US5436305A
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Organometallic fluorenyl compounds, preparation, and use
Assignee: Phillips Petroleum Co
•
Filing: 1991-07-23
•
Granted: 1995-07-25
•
Expires: 2011-07-23
Abstract
Abstract Fluorenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.
Inventors
- 👤 Helmut G. Alt
- 👤 Syriac J. Palackal
- 👤 Konstantinos Patsidis
- 👤 M. Bruce Welch
- 👤 Rolf L. Geerts
- 👤 Eric T. Hsieh
- 👤 Max P. McDaniel
- 👤 Gil R. Hawley
- 👤 Paul D. Smith
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 19:36
CPC Classifications
C; C07; C07F; C07F7/00; B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/143; B01J31/16; B01J31/22; B01J31/2282; B01J31/2295; C07C; C07C13/00; C07C13/28; C07C13/32; C07C13/54; C07C13/547; C07C13/567; C07C22/00; C07C22/02; C07C22/04; C07C49/00; C07C49/587; C07C49/703; C07C49/747; C07C51/00; C07C51/16; C07C51/31; C07C51/347; C07C51/373; C07C51/377; C07C63/00; C07C63/33; C07C63/331; C07C63/49; C07C65/00; C07C65/32; C07C65/34; C07C65/36; C07F17/00; C07F7/02; C07F7/08; C07F7/0803; C07F7/0805; C07F7/081; C08; C08F; C08F10/00; B01J2531/00; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/49; C07C2601/00; C07C2601/06; C07C2601/10; C07C2603/00; C07C2603/02; C07C2603/04; C07C2603/06; C07C2603/10; C07C2603/12; C07C2603/18; C08F110/00; C08F110/02; C08F110/04; C08F110/06; C08F210/00; C08F210/16; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/639; C08F4/63912; C08F4/6392; C08F4/63922; C08F4/64; C08F4/659; C08F4/65912; C08F4/6592; C08F4/65922; C08F4/65927
Claims Analysis
Total Claims: 71
Claim 1
Independent Claim
151 words
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeO k in the presence of a non-halogenated liquid diluent consisting essentially of a solvent for the fluorenyl salt which is non-coordinating with the transition metal compound, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
Claim 2
Dependent Claim
151 words
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeO k in the presence of a non-halogenated liquid diluent consisting essentially of a solvent for the fluorenyl salt which is non-coordinating with the transition metal compound, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
Claim 3
Dependent Claim
147 words
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeQ k in the presence of a non-halogenated liquid diluent consisting essentially of at least one liquid selected from hydrocarbons and diethyl ether, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
Claim 4
Dependent Claim
147 words
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeQ k in the presence of a non-halogenated liquid diluent consisting essentially of at least one liquid selected from hydrocarbons and diethyl ether, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
Claim 5
Dependent Claim
24 words
A process according to claim 2 wherein said liquid diluent of step (2) is selected from the group consisting of toluene pentane, and hexane.
Claim 6
Dependent Claim
29 words
A process according to claim 2 wherein said fluorenyl-containing salt is a bridged compound in which a fluorenyl radical is bonded to another cyclopentadienyl-type radical by a bridging group.
Claim 7
Dependent Claim
192 words
A process according to claim 2 producing a metallocene of the R" x (FlR n )(CpR m )MeQ k wherein Fl is a fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydro indenyl, or fluorenyl radical, each R is the same or different and is an organo radical having 1 to 20 carbon atoms, R" is a structural bridge linking (FlR n ) and (CpR m ), Me is metal selected from the group consisting of IVB, VB, and VIB metals of the Periodic Table, each Q is the same or different and is selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogen, x is 1 or 0, k is a number sufficient to fill out the remaining valences of Me, n is a number in the range of 0 to 7, m is a number in the range of 0 to 7, further characterized by the fact that if (CpR m ) is unsubstituted fluorenyl and x is 0, then n is 1 to 7, and if (CpR m ) is unsubstituted cyclopentadienyl or 3-methylcyclopentadienyl and R' is 1,1-dimethyl-methylene, then n=1 to 7.
Claim 8
Dependent Claim
16 words
A process according to claim 2 wherein Me is selected from Ti, V, HF, and Zr.
Claim 9
Dependent Claim
14 words
A process according to claim 6 wherein at least one Q is a halide.
Claim 10
Dependent Claim
12 words
A process according to claim 7 wherein each Q is a halide.
Claim 11
Dependent Claim
18 words
A process according to claim 6 wherein said liquid diluent of step (2) consists essentially of a hydrocarbon.
Claim 12
Dependent Claim
13 words
A process according to claim 9 wherein said liquid diluent is an alkane.
Claim 13
Dependent Claim
19 words
A process according to claim 10 wherein said liquid diluent is an alkane having 5 to 6 carbon atoms.
Claim 14
Dependent Claim
12 words
A process according to claim 11 wherein said liquid diluent is pentane.
Claim 15
Dependent Claim
20 words
A process according to claim 12 wherein said salt and said transition metal compound are reacted at ordinary room temperature.
Claim 16
Dependent Claim
18 words
A process according to claim 2 wherein said liquid diluent of step (2) consists essentially of a hydrocarbon.
Claim 17
Dependent Claim
18 words
A process according to claim 2 wherein said liquid diluent of step (2) consists essentially of diethyl ether.
Claim 18
Dependent Claim
16 words
A process according to claim 2 wherein said liquid diluent consists essentially of an aromatic hydrocarbon.
Claim 19
Dependent Claim
14 words
A process according to claim 16 wherein said liquid diluent consists essentially of toluene.
Claim 20
Dependent Claim
11 words
A process according to claim 14 wherein each Q is Cl.
Claim 21
Dependent Claim
25 words
A process according to claim 18 wherein said fluorenyl-containing alkali metal salt and the metallocene are prepared in a liquid diluent consisting essentially of toluene.
Claim 22
Dependent Claim
23 words
A process according to claim 14 wherein said fluorenyl-containing alkali metal salt is prepared in a liquid diluent consisting essentially of diethyl ether.
Claim 23
Dependent Claim
40 words
A process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a catalyst system comprising a fluorenyl-containing metallocene and a suitable cocatalyst, wherein said fluorenyl containing metallocene has been produced by the process of claim 2.
Claim 24
Dependent Claim
26 words
A process according to claim 21 wherein said fluorenyl precursor is a compound having a fluorenyl group bonded to a cyclopentadienyl group by an alkylene radical.
Claim 25
Dependent Claim
63 words
A process according to claim 22 wherein said fluorenyl precursor is formed by reacting an alkali metal fluorenyl with a dihaloalkylene in the presence of a non-halogenated liquid diluent consisting essentially of a hydrocarbon to form a fluorenyl alkylene halide which is then reacted with an alkali metal cyclopentadienyl-type compound also in the presence of a liquid diluent consisting essentially of a hydrocarbon.
Claim 26
Dependent Claim
35 words
A process according to claim 23 wherein said fluorenyl precursor is of the formula Fl-R-Cp wherein Fl is unsubstituted fluorenyl, R is a C 1 to C 6 alkylene radical and Cp is unsubstituted cyclopentadienyl.
Claim 27
Dependent Claim
14 words
A process according to claim 2 wherein Me is selected from Zr and Hf.
Claim 28
Dependent Claim
240 words
A process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a catalyst system comprising a fluorenyl-containing metallocene and a suitable cocatalyst, wherein said fluorenyl-containing metallocene is selected from the group consisting of metallocenes of the formula R" x (FlR n )(CpR m )MeQ k wherein Fl is a fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl radical, each R is the same or different and is an organo radical having 1 to 20 carbon atoms, R" is a structural bridge linking (FlR n ) and (CpR m ), Me is a metal selected from the group consisting of IVB and VB metals of the Periodic Table, each Q is the same or different and is selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogen, x is 1 or 0, k is a number sufficient to fill out the remaining valances of Me, n is a number in the range of 0 to 7, m is a number in the range of 0 to 7, further characterized by the fact that if Cp is cyclopentadienyl and R" is a alkylene radical then R" is selected from the group consisting of --CH 2 -- and alkylene radicals having at least two carbon atoms in the main alkylene chain and if (CpR m ) is unsubstituted fluorenyl and x is 0, then n is 1 to 7.
Claim 29
Dependent Claim
240 words
A process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a catalyst system comprising a fluorenyl-containing metallocene and a suitable cocatalyst, wherein said fluorenyl-containing metallocene is selected from the group consisting of metallocenes of the formula R" x (FlR n )(CpR m )MeQ k wherein Fl is a fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl radical, each R is the same or different and is an organo radical having 1 to 20 carbon atoms, R" is a structural bridge linking (FlR n ) and (CpR m ), Me is a metal selected from the group consisting of IVB and VB metals of the Periodic Table, each Q is the same or different and is selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogen, x is 1 or 0, k is a number sufficient to fill out the remaining valances of Me, n is a number in the range of 0 to 7, m is a number in the range of 0 to 7, further characterized by the fact that if Cp is cyclopentadienyl and R" is a alkylene radical then R" is selected from the group consisting of --CH 2 -- and alkylene radicals having at least two carbon atoms in the main alkylene chain and if (CpR m ) is unsubstituted fluorenyl and x is 0, then n is 1 to 7.
Claim 30
Dependent Claim
13 words
A process according to claim 26 wherein said metallocene is an unbridged metallocene.
Claim 31
Dependent Claim
12 words
A process according to claim 27 wherein Cp is a fluorenyl radical.
Claim 32
Dependent Claim
19 words
A process according to claim 28 wherein (FlR n ) and (CpR m ) are identical substituted fluorenyl radicals.
Claim 33
Dependent Claim
13 words
A process according to claim 29 wherein the metallocene is bis(1-methylfluorenyl) zirconium dichloride.
Claim 34
Dependent Claim
13 words
A process according to claim 29 wherein the metallocene is bis(1-methylfluorenyl) hafnium dichloride.
Claim 35
Dependent Claim
40 words
A process according to claim 26 wherein Cp is indenyl and x is 1 and R" is selected from the group consisting of --CH 2 -- and alkylene radicals having at least two carbon atoms in the main alkylene chain.
Claim 36
Dependent Claim
16 words
A process according to claim 26 wherein x is 0 and Cp is a fluorenyl radical.
Claim 37
Dependent Claim
16 words
A process according to claim 29 wherein x is 0 and Cp is an indenyl radical.
Claim 38
Dependent Claim
16 words
A process according to claim 26 wherein x is 0 and Cp is a cyclopentadienyl radical.
Claim 39
Dependent Claim
16 words
A process according to claim 26 wherein x is 0 and FlR n is unsubstituted fluorenyl.
Claim 40
Dependent Claim
12 words
A process according to claim 26 wherein said cocatalyst comprises an alkylaluminoxane.
Claim 41
Dependent Claim
10 words
A process according to claim 37 wherein ethylene is polymerized.
Claim 42
Dependent Claim
11 words
A process according to claim 38 wherein said metallocene is unbridged.
Claim 43
Dependent Claim
11 words
A process according to claim 38 wherein said metallocene is bridged.
Claim 44
Dependent Claim
28 words
A process according to claim 38 wherein said metallocene is selected from the group consisting of (1,2-difluorenylethane) zirconium dichloride, (1-fluorenyl-2-indenyl ethane) zirconium dichloride, and (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride.
Claim 45
Dependent Claim
11 words
A process according to claim 41 wherein ethylene homopolymer is produced.
Claim 46
Dependent Claim
23 words
A process according to claim 41 wherein ethylene is polymerized n the presence of another alpha olefin having 4 to 8 carbon atoms.
Claim 47
Dependent Claim
10 words
A process according to claim 37 wherein propylene is polymerized.
Claim 48
Dependent Claim
11 words
A process according to claim 44 wherein propylene homopolymer is produced.
Claim 49
Dependent Claim
29 words
A process according to claim 45 wherein said metallocene is selected from (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride, (1,2-di(2-tertbutyl fluorenyl)ethane) zirconium dichloride, (1,2-difluorenyl ethane) zirconium dichloride, and (1,2-difluorenyl ethane) hafnium dichloride.
Claim 50
Dependent Claim
17 words
A process according to claim 45 wherein FlR n and CpR m in said metallocene are different.
Claim 51
Dependent Claim
10 words
A process according to claim 37 wherein 4-methyl-1-pentene is polymerized.
Claim 52
Dependent Claim
17 words
A process according to claim 48, wherein FlR n and CpR m in said metallocene are different.
Claim 53
Dependent Claim
14 words
A process according to claim 49 wherein said metallocene is (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride.
Claim 54
Dependent Claim
14 words
A process according to claim 47 wherein said metallocene is (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride.
Claim 55
Dependent Claim
14 words
A process according to claim 37 wherein Cp is cyclopentadienyl and x is 1.
Claim 56
Dependent Claim
12 words
A process according to claim 52 wherein R" is an alkylene radical.
Claim 57
Dependent Claim
12 words
A process according to claim 53 wherein R" is --CH 2 --.
Claim 58
Dependent Claim
10 words
A process according to claim 54 wherein propylene is polymerized.
Claim 59
Dependent Claim
13 words
A process according to claim 55 wherein a homopolymer of propylene is produced.
Claim 60
Dependent Claim
16 words
A process according to claim 37 wherein Cp is an indenyl radical and x is 1.
Claim 61
Dependent Claim
12 words
A process according to claim 57 wherein R" is an alkylene radical.
Claim 62
Dependent Claim
18 words
A process according to claim 58 wherein R" has two or more carbons in the main alkylene chain.
Claim 63
Dependent Claim
16 words
A process according to claim 37 wherein CpR m and FlR n are substituted fluorenyl radicals.
Claim 64
Dependent Claim
15 words
A process according to claim 60 wherein CpR m and FlR n are the same.
Claim 65
Dependent Claim
18 words
A process according to claim 47 wherein Fl is a fluorenyl radical and Cp is an indenyl radical.
Claim 66
Dependent Claim
16 words
A process according to claim 37 wherein x is 1 and R" is a silyl radical.
Claim 67
Dependent Claim
14 words
A process according to claim 43 wherein said metallocene is (1-fluorenyl-2-indenyl ethane) zirconium dichloride.
Claim 68
Dependent Claim
14 words
A process according to claim 43 wherein said metallocene is (1-fluorenyl-1-cyclopentadienyl methane) zirconium dichloride.
Claim 69
Dependent Claim
13 words
A process according to claim 43 wherein said metallocene is (1,2-difluorenylethane) zirconium dichloride.
Claim 70
Dependent Claim
118 words
A process comprising reacting fluorenyl methyl chloride with an alkali metal salt of cyclopentadiene to produce 1-fluorenyl-1-cyclopentadienyl methane; forming a divalent alkali metal salt of 1-fluorenyl-1-cyclopentadienyl methane; reacting the said divalent alkali metal salt with a transition metal compound of the formula MeQ k wherein Me is selected from Zr, Hf, and Ti; each Q is individually selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogens; at least one Q is a halogen; and k is a number corresponding to the valence of Me; to produce the corresponding bridged metallocene; and using said metallocene with a cocatalyst to polymerize an alpha olefin containing at least three carbons per molecule.
Claim 71
Dependent Claim
118 words
A process comprising reacting fluorenyl methyl chloride with an alkali metal salt of cyclopentadiene to produce 1-fluorenyl-1-cyclopentadienyl methane; forming a divalent alkali metal salt of 1-fluorenyl-1-cyclopentadienyl methane; reacting the said divalent alkali metal salt with a transition metal compound of the formula MeQ k wherein Me is selected from Zr, Hf, and Ti; each Q is individually selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogens; at least one Q is a halogen; and k is a number corresponding to the valence of Me; to produce the corresponding bridged metallocene; and using said metallocene with a cocatalyst to polymerize an alpha olefin containing at least three carbons per molecule.
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