Transition metal catalyzed polymerization of butadiene in supercritical CO{sub 2}

Technical Report · Sat Aug 01 04:00:00 EDT 1998

DOI:https://doi.org/10.2172/631181· OSTI ID:631181

Borkowsky, S ^[1]; Tumas, W ^[1]; Waymouth, R M ^[2]

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1. Los Alamos National Lab., NM (United States)
2. Stanford Univ., CA (United States)

A class of Ni(II) catalysts has been shown to stereoselectively catalyze the 1,4-polymerization of butadiene. The authors have been investigating the use of supercritical CO{sub 2} as an environmentally benign replacement solvent for conventional hydrocarbon and halocarbon solvents for a variety of chemical transformations. Above 31 C, CO{sub 2} enters a supercritical phase, where its physical properties are both liquid-like and gas-like. Importantly, the solvent properties such as dielectric constant for supercritical fluids can be varied by changing the pressure of the fluid. In this report, the authors present results of an investigation of the polymerization of 1,3-butadiene using [({pi}-allyl) Ni(CF{sub 3}CO{sub 2})]{sub 2} in supercritical CO{sub 2}. They conducted 1,3-butadiene polymerizations in CO{sub 2} to determine whether or not they could systematically and predictably adjust the regiochemistry/stereochemistry of the polybutadiene product by varying the solution properties at different pressures. They also mention experiments with CO catalysts that are known to give 1,2-syndiotactic polybutadiene, and with a Pd catalyst system that is known to copolymerize olefin with CO to give perfectly alternating copolymers.

• Research Organization: Los Alamos National Lab., NM (United States)
• Sponsoring Organization: USDOE Assistant Secretary for Management and Administration, Washington, DC (United States)
• DOE Contract Number: W-7405-ENG-36
• OSTI ID: 631181
• Report Number(s): LA-SUB--98-12; ON: DE98003694
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
BUTADIENE
CARBON DIOXIDE
CATALYSTS
MATERIAL SUBSTITUTION
NICKEL COMPOUNDS
ORGANIC SOLVENTS
POLYMERIZATION
SOLVENT PROPERTIES
SUPERCRITICAL STATE