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US5486585A - Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts. - Google Patents
Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts. Download PDF
US5486585A
US5486585A US08112491 US11249193A US5486585A US 5486585 A US5486585 A US 5486585A US 08112491 US08112491 US 08112491 US 11249193 A US11249193 A US 11249193A US 5486585 A US5486585 A US 5486585A
US08112491
Disclosed is a mono- or di-amido siladiyl bridged composition of matter useful as a catalyst component for the homo or copolymerization of olefins.
This invention relates generally to bridged catalyst systems and more particularly to bridged transition metal catalyst components having mono or di-amido siladiyl bridging groups. The invention also relates to methods of making and using the catalyst components.
For example, Hoechst AG, of Germany, discloses carbon bridged indenyl catalyst components which are chiral and useful for the production of high molecular weight isotactic polypropylene ("IPP") (EPA 413,326; EPA 485,822; EPA 485,823; U.S. Pat. No. 4,769,510 and U.S. Pat. No. 5,145,819). EPA 485,821 discloses indenyl catalyst components bridged with carbon-silicon, germanium-silicon, or tin-silicon combination of atoms. These catalyst components are useful in the production of IPP having a melting point of about 150° C. or greater.
Catalyst components having mono or diamido siladiyl bridging cyclopentadienyl groups are not well known. Jutzi, et al., disclosed in Chemical Ber, 1988, 121, 1299 preparation of a siladiyl-amine-bridge pentamethyl cyclopentadienyl derivative. However, this derivative is not a catalyst component, nor can it be converted to a cyclopentadienyl catalyst component since no transition metal is present.
It would be desirable to provide a novel catalyst component which can be useful for the polymerization of olefins or alpha-olefins wherein the catalyst component comprises mono- or diamido-siladiyl bridging atoms.
Accordingly, the present invention provides transition metal catalyst component comprising mono-or diamido-siladiyl bridged compositions useful as catalyst components for the polymerization of monomers, especially olefinic monomers. This invention provides a method for preparing such catalyst compositions. The inventive catalyst component is useful for the production of homo- or copolymers having varying molecular weights and melting points. The catalyst components yield polymers of relatively narrow molecular weight distribution. The catalyst component comprises a bridging group having at least one nitrogen bonded to a silicon atom, which silicon atom is bonded to at least one ligand coordinated with a transition metal.
The catalyst composition is represented by the general formula ##STR1## wherein L is an anionic ligand and can be the same or different
(i) Cpz ;
Cp is the same or different cyclopentadienyl ring substituted with from zero to four substitutent groups, each group being, independently, the same or different hydrocarbyl, substituted hydrocarbyl, silahydrocarbyl, halocarbyl, substituted halocarbyl, or taken together, two or more adjacent carbons form part of a ring structure having between 2 and 10 carbons.
R, R1, R2, R3 are the same or different hydrogen, halogen, C1-20 alkyl, C2-20 alkenyl, preferably C2-10 alkenyl, C6-20 aryl, preferably C6-10 aryl, C7-40 alkylaryl, preferably C7-20 alkylaryl, C7-40 arylalkyl, preferably C7-20 arylalkyl, C8-40 arylalkenyl, preferably C8-20 arylalkenyl, or taken together, two or more adjacent carbons form part of a ring structure having between 2 and 10 carbons, alkoxy, ketones, SiR, SiOR, NR, SR, AlR, PR;
An alternative embodiment of the composition is represented by general formula ##STR3## wherein L is a neutral ligand and can be the same or different
(i) Cpz ; or
Formula (3) may also be represented with the bridging structure of formula (2) for the diamido version of the siladiyl bridge derivative.
The prefered catalyst composition is represented by formula (4) ##STR4## wherein all symbols are as defined above. Formula (4) may also be represented with the bridging structure of formula (2) for the diamido version of the siladiyl bridge derivative.
Prefered silicon bridging group substituents, R, R1, R2, R3, R4 which are exemplified include: H, halogen, C1-20 alkyl, (CH3)2 N, ##STR5##
The catalyst system which comprises the siladiyl amine composition with an activator component may optionally be placed on a support (or carrier), according to known techniques, such as those described in U.S. Pat. No. 4,808,561 (Welborn), U.S. Pat. No. 4,871,705 (Hoel) or U.S. Pat. No. 5,240,894 (Burkhardt), all references herein incorporated by reference in their entirety. Supports include organic or inorganic solids. Exemplary supports include silica, alumina, silica-alumina and the like, or combinations thereof. Alternatively, the support may be a magnesium compound, such as MgCl2. Any support material is acceptable provided it does not adversely interfere with the catalyst component or catalyst system.
The catalyst system in accordance with this invention may be used to produce homo- or copolymers of polyolefins such as polyethylene, polypropylene, blends of ethylene/propylene or ethylene and higher alpha olefins (e.g., C4 -C20) or stereoregular polymers such as isotactic polypropylene. Monomers containing between about 2 to about 20 carbon atoms under suitable polymerization conditions may be employed. The monomers may be alpha olefins, olefins, diolefins, cyclic olefins or acetylenically unsaturated monomer(s). Preferred olefins include ethylene, propylene, 1-butene, isobutylene, 4-methyl-1-pentene, 1-hexene, 1-octene and mixtures thereof. Vinylidene monomers may also be employed, examples which include styrene, cyclohexene, cyclooctene, norbornene or ring alkyl or ring aryl derivatives. Generally the polymerization is carried out in bulk, gas, slurry, solution and high pressure phase reactors. Generally, the polymerization process is carried out with a pressure of from about 70 to about 7000 kPa (about 10 to about 1000 psi), most preferably from about 275 to about 4100 kPa (about 40 to about 600 psi). The polymerization diluent is maintained at a temperature of from about -10° C. to about 150° C., preferably from about 20° C. to about 100° C., and most preferably from about 30° C. to about 90° C. The catalyst system may also be employed in a high temperature/high pressure polymerization process where the presure can range from about 35 MPa to about 275 MPa (about 5,000-40,000 psi) and the temperature can range from about 120° to about 300° C. The polymerization may be carried out as a batch or continuation process.
The preparation of the amido siladiyl bridged catalyst composition of the present invention and use thereof are illustrated by way of the examples that follow.
The catalyst components of Examples 1-7 were reacted with MAO to form an active catalyst. Polymerization results employing these catalysts are in Table 2. The polymerization procedure, which employed a bulk phase reactor, at a pressure of about 30 kg/cm2 is as follows. In a clean, dry two liter stainless steel autoclave which had been flushed with propylene vapor, MAO (1.0 ml, 10% in toluene) was added and then the reactor closed and filled with 750 ml liquid propylene. The reactor was heated to the desired temperature, generally about 40° C., and the catalyst, prepared by reacting the transition metal component (10 mg in 1.0 ml toluene) with MAO (1.25 ml, 10% MAO in toluene), was washed in via an addition tube with 250 ml propylene. After the desired reaction time, usually about 30 minutes, the reactor was cooled and the excess propylene vented. The polymer was removed and dried.
Polymer analysis was carried out as described in U.S. Pat. No. 5,026,798 and U.S. Pat. No. 5,017,714. Tacticity measurements were determined by 13C NMR as described in "Polymer Sequence Distributions", J. C. Randall, Academic Press, New York, (1986). DSC melting points were determined on commercial DSC instruments and are reported as the second melting point.
EXAMPLE 1 (C8 H14 N) (CH3)Si(3-t-butylC5 H3)2 ZrCl2
Part 1. t-BuCpLi
MeLi (0.183 mol in ether) was added dropwise over 30 min to 6,6-dimethylfulvene (19.466 g, 0.183 mol) dissolved in ether (500 ml, dried over Na and freshly distilled) and cooled to 0° C. After stirring at room temperature for 3 days, the solvent was removed under vacuum. The residual solid was washed twice with n-pentane (200 ml) and dried under vacuum. (t-butylC5 H4)Li (20 g, 90%) was obtained as a white powder.
Part 2. Cl2 Si(3-t-BuCp)2
To SiCl4 (1.989 g, 0.0117 mol) dissolved in THF (200 ml), t-BuCpLi (3 g, 0.0234 mol) slurried in THF (50 ml) was added dropwise. After stirring at room temperature for 1.5 hrs, the solvent was removed under vacuum, and the residue extracted with n-pentane (200 ml). Cl2 Si(3-t-BuCp)2 (4.0 g, 100%) was obtained as a yellowish liquid after evaporation of the n-pentane.
Part 4. (C8 H14 N)(Cl)Si(3-t-BuCp)2
To Cl2 Si(t-BuCp)2 (2 g) dissolved in ether (200 ml) C8 H14 NLi (0.769 g) dissolved ether (100 ml) was added dropwise. After stirring overnight at room temperature the solvent was removed under vacuum, and the residue extracted with n-pentane (200 ml). (C8 H14 N)(Cl)Si(3-t-BuCp)2 (2.35 g, 93%) was obtained as a yellow, clear oil.
Part 5. (C8 H14 N)(Me)Si(3-t-BuCp)2 ZrCl2
To (C8 H14 N)(Cl)Si(3-t-BuCp)2 (2.35 g, 5.46×10-3 mol) dissolved in ether (200 ml) an ether solution of MeLi (0.0164 mol) was added dropwise. After stirring overnight at room temperature, the solution was cooled to 0° C. and ZrCl4 (1.273 g) was added. After stirring overnight, evaporation of ether, extraction with n-pentane, and recrystallization at -20° C., (C8 H14 N)(Me)Si(3-t-BuCp)2 ZrCl2, was obtained (0.1 g).
EXAMPLE 2 (C8 H14 N) (Me)Si(C9 H6)2 ZrCl2
Part 1. Indenyl Lithium ("INDLi")
Part 2, Cl2 Si(C9 H7)2
To SiCl4 (5.56 g) dissolved in ether (200 ml), INDLi (8 g) in ether was added dropwise and stirred overnight. By repeating the purification procedure in Example 1, Part 2, Cl2 Si(C9 H7)2 (10.3 g,96%) was obtained as a yellowish oily solid.
Part 3, (C8 H14 N)(Cl)Si(C9 H7)2
To Cl2 Si(C9 H7)2 (5.9 g) dissolved in ether (200 ml) an ether solution of C8 H14 NLi (2.35 g) was added. After stirring overnight at room temperature, the same purification procedure in Example 1 Part 4, was used. (C8 H14 N)(Cl)Si(C9 H7)2 (7 g, 93%) was obtained as a yellowish white waxy solid.
Part 4, (C8 H14 N)(Me)Si(C9 H6 Li)2
To (C8 H14 N)(Cl)Si(C9 H7)2 (3 g) dissolved in ether (200 ml), MeLi (0.0216 mol ) was added dropwise and stirred overnight. The purification procedure for t-BuCpLi in Example 1, Part 1, was used to give (C8 H14 N) (Me)Si(C9 H6 Li)2 (3.17 g,100%) as a pale pink powder.
Part 5, (C8 H14 N)(Me)Si(C9 H6)2 ZrCl2
To (C8 H14 N)(Me)Si(C9 H6 Li)2 (3.17 g) dissolved in ether (200 ml) and cooled to 0° C., ZrCl4 (1.807 g) was added and stirred at room temperature overnight. After evaporation of the ether, the residual solid was extracted with CH2 Cl2 (200 ml). Evaporation and twice washing with n-pentane (100 ml) gave (C8 H14 N)(Me)Si(C9 H6)2 ZrCl2 (2.4 g, 56%) as an orange/brown solid.
EXAMPLE 3 [(CH3)2 N]2 Si(3-methylcyclopentadienyl)2 ZrCl2
Part 1: (MeCpLi)
To a solution of SiCl4 (2.965 g) in THF (200 ml) MeCpLi (3 g) in THF was added dropwise over 30 minutes. After stirring for 90 minutes, the THF was evaporated under vacuum. The residue was extracted with n-pentane (200 ml). From the n-pentane solution Cl2 Si(3-MeCp)2 (4.06 g, 90%) was recovered.
Part 3: (Me2 N)2 Si(3-MeCp)2
To Cl2 Si(MeCp)2 (2 g) dissolved in ether (200 ml), Me2 NLi (0.794 g suspended in 50 ml of ether) was slowly added. After stirring overnight, the same purification procedure in Example 1, Part 2, was used to give (Me2 N)2 Si(3-MeCp)2 (2.0 g,94%) as a yellow, oily liquid.
Part 4: (Me2 N)2 Si(3-MeCpLi )2
To (Me2 N)2 Si(3-MeCp)2 (2.0 g) dissolved in ether (200 ml), MeLi (0.0146 mol) in ether was added dropwise. After stirring overnight, the solvent was evaporated. The residual solid was washed twice with n-pentane (100 ml) and dried under vacuum to give ((Me2 N)2 Si(3-MeCpLi)2 (2.1 g) as a white powder.
Part 5: (Me2 N)2 Si(3-MeCp)2 ZrCl2
To (Me2 N)2 Si(3-MeCpLi)2 (2.1 g) dissolved in ether (200 ml) and cooled to 0° C., ZrCl4 (1.705 g) was added, and the reaction mixture stirred for 3 days at ambient temperature. After evaporation of the solvent, the residue was extracted with pentane to give (Me2 N)2 Si(MeCp)2 ZrCl2 (0.96 g).
EXAMPLE 4 (C8 H14 N) (methyl)Si(2-methylindenyl)2 ZrCl2
Part 1: 2-methylindene
To an ether solution of MeMgBr (260 ml, 3M) diluted with ether (300 ml) and cooled to 03 C, 2-methylindanone (99.16 g) was added dropwise as an ether solution over 2.5 hours. After stirring 2.0 hours, the reaction mixture was hydrolyzed with aqueous HCl. The water phase was separated and extracted twice with ether (300 ml). The combined organic phases were dried over sodium sulfate. Evaporation of the solvent gave a crude brown product (107 g) which was distilled under reduced pressure to give 2-methyl-2-indanol (66.2 g) as a white crystalline solid.
2-Methyl-2-indanol (66.2 g) was dissolved in toluene (500 ml) in a 1 liter flask equipped with a Dean-Stark trap. To this solution p-toluene sulfonic acid (2 g) and a small amount of hydroquinone were added, and the mixture was refluxed for 2.5 hours. After 8 ml of H2 O was generated, the reaction mixture was cooled to 0° C. and H2 O (1 liter), also cooled to 03 C, was added. The organic phase was separated and washed three times with water (500 ml). The toluene was evaporated and the residue (with trace of hydroquinone added) was distilled at reduced pressure to give 2-methylindene (47.2 g, 48%) as clear slightly green liquid.
Part 3: Cl2 Si(2-Me-IND)2
The procedure of Example 1, Part 2, was followed except using SiCl4 (2.5 g) and 2-MeINDLi (4 g). Cl2 Si(2-MeIND)2 (4.79 g, 91%)) was obtained as a yellowish, slightly waxy solid.
Part 4: (C8 H14 N) (Me)Si(2-Me-INDLi)2
The preparation procedures Example 2, Part 3, and Part 4 was repeated except using Cl2 Si(2-Me-IND)2 (4.79 g) in place of Cl2 Si(IND)2. (C8 H14 N)(Me)Si(2-Me-INDLi)2 (5.55 g) was recovered as a pale yellow powder.
Part 5: (C8 H14 N)(Me)Si(2-Me-IND)2 ZrCl2
ZrCl4 (2,635 g) was suspended in CH2 Cl2 (300 ml) and cooled to -78° C. To this suspension, (C8 H14 N)(Me)Si(2-MeIND)2 (5.55 g) was added and stirred at -78° C. for 8 hours. After raising to -30° C., the mixture was allowed to warm to room temperature overnight. The mixture was dried, and the residue extracted with CH2 Cl2 for six days to give [(C8 H14 N)(Me)Si(2-Me-IND)2 ZrCl2 ] as an orange powder (3.7 g).
EXAMPLE 5 (CH3)2 N]2 Si(2-methyl-Indenyl)2 ZrCl2 synthesis
Part 1: (Cl2 Si(2-Me-IND)2
The procedure in Example 4, Part 3, was repeated except using SiCl4 (5 g) and 2-MeINDLi (8 g) to gave Cl2 Si(2-methylIND)2 (9.36 g, 89%).
Part 2: (Me2 N)2 Si(2-Me-IND)2
Following the procedure in Example 3, Part 3, except using Cl2 Si(2-Me-IND)2 (4.73 g) and Me2 NLi (1.42 g), gave (Me2 N)2 Si(2-MeIND)2 (4 g) as a yellow oil.
Part 3: Me2 N)2 Si(2-Me-INDLi)2
Following the procedure of Example 3, Part 4, except using (Me2 N)2 Si(2-MeIND)2 (4 g), and MeLi (0.0216 mol) gave (Me2 N)2 Si(2-Me-INDLi)2 (4 g, 97%) as a white powder.
Part 4: (Me2 N)2 Si(2-Me-IND)2 ZrCl2
Following the procedure of Example 4, Part 5 was repeated except using (Me2 N)Si(2-Me-INDLi) (4 g) and ZrCl4 (2.425 g). The CH2 Cl2 solution was filtered and evaporated. The residue was washed with n-pentane (100 ml) and dried to gave a yellow powder (4.6 g, 83%).
The polymer (9.17 g) obtained from polymerization run of Example 5 and 300 ml of n-heptane were introduced to a 500 ml round bottom flask connected with a reflux condenser. After 2 hours of reflux, the solution was decanted while hot. 300 ml of fresh n-heptane was introduced to the residual polymer and the 2 hour reflux repeated. After filtration and drying, 2.7 g of n-heptane insoluble polymer was recovered. From the n-heptane solution, a total of 6.2 g of gummy polymer was recovered (Tm=147.5° C., Mw=480,000, Mw/Mn=2.6).
EXAMPLE 6 (C4 H8 N)2 Si(2-methyl-indenyl)2 ZrCl2
Part 1: (C4 H8 NLi)
Part 2: (C4 H8 N)2 Si(2-ME-IND)2
The procedure of Example 5, Part 2, was repeated except with Cl2 Si(2-Me-IND)2 (4.6 g) and C8 H14 NLi (1.99 g) to give (C4 H8 N)2 Si(2-MeIND)2 (5.72 g) as an oil.
Part 3: (C4 H8 N)2 Si(2-Me-INDLi)2
The procedure of Example 3, Part 4, as repeated except with (C4 H8 N)2 Si(2-Me-IND)2 (5.72 g) and MeLi (0.0258 mol) to give (C4 H8 N)2 Si(2-Me-INDLi)2 (5.42 g, 96%) as pale yellow powder.
Part 4: (C4 H8 N)2 Si(2-Me-IND)2 ZrCl2
The procedure in Example 5, Part 4, was repeated except using ZrCl4 (2.9 g) to give (C4 H8 N)2 Si(2-Me-IND)2 ZrCl2 as a yellow-orange powder (5.6 g).
1 gram of (C4 H8 N)2 Si(2-Me-IND)2 ZrCl2 having 68% rac content was dissolved in 30 mls of methylene chloride solvent. 10 mls of n-pentane was added to the solution and stirred for 15 minutes. The solvent was stripped off via vacuum until crystals begun to appear at which point the mixture was placed in freezer and chilled at -30° C. for about 1 hr. The crystals were isolated in a frit, washed with cold pentane and collected. The procedure was repeated utilizing the collected filtrate until no further crystals appeared (0.7 g, 92% rac content).
A. Catalyst Preparation: The catalyst component of Example 6 (4.8 mg., 8.19×10-3 mmoles) was pre-activated just prior to the polymerization run with 2.0 mls of a 1M MAO/toluene solution. An additional 10.2 mls of the MAO solution was prepared separately.
B. Polymerization Procedure: Toluene, 400 ml., distilled from benzophenone/sodium then passed through an alumina column while under a nitrogen atmosphere, was added to a 1-liter zipperclave reactor at room temperature. The reactor was then cooled to 0° C., using an IPA bath chiller. A 1M MAO solution (10.2 ml.) was then cannulated into the reactor and allowed to stir for approximately 30 seconds. The pre-activated catalyst solution then followed in the same manner.
While stirring this solution a 60/40 EP monomer mixture (11.08 g.) was allowed to flow into the reactor at a rate of approximately 6.8 kPa/sec (about 1 psi/second). The EP mixture was premixed in a 1 liter stainless steel vessel. Samples were taken at various intervals via a sampling tube connected to the reactor vessel. The reaction was allowed to proceed for 45 minutes at which a conversion of 38.3% was yielded. There was no exotherm during the polymerization. The recovered EP polymer was precipitated in acetone and was completely amorphous.
EXAMPLE 7 (dicyclohexylamino)2 Si(2-methylindenyl)2 ZrCl2
Part 1: Cl2 Si(2-Me-IND)2
The procedure in Example 5, Part 1 was repeated to give Cl2 Si(2-Me-IND)2 (10.3 g, 98%).
Part 2: (c-C6 H11)2 N](Cl)Si(2-Me-IND)2
The procedure of (C4 H8 N)2 Si(2-ME-IND)2 in Example 6 was repeated employing 5.14 g of Cl2 Si(2-Me-Ind)2 and 2.70 g of (C6 H11)2 NLi. A brown product was obtained. (7.92 g, 110%).
The above procedure was repeated using (C6 H11)2 NLi (1.348 g) to give [c-C6 H11)2 N](Cl)Si(2-MeIND)2 and CH2 Cl2 as extraction solvent to give brown oil (4.66 g). (Yield=100%)
Part 4: [(C6 H11)2 N]2 Si(2-Me-IND)2)Li2
The procedure Example 6,. Part 4, was repeated except using (C6 H11 N)2 Si(2-MeIND)2 (4.66 g) and MeLi (0.0145 mol) to give a light brown powder (2.6 g, 55%)
Part 5: [(C6 H11)2 N]2 Si(2-Me-IND)2 ZrCl2
The procedure in Example 5, Part 4, was repeated except using [(C6 H11)2 N]2 Si(2-Me-IND)2 Li (2.6 g) and ZrCl4 (1.7 g) to give [(C6 H11)2 N]2 Si(2-MeIND)2 ZrCl2 as a brown powder (2.6 g).
TABLE 1______________________________________Tacticity Measurements for decaline fractionatedPolymer of Example 5Label   Whole       Insoluble  SolubleCol.    Polymer     (IPP region)                          (atactic region)______________________________________[mm]    0.498       0.947      0.243[mr]    0.364       0.034      0.496[rr]    0.138       0.019      0.260______________________________________
TABLE 2______________________________________Results of Polymerzation Runs with CatalytComponent of Ex. 1-7         DSC MP Mw         (°C.)                (× 10.sup.-3)______________________________________EXAMPLE 1       142.5     48EXAMPLE 2       138.3     50EXAMPLE 3       --        6EXAMPLE 4       149.2    300EXAMPLE 5       152.6    500EXAMPLE 6       149.5    600EXAMPLE 7       147.5    300______________________________________ Conditions: 1.0 liter liq. C.sub.3 ═, 40° C., 1.0 ml 10% MAO a scavenger, 10 mg transition metal catalyst component mixed with 1.25 ml 10% MAO
1. A polymerization catalyst system comprising a transition metal catalyst component represented by the formulae: ##STR7## wherein L is an anionic ligand and can be (i) Cp;
X is the same or different hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, C1-20 alkyl, C2-20 alkenyl, C6-20 aryl, C7-40 alkyaryl, C7-40 arylalkyl, C8-40 arylalkenyl, alkoxy, aryloxy, siloxy, or amide radicals or combinations thereof;
Cp is the same or different cyclopentadienyl ring substituted with from zero to four substituent groups, each group being, independently, the same or different hydrocarbyl, substituted hydrocarbyl, hydrocarbyl substituted silyl group, halocarbyl, substituted halocarbyl, or taken together, two or more adjacent substituents form part of a ring structure having between 2 and 10 carbons;
m is equal to or greater than 2 and is equal to the oxidation state of the transition metal;
R, R1, R2, R3, R4 are the same or different hydrogen, halogen, C1-20 alkyl, C2-20 alkenyl, C6-20 aryl, C7-40 alkylaryl, C7-40 arylalkyl, C8-40 arylalkenyl, or taken together, two or more adjacent substituents form part of a ring structure having between 2 and 10 carbons;
a=b=1, or a=0 when b=2;
and a catalyst activating compound.
2. The catalyst system of claim 1 wherein the transition metal catalyst component is represented by the formulae ##STR8## wherein L, Cp, M, X, m, Ra, R1, R2, R3, R4, Si, N, a, and b are as defined in claim 1.
3. The catalyst system of claim 1 wherein M is Group 4 transition metal.
4. The catalyst system of claim 1 wherein R, R2, R3, and R4 are selected from the group consisting of
C1-20 alkyl, H, halogen, (CH3)2 N, ##STR9##
5. The catalyst system of claim 1 wherein the transition metal catalyst component is selected from the group consisting of
(Me2 N)2 Si(t-BuCp)2 ZrCl2, ##STR10## wherein Me=methyl, Ind=indenyl, and Bu=butyl.
6. The catalyst system of claim 1 wherein the catalyst activating compound is alumoxane.
7. The catalyst system of claim 1 wherein the catalyst activating compound is methylalumoxane.
8. The catalyst system of claim 1 wherein the catalyst activating compound is a single or mixed compound that will form a charge balanced catalytic species.
9. The catalyst system of claim 8 wherein the catalyst activating compound is a compound comprising a non coordinating anion.
10. The catalyst system of claim 9 wherein the non coordinating anion is tetra(pentafluorophenyl)boron.
11. The catalyst system of claim 8 wherein the catalyst activating compound is tris(pentafluorophenyl)borane.
12. The catalyst system of claim 1 placed on a support.
13. The catalyst system of claim 12 wherein the support is silica, alumina, or combinations thereof.
14. The catalyst system of claim 12 wherein the support is a magnesium compound.
15. The catalyst system of claim 12 prepolymerized with olefinic monomer having from about 2 to about 20 carbon atoms.
16. A process for polymerizing one or more monomers having between about 2 to about 20 carbon atoms comprising contacting the monomer(s) under suitable polymerization conditions with the catalyst system of claim 1.
17. The process of claim 16 wherein the monomers are alpha olefins, olefins, diolefins, cyclic olefins or acetylenically unsaturated monomer(s).
18. The process of claim 17 wherein an additive is employed during polymerization.
19. The process according to claim 16 wherein polymerization conditions are selected from bulk, gas, slurry, solution and high pressure phase polymerization.
US08112491 1993-08-26 1993-08-26 Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts. Expired - Lifetime US5486585A (en)
US08112491 US5486585A (en) 1993-08-26 1993-08-26 Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts.
EP19940925817 EP0739361B1 (en) 1993-08-26 1994-08-10 Amido siladiyl bridged catalyst components, methods of making and using
PCT/US1994/009054 WO1995006071A1 (en) 1993-08-26 1994-08-10 Amido siladiyl bridged catalyst components, methods of making and using
DE1994620975 DE69420975T2 (en) 1993-08-26 1994-08-10 Amido siladiylverbrückte catalyst component, methods for production and use
DE1994620975 DE69420975D1 (en) 1993-08-26 1994-08-10 Amido siladiylverbrückte catalyst component, methods for production and use
ES94925817T ES2139094T3 (en) 1993-08-26 1994-08-10 catalyst components bridged amido siladiyl, method of manufacture and use.
US08515627 US5541350A (en) 1993-08-26 1995-08-16 Amido silyldiyl bridged catalyst components, methods of making and using
US08515627 Division US5541350A (en) 1993-08-26 1995-08-16 Amido silyldiyl bridged catalyst components, methods of making and using
US5486585A true US5486585A (en) 1996-01-23
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US08112491 Expired - Lifetime US5486585A (en) 1993-08-26 1993-08-26 Amidosilyldiyl bridged catalysts and method of polymerization using said catalysts.
US08515627 Expired - Lifetime US5541350A (en) 1993-08-26 1995-08-16 Amido silyldiyl bridged catalyst components, methods of making and using
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WO (1) WO1995006071A1 (en)
WO1998045039A1 (en) * 1997-04-04 1998-10-15 The Regents Of The University Of California Polymerization catalysts containing electron-withdrawing amide ligands
US6002033A (en) * 1995-11-22 1999-12-14 Fina Research, S.A. Bridged metallocenes for use in catalyst systems
US6177529B1 (en) 1994-11-22 2001-01-23 Fina Research, S.A. Polymerization of olefins with bridged metallocene catalysts
ES2139383T3 (en) * 1995-10-27 2000-02-01 Dow Chemical Co Metal complexes supported easily.
DE19642354A1 (en) * 1996-10-14 1998-04-16 Basf Ag Metal complexes with adamantanähnlicher structure
CN1152891C (en) * 1998-10-08 2004-06-09 英国石油化学品有限公司 Bridged metal complexes for gas phase polymerizations
JPH05230135A (en) * 1992-02-24 1993-09-07 Mitsui Toatsu Chem Inc Production of polyolefin with broad molecular weight distribution
Jutzi, et al., "Mono-and Bis(η1 -pentamethylcycopentadienyl)silane-Synthese, Stuktur and Eigenschaften," Chemical Ber, 121, pp. 1299-1305, Weinheim, 1988.
Jutzi, et al., Mono and Bis( 1 pentamethylcycopentadienyl)silane Synthese, Stuktur and Eigenschaften, Chemical Ber, 121, pp. 1299 1305, Weinheim, 1988. *
Kaminsky, W., "Metallocene Catalysts", SP '92-Polyethlene World Congress, Zurich, 1992, pp. 1-20.
Kaminsky, W., Metallocene Catalysts , SP 92 Polyethlene World Congress, Z rich, 1992, pp. 1 20. *
Sax Irving N. and Richard J. Lewis, Sr. (eds.), "Periodic table of the elements", Hawley's Condensed Chemical, p. 6.
Sax Irving N. and Richard J. Lewis, Sr. (eds.), Periodic table of the elements , Hawley s Condensed Chemical, p. 6. *
US6335303B1 (en) * 1997-04-04 2002-01-01 The Regents Of The University Of California Polymerization catalysts containing electron-withdrawing amide ligands
US6960676B2 (en) 2000-02-08 2005-11-01 Exxonmobil Chemical Patents Inc. Method of preparing group 14 bridged biscyclopentadienyl ligands
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