After adding RMgBr, the slurry is mixed for at least about four hours. An alkylated organometallic is isolated, in which the methylated species has a meso / rac ratio that is between about 0.9 and about 1.2.
[0009] Another exemplary embodiment described here provides a method of alkylating an organometallic compound, substantially normalizing the stereochemical configuration. The method includes forming slurry of the organometallic compound in ether and adding a solution of RLi in ether, where R is a methyl group or a benzyl group, and where RMgBr is greater than about 2.3 equivalents with respect to the compound organometallic. After adding RMgBr, the slurry is mixed for at least about four hours. An alkylated organometallic is isolated, in which the methylated species has a meso / rac ratio that is between about 0.9 and about 1.2.
[0010] Another exemplary embodiment provides a catalyst composition comprising a first catalyst compound and a second catalyst compound that are co-supported to form a generally supported catalyst system, wherein the first catalyst compound comprises the following formula: (C5HaR1b (C5HcR2d) HfX2 Each R1 is independently H, a hydrocarb group, a substituted hydrocarb group, or a heteroatom group Each R2 is independently H, a hydrocarb group, a substituted hydrocarb group, or a hetero atom group. values for a and c are>3; a + b = c + d = 5. At least one R1 and at least one R2 is a substituted hydrocarbyl or hydrocarbyl group.Adjacent groups R1 and groups R2 can be coupled to form a ring Each X is, independently, a leaving group selected from a group of labile hydrocarbons, substituted hydrocarbons, or heteroatoms The second catalyst compound comprises a mixture of ena nthiomers:
The ratio of meso enantiomer to rac enantiomer is substantially normalized during alkylation to between about 1.0 and about 1.2. Each R3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. Each R5 is, independently, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R3, R4, and R5 can be the same or different. Each X is a methyl group.
[0011] Another exemplary embodiment provides a method of polymerizing olefins to produce a polyolefin polymer with a multimodal composition distribution, including the contact of ethylene and a comonomer with a catalyst system, wherein the catalyst system comprises a first catalyst compound and a second catalyst compound that are co-supported to form a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula: (C5HaR1b (C5HcR2d) HfX2 Each R1 is independently H, a hydrocarbon group, a substituted hydrocarb group, or a hetero atom group. Each R2 is independently H, a hydrocarb group, a substituted hydrocarb group, or a hetero atom group. Values for a and c are>3; a + b = c + d = 5. At least one R1 and at least one R2 is a substituted hydrocarbyl or hydrocarbyl group. Adjacent groups R1 and groups R2 can be coupled to form a ring. da X is, independently, a leaving group selected from a group of labile hydrocarbons, substituted hydrocarbons, or heteroatoms. The second catalyst compound comprises a mixture of enantiomers:
The meso enantiomer is at least about 15 parts of the mixture, the rac enantiomer is less than about 5 parts in the mixture. Each R3 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. Each R5 is, independently, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group. R3, R4, and R5 can be the same or different. Each X is, independently, a leaving group selected from a labile hydrocarbyl group, a substituted hydrocarbyl, a heteroatom, or a bivalent radical that binds to an R3, R4, or R5 group.
[0012] Another exemplary embodiment provides a polyolefin polymer, comprising ethylene and an alpha-olefin having from 4 to 20 carbon atoms, wherein the polyolefin polymer is formed using a catalyst mixture comprising a first catalyst compound and a second catalyst compound that is co-supported forming a commonly supported catalyst system, wherein the first catalyst compound comprises the following formula: (C5HaR1b) (C5HcR2d) HfX2 where each R1 is independently H, a group of hydrocarbons, a group of substituted hydrocarbil, or a heteroatom group; each R2 is independently H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; a and c are> 3; a + b = c + d = 5; at least one R1 and at least one R2 is a substituted hydrocarbyl or hydrocarbyl group; adjacent groups R1 and groups R2 can be coupled to form a ring; and each X is, independently, an leaving group selected from a group of labile, substituted hydrocarbyl, or heteroatom; and the second catalyst compound comprises a mixture of enantiomers: the ratio of one enantiomer to another enantiomer is at least about 3. Each R3 is independently H, a hydrocarb group, a substituted hydrocarb group, or a heteroatom group. R4 is a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; each R5 is, independently, H, a hydrocarbyl group, a substituted hydrocarbyl group, or a heteroatom group; wherein R3, R4, and R5 can be the same or different; and each X is, independently, a leaving group selected from a group of labile, substituted hydrocarbyl, or heteroatom, or a divalent radical that binds to a group R3, R4, or R5.
[0013] Another exemplary embodiment provides a method of forming a catalyst composition. The method comprises dissolving 1-ethylindenyl lithium in dimethoxyethane to form a precursor solution, cooling the precursor solution to about -20 ° C, adding solid ZrCl4 for about five minutes to start the reaction, continuing the reaction overnight another, removing the volatiles to form a crude product, extracting the crude product with CH2Cl2; and removing the CH2Cl2 under vacuum to form a mixture comprising about 19 parts of meso (1-EtInd) 2ZrCl2 and about 1 part of rac- (1-EtInd) 2ZrCl2. Brief description of the drawings
[0014] Fig. 1 is a schematic diagram of a gas-phase reactor system, showing the addition of at least two catalysts, at least one of which is added as a compensating catalyst.
[0015] Fig. 2 is a graphical representation of a series of polymers that have been prepared to test the relative abilities of a series of metallocene catalysts to prepare a resin having a melting index 1 (MI) and a density (D) of about 0.92.
[0016] Fig. 3 is a graphical representation of a series of polymers in Fig. 2, showing the ratio of the melting index (MIR) of the series of polymers made by different metallocene catalysts (MCN).
[0017] Fig. 4 is a flow chart of a method for producing a co-supported polymerization catalyst. Detailed Description
[0018] It has been found that when a support is impregnated with various catalysts, new polymeric materials with a balance of improved rigidity, strength and processability can be achieved, for example, by controlling the quantities and types of ecimal catalysts in the support. As described in the modalities here, an appropriate selection of catalysts and ratios can be used to adjust the molecular weight distribution (MWD), the short chain branch distribution (SCBD), and the long chain branch distribution (LCBD) of the polymer, for example, to provide a polymer with a wide ecimal composition distribution (BOCD). MWD, SCBD, and LCBDs would be controlled by combining catalysts with the appropriate average molecular weight (Mw), comonomer incorporation and the formation of long chain branching (LCB) under the conditions of polymerization.
[0019] With the use of multiple pre-catalysts that are co-supported on a single support mixed with an activator, such as methyl aluminoxane in ecima (SMAO), it can provide an ecimal cost of manufacturing the product in a reactor instead of multiple reactors. In addition, the use of a single support also ensures a close mixing of the polymers and offers improved operability with respect to the preparation of a mixture of polymers of different Mw and densities independently from several catalysts in a single reactor. As used here, a pre-catalyst is a catalyst ecimal prior to exposure to the activator.
[0020] As an example, for film applications for linear low density polyethylene (LLDPE) film, it would be desirable to prepare an ethylene hexene copolymer with a molecular weight between about 90 kg / mol and 110 kg / mol, or about 100 kg / mol and an average density between about 0.9 and 0.925, or about 0.918. The typical MWD for linear metallocene resins is 2.5 - 3.5. Mixtures studied indicate that it would be desirable to extend this distribution, with the use of two catalysts that each provide different average molecular weights. The ratio of Mw to the low molecular weight component and the high molecular weight component would be between 1: 1 and 1:10, or about 1: 2 and 1: 5.
[0021] The density of a polyethylene copolymer provides an indication of the comonomer incorporation in a polymer, with lower densities indicating greater incorporation. The difference in densities of the low molecular weight component (LMW) and the high molecular weight component (HMW) should preferably be greater than about 0.02, or greater than about 0.04, with the HMW with a lower density than the LMW component. For two resins with 25 kg / mol and 125 kg / mol Mw, the density difference requires around 1.5: 1 or, preferably, about 2: 1, preferably about 3: 1 or more, preferably 4: 1 or even greater than 4: 1 difference in the ability to incorporate comonomers. It is also desirable to minimize the level of branching of the long chain (LCB) in the polymer as that which provides strong guidance in film making that unbalances the MD / TD tension and reduces toughness.
[0022] These factors can be adjusted by controlling the MWD and SCBD, which, in turn, can be adjusted by changing the relative quantity of the two pre-catalysts on the support. This can be adjusted during the formation of pre-catalysts, for example, by supporting two catalysts on a single support. In some embodiments, the relative amounts of pre-catalysts can be adjusted by adding one of the components of a catalyst mixture en route to the reactor in a process called "compensation". Feedback of polymer property data can be used to control the amount of catalyst addition. Metallocenes (MCNs) are known for compensation as well as other catalysts.
[0023] In addition, a variety of resins with different MWD, SCBD, and LCBD can be prepared from a limited number of catalysts. To perform this function, pre-catalysts must compensate on activating supports. Two parameters that benefit from this are solubility in alkane solvents and rapid support in the catalyst slurry en route to the reactor. This favors the use of MCNs to achieve controlled MWD, SCBD and LCBD. Techniques for selecting catalysts that can be used to generate desired molecular weight compositions, including BOCD polymer systems, are disclosed herein.
[0024] Various catalyst systems and components can be used to generate the disclosed polymers and molecular weight compositions. These are discussed in the following sections. The first section describes catalyst compounds that can be used in modalities. The second section addresses the generation of catalyst slurry that can be used to implement the techniques described. The third section describes catalyst supports that can be used. The fourth section discusses the catalyst activators that can be used. The fifth section discusses the catalyst component solutions that can be used to add additional catalysts in compensation systems. Gas phase polymerizations may use static or continuity control agents, which are discussed in the sixth section. A gas phase polymerization reactor with a compensation feed system is discussed in section seven. The use of the catalyst composition to control product properties is discussed in the eighth section and an exemplary polymerization process is discussed in the ninth section. Examples of the application of the discussed procedures are incorporated in the tenth section. Catalyst Compounds Metallocene Catalyst Compounds
[0025] Metallocene catalyst compounds may include "half sandwich" and / or "full sandwich" type compounds that have one or more Cp linkers (cyclopentadienyl and isolobal cyclopentadienyl linkers) coupled to at least one Group 3 metal atom to Group 12, and one or more leaving groups coupled to at least one metal atom. As used here, any reference to the Periodic Table of the Elements and its groups is applied to the NEW NOTATION published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997) (reproduced with permission from IUPAC ), unless reference is made to the previous form of IUPAC annotated with Roman numerals (they also appear in it), or unless otherwise specified.
[0026] Cp linkers are one or more rings or ring system (s) at least a portion of which include π-coupled systems, such as cycloalkadienyl and heterocyclic analogs. The ring (s) or ring system (s) typically includes atoms selected from the group consisting of groups of 13 to 16 atoms, and, in an exemplary embodiment in particular, the atoms that form the Cp ligands are selected at from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron, aluminum, and combinations thereof, in which carbon constitutes at least 50% of the ring members. In a more particular exemplary embodiment, the Cp ligand (s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and isolobal to cyclopentadienyl ligands, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenil and other structures. Other non-limiting examples of such binders include cyclopentadienyl, cyclopentafenanthrene, indenyl, benzinden, fluorenyl, octahidrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenantrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 7-phenylfluorenyl, 7-phenylfluorenyl, H- dibenzofluorenyl, indene [1,2-9] anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (for example, 4,5,6,7-tetrahydroindenyl, or "H4 Ind"), the replaced versions thereof (as discussed and described in detail below), and heterocyclic versions thereof.
[0027] The metal atom "M" of the compound of the metallocene catalyst can be selected from the group consisting of groups of 3 to 12 atoms and the atoms of the group of lanthanides in an exemplary mode; and selected from the group consisting of groups of 3 to 10 atoms in a more particular exemplary modality, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe , Ru, Os, Co, Rh, Ir, and Ni, in yet a more particular exemplary modality; and selected from the group consisting of groups of 4, 5, and 6 atoms in yet another more particular exemplary modality, and Ti, Zr, Hf atoms in still a more particular exemplary modality, and Hf still in an exemplary modality more particular. The oxidation state of the metal atom "M" can vary from 0 to +7 in an exemplary embodiment; and in a more particular exemplary modality, they can be +1, +2, +3, +4, or +5; and in yet a more particular exemplary modality they can be +2, +3 or +4. The groups coupled to the metal atom "M" are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp linkers form at least one chemical bond with the metal atom M to form the "metallocene catalyst compound". Cp ligands are different from the leaving groups coupled to the catalyst compound since they are not highly susceptible to substitution / abstraction reactions.
[0028] The one or more metallocene catalyst compounds can be represented by the formula (I): CpACpBMXn (I) where M is as described above; each X is chemically coupled to M; each Cp group is chemically coupled to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular exemplary embodiment.
[0029] The linkers represented by CPA and CpB in formula (I) can be the same or different cyclopentadienyl ligands or isolobal to cyclopentadienyl ligands, one or both of which may contain heteroatoms and one or both of which can be replaced by one group R. In at least one specific modality, CPA and CPB are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
[0030] Regardless, each CpA and CpB of formula (I) can be unsubstituted or substituted with any or combination of the substituent groups R. Non-limiting examples of substituent groups R, as used in structure (I), as well as substituents of the ring in Va-d structures, discussed and described below, include groups selected from the group consisting of hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aryls, alkoxys, aryloxies, alkylthiois, dialkylamines, alkylamidos , alkoxy carbonyls, aryloxy carbonyls, carbamoyl, alkyl- and dialkyl-carbamoyl, acyloxis, acylaminos, aroylaminos, and combinations thereof. More particularly, non-limiting examples of R with alkyl substituents associated with formulas (I) to (Va-d) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl groups and tert-butylphenyl and the like, including all of its isomers, for example, tert-butyl, isopropyl and the like.
[0031] As used herein, and in the claims, the substituents or groups of hydrocarbyl, are made up of between 1 and 100 or more carbon atoms, the remainder being hydrogen. Non-limiting examples of hydrocarbyl substituents include linear or branched or cyclic radicals: alkyl radicals; alkenyl radicals; alkynyl radicals; cycloalkyl radicals; aryl radicals; alkylene radicals, or a combination thereof. Non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; olefinically unsaturated substituents, including binders terminated by vinyl groups (for example but-3-enyl, prop-2-enyl, hex-5-enyl and the like), benzyl or phenyl groups and the like, including all their isomers, for example, tertiary butyl, isopropyl and the like.
[0032] As used herein, and in the claims, the substituted hydrocarbon substituents or groups are comprised of between 1 and 100 or more carbon atoms, the remainder being hydrogen, fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen , phosphorus, boron, silicon, germanium or tin atoms or other atom systems tolerant to olefin polymerization systems. Substituted hydrocarbon substituents are carbon-based radicals. Non-limiting examples of substituted hydrocarbon substituents are trifluoromethyl radical, trimethylasilanomethyl radicals (2-Me3SiCH).
[0033] As used herein, and in the claims, the substituents or groups of heteroatoms are fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, germanium or tin-based radicals. They can be the heteroatom atom, by itself. In addition, heteroatom substituents include organometalloid radicals. Non-limiting examples of heteroatom substituents include chlorine radicals, fluorine radicals, methoxy radicals, amino radicals, diphenyl thioalkyl radicals, thioalkenyl radicals, trimethylsilyl, aluminum dimethyl radicals, alkoxy-dihydrocarbylsilyl radicals, siloxy-di-hydrocabilyl radicals, perflourophenyl) boron and the like.
[0034] Other possible radicals include substituted alkyls and aryls, such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl organometalloid radicals including trimethylsilyl, trimethylgermyl, methylldiethyl, and the like, and substituted organometalloidal radicals. , including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboro, for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, as well as Group 16 radicals, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfite. Other substituent groups R include, but are not limited to, olefins, such as olefinically unsaturated substituents, including vinyl group-terminated linkers, such as, for example, 3-butenyl, 2-propenyl, 5-hexenyl, and the like. In an exemplary embodiment, at least two R groups (two adjacent R groups in a particular exemplary embodiment) are joined to form a ring structure having 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron, and combinations thereof. In addition, a substituent group R such as 1-butanyl may form a binding association to the M element.
[0035] Each X in the formula (I) above and for the formula / structures (II) to (Va-d) below is independently selected from the group consisting of: any leaving group, in an exemplary mode; halogen ions, hydrides, C1 to C12 alkyl groups, C2 to C12 alkenyl, C6 to C12 aryl, C7 to C20 alkylaryls, C1 to C12 alkoxides C6 to C16 aryloxy, C7 to C8 alkylaryloxys, C1 to C12 fluoroalkyls, C6 to C12 fluoroaryls , and heteroatoms C1 to C12 substituents derived therefrom, in an exemplary embodiment, more particularly; hydride, halogen ions, C1 to C6 alkyls, C2 to C6 alkenyls, C7 to C18 alkylaryls, C1 to C6 alkoxys, C6 to C14 aryloxy, C7 to C16 alkylaryloxys, C1 to C6 alkylcarboxyl, producing new fluorinated polymerisation catalysts, fluorinated alkylcarboxylates1 to C6, C6 to C12 arylcarboxylates, C7 to C18 alkylarylcarboxylates, C1 to C6 fluoroalkyls, C2 to C6 fluoroalkenyls, and C7 to C18 fluoroalkylyls in yet an exemplary, more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls, fluorophenyls, and in yet a more particular exemplary embodiment; alkyls C1 to C12, alkenyls C2 to C12, aryls C6 to C12, alkyls C7 to C20, alkyls substituted C1 to C12, aryls substituted C6 to C12, alkyls substituted C7 to C20 and alkyls containing heteroatoms C1 to C12, alkyls containing C1 to heteroatoms C12, in an even more particular exemplary modality; chloride, fluoride, C1 to C6 alkyls, C2 to C6 alkenyls, C7 to C18 alkylaryls, C1 to C6 halogenated alkyls, C2 to C6 halogenated alkenyls, and C7 to C18 halogenated alkylaryls, in yet a more particular exemplary embodiment; fluorine, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls), in yet an exemplary modality, particular; and fluorine, in yet a more particular exemplary modality.
[0036] Other non-limiting examples of groups X include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g. -C6F5 (pentafluorophenyl)), fluorinated alkylcarboxylates ( for example, CF3C (O) O-), hydrides, halogen ions and combinations thereof. Other examples of X linkers include alkyl groups, such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyloxy, ethioxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In an exemplary embodiment, two or more groups X 'form a part of a ring or fused ring system. In at least one specific embodiment, X may be a leaving group selected from the group consisting of chloride ions, bromide ions, C1 to C10 alkyls, alkenyls and C2 to C12, carboxylates, acetylacetonates and alkoxides.
[0037] The metallocene catalyst compound includes those of formula (I) in which CPA and CpB and are bridged to each other by at least one bridged group, (A), such that the structure is represented by formula (II): CpA (A) CpBMXn (II) These bridged compounds represented by formula (II) are known as "bridged metallocenes". The elements of CPA and CpB, M, X and n in structure (II) are defined as above for formula (I); wherein each Cp ligand is chemically coupled to M, and (A) is chemically coupled to each Cp. The bridged group (A) may include divalent hydrocarbon groups containing at least one atom from Group 13 to 16, such as, but not limited to, at least one of a carbon atom, oxygen, nitrogen, silicon, aluminum, boron , germanium, tin atom, and combinations thereof; wherein the heteroatom can also be C1 to C12 alkyl or substituted aryl to satisfy the neutral valence. In at least one specific embodiment, the bridged group (A) can also include substituent groups R as defined above (for formula (I)), including the halogen and iron radicals. In at least one specific embodiment, the bridged group (A) can be represented by C1 to C6 alkylenes, substituted C1 to C6 alkylenes, oxygen, sulfur, R'2C =, R'2Si =, = Si (R ') 2Si (R'2) =, R'2Ge =, and R'P =, where "=" represents two chemical bonds, R 'is independently selected from the group consisting of hydride, hydrocarbil, substituted hydrocarbil, halocarbil, substituted halocarbil , substituted hydrocarbyl organometaloids, substituted halocarbyl organometaloids, disubstituted boron, atoms of Group 15 disubstituted, atoms of Group 16 substituted, halogen radical; and wherein two or more groups R 'can be joined to form a ring or ring system. In at least one specific embodiment, the bridged metallocene catalyst compound of formula (II) includes two or more bridging groups (A). In one or more modalities, (A) can be a divalent bridge group coupled to both CPA and CpB selected from the group consisting of divalent Cl to C20 hydrocarbon and hydrocarbonyls containing Cl to C20 heteroatom, where hydrocarbonyls containing heteroatom include from one to three heteroatoms.
[0038] The bridged group (A) can include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl - ethylsilyl, trifluoromethylbutylsilyl, bis (trifluoromethyl) silyl, di (n-butyl) silyl, di (n-propyl) silyl, di (i-propyl) silyl, di (n-hexyl) silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di (t-butylphenyl) silyl, di (p-tolyl) silyl, and the corresponding radicals in which the Si atom is replaced by a Ge or a C atom; as well as dimethylsilyl, diethylsilyl, dimethylgermil and diethylgermil. The bridged group (A) can also include groups -Si (hydrocarbyl) 2-O- (hydrocarbyl) 2Si-- Si (substituted hydrocarbyl) 2-O- (substituted hydrocarbyl) 2Si- and the like, such as -SiMe2-O -SiMe2- and -SiPh2-O- SiPh2-.
[0039] The bridged group (A) can also be cyclic, having, for example, from 4 to 10 ring members; in an exemplary, more particular embodiment, the bridged group (A) can have 5 to 7 ring members. The ring members can be selected from the elements mentioned above, and, in a particular embodiment, they can be selected from one or more of B, C, Si, Ge, N and O. The non-limiting examples of structures in ring that may be present as, or as part of, the bridged portion are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, octylidene and the corresponding rings, in which one or two carbon atoms are replaced by at least one of Si, Ge, N and O. In one or more modalities, one or two carbon atoms can be replaced by at least one from Si and Ge. The bonding arrangement between the ring and the Cp groups can be cis, trans, or a combination thereof.
[0040] Cyclic bridged groups (A) can be saturated or unsaturated and / or can carry one or more substituents and / or can be fused with one or more other ring structures. If present, the one or more substituents can be, in at least one specific modality, selected from the group consisting of hydrocarbyl (eg, alkyl, such as methyl) and halogen (eg, F, Cl). The one or more Cp groups to which the previous cyclic bridged groups can optionally be fused, can be saturated or unsaturated, and are selected from the group consisting of those having 4 to 10, preferably 5, 6, to 7 ring members (selected from a group consisting of C, N, O and S, in a particular exemplary embodiment), such as, for example, cyclopentyl, cyclohexyl and phenyl. Furthermore, these ring structures can themselves be fused together, for example, in the case of a naphthyl group. In addition, these ring structures (optionally fused) can carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl groups (particularly alkyl) and halogen atoms. The CPA binders and the CPB of formula (I) and (II) can be different from each other. The CPA binders and the CPB of structural formula (I) and (II) can be the same. The metallocene catalyst compound can include mono-linker bridged metallocene compounds (e.g., mono cyclopentadienyl catalyst components).
[0041] It is contemplated that the metallocene catalyst components discussed and described above include their structural or optical or enantiomeric isomers (racemic mixture), and, in an exemplary embodiment, may be pure enantiomers. As used herein, a single, asymmetrically substituted, bridged metallocene catalyst compound having a racemic and / or meso isomer does not in itself constitute at least two different bridged metallocene catalyst components.
[0042] As noted above, the amount of the transition metal component of one or more metallocene catalyst compounds in the catalyst system can vary from a low point of about 0.001% by weight, about 0.2% by weight , about 3% by weight, about 0.5% by weight or about 0.7% by weight. For a maximum of about 1% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, about 3.5% by weight or about 4% by weight, based on the total weight of the catalyst system.
[0043] The "metallocene catalyst compound" may include any combination of any "embodiments" discussed and described herein. For example, the metallocene catalyst compound may include, but is not limited to, bis (n-propylcyclopentadienyl) hafnium (CH3) 2 , bis (n-propylcyclopentadienyl) hafniumF2, bis (n-propylcyclopentadienyl) hafnium Cl2, bis (n-butyl, methyl cyclopentadienyl) zirconiumCl2, or [(2,3,4,5,6- Me5C6N) CH2CH2] 2NHZrBn2, where Bn is a benzyl group, or any combination thereof.
[0044] Other metallocene catalyst compounds that can be used are supported restricted geometry catalysts (sCGC) that include (a) an ionic complex, (b) a transition metal compound, (c) an organometallic compound, and ( d) a support material. In some embodiments, the sCGC catalyst may include a borate ion. The borate anion is represented by the formula [BQ4-z '(Gq (T - H) r) z'] d-, where: B is boron in a valence state of 3; Q is selected from the group consisting of hydride, dihydrocarbyl starch, halide, hydrocarbyl oxide, hydrocarbyl, and substituted hydrocarbyl radicals; Z 'is an integer in a range from 1 to 4; G is a polyvalent hydrocarbon radical having valences r + 1 linked to M 'and groups (T - H); q is an integer, 0 or 1; the group (T - H) is a radical in which T comprises O, S, NR, or PR, the atom O, S, N or P which is attached to the hydrogen atom H in which R is a hydrocarbyl radical, a trihydrocarbylsilyl, a germyl trihydrocarbylaluminum radical or hydrogen; r is an integer from 1 to 3; and d is 1. Alternatively, the borate ion can be represented by the formula [BQ4-z '(Gq (T - MoRCx-1Xay) r) z'] d-, where: B is boron in a valence state of 3; Q is selected from the group consisting of hydride, dihydrocarbyl starch, halide, hydrocarbyl oxide, hydrocarb, and hydrocarbyl-substituted radicals; z 'represents an integer in a range from 1 to 4; G is a polyvalent hydrocarbon radical having r + 1 valences linked to the groups of B and r (T - MoRCx-1Xay); q is an integer, 1 or 0; the group (T-- MoRCx-1Xay) is a radical in which T comprises O, S, NR, or PR, the atom of O, S, N or P of which Mo is coupled, in which R is a hydrocarbyl radical , a trihydrocarbylsilyl radical, a germyl trihydrocarbyl aluminum radical or hydrogen; Mo is a metal or metalloid selected from Groups 1-14 of the elements of the Periodic Table, Rc regardless of whether each occurrence is hydrogen or a group having 1 to 80 non-hydrogen atoms that is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilyl hydrocarbyl; Xa is a non-interfering group that has from 1 to 100 non-hydrogen atoms that is halocarbylated hydrocarbyl, hydrocarbyl-substituted hydrocarbyl, hydrocarbyl-substituted hydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is a different non-zero integer, which can vary between 1 and an integer equal to the valence of Mo; y is zero or an integer other than zero, which can vary from 1 to an integer equal to 1 less than the valence of Mo; and x + y is equal to the valence of Mo; r is an integer from 1 to 3 ;, and d is 1. In some embodiments, the borate ion can be of the formulas described above where z 'is 1 or 2, q is 1, and r is 1.
[0045] The catalyst system may include other single site catalysts, such as catalysts containing Group 15 elements. The catalyst system may include one or more second catalysts in addition to the single site catalyst compound, such as base catalysts chromium, Ziegler-Natta catalysts, one or more single site catalysts such as metallocenes or catalysts containing Group 15 elements, bimetallic catalysts and mixed catalysts. The catalyst system can also include AlCl3, cobalt, iron, palladium, or any combination thereof.
[0046] Examples of MCN compound structures that can be used in modalities include the hafnium compound indicated by Formula (II), the zirconium compounds shown as formulas (IV-AC), and zirconium bridge compounds, shown as the formulas (VAB).
Although these compounds are presented with methyl- and chloro-groups attached to the central metal, it can be understood that these groups can be different without changing the catalyst involved. For example, each of these substituents can be, independently, a methyl group (Me), a chlorine group (Cl), a fluoro group (F), or any number of other groups, including organic groups, or groups of hetero atoms. In addition, these substituents will change during the reaction, as a pre-catalyst is converted into the active catalyst for the reaction. In addition, any number of other substituents can be used on the ring structures, including any of the substituents described above in relation to formulas (I) and (II). Catalyst Compounds containing Metal and Atoms of Group 15
[0047] The catalyst system can include one or more catalyst compounds containing Group 15 metals. The compound containing a Group 15 metal generally includes a Group 3 to 14 metal atom, a group of 3 to 7, or a Group 4 to 6 metal atom. In many embodiments, the Group 15 metal-containing compound includes a Group 4 metal atom attached to at least one leaving group and also attached to at least two Group 15 atoms, at least one of which is also attached to an atom of Group 15 or 16 by means of another group.
[0048] In one or more embodiments, at least one Group 15 atom is also coupled to a Group 15 or 16 atom by means of another group which may be a C1 to C20 hydrocarbon group, a group containing heteroatom, silicon, germanium, tin, lead, or phosphorus, in which the Group 15 or 16 atom may also be coupled to nothing or be coupled to a hydrogen, a group containing a Group 14 atom, a halogen, or a group containing a heteroatom , and wherein each of the two atoms in Group 15 is also attached to a cyclic group and, optionally, may be attached to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a group containing a heteroatom.
[0049] The compounds containing a Group 15 metal can be described more particularly with formulas (VI) or (VII):
where M is a transition metal from Group 3 to 12, or a metal from the main Group 13 or 14, a metal from Group 4, 5, or 6. In many embodiments, M is a Group 4 metal, such as zirconium, titanium or hafnium. Each X is, independently, an leaving group, just like an anionic leaving group. The leaving group can include a hydrogen, a hydrocarbyl group, a heteroatom, a halogen, or an alkyl; y is 0 or 1 (when y is 0 the group L 'is absent). The term "n" is the oxidation state of M. In several embodiments, n is +3, +4, or +5. In many modalities, n is 4. The term 'm' represents the formal charge of YZL or the ligand YZL ', and is 0, -1, -2 or -3 in various modalities. In many modalities, m is -2. L is an element of Group 15 or 16, like nitrogen; L 'is an element of Group 15 or 16 or a group containing a Group 14, such as carbon, silicon or germanium. Y is an element of Group 15, such as nitrogen or phosphorus. In many embodiments, Y is nitrogen. Z is an element of Group 15, like nitrogen or phosphorus. In many embodiments, Z is nitrogen. R1 and R2 are, independently, a C1 to C20 hydrocarbon group, a group containing a heteroatom containing up to twenty carbon atoms, silicon, germanium, tin, lead or phosphorus. In many embodiments, R1 and R2 are a C2 to C20 alkyl, aryl, or aralkyl group, such as a linear, branched, or cyclic C2 to C20 alkyl group, or a C2 to C6 hydrocarbon group. R1 and R2 can also be interconnected to each other. R3 may be absent or it may be a hydrocarbon group, a hydrogen, a halogen, a group containing a hetero atom. In many embodiments, R3 is absent or hydrogen, or an alkyl group having 1 to 20 linear, cyclic or branched carbon atoms. R4 and R5 are independently an alkyl group, an aryl group, substituted aryl group, a cyclic alkyl group, a substituted cyclic alkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group or a multiple ring system, often having up to 20 carbon atoms. In many embodiments, R4 and R5 have between 3 and 10 carbon atoms, or are a C1 to C20 hydrocarbon group, a C1 to C20 aryl group or a C1 to C20 aralkyl group, or a group containing a heteroatom. R4 and R5 can be interconnected to each other. R6 and R7 are independently absent, hydrogen, an alkyl, halogen, heteroatom group, or a hydrocarbyl group, such as a linear, cyclic, or branched alkyl group with 1 to 20 carbon atoms. In many modalities, R6 and R7 are absent. R * may be absent, or it may be a hydrogen, a group containing atoms of Group 14, a halogen, or a group containing heteroatom
[0050] By "formal charge of YZL or YZL ligand '" is meant the charge of the entire ligand, in the absence of metal and the leaving groups X. "R1 and R2 can also be interconnected" means that R1 and R2 can be directly coupled to each other or can be coupled to each other by means of other groups. By "R4 and R5 can also be interconnected" it is meant that R4 and R5 can be coupled directly to each other or can be coupled to each other by means of other groups. An alkyl group can be linear, branched alkyl radicals, alkenyl radicals, alkynyl radicals, cycloalkyl radicals, aryl radicals, aryl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbon radicals alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, linear, branched or cyclic radicals, alkylene radicals, or a combination thereof. An aralkyl group is defined as a substituted aryl group.
[0051] In one or more modalities, R4 and R5 are, independently, a group represented by the following formula (VIII).
When R4 and R5 are according to formula VII, R8 to R12 are each independently hydrogen, a C1 to C40 alkyl group, a halide, a heteroatom, a group containing heteroatom containing up to 40 carbon atoms. In many embodiments, R8 to R12 are a straight or branched C1 to C20 alkyl group, such as methyl, ethyl, propyl or butyl. Either of the two R groups can form a cyclic group and / or a heterocyclic group. Cyclic groups can be aromatic. In an R9 embodiment, R10 and R12 are, independently, a methyl, ethyl, propyl, or butyl group (including all isomers). In another modality, R9, R10 and R12 are methyl groups, and R8 and R11 are hydrogen.
[0052] In one or more modalities, R4 and R5 are both a group represented by the following formula (IX).
When R4 and R5 follow formula IX, M is a Group 4 metal, such as zirconium, titanium, or hafnium. In many embodiments, M is zirconium. Each of L, Y, and Z can be a nitrogen atom. Each of R1 and R2 can be a -CH2-CH2- group. R3 may be hydrogen, and R6 and R7 may be absent.
[0053] The catalyst compound containing a Group 15 metal can be represented by the following formula (X).
In formula X, Ph represents phenyl. Catalyst slurry
[0054] The catalyst system may include a catalyst or catalyst component in a slurry, which may have an initial catalyst compound, and an added solution catalyst component that is added to the slurry. The initial catalyst component slurry may lack catalysts. In this case, two or more catalysts in solution can be added to the slurry to produce that each can be supported.
[0055] Any number of combinations of catalyst components can be used in the modalities. For example, the catalyst component slurry may include an activator and a support, or a supported activator. In addition, the slurry may include a catalyst compound in addition to the activator and support. As noted, the catalyst compound in the slurry can be supported.
[0056] The slurry may include one or more activators and supports, and one or more catalyst compounds. For example, the slurry can include two or more activators (such as alumoxane and a modified alumoxane) and a catalyst compound, or the slurry can include a supported activator and more than one catalyst compound. In one embodiment, the slurry includes a support, an activator, and two catalyst compounds. In another embodiment, the slurry includes a support, an activator and two different catalyst compounds, which can be added to the slurry separately or in combination. The slurry, containing silica and aluminoxane, can be contacted with a catalyst compound, to react, and after that the slurry is brought into contact with another catalyst compound, for example, in a compensation system.
[0057] The molar ratio of metal in the activator to metal, such as aluminum, or metalloid, such as boron, in the catalyst compound in the slurry can be from 1000: 1 to 0.5: 1, 300: 1 to 1: 1, or 150: 1 to 1: 1. The slurry may include a support material which can be any inert particulate carrier material known in the art, including, but not limited to, silica, fumed silica, alumina, clay, talc or other support materials, such as described above. In one embodiment, the slurry contains silica and an activator, such as methyl aluminoxane ("MAO"), modified methyl aluminoxane ("MMAO"), as will be discussed below.
[0058] One or more diluents or carriers can be used to facilitate the combination of any two or more components of the catalyst system in the slurry or compensation catalyst solution. For example, the single site catalyst compound and the activator can be combined together in the presence of toluene or another hydrocarbon or non-reactive hydrocarbon mixture to provide the catalyst mixture. In addition to toluene, other suitable diluents may include, but are not limited to, ethylbenzene, xylene, pentane, hexane, heptane, octane, and other hydrocarbons, or any combination thereof. The support, dried or mixed with toluene, can then be added to the catalyst mixture or the catalyst mixture / activator can be added to the support. Catalyst Support
[0059] As used here, the terms "support" and "carrier" are used interchangeably and refer to any support material, including a porous support material, such as talc, inorganic oxides, inorganic chlorides. The one or more compounds of single-site catalysts in the slurry can be supported on the same supports or separate supports together with the activator, or the activator can be used in an unsupported manner, or it can be deposited on a support different from the compounds of single site catalysts, or any combination thereof. This can be achieved by any technique commonly used in the prior art. There are several other methods in the art for supporting a single site catalyst compound. For example, the single site catalyst compound can contain a linker coupled to the polymer. The slurry single-site catalyst compounds can be spray dried. The support used with the single site catalyst compound can be functionalized.
[0060] The support can be or include one or more inorganic oxides, for example, elements of Group 2, 3, 4, 5, 13, or 14. Inorganic oxide can include, but is not limited to silica, alumina, titania , zirconia, boron, zinc oxide, magnesium, or any combination thereof. Illustrative combinations of inorganic oxides may include, but are not limited to, alumina-silica, silica-titania, alumina-silica-titania, alumina-zirconia, alumina-titania and the like. The support can be or include alumina, silica, or a combination thereof. In an embodiment described here, the support is silica.
[0061] Suitable commercially available silica supports may include, but are not limited to, ES757, ES70, and ES70W available from PQ Corporation. Suitable commercially available silica-alumina supports may include, but are not limited to, SIRAL® 1, SIRAL® 5, SIRAL® 10, SIRAL® 20, SIRAL® 28M, SIRAL® 30, and SIRAL® 40, available from SASOL ®. Generally, catalyst supports comprising silica gels with activators, such as methyl aluminoxanes (MAOs), are used in the described compensation systems, since these supports can work best for the support cocatalyst solution performed. Suitable supports can also be selected from CAB-o-sil® materials available from Cabot Corporation and silica materials available from Grace Davison Corporation.
[0062] Catalyst supports can also include polymers that are covalently coupled to a binder in the catalyst. For example, two or more catalyst molecules can be coupled to a single polyolefin chain. Catalyst activators
[0063] As used here, the term "activator" can refer to any compound or combination of compounds, supported or unsupported, that can activate a single site catalyst compound or component, such as by creating a cationic species of catalyst component. For example, this may include the capture of at least one leaving group (the "X" group in the single site catalyst compounds described herein) from the metal center of the single site catalyst compound / component. The activator can also be called a "cocatalyst".
[0064] For example, the activator may include a Lewis acid or a non-coordinating ionic activator or ionizing activator, or any other compound, including Lewis bases, aluminum alkyls, and / or conventional type cocatalysts. In addition to methyl aluminoxane ("MAO") and modified methyl aluminoxane ("MMAO") mentioned above, illustrative activators may include, but are not limited to, aluminoxane or modified aluminoxane, and / or ionic neutral ionizing compounds, comodimethylanilinium tetraquis (pentafluorofenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (3,5- (CF3) 2phenyl) borate, triphenylcarbenium tetrakis (3,5- (CF3) 2phenyl) borate, triphenylcarbene tetraquis pentafluorophenylphenylate, boron, tetraquisylate triphenylcarbenium tetraquis (pentafluorophenyl) aluminate, dimethylanilinium tetrakis (pentafluoronaftil) aluminate, triphenylcarbene tetraquispentafluoronaftil) aluminate, tris (perfluorophenyl), boron, tris (perfluorophenyl) (perfluorophenyl)
[0065] It is recognized that these activators can bind directly to the support surface or be modified to allow them to be coupled to a support surface, maintaining their compatibility with the polymerization system. Such anchoring agents can be derived from groups that are reactive with surface hydroxyl species. Non-limiting examples of reactive functional groups that can be used to create anchorage include aluminum halides, aluminum hydrides, aluminum alkyls, aluminum aryls, aluminum alkoxides, electrophilic silicone reagents, alkoxy silanes, amino silanes, boranes.
[0066] Aluminoxanes can be described as oligomeric aluminum compounds that have -Al subunits (RO-, where R is an alkyl group. Examples of aluminoxanes include, but are not limited to, methyl aluminoxane ("MAO"), methyl modified aluminoxane ("MMAO"), ethylaluminoxane, isobutylaluminoxane, or a combination thereof. Aluminoxanes can be produced by hydrolysis of the corresponding trialkylaluminium compound.MMAO can be produced by the hydrolysis of trimethylaluminium and a higher trialkylaluminium, such as tri-isobutylaluminum MMAOs are generally more soluble in aliphatic solvents and more stable during storage.There are a variety of methods for preparing aluminoxanes and modified aluminoxane.
[0067] In one or more modalities, a visually clear MAO can be used. For example, a cloudy or gelled aluminoxane can be filtered to produce a clear aluminoxane or clear aluminoxane can be decanted from a cloudy aluminoxane solution. In another embodiment, a cloudy and / or gelled aluminoxane can be used. Another aluminoxane may include a modified type 3A methyl aluminoxane ("MMAO") (commercially available from Akzo Chemicals, Inc. under the trade name modified Type 3A methyl aluminoxane). A suitable source of MAO can be a solution having from about 1% by weight to about 50% by weight of MAO, for example. Commercially available MAO solutions may include commercially available 10% by weight and 30% by weight MAO solutions from Albemarle Corporation, Baton Rouge, LA.
[0068] As mentioned above, one or more organo-aluminum compounds, such as one or more alkyl aluminum compounds can be used in conjunction with aluminoxanes. For example, the alkyl aluminum species that can be used are diethyl aluminum ethoxide, diethyl aluminum chloride, and / or diisobutyl aluminum hydride. Examples of trialkyl aluminum compounds include, but are not limited to, trimethyl aluminum, triethyl aluminum ("TEAL"), tri isobutyl aluminum ("TIBAL"), tri-n-hexyl aluminum, tri-n-octyl aluminum, tripropyl aluminum, tributyl aluminum and the like. Catalyst Component Solutions
[0069] The catalyst component solution may include only one catalyst compound or may include an activator, in addition to the catalyst compound. The catalyst solution used in the compensation process can be prepared by dissolving the catalyst compound and optional activators in a liquid solvent. The liquid solvent can be an alkane, such as a C5 to C30 alkane, or a C5 to C10 alkane. Cyclic alkanes can also be used, such as cyclohexane and aromatic compounds, such as toluene. In addition, mineral oil can be used as a solvent. The solution used must be liquid under the conditions of polymerization and relatively inert. In one embodiment, the liquid used in the catalyst compound solution is different from the diluent used in the catalyst component slurry. In another embodiment, the liquid used in the catalyst compound solution is the same as the diluent used in the catalyst component solution.
[0070] If the catalyst solution includes both the activator and the catalyst compound, the ratio of metal in the activator to metal, such as aluminum, or metalloid, such as boron, in the catalyst compound solution can be 1000: 1 to 0.5: 1, 300: 1 to 1: 1, or 150: 1 to 1: 1. In certain cases, it may be advantageous to have an excess of catalyst compound such that the ratio is <1: 1, for example, 1: 1 to 0.5: 1 or 1: 1 to 0.1: 1 or 1: 1 to 0.01. In various embodiments, the activator and the catalyst compound is present in the solution at about 90% by weight, at about 50% by weight, at about 20% by weight, preferably at about 10% by weight. weight, at about 5% by weight, at least 1% by weight, or between 100 ppm and 1% by weight, based on the weight of the solvent and the activator or catalyst compound.
[0071] The catalyst component solution can comprise any of the soluble catalyst compounds described in the catalyst section described herein. As the catalyst is dissolved in the solution, higher solubility is desirable. As a consequence, the catalyst compound in the catalyst component solution can often include a metallocene, which may have a higher solubility than other catalysts.
[0072] In the polymerization process, described below, any of the catalyst components described above, containing the solutions can be combined with any slurry / slurry containing catalyst components described above. In addition, more than one catalyst component solution can be used. Continuity Additives / Static Control Agents
[0073] In gas phase polyethylene production processes, as disclosed herein, it may be desirable to additionally use one or more static control agents to assist in the regulation of static levels in the reactor. As used here, a static control agent is a chemical composition that, when introduced into a fluidized bed reactor, can influence or direct the static charge (negatively, positively, or zero) in the fluidized bed. The specific static control agent used may depend on the nature of the static charge, and the choice of static control agent can vary depending on the polymer to be produced and the single site catalyst compounds to be used.
[0074] Control agents such as aluminum stearate can be used. The static control agent used can be selected for its ability to receive the static charge in the fluidized bed, without adversely affecting productivity. Other suitable static control agents may also include aluminum distearate, ethoxylated amines, and antistatic compositions, such as those provided by Innospec Inc. under the trade name OCTASTAT. For example, OCTASTAT 2000 is a mixture of a polysulfone copolymer, a polymeric polyamine, and oil-soluble sulfonic acid.
[0075] Any of the aforementioned control agents can be used alone or in combination, as a control agent. For example, a metal carboxylate salt can be combined with an amine-containing control agent (for example, a metal carboxylate salt with any member of the KEMAMINE® family (available from Crompton Corporation) or the ATMER® product family (available from ICI Americas Inc.).
[0076] Other useful continuity additives include ethyleneimine additives useful in the embodiments disclosed herein which may include polyethyleneimines having the following general formula: - (CH2-CH2-NH) n- where n can be between about 10 to about 10,000. Polyethyleneimines can be linear, branched or hyper-branched (for example, forming structures of dendritic or arborescent polymers). They can be an ethyleneimine homopolymer or copolymer or mixtures thereof (called polyethyleneimine (s) hereinafter). Although linear polymers, represented by the chemical formula - [CH2-CH2-NH] - can also be used as polyethyleneimine, materials with primary, secondary, and tertiary branches can be used. Commercial polyethyleneimine can be a compound that has branches of the ethyleneimine polymer. Suitable polyethyleneimines are commercially available from BASF Corporation, under the trade name Lupasol. These compounds can be prepared as a wide range of molecular weights and product activities. Examples of suitable commercial polyethyleneimines sold by BASF for use in the present techniques include, but are not limited to, Lupasol FG and Lupasol WF. Another useful continuity additive may include a mixture of aluminum distearate and an ethoxylated amine type compound, for example, IRGASTAT AS-990, available from Huntsman (for example, Ciba Specialty Chemicals). The mixture of aluminum distearate and compound of the ethoxylated amine type can be made into a slurry in mineral oil, for example, Hydrobrite 380. For example, the mixture of aluminum distearate and an ethoxylated amine type compound can be transformed into a fluid paste. in mineral oil to have the total slurry concentration ranging from about 5% by weight to about 50% by weight, or about 10% by weight to about 40% by weight, or about 15% by weight at about 30% by weight.
[0077] The continuity additive or static control agent (s) can be added to the reactor in an amount varying from 0.05 to 200 ppm, based on the weight of all those fed to the reactor, excluding recycling. In some embodiments, the continuity additive can be added in an amount ranging from 2 to 100 ppm, or in an amount ranging from 4 to 50 ppm. Gas phase polymerization reactor
[0078] Fig. 1 is a schematic ontend of a gas phase reactor system 100, which shows the addition of at least two catalysts, at least one of which is added as a compensating catalyst. The catalyst ontend u slurry, preferably a mineral ont slurry including at least one support and at least one activator, at least one supported activator, and optional catalyst compounds can be placed in an ontend u or ontend u of catalyst (catalyst pot) 102. In this modality, catalyst pot 102 is an agitated holding tank designed to maintain homogeneous solids concentration. A catalyst ontend u solution, prepared by mixing one ontend and at least one catalyst ontend and / or activator, is placed in another ontend u, which can be called a netting pot 104. catalyst ontend u can then be combined in line with the catalyst ontend u solution to form a final catalyst composition. A nucleating agent 106, such as onten, alumina, smoked onten or any other particulate material can be added to the slurry and / or to the in-line solution or to the ontend ur 102 or 104. Similarly, activators or catalyst compounds Additional information can be added online. For example, a second catalyst slurry that includes a different catalyst can be introduced from an ontend catalyst pot. The two catalyst slurries can be used according to the catalyst system with or without the addition of a catalyst solution from the compensation ontend u.
[0079] The catalyst ontend u slurry and the solution can be mixed in line. For example, the solution and the slurry can be mixed using a static mixer 108 or a stirring unit (not shown). The mixture of the catalyst ontend u slurry and the catalyst ontend u solution should be long enough to allow the catalyst ontend in the catalyst ontend u solution to disperse in the catalyst ontend u slurry such that the ontend u of catalyst, initially in the solution, migrates to the supported activator originally present in the slurry. The combination forms a uniform dispersion of catalyst compounds over the supported activator to form the catalyst composition. The amount of time that the slurry and solution are brought into contact is typically about 120 minutes, such as about 0.01 to about 60 minutes, about 5 to about 40 minutes, or about 10 about 30 minutes.
[0080] When ontend the catalysts, the activator and the optional support or additional cocatalysts in the hydrocarbon ontend just before a polymerization reactor, it is desirable that the combination produces a new polymerization catalyst in less than 1 h, in less than 30 minutes, or in less than 15 minutes. Shorter times are more effective, as the new catalyst is prepared before being introduced into the reactor, providing the potential for faster flow rates.
[0081] onten another modality, an alkyl aluminum, an ethoxylated alkyl aluminum, an aluminoxane, an antistatic agent or a borate activator, such as a C1 to C15 alkyl aluminum (e.g., tri-isobutyl aluminum, trimethyl aluminum or the like), an ethoxylated C1 to C15 alkyl aluminum or methyl aluminoxane, ethyl aluminoxane, isobutylaluminoxane, modified aluminoxane or the like are added to the slurry mixture and the in-line solution. Alkyls, antistatic agents, borate activators and / or aluminoxanes can be added from an alkyl ontend u 110 directly to the solution and slurry combination, or can be added via an additional alkane (such as isopentane, onten, heptane, and or octane) in the carrier flow, for example, from a hydrocarbon ontend u 112. Additional alkyls, antistatic agents, borate activators and / or aluminoxanes can be ontend at about 500 ppm, in about 1 at about 300 ppm, between 10 and about 300 ppm, or at about 10 to about 100 ppm. Carrier streams that can be used include, isopentane and or onten, among others. The carrier can be added to the slurry mixture and solution, typically at a rate of about 0.5 to about 60 lbs / h (27 kg / h) or more, depending on the size of the reactor. Likewise, a carrier gas 114, such as nitrogen, argon, ethane, propane and the like, can be added in line with the mixture of slurry and the solution. Typically, carrier gas can be added at a rate of about 1 to about 100 lb / h (0.4 to 45 kg / h), or about 1 to about 50 lb / h (5 to 23 kg / h) h), or about 1 to about 25 lb / h (0.4 to 11 kg / h).
[0082] On another modality, a liquid carrier current is introduced in the combination of the solution and slurry that moves downwards. The mixture of the solution, slurry and liquid carrier stream can flow through a mixer or tube length into the mix before being brought into contact with a gaseous carrier stream.
[0083] Likewise, a comonomer 116, such as hexene, another alpha-olefin or diolefin, can be added in line with the mixture of slurry and the solution. The slurry / solution mixture is then passed through an injection tube 118 into a reactor 120. To assist in the formation of suitable particles in reactor 120, a nucleating agent 122, such as smoked oil, can be added directly inside of reactor 120. In some embodiments, the injection tube can be mixed with the slurry / solution mixture. Any number of suitable tube sizes and configurations can be used to disperse and / or inject the slurry / solution mixture ontend. onten modality, a gas stream 124, such as cycle gas, or recycle gas 126, ontend, nitrogen, or other materials, is introduced into a support tube 128 that surrounds the injection tube 118.
[0084] When a metallocene catalyst or similar catalyst is used in the gas phase reactor, oxygen or fluorobenzene can be added to reactor 120 or directly to gas stream 124 to control the polymerization rate. Thus, when a metallocene catalyst (which is sensitive to oxygen or fluorobenzene) is used in combination with another catalyst (which is not sensitive to oxygen) in a gas phase reactor, oxygen can be used to modify the ontend polymerization rate of metallocene for the rate of polymerization of another catalyst. An example of such a catalyst combination is bis (n-propyl cyclopentadienyl) zirconium dichloride and [(2,4,6-Me3C6H2) NCH2CH2] 2NHZrBn2, where Me is methyl or bis (indenyl) zirconium dichloride and [( 2,4,6-Me3C6H2) NCH2CH2] 2NHHfBn2, where Me is methyl. For example, if the oxygen concentration in the nitrogen feed is changed from 0.1 ppm to 0.5 ppm, significantly less bisindenyl ZrCI2 polymer will be produced and the ontend amount of polymer produced from [(2.4 , 6-Me3C6H2) NCH2CH2] 2NHHfBn2 is increased. WO / 1996/09328 discloses the addition of water or ontend of onten to gas phase polymerization reactors, for example, for similar purposes. onten modality, the contact temperature of the slurry and the solution is in the range of 0 ° C to about 80 ° C, from about 0 ° C to about 60 ° C, from about 10 ° C, to about 50 ° C and from about 20 ° C to about 40 ° C.
[0085] The example above is not limiting, as additional solutions and slurries can be included. For example, a slurry can be combined with two or more solutions having the same or different compounds of catalysts or activators. Likewise, the solution can be combined with two or more slurries, each having the same support or different supports, and the same or different compounds of catalysts or activators. Likewise, two or more slurries combined with two or more solutions, preferably in line, where the slurries each comprise the same support or different supports, can comprise the same or different compounds of catalysts and or activators and the solutions comprise the same or different compounds of catalysts and or activators. For example, the slurry may contain a supported activator and two different catalyst compounds, and two solutions, each ontend one of the catalysts in the slurry are each, independently, combined, in line, with the slurry. Using Catalyst Composition to Control Product Properties
[0086] The properties of the polymeric product can be controlled by adjusting the timing, temperature, concentrations and sequence of mixing the solution, the slurry and any optional materials added (nucleating agents, catalyst compounds, activators, etc.) described above . MWD, composition distribution, melt index, relative amount of polymer produced by each catalyst, and other properties of the polymer produced can also be changed by manipulating process parameters. Any number of process parameters can be adjusted, including manipulating the hydrogen concentration in the polymerization system, changing the amount of the first catalyst in the polymerization system, changing the amount of the second catalyst in the polymerization system. Other process parameters that can be adjusted include changing the relative ratio of the catalyst in the polymerization process (and optionally adjusting their individual feed rates to maintain a stable or permanent resin production rate). Reagent concentrations in reactor 120 can be adjusted by changing the amount of liquid or gas that is removed or purged from the process, changing the amount and / or composition of a recovered liquid and / or recovered gas returned to the process polymerization process, in which the recovered liquid or recovered gas can be recovered from polymer discharged from the polymerization process. Other concentration parameters that can be adjusted include changing the polymerization temperature, changing the partial pressure of ethylene in the polymerization process, changing the ratio of ethylene to comonomer in the polymerization process, changing the transition metal activator in relation to activation sequence. Time-dependent parameters can be adjusted, such as changing the relative feed rates of the slurry or solution, changing the mixing time, temperature and or degree of mixing of the slurry and the in-line solution, adding different types of activating compounds to the polymerization process, and add oxygen or fluorobenzene or other catalyst poison to the polymerization process. Any combinations of these settings can be used to control the properties of the final polymer product.
[0087] In one embodiment, the composition distribution of the polymer product is measured at regular intervals and one of the above process parameters, such as temperature, feed rate of the catalyst compound, ratio between the two or more catalysts for each other , the ratio of the comonomer to the monomer, the partial pressure of the monomer and / or the hydrogen concentration, is changed to bring the composition to the desired level, if necessary. The distribution of the composition can be carried out by fractionation by elution at increasing temperature (TREF), or similar techniques for measuring the TREF composition as a function of elution temperature.
[0088] In one embodiment, a property of the polymer product is measured online, and in response to the reason the catalysts are combined it is changed. In one embodiment, the molar ratio of the catalyst compound in the catalyst component slurry to the catalyst compound in the catalyst component solution, after the slurry and solution are mixed to form the final catalyst composition, is 500 : 1 to 1: 500, or 100: 1 to 1: 100, or 50: 1 to 01:50, or 10: 1 to 1:10, or 5: 1 to 1: 5. In another embodiment, the molar ratio of a Group 15 catalyst compound in the slurry to a metallocene binder catalyst compound in solution, after the slurry and the solution are mixed to form the catalyst composition, is 500: 1, 100: 1, 50 : 1, 10: 1, 5: 1, 1: 5, 1:10, 1: 100, or 1: 500. The property of the measured product may include the polymer product's melt index, melt index, density, MWD, comonomer content, composition distribution, and combinations thereof. In another embodiment, when the ratio of the catalyst compounds is changed, the rate of introduction of the catalyst composition to the reactor, or other process parameters, is changed to maintain a desired production rate.
[0089] Although it is not intended to stick to the theory or be limited to any theory, it is believed that the processes described here immobilize the catalyst compound in solution and on a support, preferably a supported activator. The in-line immobilization techniques described here preferably result in a supported catalyst system that, when introduced to the reactor, provides suitable polymer properties, with appropriate particle morphology, bulk density, or higher catalyst activities and without need for additional equipment in order to introduce solution of the catalyst compound to a reactor, in particular a gas phase or slurry phase reactor. Polymerization Process
[0090] The catalyst system can be used to polymerize one or more olefins to supply one or more polymeric products thereof. Any suitable polymerization process can be used, including, but not limited to, high pressure, solution, slurry and / or gas phase polymerization processes. In modalities that use other techniques, in addition to gas phase polymerization, modifications to a catalyst addition system, which are similar to those discussed with reference to Fig. 1, can be used. For example, a compensation system can be used to feed catalyst to a slurry loop reactor for the production of polyethylene copolymer.
[0091] The terms "polyethylene" and "polyethylene copolymer" refer to a polymer that has at least 50% by weight of ethylene-derived units. In various embodiments, polyethylene can have at least 70% by weight of ethylene-derived units, at least 80% by weight of ethylene-derived units, at least 90% by weight of ethylene-derived units, at least 95% by weight of ethylene-derived units, or 100% by weight of ethylene-derived units. The polyethylene can thus be a homopolymer or a copolymer, including a terpolymer, with one or more other monomer units. As described herein, a polyethylene can include, for example, at least one or more other olefins or comonomers. Suitable comonomers can contain from 3 to 16 carbon atoms, from 3 to 12 carbon atoms, from 4 to 10 carbon atoms, and from 4 to 8 carbon atoms. Examples of comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-ene, 1-decene, 1-dodecene, 1 -hexadecene and the like. In addition, small amounts of diene monomers, such as 1,7-octadiene can be added to the polymerization to adjust the properties of the polymer.
[0092] Referring again to Fig. 1, the fluidized bed reactor 120 may include a reaction zone 130 and a speed reduction zone 132. Reaction zone 130 may include a bed 134, which includes polymer particles in growth, polymer particles formed and a smaller amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove the heat of polymerization through the reaction zone. Optionally, some of the recirculated gases 124 can be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. An adequate rate of gas flow can be easily determined by experimentation. The composition of the gaseous monomer for the flow of circulating gas can be at a rate equal to the rate at which the particulate polymeric product and the associated monomer are removed from the reactor and the composition of the gas that passes through the reactor can be adjusted to maintain a gaseous composition of essentially constant state within the reaction zone. The gas leaving the reaction zone 130 can be passed to the speed reduction zone 132, where the entrained particles are removed, for example, slowing and falling back to reaction zone 130. If desired, the finer particles scraps and dust can be removed in a separation system 136, such as a cyclone and / or fines filter. The gas 124 can be passed through a heat exchanger 138, where at least part of the polymerization heat can be removed. The gas can then be compressed in a compressor 140 and returned to reaction zone 130.
[0093] The temperature of the fluidized bed reactor can be greater than about 30 ° C, about 40 ° C, about 50 ° C, about 90 ° C, about 100 ° C, about 110 ° C, about 120 ° C, about 150 ° C, or higher. In general, the reactor temperature is operated at the highest possible temperature, considering the sintering temperature of the polymer product inside the reactor. Reactor temperatures are preferably between 70 and 95 ° C. Reactor temperatures are preferably between 75 and 90 ° C. Thus, the upper temperature limit in one embodiment is the melting temperature of the polyethylene copolymer produced in the reactor. However, higher temperatures can result in narrower MWDS, which can be improved by the addition of MCN, or other, cocatalysts, as described acquisition.
[0094] Hydrogen gas can be used in the polymerization of olefins to control the final properties of the polyolefin. When using certain catalyst systems, increasing the concentrations (partial pressures) of hydrogen can increase the fluidity index (FI) of the generated polyethylene copolymer. The fluidity index can therefore be influenced by the hydrogen concentration. The amount of hydrogen in the polymerization can be expressed as a molar ratio to the total polymerizable monomer, for example, ethylene, or a mixture of ethylene and hexene or propylene.
[0095] The amount of hydrogen used in the polymerization process may be an amount necessary to achieve the desired flow rate of the final polyolefin resin. For example, the molar ratio of hydrogen to the total monomer (H2: monomer) can be greater than about 0.0001, greater than about 0.0005, or greater than about 0.001. In addition, the molar ratio of hydrogen to total monomer (H2: monomer) can be less than about 10, less than about 5, less than about 3, and less than about 0.10. A desirable range for molar ratio between hydrogen and monomer can include any combination of any upper molar ratio limit with any lower molar ratio limit described herein. Expressed in another way, the amount of hydrogen in the reactor at any one time can vary from about 5000 ppm, to about 4000 ppm in another embodiment, about 3000 ppm, or between about 50 ppm and 5,000 ppm, or between about 50 ppm and 2,000 ppm in another mode. The amount of hydrogen in the reactor can vary from a minimum of about 1 ppm, about 50 ppm, or about 100 ppm and a maximum of about 400 ppm, about 800 ppm, about 1000 ppm, about 1500 ppm, or about 2000 ppm. In addition, the ratio of hydrogen to total monomer (H2: monomer) can be from about 0.00001: 1 to about 2: 1, about 0.005: 1 to about 1.5: 1, or about 0 .0001: 1 to about 1: 1. The one or more pressures of the reactor in a gas phase process (either single phase or two or more phases) can vary from 690 kPa (100 psig) to 3448 kPa (500 psig), in the range of 1379 kPa (200 psig) to 2759 kPa (400 psig), or in the range from 1724 kPa (250 psig) to 2414 kPa (350 psig).
[0096] The gas phase reactor may be capable of producing from about 10 kg of polymer per hour (25 lb / h) to about 90,900 kg / h (200,000 lb / h), or greater, and greater than about 455 kg / h (1,000 lb / h), greater than about 4,540 kg / h (10,000 lb / h), greater than about 11,300 kg / h (25,000 lb / h), greater than about 15,900 kg / h ( 35,000 lb / h), and greater than about 22,700 kg / h (50,000 lb / h), and from about 29,000 kg / h (65,000 lb / h) to about 45,500 kg / h (100,000 lb / h).
[0097] As mentioned, a process of polymerization in slurry can also be used in the modalities. A slurry polymerization process generally uses pressures in the range of about 101 kPa (1 atmosphere) to about 5070 kPa (50 atmospheres) or higher, and temperatures in the range of about 0 ° C to about 120 ° C, and more particularly between about 30 ° C to about 100 ° C. In a slurry polymerization, a solid particulate polymer slurry can be formed in a liquid polymerization diluent medium to which ethylene, comonomers, and hydrogen can be added, together with the catalyst. The slurry including diluent can be intermittently or continuously removed from the reactor, where the volatile components are separated from the polymer and recycled, optionally after distillation, to the reactor. The liquid diluent used in the polymerization medium can be an alkane having 3 to 7 carbon atoms, such as, for example, a branched alkane. The medium used must be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the critical temperature and diluent reaction pressure. In one embodiment, a mixture of hexane, isopentane or isobutane medium can be used. The slurry can be transmitted in a continuous cycle system.
[0098] The polyethylene product can have a melt index ratio (MIR or I21 / I2), ranging from about 5 to about 300, or between about 10 to less than about 150, or, in many embodiments , from about 15 to about 50. The melt index (FI, HLMI, or I21 can be measured according to ASTM D1238 (190 ° C, 21.6 kg). The melt index (MI, I2) can be measured according to ASTM D1238 (at 190 ° C, 2.16 kg weight).
[0099] The density can be determined according to ASTM D-792. Density is expressed in grams per cubic centimeter (g / cm3), unless otherwise stated. The polyethylene can have a density ranging from a minimum of about 0.89 g / cm3, about 0.90 g / cm3, or about 0.91 g / cm3 to a maximum of about 0.95 g / cm3 , about 0.96 g / cm3, or about 0.97 g / cm3. The polyethylene can have an apparent density, measured according to ASTM D1895 Method B, from about 0.25 g / cm3 to about 0.5 g / cm3. For example, the apparent density of polyethylene can vary from a minimum of about 0.30 g / cm3, about 0.32 g / cm3, or about 0.33 g / cm3 to a maximum of about 0.40 g / cm3, about 0.44 g / cm3, or about 0.48 g / cm3.
[0100] Polyethylene can be suitable for articles such as films, fibers, non-woven and / or fabrics, extruded articles, and / or molded articles. Examples of films include blown or molded films formed by coextrusion or laminating, useful as shrink films, cling film, drawn film, sealing film, oriented films, packaging, heavy bags, grocery bags, cooked and frozen food packaging, packaging of medicines, industrial linings, membranes, etc., in food contact and non-contact applications with food, films and agricultural blades. Examples of fibers include melt spinning, solution spinning and melt blowing fibers for use in molding woven or non-woven fabrics to produce filters, diaper fabrics, hygiene products, medical clothing, geotextiles, etc. Examples of extruded articles include piping, medical tubes, wire and cable coatings, conduits, geomembranes and pond liners. Examples of molded articles include individual and multilayer constructions in the form of bottles, tanks, large hollow articles, containers for rigid foods and toys, etc. EXAMPLES
[0101] To provide a better understanding of the previous description, the following non-limiting examples are provided. All parts, proportions and percentages are by weight, unless otherwise specified.
[0102] As described in this document, a comonomer, such as a C4-C8 alpha-olefin is added to a reaction, together with the ethylene monomer, to create short chain branching (SCB) in polyethylene copolymers. Without intending to stick to the theory, the SCB can cause a long chain of PE to break free from a crystallite and be partially incorporated into other crystals. Thus, polymers that have SCB in longer chains may exhibit greater toughness.
[0103] In contrast, long chain branches (LCB) are points at which two polymer chains can divide outside individual polymer chains. LCB can improve toughness, but it can make polymers more vulnerable to orientation, causing less tear resistance in the direction of extrusion.
[0104] The inclusion of shorter chains decreases the melting temperature of the polymer, and can increase the processing capacity. However, SCBs in shorter chains can force these chains out of the crystallites and into amorphous regions, reducing the toughness of the resulting polymeric product.
[0105] Hydrogen can be added to polymer reactions to control molecular weight. Hydrogen acts as a chain terminating agent, essentially replacing a monomer or comonomer molecule in the reaction. This prevents the formation of a current polymer chain, and allows a new polymer chain to start. Catalyst System Comonomer Incorporation versus MWD Control, Results of 15.24 cm (six inch) gas phase reactor Polymerization experiments in 15.24 cm (six inch) gas phase reactor
[0106] The catalysts A-J shown in Table 1 were prepared as described here. All prepared catalysts were tested in a fluidized bed reactor equipped with temperature control devices, catalyst feed or injection equipment, gas chromatography (GC) analyzer to monitor and control monomer and comonomer gas feeds and sampling equipment and polymer collection. The reactor consisted of a bed section of 15.24 cm (6 inches) in diameter, increasing to 25.4 cm (10 inches) at the top of the reactor. Gas enters through a perforated distributor plate allowing fluidization of the bed contents and a polymer sample is discharged into the upper part of the reactor. The comonomer in the polymerization examples here is 1-hexene. The polymerization parameters are described in table 1 below and plotted in Figs. 2 and 3.
[0107] The bed reaction of growing polymer particles was maintained in a fluidized state by the continuous flow of the composition feed and recycle gas through the reaction zone at a surface gas velocity of 0.3 to 0.6 m / s (1-2 feet / s). The reactor was operated at a temperature of 79 ° C (175 ° F) and a total pressure of 2274 kPa (300 psig), including 35 mol% of ethylene. Table 1: Polymerization lengths in a 15.24 cm (6 inch) gas phase reactor

[0108] Fig. 2 is a graph 200 of a series of polymers that have been prepared to test the relative capabilities of a series of metallocene catalysts to prepare a resin having a melt index (MI) of about 1 and a density (D) of about 0.92. The polymerizations were carried out in the 15.24 cm (6 inch) continuous gas phase reactor (LGPR) described here. The left axis 202 represents the hydrogen gas to ethylene monomer (H2 / C2) ratios used to obtain the target properties, in units of parts per million (mol) of H2 per mol% of C2 (ppm / mol% ). The right-hand axis 204 represents the ethylene comonomer (C6 / C2) used to obtain the target properties, in units of mole per mole.
[0109] When comparing the C6 / C2 contents used to achieve the target properties, they indicate the relative capacities of the catalysts to incorporate comonomer. For example, comparing the C6 / C2 206 content for (1-EtInd) 2ZrCl2 (B) with the C6 / C2 208 level for (PrCp) 2HfF2 (I) produces a ratio of about 36/9, or about four. This indicates that for a given C6 / C2 gas ratio, a polymer prepared with (PrCp) 2HfF2 will have approximately four times the short chain branch (SCB) of a polymer prepared using (1-EtInd) 2ZrCl2. These data are useful for controlling polymer composition distributions made as IN-SITU mixtures using catalyst mixtures, for example, as co-supported catalysts on a single support. The data is also useful in determining which catalysts must be combined to have a composition distribution containing both the comonomer-rich (low density) and comonomer-low (high density) component.
[0110] The effects of the steady state gas to H2 / C2 (ppm / mol) 202 ratios are shown by the bars. The contents of these bars approximately indicate the relative molecular weight capacities of the catalysts. For example, (CH2) 3Si (CpMe4) CpZrCl2 (J) requires an H2 / C2 210 ratio of about 23.4 ppm / mol to achieve a target melt index of about one, and (CpMe5) (1- MeInd) ZrCl2 (A) requires an H2 / C2 212 ratio of about 0.4 ppm / mol to achieve the same target melt index. These results indicate that (CH2) 3Si (CpMe4) CpZrCl2 (J) produces a higher molecular weight polymer than (CpMe5) (1-MeInd) ZrCl2 (A) in the same ratio as H2 / C2. In this example, the data is approximate since the change in Mw is not measured as a function of H2 / C2.
[0111] Fig. 3 is a graph 300 of the polymer series of Fig. 2, which shows the ratio of melting index (MIR) of the series of polymers made by different metallocene catalysts (MCN). As used here, the terms melt ratio (MIR), melt index (MFR), and "I21 / I2" refer to the melt index ("FI" or "I21") interchangeably for the fusion index ("MI" or "I2"). MI (I2) can be measured according to ASTM D1238 (at 190 ° C, 2.16 kg in weight). FI (I21) can be measured according to ASTM D1238 (at 190 ° C, 21.6 kg in weight). Items with similar numbering are as described in relation to Fig. 2. In this graph 300, the left axis 302 represents the MIR. The MIR (which can also be called fusion flow ratio or MFR) is the ratio between the fusion indices I21 and I2 and can indicate the presence of long chain branching. For linear resins, without LCB, the ratio is about 25 or less. Higher MIR values may indicate the presence of LCB which can be detrimental to the properties of the film, as noted above. The major ratio of MIR 304 was for (CH2) 3Si (CpMe4) CpZrCl2 (J), indicating that the polymer produced by this catalyst has the most LCB. In contrast, mixing the resins with the two different catalysts creates a final product that will have a higher MIR.
[0112] Based on the results shown in Figs. 2 and 3, five catalysts were selected to determine the molecular weight dependence (Mw) on the H2 ratio. These catalysts included three catalysts that generate lower molecular weight (MW) polyethylene (CpMe5) (1- MeInd) ZrCl2 (A) 306, (1-EtInd) 2ZrCl2 (B) 308, and (Me4Cp) (1,3- Me2Ind ) ZrCl2 (E) 310. The catalysts also included a catalyst that generates an average Mw polyethylene, (PrCp) 2HfF2 (I) 312. Table 2 contains data on Mw's dependence on H2 / C2 content. Table 2 Mw versus C2 / H2 content for selected MCNs

[0113] These results were used to generate a series of graphs that can be used to determine the sensitivity of MW for H2 / C2 ratios. Table 3 indicates the slope and intercepts the reciprocal plots. The lower MW catalysts had higher angular coefficients, indicating a greater influence of the H2 / C2 ratios in Mw. The second catalyst, (1-EtInd) 2ZrMe2, had the greatest dependence on Mw in the H2 / C2 ratio. Angular coefficients can be used to select catalysts having very divergent responses to hydrogen.
[0114] The data shown in Figs. 2 and 3 and in Tables 2 and 3 indicate that a combination of (1-EtInd) 2ZrCl2 (B) and (PrCp) 2HfF2 (I) will produce a polymer with a wide MWD and SCBD without LCB. As shown in graph 300 in Fig. 3, the resins made with these two catalysts have MIR close to 20 and, therefore, are essentially free of LCB. The information in Tables 2 and 2 indicates that (1-EtInd) 2ZrCl2 has approximately one third of the Mw of (PrCp) 2HfF2 in about 4.2 ppm / mol of H2 / C2. The information in Graph 200 shown in Fig. 2, indicates that (1-EtInd) 2ZrCl2 has approximately a quarter of the SCB of (PrCp) 2HfF2 under comparable conditions. Table 3. Angular coefficient and intercept for H2 / C2 vs. V graphs. 1 / Mw for selected MCNs

[0115] The equations in Table 3 can be used to predict the amounts of (1-EtInd) 2ZrCl2 needed in a combination with the catalyst (PrCp) 2HfF2 to produce a global resin with Mw of 100 kg / mol in four levels of H2 many different. These values can be used to define initial control points, for example, if (PrCp) 2HfF2 is used as a supported catalyst component, and (1- EtInd) 2ZrCl2 is a solution catalyst component, to be added as a catalyst compensation. In this embodiment, the amount of 2ZrCl2 (1-EtInd) catalyst that is added can be controlled to achieve Mw and other performance targets. The results for various combinations are shown in Table 4. Table 4: Mw of (1-EtInd) 2ZrCl2 (lmw) and (PrCp) 2HfF2 (hmw) as a function of H2 / C2 and low molecular weight polymer fraction ( Flmw) required to produce a total Mw of 100 kg / mol
Pilot Plant Executions Using Compensation Feed
[0116] The use of a catalyst compensation feed to control molecular weight and molecular weight distribution was tested on a pilot plant, with the results detailed in Table 5. In Table 5, the type of catalyst corresponds to the numbered catalyst structures shown in the detailed description. Five of the catalyst runs (AE) were control runs performed without the use of a compensating catalyst. Table 5: Results of the pilot plant reactor of 33.65 cm (13.25 Inches) using compensation addition.


[0117]
[0118] Control of molecular weight distribution and composition distribution using co-supported catalysts in combination with (CpPr) 2HfF2.
[0119] The tests were performed using a primary catalyst, which included (CpPr) 2HfF2 (HfP, structure III). HfP is capable of polymerizing ethylene and mixtures of ethylene and comonomers in the presence of an activator and a support, a cocatalyst, or both. The activator and the support can be the same or different. Several activators, supports and or cocatalysts can be used simultaneously. Cocatalysts can be added to modify any of the ingredients. The descriptor catalyst, HfP, activator, and supports or cocatalysts refer to the actual compounds and also to solutions of these compounds in hydrocarbon solvents.
[0120] For use as cocatalysts, especially in compensation systems, the catalysts must be soluble in alkane solvents such as hexane, paraffinic solvents and mineral oil. Solubility can be greater than 0.0001% by weight, greater than 0.01% by weight, greater than 1% by weight, or greater than 2%. Toluene can also be used as a solvent since the catalyst can be more soluble in an aromatic solvent
[0121] As described here, a combination of HfP, an activator (MAO), and a support (silica) was reacted with compensation catalysts in hydrocarbon solvents to produce a polymerization catalyst with a different polymerization behavior than expected at from the combination of individual components. More specifically, the molecular weight distribution for a polymer generated by co-supported cocatalysts is broader than can be achieved by mixtures of polymers formed from the catalysts of individual components. This change in polymerization behavior is exemplified by changes in MWD, the CD or MWD and CD of polymers formed by the mixture of HfP and selected cocatalysts. Thus, the combination of catalysts, HfP, activator and, optionally, a support, additional cocatalysts, or both, in hydrocarbon solvents in an in-line mixer just before a polymerization reactor gives rise to a new polymerization catalyst.
[0122] Any combination sequence of catalysts, HfP, activator and, optionally, a support, additional cocatalysts, or both, in hydrocarbon solvents can be used. For example, catalysts can be added to a mixture that includes HfP, activator and, optionally, a support, additional cocatalysts, or both. In addition, catalysts and cocatalysts can be added to a mixture of {HfP, activator and, optionally, a support}. In addition, catalysts and HfP can be added to a mixture that includes {activator and, optionally, a support and cocatalysts}.
[0123] It is desirable to combine the catalysts, HfP, the activator and, optionally, a support, additional cocatalysts, or both, in hydrocarbon solvents, then obtain a catalyst from the dry mixture. This dry mixture can be fed directly, or as a suspension, into a polymerization reactor.
[0124] The change in MWD and CD with the use of catalysts and HfP can be controlled by changing the ratio between the HfP catalysts. When none of the catalysts are used, the MWD and CD is that of HfP. When individual catalysts are used, MWD and CD are those generated by the catalysts themselves. Changing the catalyst ratio changes the MWD and CD of the originals. The ratio can be changed to target specific MWD targets and DC targets.
[0125] Catalysts can be chosen to control the change in MWD or CD of the polymer formed. The use of catalysts that produce polymers of higher and lower molecular weights than HfP will expand the molecular weight distribution. The Mw response of the polymers made from the individual components compared to H2 / C2 can be used as a guide for selection. For example, a catalyst having less response to hydrogen than HfP will produce a Mw greater than a polymer produced by HfP alone, as shown in Fig. 2. In addition, a catalyst having a greater response to hydrogen than HfP will , in combination with an HfP, produce an Mw less than HfP alone.
[0126] In addition to selecting catalysts to extend MWD, catalysts can be selected to change the composition distribution. For example, the use of catalysts that incorporate less or more than comonomers than HfP will expand the composition distribution. An approximate guide for this purpose, as discussed further below, are the relative C6 / C2 gas ratios required to prepare an approximately 0.92D resin from different catalysts. Those catalysts that produce the biggest differences in HfP C6 / C2 gas ratios will further expand the CD. The molecular weight distributions can also be changed by using a catalyst that gives rise to a different MWD, but similar average molecular weight to that originated from HfP.
[0127] The combination of catalysts with HfP can produce an MWD that is greater than expected from the theoretical combination of the individual catalysts. Desirable materials based on an HfP catalyst base are made when the comonomer and Mw incorporation capabilities of the catalysts are both greater than that of HfP. Likewise, desirable materials are also formed when the comonomer incorporation capacities and the Mw of the catalysts are both less than that of HfP. In addition, desirable materials are made when Mw and catalysts are similar and comonomer incorporation capabilities are less than that of HfP. Production of a Co-Supported Polymerization Catalyst
[0128] Fig. 4 is a flow chart of a 400 method for producing a co-supported polymerization catalyst. Method 400 starts at block 402 by generating a graph of the hydrogen / ethylene ratio versus the reciprocal of the molecular weight of a polymer generated by each of a series of catalysts. As discussed here, the slope of each diagram indicates the catalyst response corresponding to a hydrogen level.
[0129] In block 404, a value is determined for the comonomer / ethylene ratio for each of the catalysts that can be used to achieve a single target density, such as 0.92. The ratio value used to achieve the target density indicates the catalyst's ability to incorporate the comonomer. In block 406, a first catalyst is selected for the co-supported polymerization catalyst. For example, the first catalyst can be a commonly used commercial catalyst, or it can be selected to have a low or a high capacity to incorporate a comonomer and a high or low response to hydrogen.
[0130] In block 408, a second catalyst is selected for the co-supported polymerization catalyst. The second catalyst can be selected to have a slope of the graph for the hydrogen / ethylene ratio versus the reciprocal of the molecular weight which is at least about 1.5 times as large as the slope of the graph for the first catalyst. In addition, the second catalyst can be selected to have a value for the comonomer / ethylene ratio that is less than about 0.5 as large as the comonomer / ethylene ratio of the first catalyst. In block 410, the first catalyst and the second catalyst can be co-supported on a single support to create the co-supported polymerization catalyst, for example, using the compensation techniques described here, among others. General Procedures for the formation of Catalyst Catalyst Components

[0131] All manipulations were performed in a glove box purged with N2 or using standard Schlenk techniques. All anhydrous solvents were purchased from Sigma-Aldrich and were degassed and dried over calcined Al2O3 microspheres or molecular sieves before use. Toluene for catalyst preparations was pre-dried with Al2O3 microspheres, then dried over SMAO 757 before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and were degassed and dried over alumina microspheres or molecular sieves before use. The reagents used were purchased from Sigma-Aldrich, with the exception of ZrCl4 99 +%, which was purchased from Strem Chemicals, and bis (n-propyl-cyclopentadienyl) dimethyl hafnium chloride (HfPMe2) was purchased from Boulder Scientific Lot n ° BSC3220-8-0002. The 1H NMR measurements were recorded on a 250Mz Bruker and 500Mz Bruker spectrometer. Synthesis of rac-meso - bis (1-Ethyl-indenyl) zirconium dimethyl (1- EtInd) 2ZrMe2 (IV-A / IV-B)
[0132] Indenyl-lithium. The freshly distilled indene (50.43g, 434.1 mmol) was dissolved in 1 L of pentane. Et2O (25 mL), then n-butyllithium in 1.6 M hexanes (268.5 mL, 429.6 mmol) was added to the clear stirring solution over a period of 5 min. A white solid precipitated and the supernatant took on a light yellow color. After stirring overnight, the suspension was filtered, then dried in vacuo to obtain a white solid (46.51 g, 381.0 mmol, 88.7%). 1H NMR (THF-d8): δ 5.91 (d, 2H), 6.44 (m, 2H), 6.51 (t, 1H), 7.31 (m, 2H).
[0133] 1-Ethylidene. 46.51g (380.95mmol) of lithium indenyl were dissolved in 250 ml of Et2O, and a separate solution was made of 95.94g (615.12mmol) of ethyl iodide in 400 ml of Et2O. The ethyl iodide solution was cooled to -30 ° C and the lithium indenyl solution was cooled to 0 - 10 ° C using a dry ice / acetone bath. Indenyl lithium was added to the clear stirring solution of ethyl iodide via cannula transfer. The solution turned from light yellow to yellow with the addition of the lithium indenyl solution. The reaction was left stirring overnight and warmed up slowly to room temperature. After stirring overnight, the flask was taken into the box and the Et2O was reduced TO VACUUM. Once LiI started to precipitate, 300 ml of pentane was added and the white suspension was filtered resulting in a light orange solution. The pentane was evaporated when more LiI precipitated and a light orange colored oily liquid was obtained. The crude product was distilled under reduced pressure using a rotary vacuum pump to obtain a clear, pale yellow liquid. 1H NMR revealed ~ 90% 1-Ethylidene and ~ 10% 3-Ethylidene. The possible isomerization could have occurred due to a small amount of acid present during the distillation as none was present in the spectrum of crude 1H NMR. 44.27g (306.96mmol) of product were isolated for a yield of 80.6%. 1H NMR (CD2Cl2): δ 0.96 (3H, t), 1.59 (1H, q), 1.99 (1H, q), 3.41 (1H, m), 6.58 (1H, d ), 6.59 (1H, d), 7.24 (2H, m), 7.41 (2H, dd).
[0134] 1-Ethyl indenyl-lithium. 44.27g (306.98mmol) of 1-ethylidene containing ~ 10% of 3-ethylidene were dissolved in 500 ml of pentane and about 3 ml of Et2O. To the clear stirring solution, 188.28mL (301.25mmol) of 1.6M n-butyl lithium in hexanes was added over 10 minutes. Immediately a flaky white precipitate formed and caused the stirring to stop. The mixture was stirred manually to ensure proper incorporation of the reagents and the suspension was allowed to settle overnight. The suspension was filtered and the white solid was dried in vacuo. 43.27g (288.18mmol) of the product were obtained with a 95.7% yield. 1H NMR (THF-d8): δ 1.26 (3H, triplet), 2.86 (2H, quartet), 5.72 (doublet, 1H), 6.38 (dd, 1H), 6.43 (2H , m), 7.26 (1H, t), 7.30 (1H, m). Rac-meso-bis (1-Ethyl-indenyl) zirconium dimethyl (1-EtInd) 2ZrMe2 (IV-A / B)
[0135] 7.00 g (46.65 mmol) of 1-ethyl-indenyl-lithium were dissolved in 74 ml of 1,2-dimethoxyethane (DME), and a separate solution was made with 5.43 g (23.30 mmol) of ZrCl4 in 75 mL of DME. To the clear ZrCl4 solution, the bright yellow solution of 1-ethyl-indenyl-lithium was added via pipette over a period of 15 minutes. After the initial addition of the solution turns yellow, and after 5 minutes of addition, a precipitate formed and a yellow-orange color formed. Ten minutes of adding the supernatant made it orange with a yellow precipitate, and after all the 1-ethyl-indenyl-lithium solution was added, the mixture turned yellow again. The reaction was left with stirring overnight. A 1H NMR crude spectrum of the slurry showed a meso / rac ratio of ~ 1.1: 1; however, this can be misleading since the rac isomer is more soluble in DME than the meso isomer. Regardless of the isomer ratio, 15.61mL (46.83mmol) of CH3MgBr in 3.0 M Et2O was added in 1 mL portions over ten minutes. After the tenth addition, the yellow mixture turned orange. After the final addition of the Grignard reagent, the mixture became brown and the reaction was left stirring overnight. A 1H NMR spectrum of the crude mixture revealed a 1.1: 1 meso / rac ratio. The DME was evaporated and the brown solid was extracted with 3 x 20 ml of toluene plus an additional 10 ml. The light brown solid obtained after removing the solvent was washed with 10 ml of pentane and dried in vacuo. 8.26g (20.26mmol) were obtained from the whitish solid for a yield of 87%.
[0136] Dichloride spectral data: 1H NMR (CD2Cl2): δ 1.16 (6.34H, t, rac), 1.24 (6H, t, meso), 2.73-2.97 (8H, q overlap), 5.69 (1.82H, dd, meso), 5.94 (1.92H, dd, rac), 6.06 (1.99H, d, rac), 6.35 (1.84H, d, meso), 7.22-7.65 (16H, m).
[0137] Dimethyl spectral data: 1H NMR (C6D6): δ -1.40 (3.33H, s, meso), -0.895 (6H, s, rac), -0.323 (3.34H, s, meso) , 1.07 (13H, overlapping t), 2.47 (4H, q overlapping), 2.72 (4H, q), 5.45-5.52 (8H, m), 6.91 (8H, m ), 7.06-7.13 (4H, m), 7.30 (4H, m). Synthesis of rac-meso-bis (1-Ethyl-indenyl) zirconium dimethyl (1-EtInd) 2ZrMe2 (IV-A / B)
[0138] To a solution of ZrCl4 (20.8 g; 89.3 mmol) in 1,2-dimethoxyethane (DME) (about 100 mL) was added a solution of 1-ethyl-indenyl-lithium (26.8 g; 178 mmol) dissolved in 1,2-dimethoxyethane (DME) (about 200 ml) in approximately 5 ml portions over 15 minutes. Additional DME was added as needed to prevent the reaction from becoming too thick for stirring. The total volume at the end of the addition was about 425 ml. Just before the addition of the 1-ethyl-indenyl-lithium solution and about halfway through the addition, pentane (about 10 ml) was added to the reaction mixture and was removed under vacuum to decrease the temperature. After stirring for about 4 h at room temperature, an aliquot of slurry was removed and dried to. The 1H NMR of the solid thus obtained was taken up in CD2Cl2 and showed a rac / meso ratio of 0.7: 1.
[0139] Approximately 100 ml of solvent was evaporated from the reaction and a solution of methyl lithium (1.6 M in ether; 111 ml; 178 mmol) was added in portions (about 20 ml) over about an hour . After stirring overnight, the rac / meso ratio was 0.7: 1.0. Additional MeLi solution (1.6 M in ether; 7.0 mL, 11.2 mmol) was added and the reaction was stirred at room temperature for an additional 3 days. The rac / meso ratio was 0.9: 1 as determined by 1H NMR. The solvent was removed in vacuo and the residue was extracted with hot hexanes (about 300 ml; 60 ° C), filtered and concentrated to about 100 ml in total volume, then cooled to -20 ° C overnight. The solid was isolated by filtration, washed with cold pentane (2 x 50 mL) and dried under vacuum to produce 29.2 g of a solid with a rac / meso ratio of 0.94: 1. The isolated solid was extracted with hexane hot (about 150 mL), filtered from a small amount of pink solid. The volume was reduced to about 125 ml and the solution was treated with trimethylsilyl chloride (2.0 ml). The solution was filtered, concentrated to about 100 ml, heated to redissolve the precipitated product and allowed to cool slowly. After settling overnight, the flask was cooled to -20 ° C, which caused some pink solid to precipitate. The flask was heated to 55 ° C and additional hexanes (about 75 ml) were added together with trimethylsilyl chloride (5.0 ml). This solution was maintained at 55 ° C for two hours, the reaction was filtered to produce a yellow solution. The solution was filtered, concentrated to about 100 ml, heated to redissolve the precipitated product and allowed to cool slowly. The precipitated solid was isolated by filtration, washed with cold pentane (2 x 30 ml), dried under vacuum at 55 ° C. The yield was 21.1 g with a rac / meso ratio of 1.19 / 1. Synthesis of meso (1-EtInd) 2ZrCl2
[0140] 1-Ethinyl-indenyl-lithium (1.0 g; 6.7 mmol) was dissolved in dimethoxyethane (DME) (7.7 mL) and cooled to - 20 ° C. Solid ZrCl4 (0.781 g; 3.35 mmol) was added in portions over 5 minutes and the reaction was continued overnight. After the volatiles were removed, the yellow solids thus obtained were extracted with CH2Cl2 until no yellow color remained. CH2Cl2 was removed in vacuo leaving a yellow solid. Yield = 1.14 g with a 19: 1 meso / rac ratio. Conversion from meso (1-EtInd) 2ZrCl2 to meso (1-EtInd) 2ZrMe2
[0141] meso (1-EtInd) 2ZrCl2 (1:19 rac / meso; 307 mg; 0.68 mmol) was suspended in Et2O (about 10 mL) and MeMgBr (3.0 M in Et2O; 0.47 mL, 1.41 mmol) was added. The reaction was dried and extracted with hot hexanes (about 18 ml at 60 ° C), filtered and dried to obtain a light yellow solid (240 mg). The 1H NMR in C6D6 showed that the 1:19 rac / meso ratio was maintained. Conversion from 1: 1 rac / meso (1-EtInd) 2ZrCl2 to 1: 1 rac / meso (1-EtInd) 2ZrMe2
[0142] (1-EtInd) 2ZrCl2 (1: 1 rac / meso; 12.2 g; 27.2 mmol) was suspended in Et2O (about 80 mL) and MeMgBr (2.6 M in Et2O; 23.2 ml; 60.3 mmol) was added. The reaction was stirred overnight, the reaction was dried and extracted with hot hexanes (about 300 ml), filtered and about 1 ml of the solution was dried and the 1H NMR in C6D6 showed a ratio of 1 : 1 meso / rac of (1-EtInd) 2ZrMe2 very clear. Conversion of meso-rich (1-EtInd) 2ZrCl2 to close to 1: 1 rac / meso (1-EtInd) 2ZrMe2
[0143] meso (1-EtInd) 2ZrCl2 (1: 5 rac / meso; 244 mg; 0.54 mmol) was suspended in Et2O (about 5 mL) and MeLi (1.6 M in Et2O; 0.69 mL, 1.10 mmol) was added. The reaction was stirred overnight, filtered and an aliquot of the filtered reaction mixture was dried. The 1H NMR in C6D6 showed a ratio of 1: 1.24 rac / meso. Methylation of (EtInd) 2ZrCl2
[0144] The methylation results seen in the processes discussed here have been further explored to determine the conditions under which stereochemical guidance can be restored to a known level. A series of tests using the procedures described below was performed, giving the results shown in Tables 6A and 6B. The use of MeMgBr in ether is the only condition in which substantially no isomerization occurs. The best conditions for isomerization were excess MeLi in ether or excess Grignard in DME. In addition, the use of excess MeLi in DME results in a new species that is probably (EtInd) ZrMe3.
[0145] (1-EtInd) 2ZrCl2 (0.6 g; 1.34 mmol) was placed in a 50 ml round bottom flask and Et2O or DME (20 ml) was added. MeLi (1.57 M in ether) or MeMgBr (3.0 M in ether) was added with stirring. The ratio of methylation agent to zirconium was either 2.0 to 1 or 2.3 to 1. To determine the meso / rac ratio, about mL mL of the reaction mixture was removed and dried briefly to remove the largest part of the solvent and the solid was redissolved in about 0.75 ml of C6D6. The 1H NMR was performed at 400 MHz. The sum of the integrals for the two Zr-Me resonances of the meso species (δ = -0.31 and -1.40) was divided by the value of the Zr-Me resonance integral for the rac species (δ = -0.89) to produce the meso / rac ratio.
[0146] The described processes allow a bis-indenyl polymerization catalyst to be formed with an unbalanced stereochemical composition without a bonding group between the indenyl rings. For example, an enantiomer can be formed at a ratio of three times, or greater, to the other enantiomer. In addition, the conditions provide a methylation procedure that restores stereochemistry to a substantially uniform composition. Table 6A: Methylation results under different conditions
Table 6B: Methylation results under different conditions
* Presence of about 0.3 equiv of new species, probably (EtInd) ZrMe3 together with a free equivalent of EtIndLi Synthesis of (1-Methylindenyl) (pentamethylcyclopentadienyl) zirconium (IV) dimethyl (IV-C)

[0147] In the dry box, 1-Methyl-1H-indene oil (1.85 g, 14.2 mmol) was weighed in a 250 mL round-bottom flask and dissolved in 25 mL of dry diethyl ether . N-Butyllithium (1.6 M in hexanes, 12.0 mL, 19.2 mmol) was added dropwise from a 20 mL needle / syringe to form a yellow solution. It was stirred at room temperature for 60 minutes.
[0148] To the yellow-orange solution of (1-methyl) indenyl lithium, Cp * ZrCl3 (4.51 g, 13.5 mmol, used as received from Aldrich-475181) was added quickly in one portion as a yellow crystalline solid. The yellow-orange slurry was stirred overnight at room temperature.
[0149] Mixture was left to stand for 30 min. The dark brown solution was decanted from the opaque yellow solids, the solids were washed in a glass frit with 100 ml of dry ether. The solids were extracted on frit with 100mL of dichloromethane, providing a yellow suspension. It was filtered through a plug of Celite in frit and evaporated on volatiles to obtain a yellow solid. Recrystallized from ether / pentane to obtain 2.70 g (47%). Additional material obtained from the mother liquor: 1.19 g (20%)
[0150] 1H NMR (C6D6, 500 MHz, 35 ° C): δ 1.70 (15H, s, Cp *), 2.30 (3H, s, indenyl CH3), 5.56 (2H, ABq, indenyl CH, CH), 7.05 (1H, dd, indenyl CH), 7.10 (1H, dd, indenyl CH), 7.24 (1H, dt, indenyl CH), 7.56 (1H, dq, indenyl CH).

[0151] (1-methylindenyl) (pentamethylcyclopentadienyl) zirconium (4.92 g, 11.5 mmol) was suspended in 50 ml of diethyl ether and cooled to -50 ° C. For this suspension, a solution of MeLi (14.8 mL of a solution of 1.71M in diethyl ether, 25.4 mmol) was added slowly via syringe. The mixture was allowed to stir and slowly warm to room temperature to produce a pink suspension. After 16 h, the solvent was removed in vacuo and the residue was extracted with toluene. Insolubles were removed by filtration through a Celite-coated frit and the solvent was removed to produce an orange oily solid. The solid was washed with pentane and dried in vacuo (3.89 g, 88% yield). 1H NMR δ (C6D6): 7.53 (d, 1H, 8-indH), 7.13-6.99 (m, 3H, 5.6.7-indH), 5.21 (d, 1H, 2 -indH), 5.11 (d, 1H, 3-indH), 2.20 (s, 3H, 1-MeInd), 1.69 (s, 15H, CpMe5), -0.51 (s, 3H, ZrMe), -1.45 (s, 3H, ZrMe). Synthesis of (1,3-dimethylindenyl) (tetramethylcyclopentadienyl) zirconium, dimethyl [(1,3-Me2Ind) (CpMe4)] ZrMe2 (IV-D)
[0152] 2,3,4,5-tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene:

[0153] For a 2 liter Erlenmeyer flask, yellow oil dissolved in tetramethylcyclopentadiene (50 g, 409 mmol - obtained from Boulder Scientific) in 1 liter of anhydrous THF. It was stirred at room temperature as n-butyllithium (175 ml, 437 mmol) was added via a 60 ml plastic syringe with a 20 gauge flow regulating needle dropwise. The formation of an opaque yellow precipitate was observed. Reaction is a yellow slurry after complete addition of the lithium reagent. It was stirred 1 h at room temperature, then, with vigorous stirring, chlorotrimethylsilane (60 ml, 470 mmol) was added and the reaction was allowed to stir overnight at room temperature. After stirring at room temperature for 15 h, the mixture became a yellow solution. The solvent was removed with THF under a stream of N2, to obtain an oily residue, which was then extracted with 1 liter of dry pentane and filtered through a pad of celite over coarse fries. The volatiles were removed in vacuo to give the product as a yellow oil: 62.9 g, 79%. 1H NMR (C6D6, 250 MHz): δ -0.04 (s, Si (CH3) 3), δ 1.81, (s, CH3), δ 1.90 (s, CH3), δ 2.67 ( s, CH) Synthesis of (tetramethyl cyclopentadienyl) zirconium trichloride

[0154] In a dry box, solid ZrCl4 (30.0 g, 129 mmol) was charged to a 450 mL Chemglass pressure vessel with a magnetic stir bar, suspended in 100 mL of dry toluene. 2,3,4,5-tetramethyl-1-trimethylsilyl-cyclopenta-2,4-diene was dispensed as a yellow oil (27.5 g, 142 mmol) and rinsed with an additional 100 ml of dry toluene. The containers were sealed under pressure with a screw cap with Viton O-ring, and heated in an aluminum heating mantle set at 110 ° C for 90 min. Solution darkens over time, and insolubles were present during the reaction. The vessel was left stirring overnight and cooled to room temperature. The vessel was opened and the volume of solvent reduced under N2 flow, providing a thick red sludge. It was extracted with 2 x 50 ml of dry pentane, then with 100 ml of dry ether. Red solution was removed and recovered as an opaque red solid product: 35.4 g, 85% 1H NMR (C6D6, 250 MHz): δ 1.89 (br s, CH3), δ 2.05 (br s, CH3), δ 5.78 (s wide, CH)
[0155] 1-Methyl-indenyl-lithium: 3-methylindene (259.24mmol 33.75g) recently distilled was dissolved in pentane (1 L). Et2O (10 mL), then 1.6 M n-butyl lithium in hexanes (107 mL, 2.5 M) and 171.2 mmol n-butyl lithium in hexanes (34.2 mL, 85.5 mmol) was added to the solution with clear stirring. Immediately a scaly white solid precipitated. After stirring overnight, the slurry was filtered and the white solid was vacuum dried (33.88g, 248.90 mmol, 97%). 1H NMR (THF-d8): δ 2.41 (s, 3H), 5.68 (d, 1H), 6.31 (d, 1H), 6.41 (m, 2H), 7.22 (m , 2H).
[0156] In a dry box, iodomethane (2.0 ml, 32.1 mmol) was dissolved in 80 ml of dry diethyl ether in a 250 ml round bottom flask with a magnetic stir bar. Flask was placed in a cold iso-hexane bath (-25 ° C) in a wide-mouthed Dewar vessel. In a separate 100 ml Erlenmeyer flask, a solution at room temperature of 1-methylindenyl lithium (3.50 g, 25.7 mmol) was prepared in 50 ml of dry diethyl ether, yielding a yellow solution. A solution of indenyl lithium was slowly added dropwise to the cold solution, the stirring of the iodomethane solution was carried out for 15 min. Stirring continued at low temperature for 30 min, then it was removed from the cold bath and the reaction was allowed to warm to room temperature overnight. The solution turns cloudy white after stirring for 15 hours at room temperature. The volume of the solution was reduced under nitrogen flow, then the volatile products were evaporated under high vacuum. The solids were extracted with 2x80 ml of isohexane and filtered through a layer of celite over coarse frit. The filtrates were evaporated under high vacuum to obtain a brown oil. It was dissolved in 5 ml of dichloromethane and loaded through the pipette onto the silica gel column (Biotage SNAP 100 g), eluting with dichloromethane: isohexane (gradient, 2-20%). The fractions were combined and evaporated to produce a clear oil. 2.54 g, 68%, were collected.
[0157] 1H NMR (C6D6, 500 MHz): δ 1.11 (d, J = 7.5 Hz, - CHCH3), δ 1.96 (s, CH = CCH3), δ 3.22 (m, CHCH3 ), δ 5.91 (m, CH = CCH3), δ 7.15-7.27 (aromatic CH). Mixture contains a smaller isomer of 3,3-dimethylindene in a 1:10 ratio with the desired product. δ 1.17 (s, CH3), δ 6.14 (d, J = 5.5 Hz, CHH), δ 6.51 (d, J = 5.5 Hz, CHH). dimethylindenyl lithium

[0158] 2.54 g (17.6 mmol) of clear oil, 10: 1 mixture of 1,3-dimethylindene and 3,3-dimethylindene were dissolved in 35 ml of dry pentane. Stir up to 6.2 ml of a solution of 2.5 M n-butyllithium in hexane (15.5 mmol) was added slowly dropwise. The white precipitate formed immediately. It was stirred at room temperature for 45 min, then the supernatant was filtered through a cannula. The residue was suspended in 30 ml of dry pentane and cooled in the dry box freezer (-27 ° C) for 60 min. The supernatant was filtered and dried in vacuo to obtain 2.34 g (88%) of a white powder, which was used as it is in the subsequent reaction step without characterization. [(1,3-Dimethylindenyl dichloride) synthesis ) (tetramethylcyclopentadienyl)] Zirconium:

[0159] 3.50 g (10.98 mmol) of brown (tetramethyl) zirconium trichloride powder were weighed in a 100 mL flat-bottomed glass bottle with a magnetic stir bar. It was suspended in 80 ml of dry diethyl ether. It was stirred as 1,3-dimethylindenyl lithium (1.65 g, 10.99 mmol) was added as a powder over several minutes. It was washed with an additional 20 ml of ether. The flask was capped and stirred overnight at room temperature. A yellow slurry was mixed after stirring for 15 hours at room temperature. The volatiles were evaporated under high vacuum, then the residue was extracted with 2 x 80 ml of dichloromethane. It was filtered through a layer of celite over coarse fries. It was concentrated in vacuo and filtered again through fresh celite over coarse frit. It was dried in vacuo to free flow the yellow powder, 3.6 g (77%). 1H NMR (CD2Cl2, 500 MHz): δ 1.89 (s, CH3 of CpMe4), δ 1.90 (s, CH3 of CpMe4), δ 2.40 (s, CH3 of C9 fragment), δ 5.67 (s, CpMe4 CH), δ 6.33 (s, C9 fragment CH), δ 7.24 (AA'BB ', C9 fragment aromatic CH), δ 7.52 (AA'BB', aromatic CH fragment fragment C9). Contains about 15% etherdiethyl.cyclopentadienyl)] zirconium dimethyl (IV-D)

[0160] Bright yellow powder of (1,3-Me2Ind) (CpMe4) ZrCl2 (3.6 g, 8.4 mmol) was suspended in 75 mL of dry diethyl ether in a flat bottom flask. 100 mL of amber glass, with a magnetic stir bar. The bottle was cooled to -10 ° C in an isohexane bath, stirred as a solution of methyl lithium (1.6 M in ether) using a deliverd syringe in portions (4 x 3 mL, 19.2 mmol). The bottle was capped with a septum and stirred overnight, allowing the cold bath to warm slowly to room temperature. The slurry evaporated to dryness under high vacuum. It was extracted with 3 x 50 ml of dichloromethane and filtered through celite over coarse frit. It was concentrated under a stream of nitrogen, and then pentane was added. It was stirred for 15 min, then the volatiles were evaporated. The solids were washed with cold pentane, dried in vacuo. It was collected as brown powder, 1.67 g; the second crop was recovered from the filtrate, 0.52 g. The combined yielded 2.19 g, 67%. 1H NMR (CD2Cl2, 500 MHz): δ -1.22 (s, ZrCH3), 1.78 (s, CH3 of CpMe4 fragment), 1.87 (s, CH3 of CpMe4 fragment), 2.25 (s, CH3 of C9 fragment), 4.92 (s, CH of CpMe4 fragment), 5.60 (s, CH of C9 fragment), 7.14 (AA'BB ', aromatic CH of C9 fragment), 7.44 ( AA'BB ', aromatic CH of fragment C9). 13C {1H} (CD2Cl2, 125 MHz): δ 11.64 (CH3 of the CpMe4 fragment), 12.91 (CH3 of the C9 fragment), 13.25 (CH3 of the CpMe4 fragment), 37.23 (ZrCH3), 106.34 (CH of the CpMe4 fragment), 115.55 (CH of the C9 fragment); quaternary 13C resonances 107,36,117,51,122,69,125,06. Synthesis of Meso-O (1-SiMe2lndenyl) 2Dimethyl zirconium (V-a)
[0161] To a slurry of meso-O- (SiMe2Indenyl) 2ZrCl2 (purchased from D-Chemie Catalytica; 40.0 g; 83.2 mmol) in about 300 mL of ether was added 54.0 mL of MeMgBr (3.0 M / ether; 162 mmol) at room temperature. After stirring the slurry for 1.5 hours, the volatiles were removed; heptane (about 300 ml) was added to the resulting solid and heated to 80 ° C for 30 minutes. The slurry was filtered and the supernatant was cooled to -30 ° C resulting in the formation of a crystalline solid which was isolated by filtration, washed with pentane and dried under vacuum. The yield was 26.0 g. 1H NMR δ (C6D6): 7.57 (m, 2H), 7.42 (m, 2H), 7.02 (m, 2H), 6.94 (m, 2H), 6.31 (d, 2H ), 5.82 (d, 2H), 0.44 (s, 6H), 0.34 (s, 6H), 0.00 (s, 3H), -2.07 (s, 3H). Catalyst Preparations Dehydration of silica at 610 ° C
[0162] Silica Ineos ES757 de (3969 g) was loaded into a dehydrator (6 feet long, 6.25 in diameter) equipped with a 3 zone heater, then it was fluidized with dry N2 gas at a flow rate of 0.12 ft3 / s. Then, the temperature was raised to 200 ° C over a period of 2 h. After holding at 200 ° C for 2 h, the temperature was raised to 610 ° C over a period of 6 h. After standing at 610 ° C for 4 h, the temperature was allowed to cool to room temperature over a period of 12 h. The gel was transferred under N2 to an APC and can then be stored under N2 pressure 138 kPa (20 psig). Preparation of methyl aluminoxane supported on silica (SMAO)
[0163] In a typical procedure, the silica Ineos ES757 (741 g), dehydrated at 610 ° C, was added to a stirred mixture (suspended mechanical conical stirrer) of toluene (2 L) and 30% solution by weight of methyl aluminoxane in toluene (874 g, 4.52 mol). The silica was treated with toluene (200 ml), then the mixture was heated to 90 ° C for 3 h. Then, the volatiles were removed by applying vacuum and moderate heat (40 ° C) overnight, then the solid was allowed to cool to room temperature. Preparation of typical Small Scale Catalyst for the Laboratory Salt Bed Reactor
[0164] In a dry box purged with N2, 3.00 g of SMAO (4.5 mmol MAO / g SMAO) were transferred to a 125 mL Cel-Stir mixer. Pentane (50 mL) was added to create a slurry. The slurry was stirred at room temperature. The metallocene (0.11 mmol) was dissolved in a minimum amount of toluene (~ 2 mL). This solution was then added to the slurry with stirring. The mixture was left under stirring for one hour. After the designated time, the mixture was filtered over a glass frit and washed with fresh pentane (2 x 10 ml), then dried for at least one hour. Description of the Laboratory Salt Bed Reactor
[0165] Under an N2 atmosphere, a 2 L autoclave was loaded with dry salt (200 g) and SMAO (3 g). At a pressure of 13.8 kPa (2 psig) of dry degassed N2, 1-hexene (see Table 7) was added to the reactor with a syringe. The reactor was sealed, heated to 80 ° C while the bed was stirred, then charged with N2 at a pressure of 138 kPa (20 psig). Then, the solid catalyst was injected into the reactor with ethylene at a pressure of 1517 kPa (220 psig); ethylene flow was left throughout the run. The temperature was raised to 85 ° C. Hexene was introduced into the reactor as an ethylene flow rate (0.08 g / g). Hydrogen was fed to the reactor as a reason for ethylene flow as described in the table. The hydrogen and ethylene ratios were measured by online GC analysis. The polymerizations were interrupted after 1 h by ventilation of the reactor, cooled to room temperature, then exposed to air. The salt was removed by stirring the crude product in water. The polymer was obtained by filtration followed by drying in a vacuum oven, obtaining the results shown in Table 8.Table 7: Feeding conditions for laboratory salt bed compressors
Table 8: Polymerization results for laboratory salt bed reactor experiments
Large Scale Catalyst Preparations for Gas Phase Pilot Plant Test 60.95 cm (24 inches) in diameter
[0166] A 5 L 3-neck Morton flask was loaded with pentane (4 L), then stirred (140 rpm) with a mechanical stirrer while loaded with SMAO (375 g). A solution containing (1-EtInd) 2ZrMe2 (IV-A / B), HfPMe2 (III), etoluene was added with an addition funnel over the course of an hour. A slurry took on a green color and was left stirring for an additional hour. The mixture was then filtered and vacuum dried for a total of 8 hours. The results are shown in Table 9.Table 9: Mixing Combinations

[0167] Preparation of batch 2 of 75% HfPMe2 / 25% (1-EtInd) 2ZrMe2 Catalyst. A procedure similar to that described above was used for the second 75/25 catalyst batch. A mixture of SMAO was used comprising 204.15 g of UT-331-142, 176.17 g of UT-331-101, 209.49 g of UT-331-124, and 160.19 g of UT-331-143. For the second batch, 4L of pentane was added first to the Morton flask followed by SMAO so that agglomeration did not occur. Two separate solutions were made with 2.87 g (7.09 mmol) of (1-EtInd) 2ZrMe2 and 8.94g (20.95 mmol) of HfPMe2 in 20 mL of toluene. Preparation of batch 1 & 2 of 50% HfPMe2 / 50% (1-EtInd) 2ZrMe2 Catalyst
[0168] The same procedure used to prepare the second batch of 75/25 catalyst was used for both sets of catalyst at 50/50. Lot 1 used SMAO of UT-331-143, 5.75 g (14.10mmol) of (1-EtInd) 2ZrMe2, and 5.97g (14.11mmol) of HfPMe2. Lot 2 used SMAO of UT-331-144, 5.75 g (14.09mmol) of (1-EtInd) 2ZrMe2, and 5.97g (14.11mmol) of HfPMe2. Mixing Catalysts
[0169] The two batches at 75/25 were combined in a 4L Nalgene bottle and mixed manually by rotation and shaking the bottle. The two 50/50 batches were also mixed in the same way. Spray dried catalyst preparations
[0170] Spray-Dried Lower HfP (SD- (III)). The raw material slurry was prepared by first adding 10% by weight of MAO (11.20 kg (24.7 lbs)), toluene 16.24 kg (35.8 lbs) and Cabosil TS-610 1, 54 kg (3.4 lbs) to a 37.85 liter (10 gallon) feed tank. The mixture was stirred overnight at room temperature. HfP (III) (28.75 g, 0.06798 mol) was then added and the resulting slurry was mixed for an additional hour at ~ 3840 ° C before spraying. The catalyst was spray-dried at a slurry feed rate of 42 kg / h (93 lb / h), 90% atomizer speed, and outlet temperature of 80 ° C. The yield was 2289 g (85%). The analytical data are shown in Table 10.Table 10: analytical data for supported HfP (III)
Description of Gas Phase Reactor 61 cm (24 inches) in diameter
[0171] Polymerization was carried out in a continuous gas phase fluidized bed reactor having a straight section of 61 cm (24 inches) in diameter with a length of about 3.6 m (11.75 feet) and an expanded section of 3.1 m (10.2 feet) in length and 1.3 m (4.2 feet) in diameter at the widest width. The fluidized bed consists of polymer granules. The gas feed streams of ethylene and hydrogen together with the 1-hexene liquid were mixed together in a T mixer arrangement and introduced below the reactor bed to the recycle gas line. The individual flow rates of ethylene, hydrogen and 1-hexene were controlled to keep composition targets fixed. The ethylene concentration was controlled to maintain a constant ethylene partial pressure. The hydrogen was controlled to maintain a constant hydrogen at the molar ratio of ethylene. The concentrations of all gases were measured by in-line gas chromatography to ensure a relatively constant composition of the recycle gas flow.
[0172] The solid catalyst was injected directly into the fluidized bed using purified nitrogen as a carrier. Its injection rate has been adjusted to maintain a constant rate of polymer production. The reaction bed of the growing polymer particles was kept in a fluidized state by the continuous flow of the gas constituting and recycling gas through the reaction zone at a surface gas velocity of 0.3 to 0.9 m / s (1-3 feet / s). The reactor was operated at a total pressure of 2068 kPa (300 psig). To maintain a constant reactor temperature, the temperature of the recycle gas was continuously adjusted up or down to accommodate changes in the rate of heat generation due to polymerization.
[0173] A solution of antistatic agents in hexane (1: 1 aluminum stearate: 20% by weight N-nonildiethanolamine) was introduced into the reactor, using a mixture of isopentane and nitrogen at such a rate as to maintain also about of 30 ppm of antistatic agents in the fluidized bed.
[0174] The fluidized bed was maintained at a constant height by removing a portion of the bed at a rate equal to the rate of formation of the particulate product. The product was removed semi-continuously through a series of valves to a fixed volume chamber, which was simultaneously vented back to the reactor to allow highly efficient removal of the product, while at the same time recycling a large portion of the unreacted gases. back to the reactor. This product was purged to remove entrained hydrocarbons and treated with a small stream of humidified nitrogen to deactivate any trace amounts of catalyst and residual cocatalyst. Execution Summary
[0175] Examples of execution conditions for polymerizations are shown in Table 11. Table 11: Execution conditions for polymerizations of the 61 cm (24 inch) Gas Phase Reactor

Table 11 (continued): Execution Conditions for polymerizations of the 61 cm (24 inch) Gas Phase Reactor

Description of Gas Phase Reactor 33.65 cm (13.25 inches) in diameter
[0176] A gaseous fluidized bed reactor of 0.35 meters in internal diameter and 2.3 m in height of the bed was used for the polymerizations, with the results shown in Table 12. The fluidized bed consisted of granules of polymer and the gaseous feed streams of ethylene and hydrogen together with the 1-hexene comonomer liquid were introduced below the reactor bed to the recycling gas line. The individual flow rates of ethylene, hydrogen and 1-hexene were controlled to keep composition targets fixed. The ethylene concentration was controlled to maintain a constant ethylene partial pressure. Hydrogen was controlled to keep the molar ratio of hydrogen to ethylene constant. The concentrations of all gases were measured by in-line gas chromatography to ensure a relatively constant composition of the recycle gas flow. The reaction bed of growing polymer particles was maintained in a fluidized state by the continuous flow of the gas constituting and recycling gas through the reaction zone. The surface velocity of the gas from 0.6 to 0.9 meters / s was used to achieve this goal. The fluidized bed was kept at a constant height by removing a portion of the bed at a rate equal to the rate of formation of the particulate product. The polymer production rate was in the range of 15 to 25 kg / hour. The product was removed semi-continuously through a series of valves for a fixed volume chamber. This product was purged to remove entrained hydrocarbons and treated with a small stream of humidified nitrogen to deactivate any traces of residual catalyst.
[0177] The solid catalyst was dispersed in degassed mineral oil and dried as a nominal amount of 18% by weight slurry and placed in contact with the compensating catalyst solution for a few seconds to minutes before being injected directly into the fluidized bed. using purified nitrogen and isopentane as carriers in a way that produces an effervescence of nitrogen in the liquid and pressure to help disperse the catalyst. The compensation catalyst was initially supplied as a solution, and substantially diluted with isopentane to a concentration of about 0.015% by weight, before being mixed in line with the catalyst slurry component continuously before injection into the reactor. . The relative feeds of slurry catalyst and compensation catalyst were controlled to achieve a target feed ratio of their active polymerization metals, and the feeds were adjusted according to the overall polymer production rate and the relative polymer quantities produced by each catalyst based on the MFR polymer flow rate and density, while also manipulating the reaction temperature and gas compositions in the reactor. The reaction bed of growing polymer particles was maintained in a fluidized state by continuously flowing the constitution and recycle gas feed through the reaction zone at a surface gas velocity in the range of about 0.61 and 0, 67 m / s (2.0 to 2.2 feet / s). The reactor was operated at a total pressure of about 2413 kPa (350 psig). To maintain a constant fluidized bed temperature inside the reactor, the temperature of the recycle gas was continuously adjusted upwards or downwards, passing the recirculation gas through the tubes of a shell and tube heat exchanger with the cooling water in the side of the shell to accommodate any change in the rate of heat generation due to polymerization.
[0178] A mixture of slurry of antistatic agents in dry, degassed mineral oil (1: 1 Aluminum stearate: N-nonildiethanolamine at 20% by weight of concentration) was introduced into the reactor, using a mixture of iso-pentane and nitrogen at such a rate to obtain a concentration of between 38 and 123 ppmw of antistatic agents in the fluidized bed. (Line 128) Isopentane and / or nitrogen was optionally used to assist in the transport and dispersion of the antistatic slurry mixture in the reactor fluidized bed through a 0.32 cm to 0.48 cm (1/8 OD injection overflow tube) inch to 3/16 inch) that extends a few centimeters (a few inches) into the side wall bed of the reactor.
[0179] The fluidized bed was kept at a constant height by removing a portion of the bed at a rate equal to the rate of formation of the particulate product. The product was removed semi-continuously through a series of valves for a fixed volume discharge chamber. This product was purged to remove entrained hydrocarbons and treated with a small stream of humidified nitrogen immediately upon discharge to a fiberpak receiver drum to deactivate any residual catalyst and cocatalyst traces.
[0180] All numerical values are "about" or "approximately" the indicated value, and take into account the experimental error and variations that would be expected by a person skilled in the art. In addition, several terms are defined above. Insofar as a term used in a claim is not defined above, the broadest definition that persons skilled in the relevant technique have given to the term should be given as reflected in at least one print publication or an issued patent. All patents, testing procedures and other documents cited in this application are fully incorporated by reference, insofar as such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.Table 12: Reactor Polymerization Experiments 33.65 cm (13.25 inches) diameter Gaseous Phase

Table 12 (continued): Polymerization Experiments in a 33.65 cm (13.25 inch) Gas Phase Reactor

Table 12 (Continued): Polymerization Experiments in a 33.65 cm (13.25 inch) Gas Phase Reactor


[0181] Although the foregoing is directed to embodiments of the present invention, other and more embodiments of the invention can be conceived without departing from the basic scope of the same, and its scope is determined by the claims that follow.

权利要求:
Claims (5)
[0001]
1. Method for forming a catalyst composition, while substantially normalizing the stereochemical configuration, characterized by the fact that it comprises: -form slurry of a metallocene compound in dimethoxyethane (DME); -adding a solution of RMgBr in DME, where R is a methyl group or a benzyl group, and RMgBr is greater than 2.3 equivalents in relation to the metallocene compound; -mix for four hours or more to form an alkylated metallocene compound; and -isolating the alkylated metallocene compound, with the alkylated species having a ratio of meso / rac enantiomers that is between 0.9 and 1.2.
[0002]
2. Method according to claim 1, characterized by the fact that it comprises: -dissolving 1-ethylindenyl lithium in dimethoxyethane, to form a precursor solution; - cool the precursor solution to -20 ° C; -add solid ZrCl4 for five minutes to start a reaction; -continue the reaction from one day to the next; -removing volatiles to form a crude product; -extract the crude product with CH2Cl2; and -remove CH2Cl2 under vacuum, to form the metallocene compound.
[0003]
3. Method, according to claim 1, characterized by the fact that it comprises: -fluidifying a catalyst support with an inert gas; -heat the support to remove any adsorbed water forming a dry support; and - storing the dry support under an inert gas.
[0004]
4. Method according to claim 3, characterized by the fact that it comprises: -forming a dry paste from the dry support in a mixture of toluene and methyl aluminoxane; and drying the mixture to form methyl aluminoxane supported on silica (SMAO).
[0005]
5. Method, according to claim 4, characterized by the fact that it comprises: -adding pentane to the SMAO to form a slurry; - dissolving the alkylated organometallic component in toluene to form a toluene solution; -add the toluene solution to the slurry to form a catalyst; - filter the catalyst from the slurry; and - drying the catalyst.

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法律状态:
2018-05-22| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/02/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201461938466P| true| 2014-02-11|2014-02-11|

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US201461938472P| true| 2014-02-11|2014-02-11|

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US61/938,466|2014-02-11|

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US61/938,472|2014-02-11|

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US201461981291P| true| 2014-04-18|2014-04-18|

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US61/981,291|2014-04-18|

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US201461985151P| true| 2014-04-28|2014-04-28|

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US61/985,151|2014-04-28|

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US201462032383P| true| 2014-08-01|2014-08-01|

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US62/032,383|2014-08-01|

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US201462087911P| true| 2014-12-05|2014-12-05|

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US201462088196P| true| 2014-12-05|2014-12-05|

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US201462087905P| true| 2014-12-05|2014-12-05|

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US201462087914P| true| 2014-12-05|2014-12-05|

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US62/088,196|2014-12-05|

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US62/087,914|2014-12-05|

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US62/087,911|2014-12-05|

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PCT/US2015/015130|WO2015123171A2|2014-02-11|2015-02-10|Producing polyolefin products|BR122020005071-3A| BR122020005071B1|2014-02-11|2015-02-10|catalyst composition|