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Title: Homogeneous catalysts for stereoregular olefin polymerization

Abstract

The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

Inventors:
; ;
Issue Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
869395
Patent Number(s):
5330948
Application Number:
07/860,784
Assignee:
Northwestern University (Evanston, IL)
Patent Classifications (CPCs):
C - CHEMISTRY C08 - ORGANIC MACROMOLECULAR COMPOUNDS C08F - MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
Y - NEW / CROSS SECTIONAL TECHNOLOGIES Y10 - TECHNICAL SUBJECTS COVERED BY FORMER USPC Y10S - TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
DOE Contract Number:  
FG02-86ER13511
Resource Type:
Patent
Resource Relation:
Patent File Date: 1992 Mar 31
Country of Publication:
United States
Language:
English
Subject:
homogeneous; catalysts; stereoregular; olefin; polymerization; synthesis; precatalysts; chiral; organozirconium; complexes; disclosed; structure; 4-x; 4-y; represent; unsubstituted; locations; cyclopentadienyl; substituted; alkyl; 1-30; carbon; atoms; ligand; fragment; containing; 13; 14; 15; 16; element; periodic; table; metal; hydrocarbyl; radical; halogen; ltoreq; related; prepared; alkylation; corresponding; dichorides; presence; methylalumoxane; triarylborane; cocatalysts; form; cation-like; species; highly; active; combination; lewis; acid; cocatalyst; propylene; alpha; -olefin; effected; efficiency; isospecificity; unsubstituted alkyl; homogeneous catalyst; olefin polymerization; lewis acid; carbon atoms; periodic table; carbon atom; complexes form; highly active; chiral organozirconium; organozirconium complexes; stereoregular olefin; olefin polymer; homogeneous catalysts; substituted alkyl; /502/526/999/585/

Citation Formats

Marks, Tobin J., Eisen, Moris S., and Giardello, Michael A.. Homogeneous catalysts for stereoregular olefin polymerization. United States: N. p., 1994. Web.
Marks, Tobin J., Eisen, Moris S., & Giardello, Michael A.. Homogeneous catalysts for stereoregular olefin polymerization. United States.
Marks, Tobin J., Eisen, Moris S., and Giardello, Michael A.. Sat . "Homogeneous catalysts for stereoregular olefin polymerization". United States. https://www.osti.gov/servlets/purl/869395.
@article{osti_869395,
title = {Homogeneous catalysts for stereoregular olefin polymerization},
author = {Marks, Tobin J. and Eisen, Moris S. and Giardello, Michael A.},
abstractNote = {The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1994},
month = {1}
}

Works referenced in this record:

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journal, October 1987


Asymmetric Oligomerization of Propene and 1-Butene with a Zirconocene/Alumoxane Catalyst
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Stereo- and Regioselectivity of Chiral, Alkyl-substitutedansa-Zirconocene Catalysts in Methylalumoxane-activated Propene Polymerization
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Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst
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Stereospecific Polymerization of Propylene: An Outlook 25 Years after Its Discovery
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Asymmetric hydrooligomerization of propylene
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Cation-like homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris(pentafluorophenyl)borane
journal, April 1991


Syndiospecific propylene polymerizations with Group IVB metallocenes
journal, August 1988


Isospecific polymerization of propylene catalyzed by rac-ethylenebis(indenyl)methylzirconium cation
journal, October 1991


Diastereoselectivity in the homogeneous cyclopolymerization of 1,5-hexadiene
journal, June 1990


Two-state propagation mechanism for propylene polymerization catalyzed by rac-[anti-ethylidene(1-.eta.5-tetramethylcyclopentadienyl)(1-.eta.5-indenyl)] dimethyltitanium
journal, October 1991


Synthesis of Optically Active Macromolecules Using Metallocene Catalysts
journal, January 1992