1. Field of Invention
The present invention relates to the polymerization of acyclic dienes.
2. The Prior Art
There presently exist few useful step propagation, condensation-type polymerization methods. Reaction yields must be high (.congruent.99%) in order for useful polymers to form. There are only approximately twenty such polymerization methods described in the prior art and none produce useful polymers at ambient or room temperature.
Recently, an attempt was made to incorporate the metathesis of olefins reaction in step propagation, condensation-type polymerization (SPCTP) chemistry to polymerize dienes [Lindmark-Hamberg et al, Macromolecules, Vol. 20, p. 2449 (1987)]. The dienes were exposed to a tungsten hexachloride-ethyl aluminum dichloride catalyst; however, it was found that the metathesis polymerization reaction was limited by competing vinyl addition chemical reactions.
Olefin metathesis, ring opening polymerizations of strained cycloolefins have been extensively studied over the past twenty years [Gilliam et al, J. Amer. Chem. Soc., Vol. 108, p. 733 (1986); Swager et al, J. Amer. Chem. Soc., Vol. 109, p. 894 (1987); Schrock et al, Macromolecules, Vol. 20, p. 1169 (1987); Cannizo et al, Macromolecules, Vol. 20, p. 1488 (1987); Novak et al, J. Amer. Chem. Soc., Vol. 110, p. 960 (1988); Swager et al, J. Amer. Chem. Soc., Vol. 110, p. 2973 (1988); Cannizzo et al, Macromolecules, Vol. 21, p. 1961 (1988); Wallace et al, Macromolecules, Vol. 20, p. 450 (1987); Schrock et al, Macromolecules, Vol. 20, p. 1169 (1987); Murzdek et al, Macromolecules, Vol. 20, p. 2640 (1987); Knoll et al, J. Amer. Chem. Soc., Vol. 110, p. 4424 (1988); Krouse et al, Macromolecules, Vol. 21, p. 1885 (1988); Wallace et al, J. Amer. Chem. Soc., Vol. 110, p. 4964 (1988)]. Olefin metathesis reactions and catalysts suitable therefor are also described in U.S. Pat. Nos. 4,727,215; 4,681,956 and 4,427,595.
It is an object of the present invention to provide a high yield, efficient olefin metathesis, SPCTP process for polymerizing acyclic dienes to produce novel high molecular weight polymeric products having properties and characteristics not possessed by similar products prepared according to other methods.
USPTO Backgrounds
USPTO Backgrounds