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Patent US5227440 - Mono-Cp heteroatom containing Group IVB transition metal complexes with MAO ... - Google PatenteSuche Bilder Maps Play YouTube News Gmail Drive Mehr » Erweiterte Patentsuche | Webprotokoll | Anmelden Erweiterte Patentsuche PatenteThe invention is a supported catalyst system including an inert support material, 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.de/patents/US5227440?utm_source=gb-gplus-sharePatent US5227440 - Mono-Cp heteroatom containing Group IVB transition metal complexes with MAO: supported catalysts for olefin polymerization Ver�ffentlichungsnummerUS5227440 APublikationstypErteilung Anmeldenummer07/751,392 Ver�ffentlichungsdatum13. Juli 1993Eingetragen28. Aug. 1991 Priorit�tsdatum13. Sept. 1989 ErfinderJo Ann M. CanichGary F. LicciardiUrspr�nglich Bevollm�chtigterExxon Chemical Patents Inc. US-Klassifikation526/129526/150502/120526/943502/117526/127502/103526/132526/160526/352Internationale KlassifikationC07F7/10C08F10/00C08F210/18C08F210/06C08F210/16C08F110/06C08F4/659C08F110/02C07F17/00C08F10/06C08F4/6592 UnternehmensklassifikationC08F210/06C07F7/10C07F17/00C08F4/65916C08F4/65908C08F210/16C08F210/18C08F10/00C08F110/06C08F4/65912C08F10/06C08F110/02 Europ�ische KlassifikationC08F 10/00C08F 10/06C08F 210/16C07F 17/00C07F 7/10ReferenzenPatentzitate (4)Nichtpatentzitate (4) Referenziert von (100)Externe LinksUSPTO USPTO-Zuordnung EspacenetMono-Cp heteroatom containing Group IVB transition metal complexes with MAO: supported catalysts for olefin polymerizationUS 5227440 A Zusammenfassung The invention is a supported catalyst system including an inert support material, 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.
We claim: 1. A process for the polymerization of one or more olefins comprising contacting the monomer or monomers under polymerization conditions in the presence of a catalyst system comprising: (A) an inert support; (B) a transition metal compound represented by the formulae: ##STR7## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C.sub.5 --H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals; substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or other radical containing a Lewis acidic or basic functionality; C.sub.1 -C.sub.20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C.sub.4 -C.sub.20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR'.sub.z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, each R' is, independently a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals; substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or other radical containing a Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, any univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q cannot be a substituted or unsubstituted cyclopentadienyl ring or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and (C) an alumoxane.
All procedures were performed under an inert atmosphere of nitrogen. Solvent choices are often optional, for example, in most cases either pentane or 30-60 petroleum ether can be interchanged. The lithiated amides were prepared from the corresponding amines and either n-BuLi or MeLi. Published methods for preparing LiHC.sub.5 Me.sub.4 include C. M. Fendrick et. al., Organometallics, 3:819 (1984) and F. H. Kohler and K. H. Doll, Z. Naturforich, 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. TiCl.sub.4 and ZrCl.sub.4 were purchased from either Aldrich Chemical Company or Cerac. TiCl.sub.4 was typically used in its etherate form. The etherate, TiCl.sub.4.2Et.sub.2 O, can be prepared by gingerly adding TiCl.sub.4 to diethylether. Amines, silanes, and lithium reagents were purchased from Aldrich Chemical Company or Petrarch Systems. Methylalumoxane (MAO) solutions were either toluene or heptane based and were supplied by either Schering or Ethyl Corp. The silica used was Davidson 948 grade, and was dried at 800 (TEAL), supplied by Texas Alkyls as a 1.6M solution in heptane, was used as a scavenger in the polymerizations.
Preparation of Group IV B Transition Metal Components Example A Compound A Part 1. Me.sub.4 HC.sub.5 Li (10.0 g, 0.078 mol) was slowly added to a Me.sub.2 SiCl.sub.2 (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 mixture was filtered through Celite. The solvent was removed from the filtrate. Me.sub.4 HC.sub.5 SiMe.sub.2 Cl (15.34 g, 0.071 mol) was recovered as a pale yellow liquid.
Part 2. Me.sub.4 HC.sub.5 SiMe.sub.2 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 added to precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me.sub.2 Si(Me.sub.4 HC.sub.5) (HN-t-Bu) (11.4 g, 0.044 mol) was isolated as a pale yellow liquid.
Part 3. Me.sub.2 Si(Me.sub.4 HC.sub.5) (HN-t-Bu) (11.14 g, 0.044 mol) was diluted with �100 ml of Et.sub.2 O. MeLi (1.4M, 64 ml, 0.090 mol) was slowly added. The mixture was allowed to stir for 0.5 hours after the final addition of MeLi. The ether was reduced in volume prior to filtering off the product. The product, [Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu) ]Li.sub.2 was washed with several small portions of ether, then vacuum dried.
Part 4. [Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu)]Li.sub.2 (3.0 g, 0.011 mol) was suspended in �150 ml of Et.sub.2 O. ZrCl.sub.4 (2.65 g, 0.011 mol) was slowly added and the resulting mixture was allowed to stir overnight. The ether was removed via a vacuum to a cold trap held at -196 filtered through Celite twice. The pentane was significantly reduced in volume and the pale yellow solid was filtered off and washed with solvent. Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu) ZrCl.sub.2 (1.07 g, 0.0026 mole) was recovered. Additional Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu) ZrCl.sub.2 was recovered from the filtrate by repeating the recrystallization procedure. Total yield, 1.94 g, 0.0047 mol.
Example B Compound B Part 1. MePhSiCl.sub.2 (14.9 g, 0.078 mol) was diluted with 250 ml of THF. Me.sub.4 HC.sub.5 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 added to precipitate the LiCl. The mixture was filtered through Celite and the pentane was removed from the filtrate. MePhSi(Me.sub.4 C.sub.5 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(C.sub.5 Me.sub.4 H)Cl (15.0 g, 0.054 mol) was added dropwise. The yellow solution was allowed to stir overnight. The solvent was removed in vacuo. Petroleum ether was added to precipitate the LiCl. The mixture was filtered through Celite, and the filtrate was evaporated. MePhSi(C.sub.5 Me.sub.4 H) (NH-t-Bu) (16.6 g, 0.053 mol) was recovered as an extremely viscous liquid.
Part 4. Li.sub.2 [MePhSi(C.sub.5 Me.sub.4) (N-t-Bu)](8.75 g, 0.027 mol) was suspended in �125 ml of cold ether (-30 TiCl.sub.4.2Et.sub.2 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(C.sub.5 Me.sub.4) (N-t-Bu)TiCl.sub.2.
Part 2. (C.sub.5 Me.sub.4 H)SiMe.sub.2 Cl (8.0 g, 0.037 mol) was slowly added to a suspension of LiHNC.sub.12 H.sub.23 (C.sub.12 H.sub.23 =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 precipitate the LiCl. The mixture was filtered through Celite. The solvent was removed from the filtrate. Me.sub.2 Si(C.sub.5 Me.sub.4 H) (NHC.sub.12 H.sub.23) (11.8 g, 0.033 mol) was isolated as a pale yellow liquid.
Part 3. Me.sub.2 Si(C.sub.5 Me.sub.4 H) (NHC.sub.12 H.sub.23) (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, [Me.sub.2 Si(C.sub.5 Me.sub.4) (NC.sub.12 H.sub.23)]Li.sub.2, was washed with several small portions of ether, then vacuum dried to yield 11.1 g (0.030 mol) of product.
Part 4. [Me.sub.2 Si(C.sub.5 Me.sub.4) (NC.sub.12 H.sub.23)]Li.sub.2 (3.0 g, 0.008 mol) was suspended in cold ether. TiCl.sub.4.2Et.sub.2 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 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. The solid collected was recrystallized from methylene chloride and Me.sub.2 Si(C.sub.5 Me.sub.4) (NC.sub.12 H.sub.23)TiCl.sub.2 was isolated (1.0 g, 2.1 mmol).
The transition metal compound, A, Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu)ZrCl.sub.2 (0.063 g, 0.153 mmole) prepared as described for Example A, was combined with 35 ml of 1.0M MAO in toluene. The solution was stirred for five minutes prior to the addition of the treated silica (2.5 g). The mixture was then stirred for 5 minutes, after which time the toluene was removed via vacuum, and the prepared supported catalyst was recovered.
A typical run consisted of injecting 400 ml of hexane, 0.2 ml TEAL (1.6M in heptane), and 0.5 g of the prepared supported catalyst into the reactor. The reactor was heated to 80 introduced prior to the injection of the prepared supported catalyst. The polymerization reaction was limited to 30 minutes. The reaction was stopped by rapidly cooling and venting the system. A mass of 20.2 g of polyethylene was recovered, having a molecular weight (MW) of 231,200, and a molecular weight distribution (MWD)=3.26.
Example 2 Dried silica (5.0 g) was slurried in 25 ml of toluene. MAO (12.5 ml, 1.0M) was added and the mixture was permitted to stir for five minutes. The transition metal compound A, Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu)ZrCl.sub.2 (0.100 g, 0.243 mmole) prepared as described for Example A, was then added and the mixture was stirred for five minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
Example 3 Dried silica was pretreated with methylalumoxane as described for Example 1. The transition metal compound B, MePhSi(Me.sub.4 C.sub.5) (N-t-Bu)TiCl.sub.2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 7.5 ml of 1.0M MAO in toluene and stirred for five minutes. Pretreated silica (0.5 g) was then added to this mixture with stirring for 5 minutes. The toluene was then removed via vacuum and the prepared supported catalyst was recovered.
Example 4 The transition metal compound B, MePhSi(Me.sub.4 C.sub.5) (N-t-Bu)TiCl.sub.2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 5.0 ml of 1.5M MAO in heptane and stirred for five minutes. Dried silica, which had not been pretreated (0.5 g) was then added to this mixture with stirring for 5 minutes. The heptane was removed via vacuum and the prepared supported catalyst was recovered.
Example 5 The transition metal compound B, MePhSi(Me.sub.4 C.sub.5) (N-t-Bu)TiCl.sub.2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 7.5 ml of 1.0M MAO in toluene and stirred for five minutes. Dried silica (0.5 g), which had not been pretreated, was then added to this mixture with stirring for 5 minutes. The toluene was then removed via vacuum and the prepared supported catalyst was recovered.
Example 6 Dried silica (2.5 g) was slurried with 10 ml of 1.5M MAO in heptane and stirred for 0.5 hours. This slurry was then filtered, and washed five times with 10 ml portions of pentane, followed by drying in vacuo.
The transition metal compound B, MePhSi(Me.sub.4 C.sub.5) (N-t-Bu)TiCl.sub.2 (0.015 g, 0.035 mmol), prepared as described for Example B, was combined with 5.0 ml of 1.5M MAO in heptane and stirred for five minutes. Pretreated silica/(0.5 g) was then added to this mixture with stirring for 5 minutes. The heptane was removed via vacuum and the prepared supported catalyst was recovered.
Example 7 Dried silica (2.5 g) was slurried with 10 ml of 1.5M MAO in heptane and stirred for 0.5 hours. This slurry was then filtered, and washed five times with 10 ml portions of pentane. The washed slurry was dried under vacuum.
The transition metal compound C, Me.sub.2 Si(Me.sub.4 C.sub.5) (NC.sub.12 H.sub.23)TiCl.sub.2 (40 mg, 0.084 mmol), prepared as described for Example C, was dissolved in 12.3 ml of 1.5M MAO in heptane and was permitted to stir 0.5 hours. Pretreated silica (2.5 g) was added, and the mixture stirred for an additional 0.5 hours. Toluene was then thoroughly removed via vacuum and the prepared supported catalyst was recovered.
Example 8 A solution of 1.4M trimethylaluminum (TMA) in heptane (200 ml) was placed into a 1 L flask equipped with a magnetic stirring bar. Untreated silica gel (50 g), containing 9.6% water, was slowly added to the flask. After the addition of the silica was completed, the mixture was stirred at ambient temperature for one hour. The transition metal compound B, MePhSi(Me.sub.4 C.sub.5) (N-t-Bu)TiCl.sub.2 (1.35 g, 3.1 mmol), prepared as described for Example B, was slurried in 50 ml of heptane, and then added to the flask containing the treated silica. The mixture was permitted to react for one hour, and was then heated to 65 while a nitrogen stream was passed through the flask to remove the solvent. The nitrogen stream was stopped when the mixture in the flask turned into a free flowing powder.
Example 9 Dried silica (2.5 g) was slurried in 10 ml of 1.6M triethylaluminum (TEAL) in heptane and stirred for 0.50 hours. The slurry was then filtered and washed five times with 20 ml portions of pentane. The washed slurry was then dried under vacuum.
The transition metal compound, C, Me.sub.2 Si(Me.sub.4 C.sub.5) N-C.sub.12 H.sub.23 TiCl.sub.2 (0.010 g, 0.021 mmole) prepared as described for Example C, was dissolved in 5.0 ml of 1M MAO in toluene, which contained tetraethoxysilane (TEOS) (40 mg, 0.192 mmole) as a modifier, and was permitted to stir for 5 minutes. Pretreated silica (0.50 g) was added to this mixture with stirring for 5 additional minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
The transition metal compound, C, Me.sub.2 Si(Me.sub.4 C.sub.5) N-C.sub.12 H.sub.23 TiCl.sub.2 (0.010 g, 0.021 mmole) prepared as described for Example C, was dissolved in 5.0 ml of 1M MAO in toluene, and was permitted to stir for 5 minutes. Pretreated silica (0.50 g) was added to this mixture with stirring for 5 additional minutes. Toluene was removed from the mixture via vacuum and the prepared supported catalyst was recovered.
(C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, alkylborido radicals, or any other radical containing a Lewis acidic or basic functionality, C.sub.1 -C.sub.20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals or any other radical containing a Lewis acidic or basic functionality, or (C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined forming a C.sub.4 -C.sub.20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
L is a neutral Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and "w" is a number from 0 to 3. L can also be a second transition metal compound of the same type such that the two metal centers M and M' are bridged by Q and Q', wherein M' has the same meaning as M and Q' has the same meaning as Q. Such dimeric compounds are represented by the formula: ##STR2## The alumoxane component of the catalyst may be represented by the formulas: (R.sup.3 --Al--O).sub.m ; R.sup.4 (R.sup.5 --Al--O).sub.m AlR.sup.6 or mixtures thereof, wherein R.sup.3 -R.sup.6 are, independently, a C.sub.1 -C.sub.5 alkyl group or halide and "m" is an integer ranging from 1 to about 50 and preferably is from about 13 to about 25.
(C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or other radical containing a Lewis acidic or basic functionality, C.sub.1 -C.sub.20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or any other radical containing a Lewis acidic or basic functionality, or (C.sub.5 H.sub.5-y-x R.sub.x) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C.sub.4 -C.sub.20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;
(JR'.sub.z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R' is, independently a radical selected from a group consisting of C.sub.1 -C.sub.20 hydrocarbyl radicals, substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical or other radical containing a Lewis acidic or basic functionality, and "z" is the coordination number of the element J;
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 hydrocarbyl radicals, phosphido-substituted hydrocarbyl radicals, and alkoxy-substituted hydrocarbyl 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 atoms in the cyclopentadienyl ring include halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylboride radicals, and the like. Examples of cyclopentadienyl ring groups (C.sub.5 H.sub.5-y-x R.sub.x) 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 (C.sub.5 H.sub.5-y-x R.sub.x).
Suitable R' radicals of the heteroatom J ligand are independently a hydrocarbyl radical selected from a group consisting of 1 to about 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and the like; substituted C.sub.1 -C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, and alkylborido radical, or other radical containing a Lewis acidic or basic functionality, and the like. Examples of heteroatom ligand groups (JR'.sub.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'.sub.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 Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu)ZrCl.sub.2 has greater steric requirements than the phenyl group in Me.sub.2 Si(Me.sub.4 C.sub.5) (NPh)ZrCl.sub.2.Et.sub.2 O thereby not permitting ether coordination in the former compound. Similarly, due to the decreased steric bulk of the trimethylsilylcyclopentadienyl group in [Me.sub.2 Si(Me.sub.3 SiC.sub.5 H.sub.3) (N-t-Bu)ZrCl.sub.2 ].sub.2 versus that of the tetramethylcyclopentadienyl group in Me.sub.2 Si(Me.sub.4 C.sub.5) (N-t-Bu)ZrCl.sub.2, the former compound is dimeric and the latter is not.
TABLE 1__________________________________________________________________________ ##STR5##T (when y = 1)         (C.sub.3 H.sub.3-y-a R.sub.a)                             (JR'.sub.a-l-y)                                         Q          R__________________________________________________________________________dimethylsilyl cyclopentadienyl     .sub.- t-butylamide                                         hydride    zirbonium.diethylsilyl  methylcyclopentadienyl                             phenylamido chloro     hafniumdi- -n-propylsilyl         1,2-dimethylcyclopentadienyl                             p- -n-butylphenylamido                                         methyl     titaniumdiisopropylsilyl         1,3-dimethylcyclopentadienyl                             cyclohexylamido                                         ethyldi- -n-butylsilyl         indenyl             perflurophenylamido                                         phenyldi- .sub.- 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- .sub.- t-butylphenethylsilyl)          -n-octylcyclopentadienyl                             benzylamido  -n-butyl -n-hexylmethylsilyl         &#946;-phenylpropylcyclopentadienyl                              .sub.- t-butylphosphido                                         amylcyclopentamethylenesilyl         tetrahydroindenyl   ethylphosphido                                         isoamylcyclotetramethylenesilyl         propylcyclopentadienyl                             phenylphosphido                                         hexylcyclotrimethylenesilyl          .sub.- t-butylcyclopentadienyl                             cyclohexylphosphido                                         isobutyldimethylgermanyl         bensylcyclopentadienyl                             oxo (when y = 1)                                         heptyldiethylgermanyl         diphenylmethylcyclopentadienyl                             sulfido (when y = 1)                                         octylphenylamido   trimethylgermylcyclopentadienyl                             methoxide (when y = 0)                                         nonyl .sub.- t-butylamido         trimethylstannylcyclopentadienyl                             ethoxide (when y = 0)                                         decylmethylamido   triethylplumbylcyclopentadienyl                             methylthic (when y = 0)                                         cetyl .sub.- t-butylphosphido         trifluromethylcyclopentadienyl                             ethylthic (when y = 0)                                         methoxyethylphosphido         trimethylsilylcyclopentadienyl  ethoxyphenylphosphido         pentamethylcycloopentadienyl (when y = 0)                                         propoxymethylene     fluorenyl                       butoxydimethylmethylene         octahydrofluoroxyl              phenoxydiethylmethylene         N,N-dimethylamidocyclopentadienyl                                         dimethylamideethylene      dimethylphosphidocyclopentadienyl                                         diethylamidedimethylethylene         methoxycyclopentadienyl         methylethylamidediethylethylene         dimethylboridocyclopentadienyl  di- .sub.- t-butylamidedipropylethylene         (N,N-dimethylamidomethyl)-      diphenylamidepropylene     cyclopentadienyl                diphenylphosphidedimethylpropylene                             dicyclophoxyl-diethylpropylene                              phosphide1,1-dimethyl-3,3-                             dimethylphosphidedimethylpropylene                             methylidene (both Q)tetramethyldisiloxane                         ethylidene (both Q)1,1,4,4-tetramethyldisilyl-                   propylidene (both Q)ethylene                                      ethyleneglycoldianion                                         (both Q)__________________________________________________________________________
Generally, wherein it is desired to produce an α-olefin copolymer which incorporates a high content of α-olefin, 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 R.sup.1 and R.sup.2 are each independently a C.sub.1 to C.sub.20 hydrocarbyl radicals, substituted C.sub.1 to C.sub.20 hydrocarbyl radicals wherein one or more hydrogen atom is replaced by a halogen atom; R.sup.1 and R.sup.2 may also be joined forming a C.sub.3 to C.sub.20 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 (R.sup.3 --Al--O).sub.m which is a cyclic compound, or may be R.sup.4 (R.sup.5 --Al--O--).sub.m --AlR.sup.6.sub.2 which is a linear compound. An alumoxane is generally a mixture of both the linear and cyclic compounds. In the general alumoxane formula R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are, independently a C.sub.1 -C.sub.5 alkyl radical, for example, methyl, ethyl, propyl, butyl or pentyl and "m" is an integer from 1 to about 50. Most preferably, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 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 R.sup.3-6 groups may be halide.
Inert Support The normally hydrocarbon soluble transition metal component and alumoxane are prepared as a supported catalyst by deposition on a support material. The support material for preparing the supported catalyst may be any resinous support material such as a polyolefin or any finely divided inorganic solid porous support, such as talc, silica, alumina, silica-alumina, or mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with silica or silica-alumina are magnesia, titania, zirconia, and the like. The inorganic oxides may be dehydrated, as is well known in the art, to remove water. If desired, the residual surface hydroxyl groups in the inorganic solid porous support may be removed by additional heating or by reaction with chemical dehydrating agents such as lithium alkyl, silylchlorides, aluminum aklyls, or preferably with alumoxane. Preferred catalyst supports include dehydrated inorganic oxide treated with an alumoxane, more preferably with methylalumoxane. A suitable support material of this type is a dehydrated silica gel treated with methylalumoxane. When such a alumoxane-treated support is utilized in the production of the supported catalyst, it may not be necessary to include additional alumoxane in the catalyst composition. Also preferred as a catalyst support is a wet gel, more preferably a wet silica gel, containing up to approximately 20% by weight absorbed water. Wet gels may be directly mixed with trialkyl aluminums to form the alumoxane component of the catalyst system.
Catalyst Systems-Method and Use The Supported Catalyst--Preparation Method 1 The supported catalyst of this invention can be prepared by combining in any order the Group IV B transition metal component, an alumoxane component, and the support in one or more suitable solvents or diluents. Suitable solvents and/or diluents include, but are not necessarily limited to, straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and the like; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcyclopentane and the like; and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and the like.
The Modified Supported Catalyst--Preparation Method The modified supported catalyst of this invention can be prepared by combining in any order the Group IV B transition metal component, an alumoxane component, a modifier and the support in one or more suitable solvents or diluent. A modifier may be defined as a compound containing a Lewis acid or basic functionality, such as, for example, tetraethoxysilane, phenytriethyoxysilane bis-tert-butylhydroxytoluene (BHT), N,N-dimethylanaline and the like. Suitable solvents and/or diluents are the same as those described above.
In a preferred method, the alumoxane and the modifier are combined in a first step in a suitable solvent such as an aromatic solvent to produce a solution. The Group IV B transition metal compound is then added to this solution. These combined steps may be carried out in the temperature range of -100 Holding times to allow for the completion of the reaction may range from about 10 seconds to about 60 minutes depending on the reaction variables.
The Supported Catalyst--Preparation Method 3 In an alternative procedure the alumoxane component of the catalyst complex is prepared by direct reaction of a trialkyl aluminum or trialkyl aluminum mixtures with the material utilized as the catalyst support, such as an undehydrated silica gel. Silica useful as the catalyst support is that which has a surface area in the range of about 10 to about 700 m.sup.2 /g, preferably about 100-500 and desirably about 200-400 m.sup.2, a pore volume of about 3 to about 0.5 cc/g and preferably 2-1 cc/g, and an adsorbed water content of from about 6 to about 20 weight percent, preferably from about 9 to about 15 weight percent. The average particle size (APS) of the silica may be from about 0.3.mu. to about 100μ, and for a gas phase catalyst preferably from about 30μ to about 60μ (1μ=10.sup.-6 m). For a catalyst intended for high pressure polymerization the particle size of the silica should range from about 0.3 to no greater than about 10μ. Hereafter, silica having the above identified properties is referred to as undehydrated silica gel.
A slurry polymerization process can utilize sub-or super-atmospheric pressures and temperatures in the range of -80 slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization medium to which ethylene, α-olefin, diolefin, cyclic olefin or acetylenically unsaturated comonomer, hydrogen and catalyst are added. Alkanes and cycloalkanes, such as butane, pentane, hexane, or cyclohexane, are preferred with C.sub.4 to C.sub.10 alkanes especially preferred. Preferred solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene and the like.
A gas-phase polymerization process utilizes superatmospheric pressure and temperatures in the range of about 50 polymerization can be performed in a stirred or fluidized bed of catalyst and product particles in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, including α-olefins, diolefins, cyclic olefins or acetylenically unsaturated comonomer, hydrogen and an inert diluent gas such as nitrogen can be introduced or recirculated so as to maintain the particles at a temperature of 50 can be withdrawn continuously or semicontinuously at a rate such as to maintain a constant product inventory in the reactor. After polymerization and deactivation of the catalyst, the product polymer can be recovered by any suitable means. In commercial practice, the polymer product can be recovered directly from the gas phase reactor, freed of residual monomer with a nitrogen purge, and used without further deactivation or catalyst removal. The polymer obtained can be extruded into water and cut into pellets or other suitable comminuted shapes. Pigments, antioxidants and other additives, as is know in the art, may be added to the polymer.
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