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Patent US7569646 - Group IVB transition metal compounds - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThe invention is a Group IVB transition metal compound which may be employed in the polymerization of olefins to produce high molecular weight polymers....http://www.google.com/patents/US7569646?utm_source=gb-gplus-sharePatent US7569646 - Group IVB transition metal compoundsAdvanced Patent SearchPublication numberUS7569646 B1Publication typeGrantApplication numberUS 07/728,428Publication dateAug 4, 2009Filing dateJul 11, 1991Priority dateSep 13, 1989Fee statusPaidAlso published asCA2024899A1, CA2024899C, CA2065745A1, CA2065745C, DE420436T1, DE662484T1, DE69028057D1, DE69028057T2, DE69028057T3, DE69030442D1, DE69030442T2, EP0420436A1, EP0420436B1, EP0420436B2, EP0491842A1, EP0491842B1, EP0643066A2, EP0643066A3, EP0662484A2, EP0662484A3, EP0671404A2, EP0671404A3, US5055438, US7205364, US20060178491, WO1991004257A1Publication number07728428, 728428, US 7569646 B1, US 7569646B1, US-B1-7569646, US7569646 B1, US7569646B1InventorsJo Ann Marie CanichOriginal AssigneeExxonmobil Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (11), Non-Patent Citations (6), Referenced by (6), Classifications (47), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetGroup IVB transition metal compoundsUS 7569646 B1Abstract The invention is a Group IVB transition metal compound which may be employed in the polymerization of olefins to produce high molecular weight polymers.
L is a neutral Lewis base where �w� is a number greater than 0 and up to 3;
More recently a catalyst system has been developed wherein the transition metal compound has two or more cyclopentadienyl ring ligands, such transition metal compound being referred to as a metallocene�which catalyzes the production of olefin monomers to polyolefins. Accordingly, metallocene compounds of the Group IV B metals, particularly, titanocene and zirconocene, have been utilized as the transition metal component in such �metallocene� containing catalyst system for the production of polyolefins and ethylene-α-olefin copolymers. When such metallocenes are cocatalyzed with an aluminum alkyl�as is the case with a traditional type Ziegler-Natta catalyst system�the catalytic activity of such metallocene catalyst system is generally too low to be of any commercial interest.
It has since become known that such metallocenes may be cocatalyzed with an alumoxane�rather than an aluminum alkyl�to provide a metallocene catalyst system of high activity which catalyzes the production of polyolefins.
The �Group IV B transition metal component� of the catalyst system is represented by the general formula:
(C5H5-y-xRx) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, �x� is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, C1-C20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements, and halogen radicals or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C4-C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(JR′z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R′ is, independently a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
L is a Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and �w� is a number from 0 to 3; L can also be a second transition metal compound of the same type such that the two metal centers M and M′ are bridged by Q and Q′, wherein M′ has the same meaning as M and Q′ has the same meaning as Q. Such compounds are represented by the formula:
The alumoxane component of the catalyst may be represented by the formulas: (R2�Al�O)m; R3(R4�Al�O)m�AlR5 or mixtures thereof, wherein R2-R5 are, independently, a univalent anionic ligand such as a C1-C5 alkyl group or halide and �m� is an integer ranging from 1 to about 50 and preferably is from about 13 to about 25.
A typical polymerization process of the invention such as for the polymerization or copolymerization of olefins comprises the steps of contacting ethylene or C3-C20 α-olefins alone or with other unsaturated monomers including C3-C20 α-olefins, C5-C20 diolefins, and/or acetylenically unsaturated monomers either alone or in combination with other olefins and/or other unsaturated monomers, with a catalyst comprising, in a suitable polymerization diluent, the Group IV B transition metal component illustrated above; and a methylalumoxane in an amount to provide a molar aluminum to transition metal ratio of from about 1:1 to about 20,000:1 or more; and reacting such monomer in the presence of such catalyst system at a temperature of from about −100� C. to about 300� C. for a time of from about 1 second to about 10 hours to produce a polyolefin having a weight average molecular weight of from about 1,000 or less to about 5,000,000 or more and a molecular weight distribution of from about 1.5 to about 15.0.
DESCRIPTION OF THE PREFERRED EMBODIMENT Catalyst Component The Group IV B transition metal component of the catalyst system is represented by the general formula:
(JR′z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R′ is, independently a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, substituted C1-C20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and �z� is the coordination number of the element J;
�y� is 0 or 1 when w is greater than 0, y is 1 when w=0; when �y� is 1, T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, alkyl or aryl phosphine or amine radical, or a hydrocarbyl radical such as methylene, ethylene and the like. L is defined as heretofore. Examples of the B group which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 1 of Table 1 under the heading �B�.
Exemplary hydrocarbyl radicals for the Q are methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl being preferred. Exemplary halogen atoms for Q include chlorine, bromine, fluorine and iodine, with chlorine being preferred. Exemplary alkoxides and aryloxides for Q are methoxide, phenoxide and substituted phenoxides such as 4-methylphenoxide. Exemplary amides for Q are dimethylamide, diethylamide, methylethylamide, di-t-butylamide, diisopropylamide and the like. Exemplary aryl amides are diphenylamide and any other substituted phenyl amides. Exemplary phosphides for Q are diphenylphosphide, dicyclohexylphosphide, diethylphosphide, dimethylphosphide and the like. Exemplary alkylidene radicals for both Q together are methylidene, ethylidene and propylidene. Examples of the Q group which are suitable as a constituent group or element of the Group IV B transition metal component of the catalyst system are identified in Column 4 of Table 1 under the heading �Q�.
Table 1 depicts representative constituent moieties for the �Group IV B transition metal component�, the list is for illustrative purposes only and should not be construed to be limiting in any way. A number of final components may be formed by permuting all possible combinations of the constituent moieties with each other. Illustrative compounds are: dimethylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dichloride, dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido zirconium dichloride, dimethylsilyl-tert-butylcyclopentadienyl-tert-butylamido hafnium dichloride, dimethylsilyltrimethylsilylcyclopentadienyl-tert-butylamido zirconium dichloride, dimethylsilyltetramethylcyclopentadienylphenylamido zirconium dichloride, dimethylsilyltetramethylcyclopentadienylphenylamido hafnium dichloride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido zirconium dichloride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dichloride, methylphenylsilyltetramethylcyclopentadienyl-tert-butylamido hafnium dimethyl, dimethylsilyltetramethylcyclopentadienyl-p-n-butylphenylamido zirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-p-n-butylphenylamido hafnium dichloride. For illustrative purposes, the above compounds and those permuted from Table 1 does not include the Lewis base ligand (L). The conditions under which complexes containing Lewis base ligands such as ether or those which form dimers is determined by the steric bulk of the ligands about the metal center. For example, the t-butyl group in Me2Si(Me4C5)(N-t-Bu)ZrCl2 has greater steric requirements than the phenyl group in Me2Si(Me4C5)(NPh)ZrCl2.Et2O thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me2Si(Me3SiC5H3)(N-t-Bu)ZrCl2]2 versus that of the tetramethylcyclopentadienyl group in Me2Si(Me4C5)(N-t-Bu)ZrCl2, the former compound is dimeric and the latter is not.
Suitable, but not limiting, Group IV B transition metal compounds which may be utilized in the catalyst system of this invention include those bridged species (�y�=1) wherein the B group bridge is a dialkyl, diaryl or alkylaryl silane, or methylene or ethylene. Exemplary of the more preferred species of bridged Group IV B transition metal compounds are dimethylsilyl, methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl, ethylene or methylene bridged compounds. Most preferred of the bridged species are dimethylsilyl, diethylsilyl and methylphenylsilyl bridged compounds.
The alumoxane component of the catalyst system is an oligomeric compound which may be represented by the general formula (R2�Al�O)m which is a cyclic compound, or may be R3(R4�Al�O�)m�AlR2 5 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R2, R3, R4, and R5 are, independently a univalent anionic ligand such as a C1-C5 alkyl radical, for example, methyl, ethyl, propyl, butyl, pentyl or halide and �m� is an integer from 1 to about 50. Most preferably, R2, R3, R4 and R5 are each methyl and �m� is at least 4. When an alkyl aluminum halide is employed in the preparation of alumoxane, one or more of R2-5 could be halide.
Suitable alumoxanes which may be utilized in the catalyst systems of this invention are those prepared by the hydrolysis of a alkylaluminum reagent; such as trimethylaluminum, triethylaluminum, tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride, diisobutylaluminumchloride, diethylaluminumchloride, and the like. The most preferred alumoxane for use is methylalumoxane (MAO), particularly methylalumoxanes having a reported average degree of oligomerization of from about 4 to about 25 (�m�=4 to 25) with a range of 13 to 25 being most preferred.
The catalyst system may be conveniently prepared by placing the selected Group IV B transition metal component and the selected alumoxane component, in any order of addition, in an alkane or aromatic hydrocarbon solvent�preferably one which is also suitable for service as a polymerization diluent. Where the hydrocarbon solvent utilized is also suitable for use as a polymerization diluent, the catalyst system may be prepared in situ in the polymerization reactor. Alternatively, the catalyst system may be separately prepared, in concentrated form, and added to the polymerization diluent in a reactor. Or, if desired, the components of the catalyst system may be prepared as separate solutions and added to the polymerization diluent in a reactor, in appropriate ratios, as is suitable for a continuous liquid polymerization reaction procedure. Alkane and aromatic hydrocarbons suitable as solvents for formation of the catalyst system and also as a polymerization diluent are exemplified by, but are not necessarily limited to, straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and the like, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and the like, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene and the like.
The catalyst system ingredients�that is, the Group IV B transition metal, the alumoxane, and polymerization diluent can be added to the reaction vessel rapidly or slowly. The temperature maintained during the contact of the catalyst components can vary widely, such as, for example, from −10� to 300� C. Greater or lesser temperatures can also be employed. Preferably, during formation of the catalyst system, the reaction is maintained within a temperature of from about 25� to 100� C., most preferably about 25� C.
Polymerization Process In a preferred embodiment of the process of this invention the catalyst system is utilized in liquid phase (slurry, solution, suspension or bulk phase and combination thereof), high pressure fluid phase or gas phase polymerization of an olefin monomer. These processes may be employed singularly or in series. The liquid phase process comprises the steps of contacting an olefin monomer with the catalyst system in a suitable polymerization diluent and reacting said monomer in the presence of said catalyst system for a time and at a temperature sufficient to produce a polyolefin or high molecular weight.
The monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an α-olefin having 3 to 20 carbon atoms for the production of an ethylene-α-olefin copolymer. Homopolymers of higher α-olefin such as propylene, butene, styrene and copolymers thereof with ethylene and/or C4 or higher α-olefins and diolefins can also be prepared. Conditions most preferred for the homo- or co-polymerization of ethylene are those wherein ethylene is submitted to the reaction zone at pressures of from about 0.019 psia to about 50,000 psia and the reaction temperature is maintained at from about −100� to about 300� C. The aluminum to transition metal molar ratio is preferably from about 1:1 to 18,000 to 1. A preferable range would be 1:1 to 1000:1. The reaction time is preferably from about 1 min to about 1 hr. Without limiting in any way the scope of the invention, one means for carrying out the process of the present invention is as follows: in a stirred-tank reactor liquid 1-butene monomer is introduced. The catalyst system is introduced via nozzles in either the vapor or liquid phase. Feed ethylene gas is introduced either into the vapor phase of the reactor, or sparged into the liquid phase as is well known in the art. The reactor contains a liquid phase composed substantially of liquid 1-butene together with dissolved ethylene gas, and a vapor phase containing vapors of all monomers. The reactor temperature and pressure may be controlled via reflux of vaporizing α-olefin monomer (autorefrigeration), as well as by cooling coils, jackets etc. The polymerization rate is controlled by the concentration of catalyst. The ethylene content of the polymer product is determined by the ratio of ethylene to 1-butene in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.
EXAMPLES In the examples which illustrate the practice of the invention the analytical techniques described below were employed for the analysis of the resulting polyolefin products. Molecular weight determinations for polyolefin products were made by Gel Permeation Chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector and a Chromatix KMX-6 on-line light scattering photometer. The system was used at 135� C. with 1,2,4-trichlorobenzene as the mobile phase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802, 803, 804 and 805 were used. This technique is discussed in �Liquid Chromatography of Polymers and Related Materials III�, J. Cazes editor, Marcel Dekker, 1981, p. 207 which is incorporated herein by reference. No corrections for column spreading were employed; however, data on generally accepted standards, e.g. National Bureau of Standards Polyethylene 1484 and anionically produced hydrogenated polyisoprenes (an alternating ethylene-propylene copolymer) demonstrated that such corrections on Mw/Mn (=MWD) were less than 0.05 units. Mw/Mn was calculated from elution times. The numerical analyses were performed using the commercially available Beckman/CIS customized LALLS software in conjunction with the standard Gel Permeation package, run on a HP 1000 computer.
All procedures were performed under an inert atmosphere of helium or nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The lithiated amides were prepared from the corresponding amines and either n-BuLi or MeLi. Published methods for preparing LiHC5Me4 include C. M. Fendrick et al. Organometallics, 3, 819 (1984) and F. H. K�hler and K. H. Doll. Z. Naturforsch, 376, 144 (1982). Other lithiated substituted cyclopentadienyl compounds are typically prepared from the corresponding cyclopentadienyl ligand and n-BuLi or MeLi, or by reaction of MeLi with the proper fulvene. ZrCl4 and HfCl4 were purchased from either Aldrich Chemical Company or Cerac. Amines, silanes and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane was supplied by either Sherring or Ethyl Corp.
Examples A-L of Group IV B Transition Metal Components Example A Compound A: Part 1. Me4HC5Li (10.0 g, 0.078 mol) was slowly added to a Me2SiCl2 (11.5 ml, 0.095 mol, in 225 ml of tetrahydrofuran (thf) solution). The solution was stirred for 1 hour to assure complete reaction. The thf solvent was then removed via a vacuum to a cold trap held at −196� C. Pentane was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me4HC5SiMe2Cl (15.34 g, 0.071 mol) was recovered as a pale yellow liquid.
Part 2. Me4HC5SiMe2Cl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol, �100 ml thf). The mixture was stirred overnight. The thf was then removed via a vacuum to a cold trap held at −196� C. Petroleum ether (�100 ml) was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2Si(Me4HC5)(HN-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 4. [Me2Si(Me4C5)(N-t-Bu)]Li2 (3.0 g, 0.011 mol) was suspended in �150 ml Et2O. ZrCl4 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at −196� C. Pentane was added to precipitate out the LiCl. The mixture was filtered through Celite twice. The pentane was significantly reduced in volume and the pale yellow solid was filtered off and washed with solvent. Me2Si(Me4C5)(N-t-Bu)ZrCl2 (1.07 g, 0.0026 mole) was recovered. Additional Me2Si(Me4C5)(N-t-Bu)ZrCl2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol).
Example B Compound B: The same procedure of Example A for preparing compound A was followed with the exception of the use of HfCl4 in place of ZrCl4 in Part 4. Thus, when [Me2Si(Me4C5)(N-t-Bu)]Li2 (2.13 g, 0.0081 mol) and HfCl4 (2.59 g, 0.0081 mol) were used. Me2Si(Me4C5)(N-t-Bu)HfCl2 (0.98 g, 0.0020 mol) was produced.
Part 3. Me2Si(t-BuH4C5)(NH-t-Bu) (11.4 g, 0.045 mol) was diluted with �100 ml Et2O. MeLi (1.4 M, 70 ml, 0.098 mol) was slowly added. The mixture was allowed to stir overnight. The ether was removed via a vacuum to a trap held at −196� C., leaving behind a pale yellow solid, [Me2Si(t-BuH3C5)(N-t-Bu)]Li2 (11.9 g, 0.045 mol).
Part 4. [Me2Si(t-BuH3C5)(N-t-Bu)]Li2 (3.39 g, 0.013 mol) was suspended in �100 ml Et2O. ZrCl4 (3.0 g, 0.013 mol) was slowly added. The mixture was allowed to stir overnight. The ether was removed and pentane was added to precipitate out the LiCl. The mixture was filtered through Celite. The pentane solution was reduced in volume, and the pale tan solid was filtered off and washed several times with small quantities of pentane. The product of empirical formula Me2Si(t-BuH3C5)(N-t-Bu)ZrCl2 (2.43 g, 0.0059 mol) was isolated.
Example E Compound E. Part 1. Me2SiCl2 (7.0 g, 0.054 mol) was diluted with �100 ml of ether. Me3SiC5H4Li (5.9 g, 0.041 mol) was slowly added. Approximately 75 ml of thf was added and the mixture was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at −196� C. Pentane was added to precipitate out the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate giving Me2Si(Me3SiC5H4)Cl (8.1 g, 0.035 mol) as a pale yellow liquid.
Part 2. Me2Si(Me3SiC5H4)Cl (3.96 g, 0.017 mol) was diluted with �50 ml of ether. LiHN-t-Bu (1.36 g, 0.017 mol) was slowly added, and the mixture was allowed to stir overnight. The ether was removed via a vacuum and pentane was added to precipitate the LiCl. The mixture was filtered through Celite, and the pentane was removed from the filtrate. Me2Si(Me3SiC5H4)(NH-t-Bu) (3.7 g, 0.014 mol) was isolated as a pale yellow liquid.
Part 3. Me2Si(Me3SiC5H4)(NH-t-Bu) (3.7 g, 0.014 mol) as diluted with ether. MeLi (25 ml, 1.4M in ether, 0.035 mol) was slowly added. The mixture was allowed to stir for 1.5 hours after the final addition of MeLi. The ether was removed via vacuum producing 4.6 g of a white solid formulated as Li2[Me2Si(Me3SiC5H3)(N-t-Bu)].�Et2O and unreacted MeLi which was not removed from the solid.
Part 4. Li2[Me2Si(Me3SiC5H3)(N-t-Bu)].�Et2O (1.44 g, 0.043 mol) was suspended in �50 ml of ether. ZrCl4 (1.0 g, 0.0043 mol) was slowly added and the reaction was allowed to stir for a few hours. The solvent was removed via vacuum and pentane was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was reduced in volume. The flask was placed in the freezer (−40� C.) to maximize precipitation of the product. The solid was filtered off giving 0.273 g of an off white solid. The filtrate was again reduced in volume, the precipitate filtered off to give an additional 0.345 g for a total of 0.62 g of the compound with empirical formula Me2Si(Me3SiC5H3)(N-t-Bu)ZrCl2. The x-ray crystal structure of this product reveals that the compound is dimeric in nature.
Example F Compound F: Part 1. Me4HC4SiMe2Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. LiHNPh (4.6 g, 0.0462 mol) was dissolved in �100 ml of thf. Me4HC5SiMe2Cl (10.0 g, 0.0466 mol) was slowly added. The mixture was allowed to stir overnight. The thf was removed via a vacuum. Petroleum ether and toluene were added to precipitate the LiCl, and the mixture was filtered through Celite. The solvent was removed, leaving behind a dark yellow liquid, Me2Si(Me4HC5)(NHPh) (10.5 g, 0.0387 mol).
Part 3. Me2Si(Me4HC5)(NHPh) (10.5 g, 0.0387 mol) was diluted with �60 ml of ether. MeLi (1.4 M in ether, 56 ml, 0.0784 mol) was slowly added and the reaction was allowed to stir overnight. The resulting white solid, Li2[Me2Si(Me4C5)(NPh).�Et2O (11.0 g), was filtered off and was washed with ether.
Part 4. Li2[Me2Si(Me4C5)(NPh).�Et2O (2.81 g, 0.083 mol) was suspended in �40 ml of ether. ZrCl4 (1.92 g, 0.0082 mol) was slowly added, and the mixture was allowed to stir overnight. The ether was removed via a vacuum, and a mixture of petroleum ether and toluene was added to precipitate the LiCl. The mixture was filtered through Celite, the solvent mixture was removed via vacuum, and pentane was added. The mixture was placed in the freezer at −40� C. to maximize the precipitation of the product. The solid was then filtered off and washed with pentane Me2Si(Me4C5)(NPh)ZrCl2.Et2O was recovered as a pale yellow solid (1.89 g).
Example G Compound G: The same procedure of Example F for preparing compound F was followed with the exception of the use of HfCl4 in place of ZrCl4 in Part 4. Thus, when Li2[Me2Si(Me4C5)(NPh)].�Et2O (2.0 g, 0.0059 mol) and HfCl4 (1.89 g, 0.0059 mol) were used, Me2Si(Me4C5)(NPh)HfCl2.�Et2O (1.70 g) was produced.
Example H Compound H: Part 1. MePhSiCl2 (14.9 g, 0.078 mol) was diluted with �250 ml of thf. Me4C5HLi (10.0 g, 0.078 mol) was slowly added as a solid. The reaction solution was allowed to stir overnight. The solvent was removed via a vacuum to a cold trap held at −196� C. Petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite, and the pentane was removed from the filtrate. MePhSi(Me4C5H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
Part 3. MePhSi(Me4C5H)(NH-t-Bu) (16.6 g, 0.053 mol) was diluted with �100 ml of ether. MeLi (76 ml, 0.106 mol, 1.4 M) was slowly added and the reaction mixture was allowed to stir for �3 hours. The ether was reduced in volume, and the lithium salt was filtered off and washed with pentane producing 20.0 g of a pale yellow solid formulated as Li2[MePhSi(Me4C5)(N-t-Bu)].�Et2O.
Part 4. Li2[MePhSi(Me4C5)(N-t-Bu)].�Et2O (5.0 g, 0.0131 mol) was suspended in �100 ml of Et2O. ZrCl4 (3.06 g, 0.0131 mol) was slowly added. The reaction mixture was allowed to stir at room temperature for �1.5 hours over which time the reaction mixture slightly darkened in color. The solvent was removed via vacuum and a mixture of petroleum ether and toluene was added. The mixture was filtered through Celite to remove LiCl. The filtrate was evaporated down to near dryness and filtered off. The off white solid was washed with petroleum ether. The yield of product, MePhSi(Me4C5)(N-t-Bu)ZrCl2, was 3.82 g (0.0081 mol).
Example I Compound I: Li2[MePhSi(Me4C5)(N-t-Bu)].�Et2O was prepared as described in Example H for the preparation of compound H, Part 3.
Part 4. Li2[MePhSi(Me4C5)(N-t-Bu)].�Et2O (5.00 g, 0.0131 mol) was suspended in �100 ml of Et2O. HfCl4 (4.20 g, 0.0131 mol) was slowly added and the reaction mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite. The filtrate was evaporated down to near dryness and filtered off. The off white solid was washed with petroleum ether. MePhSi(Me4C5)(N-t-Bu)HfCl2 was recovered (3.54 g, 0.0058 mole).
Part 2. Me4C5SiMe2Cl (10.0 g, 0.047 mol) was diluted with �25 ml Et2O. LiHNC5H4-p-n-Bu. 1/10Et2O (7.57 g, 0.047 mol) was added slowly. The mixture was allowed to stir for �3 hours. The solvent was removed via vacuum. Petroleum ether was added to precipitate out the LiCl, and the mixture was filtered through Celite. The solvent was removed leaving behind an orange viscous liquid, Me2Si(Me4C5H)(HNC6H4-p-n-Bu) (12.7 g, 0.039 mol).
Part 3. Me2Si(Me4C5H)(HNC6H4-p-n-Bu) (12.7 g, 0.039 mol) was diluted with �50 ml of Et2O. MeLi (1.4 M, 55 ml, 0.077 mol) was slowly added. The mixture was allowed to stir for �3 hours. The product was filtered off and washed with Et2O producing Li2[Me2Si(Me4C5)(NC6H4-p-n-Bu)].�Et2O as a white solid (13.1 g, 0.033 mol).
Part 4. Li2[Me2Si(Me4C5)(NC6H4p-n-Bu)].�Et2O (3.45 g, 0.0087 mol) was suspended in �50 ml of Et2O. ZrCl4 (2.0 g, 0.0086 mol) was slowly added and the mixture was allowed to stir overnight. The ether was removed via vacuum, and petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite. The filtrate was evaporated to dryness to give a yellow solid which was recrystallized from pentane and identified as Me2Si(Me4C5)(NC6H4-p-n-Bu)ZrCl2.⅔Et2O (4.2 g).
Example L Compound L: Li2[Me2Si(Me4C5)(NC6H4-p-n-Bu)].�Et2O was prepared as described in Example K for the preparation of compound K, Part 3.
Part 4. Li2[Me2Si(Me4C5)(NC6H4-p-n-Bu)].�Et2O (3.77 g, 0.0095 mol) was suspended in �50 ml of Et2O. HfCl4 (3.0 g, 0.0094 mol) was slowly added as a solid and the mixture was allowed to stir overnight. The ether was removed via vacuum and petroleum ether was added to precipitate out the LiCl. The mixture was filtered through Celite. Petroleum ether was removed via a vacuum giving an off white solid which was recrystallized from pentane. The product was identified as Me2Si(Me4C5)(NC6H4-p-n-Bu)HfCl2 (1.54 g, 0.0027 mol).
Examples 1-34 of Polymerization Example 1 Polymerization�Compound A
Example 2 Polymerization�Compound A
Example 3 Polymerization�Compound A
Example 4 Polymerization�Compound A
Example 5 Polymerization�Compound A
Example 6 Polymerization�Compound A
The polymerization was carried out as in Example 5 except with the following changes: 200 ml of toluene and 0.92 mg of compound A (0.8 ml of a 11.5 mg in 10 ml of toluene solution). The reaction temperature was also reduced to 50� C. An ethylene-propylene copolymer was recovered (6.0 g, MW=83,100, MWD=2.370, 75.7 SCB/1000C by IR).
Example 7 Polymerization�Compound A
Using the same reactor design and general procedure as in Example 1, 150 ml of toluene, 100 ml of 1-butene, 6.0 ml of 1.5 M MAO, and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 50� C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 25.4 g of an ethylene-butene copolymer was recovered (MW=184,500, MWD=3.424, 23.5 SCB/1000C by 13C NMR and 21.5 SCB/1000C by IR).
Example 8 Polymerization�Compound A
Example 9 Polymerization�Compound A
Example 10 Polymerization�Compound A
Example 11 Polymerization�Compound A
Example 12 Polymerization�Compound A
Example 13 Polymerization�Compound A
Example 14 Polymerization�Compound A
Example 15 Polymerization�Compound A
Example 16 Polymerization�Compound A
Example 17 Polymerization�Compound A
Example 18 Polymerization�Compound B
Example 19 Polymerization�Compound C
Example 20 Polymerization�Compound D
Using the general procedure described in Example 1, 400 ml of toluene, 5.0 ml of 1.0 M MAO and 0.278 mg compound D (0.2 ml of a 13.9 mg in 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80� C. and the ethylene (60 psi) was introduced into the system. The polymerization reaction was limited to 30 minutes. The reaction was ceased by rapidly cooling and venting the system. The solvent was evaporated off the polymer by a stream of nitrogen. Polyethylene was recovered (1.9 g, MW=229,700, MWD=2.618).
Example 21 Polymerization�Compound E
Example 22 Polymerization�Compound E
Example 23 Polymerization�Compound F
Example 24 Polymerization�Compound F
Example 25 Polymerization�Compound G
Example 26 Polymerization�Compound G
The polymerization was carried out as in Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 7.0 ml of 1.0 M MAO, 2.9 mg of compound G (2.0 ml of a 14.5 mg in 10 ml of toluene solution), 50� C., 65 psi ethylene, 30 minutes. The run provided 7.0 g of an ethylene-butene copolymer (MW=425,000, MWD=2.816, 27.11 SCB/1000C by IR technique).
Example 27 Polymerization�Compound H
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M MAO, 0.266 mg of compound H (0.2 ml of a 13.3 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 11.1 g of polyethylene (MW=299,800, MWD=2.569).
Example 28 Polymerization�Compound H
Example 29 Polymerization�Compound I
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 MAO, 0.34 mg of compound I (0.2 ml of a 17.0 mg in 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80� C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 0.9 g of polyethylene was recovered (MW=377,000, MWD=1.996).
Example 30 Polymerization�Compound J
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0 M MAO, 0.318 mg of compound J (0.2 ml of a 15.9 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 8.6 g of polyethylene (MW=321,000, MWD=2.803).
Example 31 Polymerization�Compound J
Example 32 Polymerization�Compound K
Example 33 Polymerization�Compound K
Example 34 Polymerization�Compound L
Example 35 Polymerization�Compound A
Example 36 Polymerization�Compound A
The polymerization was carried out as in Example 1 with the following reactor contents: 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50� C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 19.7 g of an ethylene-octene copolymer was recovered (MW=548,600, MWD=3.007, 16.5 SCB/1000C by 13C NMR technique).
Example 37 Polymerization�Compound A
The polymerization was carried out as in Example 1 with the following reactor contents: 300 ml of toluene, 100 ml of 4-methyl-1-pentene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50� C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 15.1 g of an ethylene-4-methyl-1-pentene copolymer was recovered (MW=611,800, MWD=1.683, 1.8 mole % determined by 13C NMR).
Example 38 Polymerization�Compound A
The polymerization was carried out as in Example 1 with the following reactor contents: 300 ml of toluene, 100 ml of a 2.2 M norbornene in toluene solution, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50� C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 12.3 g of an ethylene-norbornene copolymer was recovered (MW=812,600, MWD=1.711, 0.3 mole % determined by 13C NMR).
Example 39 Polymerization�Compound A
The polymerization was carried out as in Example 1 with the following reactor contents: 300 ml of toluene, 100 ml of cis-1,4-hexadiene, 7.0 ml of 1.0 M MAO and 2.3 mg of compound A (2.0 ml of a 11.5 mg in 10 ml of toluene solution) at 50� C. The reactor was pressurized with ethylene (65 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 13.6 g of an ethylene-cis-1,4-hexadiene copolymer was recovered (MW=163,400, MWD=2.388, 2.2 mole % determined by 13C NMR).
6.417 � 103 65 psi
1.524 � 103 65 psi
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