US4801666A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Olefin and cycloalkene polymerization with organolanthanide catalysts
Assignee: Northwestern University
•
Filing: 1987-05-14
•
Granted: 1989-01-31
•
Expires: 2007-05-14
Abstract
Abstract The reaction of the organolanthanide complexes [η 5 --(CH 3 ) 5 C 5 ] 2 MCl 2 - Li((C 2 H 5 ) 2 O) 2 + , M=La, Nd, Sm, Lu, with LiCH[Si(CH 3 ) 3 ] 2 provides a straight-forward route to ether-free and halide- free bis(pentamethylcyclopentadienyl) lanthanide alkyls, (η 5 (CH 3 ) 5 C 5 ) 2 MCH--[Si(CH 3 ) 3 ] 2 . The (η 5 (CH 3 ) 5 C 5 ) 2 NdCH[Si(CH 3 ) 3 ] 2 complexes react with H 2 under mild conditions to yield the corresponding hydrides [(η 5 (CH 3 ) 5 C 5 ) 2 MH] 2 . These complexes have been found to be extremely active homogeneous olefin polymerization catalysts, as well as catalysts for olefin and acetylene hydrogenation.
Inventors
- 👤 Tobin J. Marks
- 👤 Heiko Mauermann
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 12:43
CPC Classifications
C; C07; C07F; C07F17/00; B; B01; B01J; B01J31/00; B01J31/16; B01J31/22; B01J31/2282; B01J31/2295; C07C; C07C5/00; C07C5/02; C07C5/03; C07F5/00; C07F7/00; C07F7/02; C07F7/025; C08; C08F; C08F10/00; B01J2231/00; B01J2231/10; B01J2231/12; B01J2231/60; B01J2231/64; B01J2231/641; B01J2231/645; B01J2531/00; B01J2531/30; B01J2531/37; B01J2531/38; C07C2531/00; C07C2531/16; C07C2531/22
Claims Analysis
Total Claims: 21
Claim 1
Independent Claim
67 words
A method for polymerizing an α-olefin, comprising contacting said α-olefin with a catalyst under an inert atmosphere, said catalyst consisting essentially of a lanthanide catalyst of the formula (Cp 2 'MH) 2 wherein Cp' is η 5 (CH 3 ) 5 C 5 ; and M is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
Claim 2
Independent Claim
67 words
A method for polymerizing an α-olefin, comprising contacting said α-olefin with a catalyst under an inert atmosphere, said catalyst consisting essentially of a lanthanide catalyst of the formula (Cp 2 'MH) 2 wherein Cp' is η 5 (CH 3 ) 5 C 5 ; and M is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
Claim 3
Dependent Claim
21 words
The method of claim 1 wherein said α-olefin is selected from the group consisting of ethylene, propylene, 1-hexene, butadiene and 1-butene.
Claim 4
Dependent Claim
26 words
The method of claim 1 wherein said olefin comprises a mixture of two olefins selected from the group consisting of ethylene, propylene, 1-hexene, butadiene and 1-butene.
Claim 5
Dependent Claim
23 words
The method of claim 1 wherein said catalyst is carried by a solvent selected from the group consisting of tetrahydrofuran, cyclohexane, and toluene.
Claim 6
Dependent Claim
20 words
The method of claim 1 wherein said olefin is maintained in the gaseous state prior to contact with said catalyst.
Claim 7
Dependent Claim
10 words
The method of claim 1 wherein said catalyst is homogeneous.
Claim 8
Dependent Claim
10 words
The method of claim 1 wherein said catalyst is heterogeneous.
Claim 9
Dependent Claim
29 words
The method of claim 7 wherein said catalyst is adsorbed on an inorganic substrate selected from the group consisting of silica, silica gel, alumina, magnesium chloride and magnesium oxide.
Claim 10
Independent Claim
76 words
A method for polymerizing an unsaturated monomer selected from the group consisting of α-olefins and cycloalkenes comprising the steps of dissolving said unsaturated monomer in a solvent and contacting said monomer solution with a catalyst consisting essentially of a lanthanide catalyst of the formula (Cp 2 'MH) 2 under an inert atmosphere wherein Cp' is η 5 (CH 3 ) 5 C 5 and M is selected from the group consisting of the Lanthanide Series elements.
Claim 11
Independent Claim
76 words
A method for polymerizing an unsaturated monomer selected from the group consisting of α-olefins and cycloalkenes comprising the steps of dissolving said unsaturated monomer in a solvent and contacting said monomer solution with a catalyst consisting essentially of a lanthanide catalyst of the formula (Cp 2 'MH) 2 under an inert atmosphere wherein Cp' is η 5 (CH 3 ) 5 C 5 and M is selected from the group consisting of the Lanthanide Series elements.
Claim 12
Dependent Claim
22 words
The method of claim 9 wherein said solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof.
Claim 13
Dependent Claim
10 words
The method of claim 9 wherein said solvent is pentane.
Claim 14
Dependent Claim
21 words
The method of claim 9 wherein M is selected from the group of lanthanide elements consisting of La, Nd, and Sm.
Claim 15
Dependent Claim
23 words
The method of claim 9 wherein said unsaturated monomer comprises at least two monomers selected from the group consisting of α-olefins and cycloalkenes.
Claim 16
Independent Claim
139 words
A method for polymerizing monomers selected from the group consisting of α-olefins and cycloalkenes, comprising the steps of: (a) evacuating a reaction vessel; (b) adding a solvent to said reaction vessel; (c) adding one of said monomers to said reaction vessel; (d) maintaining pressure in said reaction vessel at approximately one atmosphere; (e) stirring the solvent and monomer mixture rapidly for several minutes; (f) injecting into the space above the olefin mixture a catalyst solution consisting essentially of an organolanthanide compound of the formula (Cp 2 'MH) 2 where M is a lanthanide selected from the group consisting of: La, Ce, Pr, Nd, Pm, Sm, Ea, Gd, Tb, Dy, Ho, Er, and Tm and Cp' is η 5 (CH 3 ) 5 C 5 ; whereby the monomer forms into a polymeric product which may be collected by filtration.
Claim 17
Independent Claim
139 words
A method for polymerizing monomers selected from the group consisting of α-olefins and cycloalkenes, comprising the steps of: (a) evacuating a reaction vessel; (b) adding a solvent to said reaction vessel; (c) adding one of said monomers to said reaction vessel; (d) maintaining pressure in said reaction vessel at approximately one atmosphere; (e) stirring the solvent and monomer mixture rapidly for several minutes; (f) injecting into the space above the olefin mixture a catalyst solution consisting essentially of an organolanthanide compound of the formula (Cp 2 'MH) 2 where M is a lanthanide selected from the group consisting of: La, Ce, Pr, Nd, Pm, Sm, Ea, Gd, Tb, Dy, Ho, Er, and Tm and Cp' is η 5 (CH 3 ) 5 C 5 ; whereby the monomer forms into a polymeric product which may be collected by filtration.
Claim 18
Dependent Claim
18 words
The method of claim 14 wherein said catalyst solution is injected so as to form a fine spray.
Claim 19
Independent Claim
54 words
A method for copolymerizing two α-olefins comprising the steps of dissolving said olefins in a solvent and contacting said olefin solution with a lanthanide catalyst of the formula (Cp 2 'MH) 2 wherein Cp'=η 5 (CH 3 ) 5 C 5 and M is selected from the group consisting of the Lanthanide Series elements.
Claim 20
Independent Claim
54 words
A method for copolymerizing two α-olefins comprising the steps of dissolving said olefins in a solvent and contacting said olefin solution with a lanthanide catalyst of the formula (Cp 2 'MH) 2 wherein Cp'=η 5 (CH 3 ) 5 C 5 and M is selected from the group consisting of the Lanthanide Series elements.
Claim 21
Dependent Claim
21 words
The method of claim 16 wherein said α-olefins are selected from the group consisting of ethylene, propylene, butadiene 1-hexene, and 1-butene.
References Cited (Backward Citations)
US29368A
Cited
US2674634A
Cited
US2831880A
Cited
US3051690A
Cited
GB840327A
Cited
US3060215A
Cited
US3366704A
Cited
US3849459A
Cited
US3969386A
Cited
US4153576A
Cited
US4450243A
Cited
US4423276A
Cited
US4699962A
Cited
US4665046A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-01-31 | 1992-08-01 | 1993-01-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-01-31 | 1996-08-01 | 1997-01-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-01-31 | 2000-08-01 | 2001-01-31 | $7700.00 | Window Closed / Lapsed |