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Patent US5096867 - Monocyclopentadienyl transition metal olefin polymerization catalysts - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThe invention is a catalyst system including a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer....http://www.google.com/patents/US5096867?utm_source=gb-gplus-sharePatent US5096867 - Monocyclopentadienyl transition metal olefin polymerization catalystsAdvanced Patent SearchPublication numberUS5096867 APublication typeGrantApplication numberUS 07/581,841Publication dateMar 17, 1992Filing dateSep 13, 1990Priority dateJun 4, 1990Fee statusPaidAlso published asUS6617466Publication number07581841, 581841, US 5096867 A, US 5096867A, US-A-5096867, US5096867 A, US5096867AInventorsJo Ann M. CanichOriginal AssigneeExxon Chemical Patents Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (1), Referenced by (337), Classifications (43), Legal Events (8) External Links: USPTO, USPTO Assignment, EspacenetMonocyclopentadienyl transition metal olefin polymerization catalysts
Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, will contain from 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals, amido-substituted hydrocarbon radicals, phosphido-substituted hydrocarbon radicals, alkoxy-substituted hydrocarbon radicals, alkylborido substituted radicals and cyclopentadienyl rings containing one or more fused saturated or unsaturated rings. Suitable organometallic radicals, which may be substituted as an R group for at least one hydrogen atom in the cyclopentadienyl ring, include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl and the like. Other suitable radicals that may be substituted for one or more hydrogen atom in the cyclopentadienyl ring include halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals and the like. Examples of cyclopentadienyl ring groups (C5 H5-y-x Rx) which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in Column 2 of Table 1 under the heading (C5 H5-y-x Rx).
Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may be used as an R' group in the heteroatom J ligand group, will contain from 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals, alkyl-substituted aromatic radicals, halogen radicals, amido radicals, phosphido radicals alkylborido radicals, and the like. Examples of heteroatom ligand groups (JR'z-1-y) which are suitable as a constituent group of the Group IV B transition metal component of the catalyst system are identified in column 3 of Table 1 under the heading (JR'z-1-y).
For illustrative purposes, the above compounds and those permuted from Table 1 do not include the neutral Lewis base ligand (L). The conditions under which complexes containing neutral Lewis base ligands such as ether or those which form dimeric compounds is determined by the steric bulk of the ligands about the metal center. For example, the t-butyl group in Me2 Si(Me4 C5)(N-t-Bu)ZrCl2 has greater steric requirements than the phenyl group in Me2 Si(Me4 C5)(NPh)ZrCl2 �Et2 O thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me2 Si(Me3 SiC5 H3)(N-t-Bu)ZrCl2 ]2 versus that of the tetramethylcyclopentadienyl group in Me2 Si(Me4 C5)(N-t-Bu)ZrCl2, the former compound is dimeric and the latter is not.
TABLE 1__________________________________________________________________________ ##STR5##T (when y = 1)         (C5 H5-y-x Rx)                            (JR'z-1-y)                                         Q          M__________________________________________________________________________dimethylsilyl cyclopentadienyl    -t-butylamide                                         hydride    zirconiumdiethylsilyl  methylcyclopentadienyl                            phenylamido  chloro     hafniumdi- -n-propylsilyl         1,2-dimethylcyclopentadienyl                            p- -n-butylphenylamido                                         methyl     titaniumdiisopropylsilyl         1,3-dimethylcyclopentadienyl                            cyclohexylamido                                         ethyldi- -n-butylsilyl         indenyl            perflurophenylamido                                         phenyldi- -t-butylsilyl         1,2-diethylcyclopentadienyl                             -n-butylamido                                         fluorodi- -n-hexylsilyl         tetramethylcyclopentadienyl                            methylamido  bromomethylphenylsilyl         ethylcyclopentadienyl                            ethylamido   iodoethylmethylsilyl          -n-butylcyclopentadienyl                             -n-propylamido                                          -n-propyldiphenylsilyl cyclohexylmethylcyclopentadienyl                            isopropylamido                                         isopropyldi(p- -t-butylphenethylsilyl)          -n-octylcyclopentadienyl                            benzylamido   -n-butyl -n-hexylmethylsilyl         &#946;-phenylpropylcyclopentadienyl                             -t-butylphosphido                                         amylcyclopentamethylenesilyl         tetrahydroindenyl  ethylphosphido                                         isoamylcyclotetramethylenesilyl         propylcyclopentadienyl                            phenylphosphido                                         hexylcyclotrimethylenesilyl          -t-butylcyclopentadienyl                            cyclohexylphosphido                                         isobutyldimethylgermanyl         benzylcyclopentadienyl                            oxo (when y = 1)                                         heptyldiethylgermanyl         diphenylmethylcyclopentadienyl                            sulfido (when y = 1)                                         octylphenylamido   trimethylgermylcyclopentadienyl                            methoxide (when y = 0)                                         nonyl -t-butylamido         trimethylstannylcyclopentadienyl                            ethoxide (when y = 0)                                         decylmethylamido   triethylplumbylcyclopentadienyl                            methylthio (when y = 0)                                         cetyl -t-butylphosphido         trifluromethylcyclopentadienyl                            ethylthio (when y = 0)                                         methoxyethylphosphido         trimethylsilylcyclopentadienyl  ethoxyphenylphosphido         pentamethylcyclcopentadienyl    propoxy         (when y = 0)methylene     fluorenyl                       butoxydimethylmethylene         octahydrofluorenyl              phenoxydiethylmethylene         N,N-dimethylamidocyclopentadienyl                                         dimethylamidoethylene      dimethylphosphidocyclopentadienyl                                         diethylamidodimethylethylene         methoxycyclopentadienyl         methylethylamidodiethylethylene         dimethylboridocyclopentadienyl  di- -t-butylamidodipropylethylene         (N,N-dimethylamidomethyl)-      diphenylamido         cyclopentadienylpropylene                                     diphenylphosphidodimethylpropylene                             dicyclohexylphosphidodiethylpropylene                              dimethylphosphido1,1-dimethyl-3,3-                             methylidene (both Q)dimethylpropylenetetramethyldisiloxane                         ethylidene (both Q)1,1,4,4-tetramethyldi-                        propylidene (both Q)silylethylene                                         ethyleneglycoldianion                                         (both Q)__________________________________________________________________________
Generally, wherein it is desired to produce an α-olefin copolymer which incorporates a high content of α-olefin, while maintaining high polymer molecular weight the species of Group IV B transition metal compound preferred is one of titanium. The most preferred species of titanium metal compounds are represented by the formula: ##STR6## wherein Q, L, R', R, "x" and "w" are as previously defined and R1 and R2 are each independently a C1 to C20 hydrocarbyl radicals, substituted C1 to C20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R1 and R2 may also be joined forming a C3 to C20 ring which incorporates the silicon bridge.
The alumoxane component of the catalyst system is an oligomeric compound which may be represented by the general formula (R3 -Al-O)m which is a cyclic compound, or may be R4 (R5 -Al-O)m -AlR6 2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R3, R4, R5 and R6 are, independently a C1 -C5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "m" is an integer from 1 to about 50. Most preferably, R3, R4, R5 and R6 are each methyl and "m" is at least 4. When an alkyl aluminum halide is employed in the preparation of the alumoxane, one or more R3-6 groups may be halide.
The catalyst systems employed in the method of the invention comprise a complex formed upon admixture of the Group IV B transition metal component with an alumoxane component. The catalyst system may be prepared by addition of the requisite Group IV B transition metal and alumoxane components to an inert solvent in which olefin polymerization can be carried out by a solution, slurry or bulk phase or high pressure-high temperature polymerization procedure.
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 -100� 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.
The monomer for such process may comprise ethylene alone, for the production of a homopolyethylene, or ethylene in combination with an o-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 copolymerization 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 20,000 to 1. A more preferable range would be 1:1 to 2000:1. The reaction time is preferably from about 10 seconds to about 10 hour. Without limiting in any way the scope of the invention, one means for carrying out the process of the present invention for production of a copolymer is as follows: in a stirred-tank reactor liquid α-olefin monomer is introduced, such as 1-butene. 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 α-olefin comonomer, 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 α-olefin comonomer in the reactor, which is controlled by manipulating the relative feed rates of these components to the reactor.
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 D-BuLi or MeLi. Published methods for preparing LiHC5 Me4 include C. M. Fendrick et al. Organometallic, 3, 819 (1984) and F. H. Kholer 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. TiCl4, ZrCl4 and HfCl4 were purchased from either Aldrich Chemical Company or Cerac. TiCl4 was typically used in its etherate form. The etherate, TiCl4 �2Et2 O, can be prepared by gingerly adding TiCl4 to diethylether. Amines, silanes and lithium reagents were Systems. Methylalumoxane was supplied by either Scherring or Ethyl Corp.
Compound A: Part 1. Me4 HC5 Li (10.0 g, 0.078 mol) was slowly added to a Me2 SiCl2 (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 the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me4 HC5 SiMe2 Cl (15.34 g. 0.071 mol) was recovered as a pale yellow liquid.
Part 2. Me4 HC5 SiMe2 Cl (10.0 g, 0.047 mol) was slowly added to a suspension of LiHN-t-Bu (3.68 g, 0.047 mol, �100 ml of 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 the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate Me2 Si(Me4 HC5)(HN-st-Bu) (11.14 g. 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(Me4 HC5)(HN-t-Bu) (11.14 g, 0.044 mol was diluted with �100 ml of Et2 O. MeLi (1.4 M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for 1/2 hour after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2 Si(Me4 C5)(N-t-Bu)]Li2, was washed with several small portions of ether, then vacuum dried.
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 [Me2 Si(Me4 C5)(N-t-Bu)]Li2 (2.13 g, 0.0081 mol) and HfCl4 (2.59 g, 0.0081 mol) were used, Me2 Si(Me4 C5)(N-t-Bu)HfCl2 0.98 g, 0.0020 mol) was produced.
Compound C: Part 1. Me2 SiCl2 (7.5 ml, 0.062 mol) was diluted with �30 ml of THF. A t-BuH4 C5 Li solution (7.29 g, 0.056 mol, �100 ml THF) was slowly added, and the resulting mixture was allowed to stir overnight. The thf was removed via a vacuum to a trap held at -196� C. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, t-BuH4 C5 SiMe2 Cl (10.4 g, 0.048 mol).
Part 2. To a THF solution of LiHN-t-Bu (3.83 g, 0.048 mol, �125 ml), t-BuH4 C5 SiMe2 Cl (10.4 g, 0.048 mol) was added drop wise. The resulting solution was allowed to stir overnight. The THF, was removed via a vacuum to a trap held at -196� C. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, Me2 Si(t-BuH4 C5)(NH-t-Bu) (11.4 g, 0.045 mol).
Part 3. Me2 Si(t-BuH4 C5)(NH-t-Bu) (11.4 g, 0.045 mol) was diluted with �100 ml Et2 O. MeLi (1.4M, 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, [Me2 Si(t-BuH3 C5)(N-t-Bu)]Li2 (11.9 g, 0.045 mol).
Part 4. [Me2 Si(t-BuH3 C5)(N-t-Bu)]Li2 (3.39 g 0.013 mol) was suspended in �100 ml of Et2 O. 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 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 Me2 Si(t-BuH3 C5)(N-t-Bu)ZrCl2 (2.43 g, 0.0059 mol) was isolated.
Compound D: The same procedure of Example C for preparing compound C was followed with the exception of the use of HfCl4 in Part 4. Thus, when [Me2 Si(t-BuH3 C5)(N-t-Bu)]Li2 (3.29 g, 0.012 mol) and HfCl4 (4.0 g, 0.012 mol) were used, the product of the empirical formula [Me2 Si(t-BuH3 C5)(N-t-Bu)HfCl2 (1.86 g, 0.0037 mol) was produced.
Compound E: Part 1. Me2 SiCl2 (7.0 g. 0.054 mol) was diluted with �100 ml of ether. Me2 SiC5 H4 Li (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 the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate giving Me2 Si(Me3 SiC5 H4)Cl (8.1 g, 0.035 mol) as a pale yellow liquid.
Part 2. Me2 Si(Me3 SiC5 H4)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. Me2 Si(Me3 SiC5 H4)(NH-t-Bu) (3.7 g, 0.014 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(M3 SiC5 H4)(NH-t-Bu) (3.7 g, 0.014 mol) as diluted with ether. MeLi (25 ml, 1.4 M 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 [Me2 Si(Me3 SiC5 H3)(N-t-Bu)]�3/4Et2 O and unreacted MeLi which was not removed from the solid.
Part 4. Li2 [Me2 Si(Me3 SiC5 H3)(N-t-Bu)]�3/4Et2 O (1.44 g, 0.0043 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 emperical formula Me2 Si(Me3 SiC5 H3) (N-t-Bu)ZrCl2. The x-ray crystal structure of this product reveals that the compound is dimeric in nature.
Part 2. LiHNPh (4.6 g, 0.0462 mol) was dissolved in �100 ml of THF. Me4 HC5 SiMe2 Cl (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, Me2 Si(Me4 HC5)(NHPh) (10.5 g, 0.0387 mol).
Part 3. Me2 Si(Me4 HC5)(NHPh) (10.5g, 0.0387 mol) was diluted with �60 ml of ether. MeLi (1.4M in ether, 56 ml, 0.0784 mol) was slowly added and the reaction was allowed to stir overnight. The resulting white solid, (11.0 g), was filtered off Li2 [Me2 Si(Me4 C5) (NPh)]�3/4Et2 O and was washed with ether.
Part 4. Li2 [Me2 Si(Me4 C5) (NPh]�3/4Et2 O (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 as 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. Me2 Si(Me4 C5)(NPh)ZrCl2 �Et2 O was recovered as a pale yellow solid (1.89 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 [Me2 Si(Me4 C5)(NPh)]�3/4Et2 O (2.0 g, 0.0059 mol) and HfCl4 (1.89 g, 0.0059 mol) were used,
Me2 Si(Me4 C5)(NPh)HfCl2 �1/2Et2 O (1.70 g) was produced.
Compound H: Part 1. MePhSiCl2 (14.9 g, 0.078 mol) was diluted with �250 ml of THF. Me4 C5 HLi (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 the LiCl. The mixture was filtered through Celite, and the pentane was removed from the filtrate. MePhSi(Me4 C5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
Part 2. LiHN-t-Bu (4.28 g, 0.054 mol) was dissolved in �100 ml of THF. MePhSi(Me4 C5 H)Cl (15.0 g, 0.054 mol) was added drop wise. The yellow solution was allowed to stir overnight. The solvent was removed via vacuum. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated down. MePhSi(Me4 C5 H)(NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.
Part 3. MePhSi(Me4 C5 H)(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(Me4 C5)(N-t-Bu)]�3/4Et2 O.
Part 4. Li2 [MePhSi(Me4 C5)(N-t-Bu)]�3/4Et2 O (5.0 g, 0.0131 mol) was suspended in �100 ml of Et2 O. 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 the 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(Me4 C5)(N-t-Bu)ZrCl2, was 3.82 g (0.0081 mol).
Compound I: Li2 [MePhSi(Me4 C5)(N-t-Bu)]�3/4Et2 O was prepared as described in Example H for the preparation of compound H, Part 3.
Part 4. Li2 [MePhSi(Me4 C5)(N-t-Bu)]�3/4Et2 O (5.00 g, 0.0131 mol) was suspended in �100 ml of Et2 O. 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 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(Me4 C5)(N-t-Bu)HfCl2 was recovered (3.54 g, 0.0058 mole).
Compound J: MePhSi(Me4 C5)(N-t-Bu)HfMe2 was prepared by adding a stoichiometric amount of MeLi (1.4M in ether) to MePhSi(Me4 C5)(N-t-Bu)HfCl2 suspended in ether. The white solid was isolated in near quantitative yield.
Compound K: Part Me4 C5 SiMe2 Cl was prepared as described in Example A for the preparation of compound A, Part 1.
Part 2. Me4 C5 SiMe2 Cl (10.0 g, 0.047 mol) was diluted with �25 ml of Et2 O. LiHNC5 H4 -p-n-Bu�1/10Et2 O (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 the LiCl, and the mixture was filtered through Celite. The solvent was removed leaving behind an orange viscous liquid, Me2 Si(Me4 C5 H)(HNCl6 H4 -p-t-Bu) (12.7 g, 0.039 mol).
Part 3. Me2 Si(Me4 C5 H)(HNC6 H4 -p-n-Bu) (12.7 g. 0.039 mol) was dilute with �50 ml of Et2 O. MeLi (1.4M, 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 Et2 O producing Li2 [Me2 Si(Me4 C5)(NC6 H4 -p-n-Bu)]�3/4Et2 O as a white solid (13.1 g, 0.033 mol).
Part 4. Li2 [Me2 Si(Me4 C5)(NC6 H4 -p-n-Bu)]�3/4Et2 O 3.45 g, 0.0087 mol) was suspended in �50 ml of Et2 O. 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 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 Me2 Si(Me4 C5)(NC6 H4 -p-n-Bu)ZrCl2 �2/3Et2 O (4.2 g).
Compound L: Li2 [MeSi(Me4 C5)(NC6 H4 -p-n-Bu].3/4Et2O was prepared as described in Example K for the preparation of compound K, Part 3.
Part 4. Li2 [Me2 Si(Me4 C5)(NC6 H4 -p-n-Bu)�3/4Et2 O (3.77 g., 0.0095 mol) was suspended in �50 ml of Et2 O. 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 Me2 Si(Me4 C5)(NC6 H4 -p-n-Bu)HfCl2 (1.54 g, 0.0027 mol).
Compound AT: Part 1. MePhSiCl2 (14.9 g, 0.078 mol)
was diluted with 250 ml of THF. Me4 HC5 Li (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 the LiCl. The mixture was filtered through Celite and the pentane was removed from the filtrate. MePhSi(Me4 C5 H)Cl (20.8 g, 0.075 mol) was isolated as a yellow viscous liquid.
Part 3. MePhSi(C5 Me4 H)(NH-t-Bu)(17.2 g, 0.055 mol) was diluted with �20 ml of ether. n-BuLi (60 ml in hexane, 0.096 mol, 1.6M) was slowly added and the reaction mixture was allowed to stir for �3 hours. The solvent was removed in vacuo to yield 15.5 g (0.48 mol) of a pale tan solid formulated as Li2 [MePhSi(C5 Me4)(N-t-Bu)].
Part 4. Li2 [MePhSi(C5 Me4)(N-t-Bu)](8.75 g, 0.027 mol) was suspended in �125 ml of cold ether (�-30� C.). TiCl4 �2Et2 O(9.1 g, 0.027 mol) was slowly added. The reaction was allowed to stir for several hours prior to removing the ether via vacuum. A mixture of toluene and dichloromethane was then added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was largely removed via vacuum and petroleum ether was added. The mixture was cooled to maximize product precipitation. The crude product was filtered off and redissolved in toluene. The toluene insolubles were filtered off. The toluene was then reduced in volume and petroleum ether was added. The mixture was cooled to maximize precipitation prior to filtering off 3.34 g (7.76 mmol) of the yellow solid MePhSi(C5 Me4)(N-t-Bu)TiCl2.
Compound BT: Part 1. C5 Me4 HLi (10.0 g, 0.078 mol) was slowly added to a Me2 SiCl2 solution (11.5 ml, 0.095 mol, in 225 ml of tetrahydrofuran). The solution was stirred for 1 hour to assure a complete reaction. The solvent was then removed in vacuo. Pentane was added to precipitate the LiCl. The mixture was filtered through Celite and the solvent was removed from the filtrate in vacuo. (C5 Me4 H)SiMe2 Cl (15.34 g, 0.071 mol) was recovered as a pale yellow liquid.
Part 2. (C5 Me4 H)SiMe2 Cl (10.0 g, 0.047 mol) was diluted with �25 ml of Et2 O. LiHNC5 H4 -p-n-Bu�1/10Et2 O (7.75 g, 0.048 mol) was added slowly. The mixture was allowed to stir for �3 hours. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl, and the mixture was filtered through Celite. The solvent was removed leaving behind an orange viscous liquid, Me2 Si(C5 Me4 H)(HNC6 H4 -p-n-Bu)(12.7 g, 0.039 mol).
Part 3. Me2 Si(C5 Me4 H)(HNC6 H4 -p-n-Bu)(12.7 g, 0.039 mol) was diluted with �50 ml of Et2 O. MeLi (1.4M, 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 Et2 O and dried. Li2 [Me2 Si(C5 Me4)(NC6 H4 -p-n-Bu)]�3/4Et2 O was isolated as a white solid (13.1 g, 0.033 mol).
Part 4. Li2 [Me2 Si(C5 Me4)(NC6 H4 -p-n-Bu)]�3/4Et2 O (2.36 g, 5.97 mmol) was suspended in cold ether.
TiCl4 �2Et2 O(2.0g, 5.92 mmol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether and dichloromethane were added. The mixture was filtered through Celite to remove the LiCl. The solvent was removed via vacuum, and toluene and petroleum ether were added. After refrigeration, the mixture was filtered off, producing an off yellow product. This was redissolved in dichloromethane, followed by the addition of petroleum ether. The mixture was then refrigerated prior to filtering off 0.83 g (1.87 mmol) of the yellow solid, Me2 Si(C5 Me4)(NC6 H4 -p-n-Bu)TiCl2 O.
Compound CT: Part 1. (C5 Me4 H)SiMe2 Cl was prepared as described in Example BT for the preparation of compound BT, Part 1.
Part 2. (C5 Me4 H)SiMe2 Cl (8.14 g, 0.038 mol) was mixed with �100 ml of THF. LiHNC6 H4 -p-OMe (4.89 g, 0.038 mol) was slowly added and the mixture was allowed to stir for 2 hours. The solvent was removed via vacuum and petroleum ether was added to precipitate the LiCl which was filtered off. The solvent was removed from the filtrate via vacuum and the product Me2 Si(C5 Me4 H)(NC6 H4 -p-OMe) (9.8 g, 0.033 mol) was isolated as a viscous orange-yellow liquid.
Part 3 Me2 Si(C5 Me4 H)(HNC6 H4 -p-OMe)(10.0 g, 0.033 mol) was diluted with THF. MeLi (47 ml, 1.4M in ether, 0.066 mol) was slowly added and the mixture was allowed to stir for a few hours. The solvent was then removed in vacuo leaving behind a white solid coordinated by thf.
The product was formulated as Li2 [Me2 Si(C5 Me4)(NC6 H4 -p-OMe)]�2THF (14.7 g, 0.032 mol).
Part 4. Li2 [Me2 Si(C5 Me4)(NC6 H4 -p-OMe)]�2THF (7.0 g, 0.015 mol) was suspended in �125 ml of cold ether. TiCl4 �2Et2 O (5.1 g, 0.015 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether, dichloromethane and toluene were added. The mixture was filtered through Celite to remove the LiCl. The solvent was reduced in volume and petroleum ether was added. The mixture was refrigerated, after which a brown solid was filtered off. Multiple extractions and recrystallizations from toluene and petroleum ether yielded 2.3 g (5.5 mmol) of Me2 Si(C5 Me4)(NC6 H4 -p-OMe)TiCl2.
Compound DT: Part 1. Me2 SiCl2 (7.5 ml, 0.062 mol) was diluted with �30 ml of THF. A t-BuH4 C5 Li solution (7.29 g, 0.057 mol, �100 ml of THF) was slowly added, and the resulting mixture was allowed to stir overnight. The THF was removed in vacuo. Pentane was added to precipitate the LiCl, and the mixture was filtered through Celite. The pentane was removed from the filtrate leaving behind a pale yellow liquid, (t-BuC5 H4)SiMe2 Cl (10.4 g, 0.048 mo)).
Part 2. (t-BuC5 H4)SiMe2 Cl (5.0 g, 0.023 mol) was added to �50 ml of THF. LiHN-2,5-t-Bu2 C6 H3 (4.94 g, 0.023 mol) was slowly added and the reaction mixture was allowed to stir for 2 hours. The solvent was removed via vacuum and petroleum ether was added to precipitate the LiCl which was filtered off. The solvent was removed from the filtrate yielding an oily/solid material, Me2 Si(t-Bu2 C5 H4)(HN-2,5-t-Bu2 C6 H3).
Part 3. To the above material, Me2 Si(t-BuC5 H4)(HN-2,5-t-Bu2 C6 H3) (assumed to be �8 g, 0.021 mol), MeLi (30 ml, 1.4M in ether, 0.042 mol) was slowly added. The mixture was allowed to stir for a few hours prior to removing the solvent via vacuum. The slightly pinkish solid was washed with ether, filtered and dried yielding 4.42 g (0.011 mol) of Li2 [Me2 Si(t-BuC5 H3)(N-2,5-t-Bu2 C6 H3 ].
Part 4. Li2 [Me2 Si(t-BuC5 H3)(N-2,5-t-Bu2 C6 H3)](7.6 g, 0.019 mol) was suspended in cold ether. TiCl4 �2Et2 O (6.5 g, 0.019 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and toluene and dichloromethane were added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. The mixture was chilled to maximize precipitation. A dark yellow solid was filtered off and was recrystallized from toluene and petroleum ether giving a tan solid. A total of 1.6 g (3.2 mmol) of Me2 Si(t-BuC5 H3)(N-2,5-t-Bu2 C6 H3)TiCl2 was isolated.
Compound ET: Part 1. LiC9 H7 (40 g, 0.33 mol, lithiated indene=Li(Hind)) was slowly added to Me2 SiCl2 (60 ml, 0.49 mol) in ether and THF. The reaction was allowed to stir for 1.5 hours prior to removing the solvent via vacuum. Petroleum ether was then added, and the LiCl was filtered off. The solvent was removed from the filtrate via vacuum, leaving behind the pale yellow liquid, (Hind)Me2 SiCl(55.7 g, 0.27 mol).
Part 2. (Hind)Me2 SiCl(20.0 g, 0.096 mol) was diluted with ether. LiHN-t-Bu(7.6 g, 0.096 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and petroleum ether and toluene were added. The LiCl was filtered off and the solvent was removed via vacuum to give the product, Me2 Si(Hind)(HN-t-Bu).
Part 3. Me2 Si(Hind)(HN-t-Bu)(21 g, 0.086 mol) was diluted with a mixture of petroleum ether and diethyl ether. t-BuLi (108 ml, 1.6M in hexanes, 0.17 mol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and the remaining solid was washed with petroleum ether and filtered off. Li2 [Me2 Si(ind)(N-t-Bu)]�1/4Et2 O was isolated as a pale yellow solid (26 g, 0.094 mol).
Part 4. Li 2 [Me2 Si(ind)(N-t-Bu)]�1/4Et2 O(10 g, 0.036 mol) was dissolved in ether. TiCl4 �2Et2 O(12.1 g, 0.036 mol) was added to the cold solution. The reaction was allowed to stir overnight prior to removal of the solvent via vacuum. A mixture of toluene and dichloromethane were added and the mixture was filtered through Celite to remove the LiCl. The solvent was removed and hot toluene was added. The insolubles were filtered off. The solution was reduced in volume and petroleum ether was added. The mixture was chilled prior to filtering off the solid, Me2 Si(ind)(N-t-Bu)TiCl2, which was recrystallized several times. The final yield was 2.5 g (6.8 mmol).
Part 3. Me2 Si(C5 Me4 H)(HNC6 H11)(6.3 g, 0.023 mol) was diluted with �100 ml of ether. MeLi (33 ml, 1.4M in ether, 0.046 mol) was slowly added and the mixture was allowed to stir for 0.5 hours prior to filtering off the white solid. The solid was washed with ether and vacuum dried. Li2 [Me2 Si(C5 Me4)(NC6 H11)] was isolated in a 5.4 g (0.019 mol) yield.
Part 4. Li2 [Me2 Si(C5 Me4)(NC6 H11)] (2.57 g, 8.90 mmol) was suspended in �50 ml of cold ether. TiCl4 2 Et2 O (3.0 g, 8.9 mmol) was slowly added and the mixture was allowed to stir overnight. The solvent was removed via vacuum and a mixture of toluene and dichloromethane was added. The mixture was filtered through Celite to remove the LiCl byproduct. The solvent was removed from the filtrate and a small portion of toluene was added followed by petroleum ether. The mixture was chilled in order to maximize precipitation. A brown solid was filtered off which was initially dissolved in hot toluene, filtered through Celite, and reduced in volume. Petroleum ether was then added. After refrigeration, an olive green solid was filtered off. This solid was recrystallized twice from dichloromethane and petroleum ether to give a final yield of 0.94 g (2.4 mmol) of the pale olive green solid, Me2 Si(C5 Me4)(NC6 H11)TiCl.
Compound GT: Part 1. Me2 SiCl2 (150 ml, 1.24 mol) was diluted with �200 ml of Et2 O. Li(C13 H9)�Et2 O (lithiated fluorene etherate, 28.2 g, 0.11 mol) was slowly added. The reaction was allowed to stir for -1 hour prior to removing the solvent via vacuum. Toluene was added and the mixture was filtered through Celite to remove the LiCl. The solvent was removed from the filtrate, leaving behind the off-white solid, Me2 Si(C13 H9) Cl (25.4 g, 0.096 mol).
Part 2. Me2 Si(C13 H9)Cl (8.0 g, 0.031 mol) was suspended in ether and THF in a ratio of 5:1. LiHNC6 H11 (3.25 g, 0.031 mol) was slowly added. The reaction mixture was allowed to stir overnight. After removal of the solvent via vacuum, toluene was added and the mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume to give a viscous orange liquid. To this liquid which was diluted in Et2 O, 43 ml of 1.4M MeLi (0.060 mol) was added slowly. The mixture was allowed to stir overnight. The solvent was removed in vacuo to produce 13.0 g (0.031 mol) of Li2 [Me2 Si(C13 H8)(NC6 H11)]�1.25 Et2 O.
Part 3. Li2 [Me2 Si(C13 H8)(NC6 H11)]�1.25 Et2 O (6.5 g, 0.015 mol) was dissolved in cold ether. TiCl4 2 Et2 O (5.16 g, 0.015 mol) was slowly added. The mixture was allowed to stir overnight. The solvent was removed via vacuum and methylene chloride was added. The mixture was filtered through Celite to remove the LiCl. The filtrate was reduced in volume and petroleum ether was added. This was refrigerated to maximize precipitation prior to filtering off the solid. Since the solid collected was not completely soluble in toluene, it was mixed with toluene and filtered. The filtrate was reduced in volume and petroleum ether was added to induce precipitation. The mixture was refrigerated prior to filtration. The red-brown solid Me2 Si(C13 H8)(NC6 H11)TiCl2 was isolated (2.3 g, 5.2 mol).
Compound HT: Part 1. (C5 Me4 H)SiMe2 Cl was prepared as described in Example BT for the preparation of compound BT, Part 1.
Part. 2 LiHNPh (4.6 g, 0.046 mol) was dissolved in �100 ml of THF. (C5 Me4 H)SiMe2 Cl (10.0 g, 0.047 mol) was slowly added. The mixture was allowed to stir overnight. The THF was removed in vacuo. 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, Me2 Si(C5 Me4 H)(NHPh) (10.5 g, 0.039 mol).
Part 3. Me2 Si(C5 Me4 H)(NHPh) (9.33 g, 0.034 mol) was diluted with �30 ml of ether. MeLi (1.4M in ether, 44 ml, 0.062 mol) was slowly added and the reaction was allowed to stir for 2 hours. After reducing the volume of the solvent, the resulting white solid, Li2 [Me2 Si(C5 Me4)(NPh)]�1/2Et2 O (9.7 g, 0.030 mol), was filtered off washed with ether and dried.
Part 4. Li2 [Me2 Si(C5 Me4 (NPh)]�1/2Et2 O (4.3 g, 0.013 mol) was suspended in �50 ml of cold ether. TiCl4 2 Et2 O (4.10 g, 0.012 mol) was slowly added, and the mixture was allowed to stir for several hours. The solvent was removed in vacuo, and toluene and dichloromethane were added to solubilize the product. The mixture was filtered through Celite to remove the LiCl. The solvent was removed in vacuo and a small portion of toluene was added along with petroleum ether. The mixture was refrigerated in order to maximize precipitation of a tan solid which was filtered off. The solid was washed with a small portion of toluene and the remaining solid was redissolved in hot toluene and filtered through Celite to remove the toluene insolubles. The toluene was then removed to produce 2.32 g (5.98 mmol) of the yellow solid, Me2 Si(C5 Me4)(NPh)TiCl2 EXAMPLE IT
Part 2. (C5 Me4 H)SiMe2 Cl (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 was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2 Si(C5 Me4 H)(NH-t-Bu) (11.14 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(C5 Me4 H)(NH-t-Bu)(11.14 g, 0.044 mol) was diluted with �100 ml of ether. MeLi (1.4M,64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for 1/2 hour after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2 Si(C5 Me4)(N-t-Bu)]Li2, was washed with several small portions of ether, then vacuum dried.
Part 4. [Me2 Si(C5 Me4)(N-t-Bu)Li2 (6.6 g, 0.025 mol) was suspended in cold ether. TiCl4 �2Et2 O(8.4 g, 0.025 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. Methylene chloride was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate the product. This mixture was refrigerated prior to filtration in order to maximize precipitation. Me2 Si(C5 Me4)(N-t-Bu)TiCl2 was isolated (2.1 g, 5.7 mmol).
Part 2. (C5 Me4 H)SiMe2 Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC12 H23 (C12 H23 =cyclododecyl, 7.0 g, 0.037 mol, �80 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 and toluene was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me2 Si(C5 Me4 H)(NHC12 H23)(11.8 g, 0.033 mol) was isolated as a pale yellow liquid.
Part 3. Me2 Si(C5 Me4 H)(NHC12 H23)(11.9 g, 0.033 mol) was diluted with �150 ml of ether. MeLi (1.4M, 47 ml, 0.066 mol) was slowly added. The mixture was allowed to stir for 2 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me2 Si(C5 Me4)(NC12 H23)]Li2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0.030 mol) of product.
Part 4. [Me2 Si(C5 Me4)(NC12 H23)]Li2 (3.0 g, 0.008 mol) was suspended in cold ether. TiCl4 2 Et2 O (2.7 g, 0.008 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. Methylene chloride was added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was significantly reduced in volume and petroleum ether was added to precipitate the product. This mixture was refrigerated prior to filtration in order to maxmize precipitation. The solid collected was recrystallized from methylene chloride and Me2 Si(C5 Me4)(NC12 H23)TiCl2 was isolated (1.0 g, 2.1 mmol).
The polymerization run was performed in a 1-liter autoclave reactor equipped with a paddle stirrer, an external water jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, 1-butene and hexane, and a septum inlet for introduction of other solvents, transition metal compound and alumoxane solutions. The reactor was dried and degassed thoroughly prior to use. A typical run consisted of injecting 400 ml of toluene, 6 ml of 1.5M MAO, and 0.23 mg of compound A (0.2 ml of a 11.5 mg in 10 ml of toluene solution) into the reactor. The reactor was then heated to 80� C. and the ethylene (60 psi) was introduced into the system. The solvent was evaporated off of the polymer by a stream of nitrogen. Polyethylene was recovered (9.2 g, MW=257,200 MWD=2.275).
The polymerization was carried out as in Example 1 with the following changes: 300 ml of toluene, 3 ml of 1.5M MAO, and 0.115 mg of compound A (0.1 ml of a 11.5 mg in 10 ml of toluene solutions). Polyethylene was recovered (3.8 g, MW=359,800, MWD=2.425).
The polymerization was carried out as in Example 1 1 except for the use of 300 ml of hexane in place of 400 ml of toluene. Polyethylene was recovered (5.4 g, MW=212,600, MWD=2.849).
Using the same reactor design and general procedure as in Example 1, 300 ml of toluene, 200 ml of propylene, 6.0 ml of 1.5 M MAO, and 0.46 mg of compound A (0.4 ml of a 11.5 mg in 10 ml of toluene solution) was introduced into the reactor. The reactor was heated to 80� C., the ethylene was added (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, 13.3 g of an ethylene-propylene copolymer was recovered (MW=24,900, MWD=2.027, 73.5 SCB/1000C by IR).
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 reduce to 50� C. An ethylene-propylene copolymer was recovered (6.0 g, MW=83,100, MWD=2.370, 75.7 SCB/1000C by IR).
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-1-butene copolymer was recovered (MW=184,500, MWD=3.424, 23.5 SCB/1000C by 13 C NMR and 21.5 SCB/1000C by IR).
The polymerization was carried out as in Example 7 except with the following changes: 100 ml of toluene and 150 ml of 1-butene. An ethylene-1-butene copolyer was recovered (30.2 g, MW=143,500, MWD=3.097, 30.8 SCB/1000C by 13 C NMR and 26.5 SCB/1000C by IR).
The polymerization was carried out as in Example 7 except with the following changes: 200 ml of toluene, 8.0 ml of 1.0M MAO, and 50 ml of 1-butene. An ethylene-1-butene copolymer was recovered (24.9 g, MW=163,200, MWD =3.290, 23.3 SCB/1000C by 13 C NMR and 18.9 SCB/1000C by IR).
The polymerization was carried out as in Example 9 except for the replacement of 200 ml of toluene with 200 ml of hexane. An ethylene-1-butene copolymer was recovered (19.5 g, MW=150,600, MWD=3.510, 12.1 SCB/1000C by 13 C NMR and 12.7 SCB/1000C by IR).
The polymerization was carried out as in Example 10 except with the following changes: 150 ml of hexane, and 100 ml of 1-butene. An ethylene-1-butene copolymer was recovered (16.0 g, MW=116,200, MWD=3.158, 19.2 SCB/1000C by 13 C NMR and 19.4 SCB/1000C by IR).
Using the same reactor design and general procedure as described in Example 1, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.2 ml of a preactivated compound A solution (11.5 mg of compound A dissolved in 9.0 ml of toluene and 1.0 ml of 1.0M MAO) were added to the reactor. The reactor was heated to 80� C., and ethylene was introduced (60 psi), and the reactor was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 3.4 g of polyethylene was recovered (MW=285,000, MWD=2.808).
Using the same reactor design and general procedure as described in Example 1, 400 ml of toluene, 0.25 ml of 1.0 M MAO, and 0.2 ml of a preactivated compound A solution (11.5 mg of compound A dissolved in 9.5 ml of toluene and 0.5 ml of 1.0M MAO) were added into the reactor. The reactor was heated to 80� C. and ethylene was introduced (60 psi), and the reactor was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 1.1 g of polyethylene was recovered (MW=479,600, MWD=3.130).
Using the same reactor design and general procedure as described in Example 1, 400 ml of toluene and 2.0 ml of a preactivated compound A solution (11.5 mg of compound A dissolved in 9.5 ml of toluene and 0.5 ml of 1.0M MAO) were added into the reactor. The reactor was heated to 80� C. and 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, 1.6 g of polyethylene was recovered (MW=458,800, MWD=2.037).
Using the general procedure as described in Example 1, 400 ml of toluene, 5.0 ml of 1.0M MAO, 0.23 mg of compound A (0.2 ml of a 11.5 mg in 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80� C., the ethylene introduced (400 psi), and the reaction was allowed to run for 30 minutes, followed by rapidly cooling and venting the system. After evaporation of the solvent, 19.4 g of polyethylene was recovered (MW=343,700, MWD=3.674).
The polymerization was performed in a stirred 100 ml stainless steel autoclave which was equipped to perform polymerizations at pressures up to 40,000 psi and temperatures up to 300� C. The reactor was purged with nitrogen and heated to 160� C. Compound A and alumoxane solutions were prepared in separate vials. A stock solution was prepared by dissolving 26 mg of compound A in 100 ml of toluene. The compound A solution was prepared by diluting 0.5 ml of the stock solution with 5.0 ml of toluene. The alumoxane solution consisted of 2.0 ml of a 4% MAO solution added to 5.0 ml of toluene. The compound A solution was added to the alumoxane solution, then 0.43 ml of the mixed solutions were transferred by nitrogen pressure into a constant-volume injection tube. The autoclave was pressurized with ethylene to 1784 bar and was stirred at 1500 rpm. The mixed solutions were injected into the stirred reactor with excess pressure, at which time a temperature rise of 4� C. was observed. The temperature and pressure were recorded continuously for 120 seconds, at which time the contents of the autoclave were rapidly vented into a receiving vessel. The reactor was washed with xylene to recover any additional polymer remaining. These washings were combined with the polymer released when the autoclave was vented to yield 0.7 g of polyethylene (MW=245,500, MWD=2.257).
Using the general procedure described in Example 1,400 ml of toluene, 5.0 ml of 1.0M MAO and 0.278 mg of compound B (0.2 ml of a 13.9 mg in 10 ml of toluene solution) were 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 10 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 (9.6 g, MW=241,200, MWD=2.628).
Using the general procedures described in Example 1, 300 ml of toluene, 4.0 ml of 1.0M MAO and 0.46 mg of compound C (0.4 ml of a 11.5 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 (1.7 g, MW=278,400, MWD=2.142).
Using the general procedure described in Example 1, 400 ml of toluene, 5.0 ml of 1.0 M MAO and 0.278 m of 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 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).
Using the general procedure described in Example 1,300 ml of hexane, 9.0 ml of 1.0M MAO and 0.24 mg of compound E (0.2 ml of a 12.0 mg in 10 ml of toluene solution) was added to the reactor. The reactor was heated to 80� C. and 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 (2.2 g, MW=258,200, MWD=2.348).
Polymerization Compound E
The polymerization was carried out as in Example 1 except with the following reactor conditions: 200 ml of toluene, 100 ml of 1-butene, 9.0 ml of 1.0M MAO and 2.4 mg of compound E (2.0 ml of a 12.0 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, 1.8 g of an ethylene-1-butene copolymer was recovered (MW=323,600, MWD=2.463, 33.5 SCB/1000C by IR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0M MAO, 0.242 mg of compound F (0.2 ml of a 12.1 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 5.3 g of polyethylene (MW=319,900, MWD=2.477).
The polymerization was carried out as in Example 1 with the following reactor conditions: 150 ml of toluene, 100 ml of 1-butene, 9.0 ml of 1.0M MAO, 2.42 mg of compound F (2.0 ml of a 12.1 mg in 10 ml of toluene solution), 50� C., 65 psi ethylene, 30 minutes. The run provided 3.5 g of an ethylene-1-butene copolymer (MW=251,300, MWD=3.341, 33.3 SCB/1000C by IR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0M MAO, 0.29 mg of compound G (0.2 ml of a 14.5 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 3.5 g of polyethylene (MW=237,300, MWD=2.549).
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 1.0M 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-1-butene copolymer (MW=425,000, MWD=2.8I6, 27.1 SCB/1000C by IR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0M 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).
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 1.0M MAO, 2.66 mg of compound H (2.0 ml of a 13.3 mg in 10 ml of toluene solution), 50� C., 65 psi ethylene, 30 minutes. The run provided 15.4 g of an ethylene-1-butene copolymer (MW=286,600, MWD=2.980, 45.4 SCB/1000C by IR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0MAO, and 0.34 mg of compound I (0.2 ml of a 17.0 mg in 10 ml of toluene solution). 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).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0M MAO, 0.318 mg of compound J (0.2 ml of a 15.9 mg in 10 ml of toluene solutions), 80� C., 60 psi ethylene, 30 minutes. The run provided 8.6 g of polyethylene (MW=321,000, MWD=2.803).
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 1.0M MAO, 3.18 mg of compound J (2.0 ml of a 15.9 mg in 10 ml of toluene solution), 50� C., 65 psi ethylene, 30 minutes. The run provided 11.2 g of an ethylene-1 -butene copolymer (MW=224,800, MWD=2.512, 49.6 SCB/1000C by IR technique, 55.4 SCB/1000C by NMR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 300 ml of toluene, 5.0 ml of 1.0M MAO, 0.272 mg of compound K (0.2 ml of a 13.6 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 26.6 g of polyethylene (MW=187,300, MWD=2.401).
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 1.0M MAO, 2.72 mg of compound K (2.0 ml of a 13.6 mg in 10 ml of toluene solution), 50� C., 65 psi ethylene, 30 minutes. The run provided 3.9 g of an ethylene-1-butene copolymer (MW=207,600, MWD=2.394, 33.9 SCB/1000C by IR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 400 ml of toluene, 5.0 ml of 1.0M MAO, 0.322 mg of compound L (0.2 ml of a 16.1 mg in 10 ml of toluene solution), 80� C., 60 psi ethylene, 30 minutes. The run provided 5.5 g of polyethylene (MW=174,300, MWD=2.193).
The polymerization was carried out as in Example 1 with the following reactor contents: 250 ml of toluene, 150 ml of 1-hexene, 7.0 ml of 1.0M 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, 26.5 g of an ethylene-1-hexane copolymer was recovered (MW=222,800, MWD=3.373, 39.1 SCB/1000C by IR).
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 1.0M 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-1-octene copolymer was recovered (MW=48,600, MWD=3.007, 16.5 SCB/1000C by 13 C NMR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 300 ml of toluene, 100 ml of 4-methyl-1-pentene, 7.0 ml of 1.0M 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 ethyleme (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 13 C NMR).
The polymerization was carried out as in Example 1 with the following reactor conditions: 300 ml of toluene, 100 ml of a 2.2M norbornene in toluene solution, 7.0 ml of 1.0M 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 13 C NMR).
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 1.0M 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 13 C NMR).
The polymerization run was performed in a 12 liter autoclave reactor equipped with a paddle stirrer, an external water jacket for temperature control, a regulated supply of dry nitrogen, ethylene, propylene, 1-butene and hexane, and a septum inlet for introduction of other solvents or comonomers, transition metal compound and alumoxane solutions. The reactor was dried and degassed thoroughly prior to use. A typical run consisted of injecting 400 ml of toluene, 5 ml of 1.0M MAO, 0.206 mg compound AT (0.2 ml of a 10.3 mg in 10 ml of toluene solution) into the reactor. The reactor was then 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 of the polymer by a stream of nitrogen. Polyethylene was recovered (11.8 g, MW=279,700, MWD=2.676).
Using the same reactor design and general procedure as described in Example 40, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.2 ml of a preactivated compound AT solution (10.3 mg of compound AT dissolved in 9.5 ml of toluene and 0.5 ml of 1.0M MAO) were 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, 14.5 g of polyethylene was recovered (MW=406,100, MWD =2.486).
Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexene, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 29.2 g of an ethylene-1-hexene copolymer was recovered (MW=129,800, MWD=2.557, 53.0 SCB/1000C by 13 C NMR).
Using the same reactor design and general procedure described in Example 40, 375 ml of toluene, 25 ml of 1-hexane, 7.0 ml of 1.0M MAO, and 1.03 mg of compound AT (1.0 ml of 10.3 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 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 15.0 g of an ethylene-1-hexene copolymer was recovered (MW=310,000, MWD=2.579, 47.2 SCB/1000C by 13 C NMR).
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100ml of propylene, 7.0 ml of 1.0M MAO, and 2.06 mg of compound AT (2.0 ml of a 10.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 46.0 g of an ethylenepropylene copolymer was recovered (MW=110,200, MWD=5.489, 20 wt% ethylene by IR).
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml of 1-octene, 7.0 ml of 1.0M MAO, and 1.04 mg of compound AT (1.0 ml of a 10.4 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (65 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 30.6 g of an ethylene-1-octene copolymer was recovered (MW=73,100, MWD=2.552, 77.7 SCB/1000C by 13 C NMR).
Polymerization--Compound BT
Using the same reactor design and general procedure described in Example 40, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.248 mg of compound BT (0.2 ml of a 12.4 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 3.8 g of polyethylene Was recovered (MW=451,400, MWD=3.692).
Polymerization--Compound CT
Using the same reactor design and general procedure described in Example 40, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.234 mg of compound CT (0.2 ml of a 11.7 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 2.7 g of polyethylene was recovered (MW=529,100, MWD=3.665).
Polymerization--Compound DT
Using the same reactor design and general procedure described in Example 40, 400 ml of toluene, 5.0 ml of 1.0M MAO, and 0.28 mg of compound DT (0.2 ml of a 14.0 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., the ethylene was introduced (60 psi), and the reaction was allowed to run for 10 minutes, followed by rapidly cooling and venting the system. After evaporation of the toluene, 9.0 g of polyethylene was recovered (MW=427,800, MWD=3.306).
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml propylene, 7.0 ml of 1.0M MAO, and 1.4 mg of compound DT (1.0 ml of a 14.0 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 30� C. and the reaction was allowed to run for 1 hour, followed by rapidly cooling and venting the system. After evaporation of the toluene, 15 g of amorphous polypropylene was recovered (MW=18,600, MWD=1.657).
Polymerization--Compound ET
Using the same reactor design and general procedure described in Example 40, 300 ml of toluene, 100 ml 1-hexene, 70 ml of 1.0 M MAO, and 1.0 mg of compound ET (1.0 ml of a 10.0 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C. and the ethylene was introduced (65 psi). During the polymerization, the reactor temperature increased by 20� C. After 10 minutes, the reactor was rapidly cooled and vented. After evaporation of the toluene, 106 g of an ethylene-1-hexene copolymer was recovered (MW=17,900, MWD=2.275, 39.1 SCB/1000C by NMR).
The polymerization was performed in a stirred 100 ml stainless steel autoclave which was equipped to perform polymerizations at temperatures up to 300� C. and pressures up to 2500 bar. The reactor was evacuated, purged with nitrogen, purged with ethylene and heated to 200� C. 1-hexane (75 ml) was added to the reactor under ethylene pressure. A stock solution of compound AT was prepared by dissolving 6.5 mg of compound AT in 12.5 ml of toluene. The test solution was prepared by adding 1.0 ml of the compound AT stock solution to 1.9 ml of 1.0M MAO solution, followed by 7.1 ml of toluene. The test solution (0.43 ml) was transferred by nitrogen pressure into a constant-volume injection tube. The autoclave was pressurized with ethylene to 1748 bar and was stirred at 1800 rpm. The test solution was injected into the autoclave with excess pressure, at which time a temperature rise of 16� C. was observed. The temperature and pressure were recorded continuously for 120 seconds, at which time the contents of the autoclave were rapidly vented into a receiving vessel. The reactor was washed with xylene to recover any polymer remaining within. These washings were combined with the polymer released when the reactor was vented. Precipitation of the polymer from the mixture by addition of acetone yielded 2.7 g of polymer (MW=64,000, MWD=3.16, 14.7 SCB/1000C by IR).
For this Example a stirred 1 L steel autoclave reaction vessel which was equipped to perform continuous Ziegler polymerization reactions at pressures to 2500 bar and temperatures up to 300� C. was used. The reaction system was supplied with a thermocouple and pressure transducer to measure temperature and pressure continuously, and with means to supply continuously purified compressed ethylene and 1-butene (or propylene). Equipment for continuously introducing a measured flow of catalysts solution, and equipment for rapidly venting and quenching the reaction, and of collecting the polymer product were also a part of the reaction system. The polymerization was performed with a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 0.888 g of solid compound AT with 0.67 L of a 30 wt% methylalumoxane solution in 4.3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.56 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer products was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 50,200, a molecular weight distribution of 2.36 and 60.1 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent. The temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 0.859 g of solid FT with 30 wt% methylalumoxane solution and toluene such that the catalyst concentration was 0.162 g/L with an Al/M molar ratio of 1200. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of1.15 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 61,400, a molecular weight distribution of 2.607 and 104.8 SCB/1000C by 13 C NMR.
Polymerization--Compound GT
Using the same reactor design and general procedure as described in Example 40, 300 ml of toluene, 100 ml of 1-hexene, 7.0 ml of 1.0M MAO, and 1.23 mg of compound GT (1.0 ml of a 12.3 mg in 10 ml of toluene solution) were added to the reactor. The reactor was heated at 80� C., and 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, 47.2 g of an ethylene-1-hexene copolymer was recovered (MW=313,000, MWD=3.497, 41.0 SCB/1000C by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 170� C. The catalyst solution was prepared by mixing 0.925 g of solid compound AT with 2 L of a 10 wt% methylalumoxane solution in 8 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.28 L/hr which resulted in a temperature of 170� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.7 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 69,500, a molecular weight distribution of 2.049 and 35.7 SCB/1000C by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 0.995 g of solid compound BT with 30 wt% methylalumoxane solution and toluene such that the catalyst concentration was 0.187 g/L and the Al/M molar ratio was 1300. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.0 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 65,000, a molecular weight distribution of 2.623 and 55.5 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.94 g of solid compound H with 2.0 L of a 10 wt% methylalumoxane solution in 3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.5 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 31,900 and 46.5 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.92 g of solid compound I with 2.0 L of a 10 wt% methylalumoxane solution in 3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.67 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 40,800, a molecular weight distribution of 2.009 and 36.9 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.80 g of solid compound K with 2.0 L of a 10 wt% methylalumoxane solution in 3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.7 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 51,700, a molecular weight distribution of 1.532 and 30.1 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and b 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.95 g of solid compound L with 2.0 L of a 10 wt% methylalumoxane solution in 3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.2 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 38,800, a molecular weight distribution of 1.985 and 39.3 SCB/1000C as measured by 13 C NMR.
Polymerization--Compound HT
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and i-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 2.01 g of solid compound HT with 30 wt% methylalumoxane solution and toluene such that the catalyst concentration was 0.354 g/L and the Al/M molar ratio was 400. The preparation was done under an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 1.15 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 61,700, a molecular weight distribution of 2.896 and 62.9 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.31 g of solid compound F with 2.0 L of a 10 wt% methylalumoxane solution in 3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.56 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 43,400, a molecular weight distribution of 2.001 and 40.1 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.53 g of solid compound G with 0.5 L of a 30 wt% methylalumoxane solution in 4.5 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.58 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 47,400, a molecular weight distribution of 2.198 and 37.6 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.95 g of solid compound A with 0.67 L of a 30 wt% methylalumoxane solution in 4.3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.4 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer products was 3.9 kg/hr of an ethylene-1-butene copolymer which had a weight average molecular weight of 71,100, a molecular weight distribution of 1.801 and 12.4 SCB/1000C as measured by 13 C NMR.
Using the same reactor design as described in Example 54, and using a molar ratio of ethylene to 1-butene of 1.6 without the addition of a solvent, the temperature of the cleaned reactor containing ethylene and 1-butene was equilibrated at the desired reaction temperature of 180� C. The catalyst solution was prepared by mixing 1.97 g of solid compound B with 0.67 L of a 30 wt% methylalumoxane solution in 4.3 L of toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 0.35 L/hr which resulted in a temperature of 180� C. in the reactor. During this run, ethylene and 1-butene were pressured into the autoclave at a total pressure of 1300 bar. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 3.9 kg/hr of an ethylene-1-butene copolymer which has a weight average molecular weight of 47,300, and a molecular weight distribution of 2.056 and 34.1 SCB/1000C as measured by 13 C NMR.
TABLE 2    TRANSITION           CAT. ACTIVITY   METAL  mmole   RXN. RXN.    SCB/ G. POLYMER/ EXP. DILUENT COMPOUND (TMC) ALUMOXANE MAO:TMC MONO- CO- TEMP. TIME YIELD   1000 C MMOLE NO. Type ml Type mmole Type mmole (�  103) MER MONOMER �C. HR. g. MW MWD NMR IR TMC-HOUR     4 Hexane 300 A 5.588 � 10-4 MAO 9 16.11 ethylene-  80 0.5 5.4 212,600 2.849   1.933 � 104         60 psi  1 Toluene 400 A 5.588 � 10-4 MAO 9 16.11 ethylene-  80 0.5 9.2 257,200 2.275  3.293 � 104         60 psi  2 Toluene 300 A 2.794 � 10-4 MAO 4.5 16.11 ethylene-  80 0.5 3.8 359,800 2.425   2.720 � 104         60 psi  3 Toluene 300 A 2.794 � 10-4 MAO 4.5 16.11 ethylene-  40 0.5 2.4 635,000 3.445   1.718 � 104         60 psi 16 Toluene 400 A 5.588 � 10-4 MAO 5 8.95 ethylene-  80 0.5 19.4 343,700 3.674   6.943 � 104   400 psi 12 Toluene 400 .sup. Aa 5.588 � 10-4 MAO 5.02 8.98 ethylene-  80 0.5 3.4 285,000 2.808   1.217 � 104  60 psi 13 Toluene 400  Aa,b 5.588 � 10-4 MAO 5.02 8.98 ethylene-  80 0.5 2.0 260,700 2.738   7.158 � 103         60 psi 14 Toluene 400 .sup.  Aa 5.588 � 10-4 MAO 0.26 0.47 ethylene-  80 0.5 1.1 479,600 3.130   3.937 � 103         60 psi 15 Toluene 400 .sup. Aa 5.588 � 10-4 MAO 0.1 0.018 ethylene-  80 0.5 1.6 458,800 2.037   5.727 � 102         60 psi 18 Toluene 400 B 5.573 � 10-4 MAO 5 8.97 ethylene-  80 0.17 9.6 241,200 2.628   1.034 � 105        60 psi 19 Toluene 300 C 1.118 � 10-3 MAO 4 3.58 ethylene-  80 0.5 1.7 278,400 2.142   3.041 � 103         60 psi 20 Toluene 400 D 5.573 � 10-4 MAO 5 8.97 ethylene-  80 0.5 1.9 229,700 2.618   6.819 � 103         60 psi 21 Hexane 300 E  5.61 � 10-4 MAO 9 16.04 ethylene-  80 0.5 2.2 258,200 2.348   7.843 � 103    60 psi 23 Toluene 400 F  4.79 � 10-4 MAO 5 10.44 ethylene-  80 0.5 5.3 319,900 2.477   2.213 � 104        60 psi 25 Toluene 400 G  5.22 � 10-4 MAO 5 9.58 ethylene-  80 0.5 3.5 237,300 2.549   1.341 � 104         60 psi 27 Toluene 400 H  5.62 � 10-4 MAO 5 8.90 ethylene-  80 0.5 11.1 299,800 2.569   3.950 � 104         60 psi 29 Toluene 400 I  5.57 � 10-4 MAO 5 8.98 ethylene-  80 0.5 0.9 377,000 1.996   3.232 � 103         60 psi 30 Toluene 400 J  5.59 � 10-4 MAO 5 8.94 ethylene-  80 0.5 8.6 321,000 2.803   3.077 � 104   60 psi 32 Toluene 300 K  5.06 � 10-4 MAO 5 9.87 ethylene-  80 0.5 26.6 187,300 2.401   1.051 � 105         60 psi 34 Toluene 400 L  5.60 � 10-4 MAO 5 8.93 ethylene-  80 0.5 15.5 174,300 2.193   5.536 � 104         60 psi  5 Toluene 300 A 1.118 � 10-3 MAO 9 8.05 ethylene- propylene- 80 0.5 13.3  24,900 2.027  73.5 2.379 � 104         60 psi 200 ml  6 Toluene 200 A 2.235 � 10-3 MAO 9 4.03 ethylene- propylene- 50 0.5 6.0  83,100 2.370  75.7 5.369 � 103 60 psi 200 ml  7 Toluene 150 A 5.588 � 10-3 MAO 9 1.61 ethylene- 1-butene- 50 0.5 25.4 184,500 3.424 23.5 21.5 9.091 � 10.sup. 3         65 psi 100 ml  8 Toluene 100 A 5.588 � 10-3 MAO 9 1.61 ethylene- 1-butene- 50 0.5 30.2 143,400 3.097 30.8 26.5 1.081 � 104         65 psi 150 ml  9 Toluene 200 A 5.588 � 10-3 MAO 8 1.43 ethylene- 1-butene- 50 0.5 24.9 163,200 3.290 23.3 18.9 8.912 � 103         65 psi 50 ml 10 Hexane 200 A 5.588 � 10-3 MAO 8 1.43 ethylene- 1-butene- 50 0.5 19.5 150,600 3.150 12.1 12.7 6.979 � 103         65 psi 50 ml 11 Hexane 150 A 5.588 � 10-3 MAO 8 1.43 ethylene- 1-butene- 50 0.5 16.0 116,200 3.510 19.2 19.4 5.727 � 103         65 psi 100 ml 22 Toluene 200 E  5.61 � 10-3 MAO 9 1.60 ethylene- 1-butene- 50 0.5 1.8 323,600 2.463  33.5 6.417 � 102         65 psi 100 ml 24 Toluene 150 F  4.79 � 10-3 MAO 9 1.88 ethylene- 1-butene- 50 0.5 3.5 251,300 3.341  33.3 1.461 � 103         65 psi 100 ml 26 Toluene 150 G  5.22 � 10-3 MAO 7 1.34 ethylene- 1-butene- 50 0.5 7.0 425,000 2.816  27.1 2.682 � 103 65 psi 100 ml 28 Toluene 150 H  5.62 � 10-3 MAO 7 1.25 ethylene- 1-butene- 50 0.5 15.4 286,600 2.980  45.4 5.480 � 103         65 psi 100 ml 30 Toluene 150 J  5.59 � 10-3 MAO 7 1.25 ethylene- 1-butene- 50 0.5 11.2 224,800 2.512  49.6 4.007 � 103         65 psi 100 ml 32 Toluene 150 K  5.06 � 10-3 MAO 7 1.38 ethylene- 1-butene- 50 0.5 3.9 207,600 2.394  33.9 1.542 � 103         65 psi 100 ml 35 Toluene 250 A 5.588 � 10-3 MAO 7 1.25 ethylene- 1-hexene- 50 0.5 26.5 222,800 3.373  39.1 9.485 � 103         65 psi 150 ml 36 Toluene 300 A 5.588 � 10-3 MAO 7 1.25 ethylene- 1-octene- 50 0.5 19.7 548,600 3.007  16.5 6.979 � 103         65 psi 100 ml 37 Toluene 300 A 5.588 � 10-3 MAO 7 1.25 ethylene- 4-methyl- 50 0.5 15.1 611,800 1.683  1.8c 5.404 � 103         65 psi 1-pentene-          100 ml 38 Toluene 300 A 5.588 � 10-3 MAO 7 1.25 ethylene- norbornene- 50 0.5 12.3 812,600 1.711  0.3c 4.402 � 103         65 psi 100 ml 2.2M 39 Toluene 300 A 5.588 � 10-3 MAO 7 1.25 ethylene- cis-1,4- 50 0.5 13.6 163,400 2.388  2.2c 4.868 � 103         65 psi hexadiene  100 ml a Compound A was preactivated by dissolving the compound in solvent containing MAO. b Preincubation of activated compound A was for one day. c Mole % comonomer.
TABLE A__________________________________________________________________________           Methyl-Transition Metal           alumoxane                 mmole  Ethylene                             Rxn Rxn              Cat ActivityExampleCompound (TMC)           (MAO) MAO:TMC                        Pressure                             Temp.                                 Time                                     Yield        g poly/mmoleNumberType    mmole  mmole (� 103)                        (psi)                             �C.                                 hr. g   MW   MWD TMC-HR__________________________________________________________________________.sup. 41aAT  4.79 � 10-4           5.01  10.5   60   80  0.5 14.5                                         406,100                                              2.486                                                  6.05 �                                                  10440   AT  4.79 � 10-4           5     10.4   60   80  0.5 11.8                                         279,700                                              2.676                                                  4.93 �                                                  10450   DT  5.59 � 10-4           5     8.94   60   80  0.166                                     9.0 427,800                                              3.306                                                  9.70 �                                                  10448   BT  5.58 � 10-4           5     8.96   60   80  0.166                                     3.8 451,400                                              3.692                                                  4.10 �                                                  10449   CT  5.59 � 10-4           5     8.94   60   80  0.166                                     2.7 529,100                                              3.665                                                  2.91 �                                                  104__________________________________________________________________________ a Transition metal compound was preactivated before polymerization b admixing it with a quantity of methylalumoxane sufficient to provide a MAO:TMC ratio of 20.9.
TABLE B__________________________________________________________________________    Transition       Methyl-   Ethy-Ex- Metal   alu- mmole                 lene                               Catample    Compound       moxane            MAO: Pres-                     Co-   Rxn.                               Rxn.                 g Poly/Num-    (TMC)   (MAO)            TMC  sure                     monomer                           Temp.                               Time                                   Yield       SCB/ mmoleber Type   mmole       mmole            (� 103)                 (psi)                     Amount                           �C.                               hr. g   MW  MWD 1000                                                    TMC-HRc__________________________________________________________________________45  AT  4.79 �       7    1.46 65  Propylene:                           80  0.166                                   46.0                                       110,200                                           5.489                                               (Propy-                                                    5.79 �                                                    104   10-3         100 ml                    lene)b                                               80 wt %46  AT  2.39 �       7    2.93 65  1-Butene:                           80  0.166                                   35.1                                        94,400                                           2.405                                               165  8.85 �                                                    104   10-3         100 ml44  AT  2.39 �       7    2.93 65  1-Hexene:                           50  0.166                                   15.0                                       310,000                                           2.579                                               47.2 3.78 �                                                    104   10-3         25 ml43  AT  2.39 �       7    2.93 65  1-Hexene:                           80  0.166                                   29.2                                       129,800                                           2.557                                               53.0 7.36 �                                                    104   10-3         25 ml42  AT  2.39 �       7    2.93 65  1-Hexene:                           80  0.166                                   48.6                                        98,500                                           1.745                                               117  1.22 �                                                    105   10-3         100 ml52  ET  2.76 �       7    2.54 65  1-Hexene:                           .sup. 80d                               0.166                                   106  17,900                                           2.275                                               39.1 2.31 �                                                    105   10-3         100 ml57  GT  2.81 �       7    2.49 65  1-Hexene:                           80  0.5 47.2                                       313,000                                           3.497                                               41.0 3.36 �                                                    104   10-3         100 ml47  AT  2.42 �       7    2.89 65  1-Octene:                           80  0.166                                   30.6                                        73,100                                           2.552                                               77.7 7.62 �                                                    104   10-3         100 ml__________________________________________________________________________ b Determined by IR c Determined by 13 C NMR d During polymerization the reactor temperature increased by 20� C.
TABLE C__________________________________________________________________________Transition          Catalyst          Rxn.                   Cat.Metal     TMC   Co-   Ethylene/                            Pres-                               Rxn.                ActivityExampleCompound      AL: Feed Rate                monomer                      Com   sure                               Temp                                   Yield       SCB/f                                                   kg Polymer/Number(TMC) TMC (mmole/hr)                (Com) Mole Ratio                            (bar)                               �C.                                   (kg/hr)                                       MW  MWD 1000                                                   mmol__________________________________________________________________________                                                   TMC.sup. 55eAT    1200          1.63  Propylene                      2.6   2200                               140 2.3 102,700                                           2.208                                               127.7                                                   1.454   AT    1500          0.231 1-Butene                      1.6   1300                               180 3.9  50,200                                           2.36                                               60.1                                                   16.967   IT     600          0.442 1-Butene                      1.6   1300                               180 3.9  50,800                                           2.467                                               69g                                                   8.864   HT     400          1.05  1-Butene                      1.6   1300                               180 3.9  61,700                                           2.896                                               62.9                                                   3.759   BT    1300          0.421 1-Butene                      1.6   1300                               180 3.9  65,000                                           2.623                                               55.5                                                   9.358   AT    1400          0.060 1-Butene                      1.6   1300                               170 3.7  69,500                                           2.049                                               35.7                                                   61.756   FT    1200          0.366 1-Butene                      1.6   1300                               180 3.9  61,400                                           2.607                                               104.8                                                   8.370   JT    1400          0.366 1-Butene                      1.6   1300                               180 3.9  72,600                                           2.385                                               110g                                                   10.7__________________________________________________________________________ e the polymer product had a density of 0.863 g/cc. f Excepted where othrwise indicated, determined by 13 CNMR. g Determined by 1 H NMR.
TABLE D__________________________________________________________________________             Catalyst             TMC   Cat. ActivityhExampleTransiton Metal             Feal Rate                   kg Polymer/NumberCompound (TMC)          TM mmole/hr                   mmol TMC                          MW     MWD SCB/1000 C                                            r1__________________________________________________________________________54   AT        Ti 0.23  17.0   50,200 2.360                                     60.1   10.160   H         Zr 1.23  3.2    31,900 12.070                                     46.6   14.161   I         Hf 0.42  9.3    40,800 2.009                                     36.9   18.459   BT        Ti 0.42  9.3    65,000 2.623                                     55.5   11.262   K         Zr 1.25  3.1    51,700 1.532                                     30.1   23.463   L         Hf 0.81  4.8    1.15   1.985                                     39.3   17.264   HT        Ti 1.05  3.7    61,700 2.896                                     62.9   9.565   F         Zr 0.34  11.5   43,400 2.001                                     40.1   16.866   G         Hf 0.34  11.5   47,400 2.198                                     37.6   18.167   IT        Ti 0.44  8.9    50,800 2.467                                     69     8.468   A         Zr 0.38  10.3   71,100 1.801                                     12.4   59.969   B         Hf 0.69  5.7    47,300 2.056                                     34.1   20.3__________________________________________________________________________ h Polymer yield was 3.90 kg/hr.
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A CORP. OF DELAWAREFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CANICH, JO ANN M.;REEL/FRAME:005709/0895Effective date: 19900921RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services