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US6380334B1 - Metallocene compositions - Google Patents
Metallocene compositions Download PDF
US6380334B1
US6380334B1 US09619757 US61975700A US6380334B1 US 6380334 B1 US6380334 B1 US 6380334B1 US 09619757 US09619757 US 09619757 US 61975700 A US61975700 A US 61975700A US 6380334 B1 US6380334 B1 US 6380334B1
US09619757
William T. Haygood
R1 and R2 are identical or different, and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C2-C40 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, or a halogen atom, or are a conjugated diene which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30 atoms not counting hydrogen;
R5 and R6 are identical or different, are one of a hydrogen atom, a halogen atom, a C1-C10 alkyl group, which may be halogenated, a C6-C10 aryl group, which may be halogenated, a C2-C10 alkenyl group, a C7-C40 -arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a —NR2 15, —SR15, —OR15, —OSiR3 15 or —PR2 15 radical, wherein: R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group,;
R3 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 -arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a —NR′2, —SR, —OR, —OSiR′3 or —PR′2 radical, wherein: R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
R1 and R2 are identical or different, preferably identical, and are one of a hydrogen atom, a C1-C10 alkyl group, preferably a C1-C3 alkyl group, a C1-C10 alkoxy group, preferably a C1-C3 alkoxy group, a C6-C10 aryl group, preferably a C6-C8 aryl group, a C6-C10 aryloxy group, preferably a C6-C8 aryloxy group, a C2-C10 alkenyl group, preferably a C2-C4 alkenyl group, a C7-C40 arylalkyl group, preferably a C7-C10 arylalkyl group, a C7-C40 alkylaryl group, preferably a C7-C12 alkylaryl group, a C8-C40 arylalkenyl group, preferably a C8-C12 arylalkenyl group, or a halogen atom, preferably chlorine; R1 and R2 may also be joined together to form an alkanediyl group or a conjugated C4-40 diene ligand which is coordinated to M1 in a metallocyclopentene fashion; R1 and R2 may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienes having up to 30 atoms not counting hydrogen and forming a π complex with M, examples include, but are not limited to: 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl- 1,3-butadiene.
R3 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 -arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a —NR′2, —SR′, —OR, —OSiR′3 or —PR′2 radical, wherein: R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; preferably R3 is not a hydrogen atom;
preferably each R3 is identical and is a fluorine, chlorine or bromine, atom, a C1-C4 alkyl group which may be halogenated, a C6-C8 aryl group which may be halogenated, a —NR′2, —SR′, —OR, —OSiR′3 or —PR′2 radical, wherein: R is one of a chlorine atom, a C1-C4 alkyl group, or a C6-C8 aryl group;
rac-9-silafluorendiyl(2-n-butyl4-phenylindenyl)2zirconium dichloride;
rac-9-silafluorendiyl(2-ethyl4-phenylindenyl)2hafnium dimethyl;
rac-9-silafluorendiyl(2-ethyl, 4-[31,5′-di-tbutylphenyl]indenyl)2hafnium dimethyl;
rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride;
rac-9-silafluorendiyl(2-ethyl, 4-[3′,5 ′-di-iso-propylphenyl]indenyl)2hafnium dichloride;
rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2zirconium η4-1,4-diphenyl- 1,3-butadiene;
rac-9-silafluorendiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)2zirconium η4-1,4-diphenyl-1,3-butadiene; rac-9-silafluorendiyl(2-methyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2zirconium η4-1,4-diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-iso-butyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2zirconium η4-1,4diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-sec-butyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)2zirconium Ti_-1,4-diphenyl-1,3-butadiene;
rac-9-silafluorendiyl(2-iso-propyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2zirconium η-1,4-diphenyl-1,3-butadiene;
Where the metal ligands include halogen moieties (for example, bis-cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (each incorporated herein by reference) fir in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
Preferably the support material is porous silica which has a surface area in the range of from 10 to 700 m2/g, a total pore volume in the range from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 μm. More preferably, the surface area is in the range of from 50 to 500 m2/g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 μm. Most desirably the surface area is in the range of from 100 to 400 m2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and the average particle size is in the range of from 30 to 100 μm. The average pore size of typical porous support materials is in the range of from 10 to 1000 Å. Preferably, a support material is used that has an average pore diameter of from 50 to 500 Å, and most desirably from 75 to 350 Å. It may be particularly desirable to dehydrate the silica at a temperature of from 100° C. to 800° C. anywhere from 3 to 24 hours.
The metallocene, activator ans support material may be combined in any number of ways. More than one metallocene may also be used. Examples of suitable support techniques are described in U.S. Pat. Nos. 4,808,561 and 43,701,432 (each fully incorporated herein by reference). Preferably the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U.S. Pat. No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference). Alternatively, the metallocenes may be preactivated separately and the combined with the support material either separately or together. If the metallocenes are separately supported, the preferably, they are dried then combined as a powder before use in polymerization.
Regardless of whether the metallocene(s) and their activator are separately precontacted or whether the metallocene(s) and activator are combined at once, in some instances it may be preferred that the total volume of reaction solution applied to porous support is less than 4 times the total pore volume of the porous support, more preferably less than 3 times the total pore volume of the porous support and even more preferably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental Methods in Catalyst Research, Academic 5 Press, 1968, pages 67-96.
Typically, the metallocene is used in the polymerization in a concentration, based on the transition metal, of from 10−3 to 10−8 mol, preferably from 10−4 to 107 mol, of transition metal per dm3 of solvent or per dm3 of reactor volume. When alumoxane is used as the cocatalyst, it is used in a concentration of from 10−5 to 10−1 mol, preferably from 10−4 to 10−2 mol, per dm3 of solvent or per dm3 of reactor volume. The other cocatalysts mentioned are used in an approximately equimolar amount with respect to the metallocene. In principle, however, higher concentrations are also possible.
All air sensitive experiments are carried out in nitrogen purged dry boxes. All solvents were purchased from commercial sources. 4-Bromo-2-methyl indene, 4-chloro-2-methyl-indene and tris (perfluorophenyl) borane in toluene were purchased from commercial sources. Aluminum alkyls were purchased as hydrocarbon solutions from commercial sources. The commercial methylalumoxane (“MAO”) was purchased from Albemarle as a 30 wt % solution in toluene. The metallocenes racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2zirconium dichloride and racemic dimethylsiladiyl(4-[1-naphthy]-2-methylindenyl)2 zirconium dichloride were obtained from commercial sources.
4-Chloro-2-methylindene (6.1 g, 37 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-Di-t-butylphenylmagnesium bromide (10 g, 37 mmol) as a Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield was 4.6 g (40%).
Supported Metallocene Catalyst System 3 Racemic 19-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]zirconium Dichloride
Example 4 Racemic [9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2isopropylindene]zirconium Dichloride 4-[3′,5′-di-t-butylphenyl]-2-isopropylindene
4-Chloro-2-isopropylindene (7.2 g, 37 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-Di-di-t-butylphenylmagnesium bromide (10 g, 37 mmol) as a Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield is 5.8 g (45%).
4-chloro-2-isopropylindene (10 g, 54 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) were dissolved in 150 mL of Et2O. 3,5-Dimethylphenylmagnesium bromide (54 mmol) as a Et20 solution was added under vigorous stirring and the reaction stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
A slurry of 9-Silafluorene, 9,9-bis-2-Methylindene (3.80 g, 8.66 mmol) in Et2O (ca. 25 mL) was treated with n-butyllithium (12 mL of a 1.6 M solution in hexanes) and the resultant mixture stirred for 1 hour at room temperature producing a pale yellow precipitate. The mixture was filtered to isolate the pale yellow solid which was dried under vacuum giving 9-Silafluorene, 9,9-bis-2-Methylindenyl dilithium·(Et2O)0.5 (3.80 g, 88%).
A mixture of 9-Silafluorene, 9,9-bis-2-Methylindenyl dilithium·(Et2O)0.5 (1.83 g, 3.69 mmol) and ZrCl4 (0.95g, 4.08 mmol) in benzene (ca. 25 mL) was stirred for 80 minutes at room temperature producing an orange solid. The mixture was filtered and the orange solid was washed with hexane. Upon mixing with the benzene filtrate, the hexane wash produced a yellow solid and this mixture was filtered to remove the yellow solid. The solvents were removed from the resulting benzene-hexane filtrate producing an orange solid. The second orange solid was washed once with benzene and twice with pentane and dried under vacuum. A slurry of this orange solid in benzene (ca. 10 mL) was treated with CH3MgBr (0.8 mL of a 3.0 M solution in Et2O) and the mixture was stirred for 15 minutes at room temperature. Dioxane (ca. 2-3 mL) was added to the mixture which was filtered to produce a clear yellow filtrate. The solvents were removed from the filtrate under vacuum giving pure rac-9-Silafluorene,9,9-bis-2-Methylindenyl Zirconium Dimethyl (0.035 g, 1.7%).
Catalyst Cat Time C2 ═/C3 ═
10 1 13.23  49.20 26.89 178.5 151.2 81.2 3.37 0.7520
12 1 7.82 50.04 15.63 127.6 150.0 100.4 3.11 0.708
13 1 5.3  38.96 13.60 201.9 150.43 91.2 3.28 0.779
Catalyst Cat Time
System Amount Yield Efficiency C2═ H2 split C2 ═/C3 ═ flow
Catalyst Amount TEMP. Yield Efficiency H2 split C2 ═/C3 ═ flow
Metallocene Total Total IV
Catalyst Ethylene Ethylene in Rubber Final MFR Melting Point Of
RUN # System (wt %) Rubber (wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer
System Amount TEMP. Yield Efficiency C2═ H2 split flow rates
RUN # (Comparison) (mg) (° C.) (g) (Kg/g cat) (delta psi) (delta psi) (min.) (l/min.)
82 4 0.87  — — 9.54 151.17 204.2 2.39 —
83 4 1.4  — — 18.53 146.17 182.3 2.14 —
84 4 2.4  — — 24.5 138.5 172.2 1.93 —
85 4 4.732 46.4 10.2 118.7 158.23 119.7 2.39 —
87 4 3.081 44.21 7.0 61.24 158.83 —
[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-
isopropylindene]zirconium dichloride/MAO
cene Cat H2
133 5 — 150.9,  467.6 4.98
134 5 32.07 156.5  104.8 2.71
Polymerizations using rac-9-
silafluorenebis(2-methylindenyl)zirconium dimethyl
Catalyst Melting
Run T Precursor Activator Yield Point
# (° C.) (mg) (mg) (g) (° C.) MW MWD
1. A polymerization process comprising contacting under suitable polymerization conditions one or more olefins and the reaction product of one or more activators and one or more compounds represented by the formula:
M1 is selected from the group consisting of titanium zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
2. The process of claim 1 wherein R3 are identical C1-C4 alkyl groups.
3. The process of claim 1 wherein R4 to R7 and R8, R10 and R12 are hydrogen atoms.
4. The process of claim 1 wherein R3 are both C3 groups.
5. The process of claim 1 wherein the olefins are ethylene, propylene, 1-butene or 1-hexene.
6. The process of claim 1 wherein R17-R24 are hydrogen.
7. The process of claim 1 wherein the activator comprises one or more non-coordinating anion activators.
8. The process of claim 1 wherein the activator comprises one or more alkylalumoxane activators.
9. The process of claim 1 wherein the activator comprises a non-coordinating anion activator and an alkylalumoxane activator.
10. The process of claim 1 wherein the reaction product is combined with support material comprising magnesium chloride, silica or a combination thereof.
11. A polymerization process comprising contacting under suitable polymerization conditions one or more olefins and the reaction product of one or more activators and one or more compounds represented by the formula:
R3 are identical or different and are each a hydrogen atom, a halogen atom, a C1-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a —NR′2, —SR′—, —OR′, —OSiR′3 or —PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group;
12. The process of claim 11 wherein the olefins are ethylene, propylene, 1-butene or 1-hexene.
13. The process of claim 11 wherein R3 are identical C3 alkyl groups.
14. The process of claim 11 wherein R4 to R7 are hydrogen atoms.
15. The process of claim 11 wherein the olefins are C2-C14 olefins.
16. The process of claim 11 wherein M2 is silicon.
17. The process of claim 11 wherein R17-R24 are hydrogen.
US09619757 2000-06-30 2000-07-19 Metallocene compositions Active US6380334B1 (en)
US09619757 US6380334B1 (en) 2000-06-30 2000-07-19 Metallocene compositions
AT01937633T AT260289T (en) 2000-06-30 2001-05-21 Bridged bisindenyl substituted metallocene compounds
ES03027480T ES2247473T3 (en) 2000-06-30 2001-05-21 Compositions of bis-indenyl metallocene bridged.
PCT/US2001/016425 WO2002002575A1 (en) 2000-06-30 2001-05-21 Metallocenes with a bridged 4-phenyl-indenyl-ligand for olefin polymerization
ES01937633T ES2211808T3 (en) 2000-06-30 2001-05-21 Compounds bridged bis (indenyl) metallocene.
DE2001614896 DE60114896T8 (en) 2000-06-30 2001-05-21 bridged Bisindenylmetallocenverbindungen
EP20030027480 EP1411058B1 (en) 2000-06-30 2001-05-21 Bridged bisindenyl metallocene compositions
EP20010937633 EP1294733B1 (en) 2000-06-30 2001-05-21 Bridged bis(indenyl)metallocene compounds
JP2002507827A JP2004502698A (en) 2000-06-30 2001-05-21 Crosslinking used in olefin polymerization 4-phenyl - indenyl - metallocenes having a ligand
AT03027480T AT309259T (en) 2000-06-30 2001-05-21 bisindenylmetallocenverbindungen bridged
DE2001602156 DE60102156T8 (en) 2000-06-30 2001-05-21 Bridged bisindenyl-substituted metallocene compounds
US6380334B1 true US6380334B1 (en) 2002-04-30
ID=26910196
US09619757 Active US6380334B1 (en) 2000-06-30 2000-07-19 Metallocene compositions
US (1) US6380334B1 (en)
WO2009054831A1 (en) * 2007-10-25 2009-04-30 Novolen Technology Holdings, C.V. Racemoselective synthesis of ansa-metallocene compounds, ansa-metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
D.P. Krut′ko et al., "Synthesis and photoinduced isomerization of ansa-{η5, η5′-[1,1′-(1-silacyclopent-3-ene3-1m,1-diyl)bis(indenyl)]}-dichlorozirconium. The crystal structure of its meso form"—Russian Chemical Bulletin vol. 47 (11), Nov., 1998—pp. 2280-2285.
D.P. Krut'ko et al., "Synthesis and photoinduced isomerization of ansa-{eta5, eta5'-[1,1'-(1-silacyclopent-3-ene3-1m,1-diyl)bis(indenyl)]}-dichlorozirconium. The crystal structure of its meso form"-Russian Chemical Bulletin vol. 47 (11), Nov., 1998-pp. 2280-2285.
U.S. application No. 09/619,748, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040C).
U.S. application No. 09/619,749, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040H).
U.S. application No. 09/619,750, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040G).
U.S. application No. 09/619,751, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039D).
U.S. application No. 09/619,752, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040F).
U.S. application No. 09/619,759, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040B).
U.S. application No. 09/619,764, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040J).
U.S. application No. 09/620,046, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039A).
U.S. application No. 09/620,175, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040A).
U.S. application No. 09/620,198, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040L).
U.S. application No. 09/620,302, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040K).
U.S. application No. 09/620,303, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040I).
U.S. application No. 09/620,304, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040D).
U.S. application No. 09/620,341, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039C).
U.S. application No. 09/620,359, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039B).
U.S. application No. 09/620,522, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. James R. Hart, James Charles Vizzini & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B040E).
U.S. application No. 09/620,613, filed Jul. 19, 2000 (Inventors Mathew C. Kuchta, Udo M. Stehling, Robert T. Li, William T. Haygood, Jr. & Terry J. Burkhardt), entitled "Metallocene Compositions". (2000B039F).
US8168556B2 (en) 2007-10-25 2012-05-01 Lummus Novolen Technology Gmbh Racemoselective synthesis of ansa-metallocene compounds, ansa-metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
RU2476449C2 (en) * 2007-10-25 2013-02-27 Люммус Новолен Текнолоджи Гмбх Racemoselective synthesis of ansa-metallocene compounds, ansa-metallocene compounds, catalysts containing said compounds, method of producing olefin polymer using catalysts and olefin homo- and copolymers
US20100261860A1 (en) * 2007-10-25 2010-10-14 Lummus Novolen Technology Gmbh Racemoselective synthesis of ansa-metallocene compounds, ansa-metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
US6472474B2 (en) 2002-10-29 Propylene impact copolymers
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