Radical high polymerization of di-tert-butyl fumarate and novel synthesis of high molecular weight poly(fumaric acid) from its polymer

Di-tert-butyl fumarate (DtBF) was found to homopolymerize easily with 1,1′-azobisisobutyronitrile and benzoyl peroxide as radical initiators at 50~80°C to give a nonflexible rod-like polymer, poly(tert-butoxycarbonylmethylene) with number-average molecular weight of more than 100,000. The colorless powderlike polymer thus obtained was soluble in benzene, toluene, carbon tetrachloride and tetrahydrofuran, and gave a transparent film or fiber from its toluene solution. This polymer did not melt, but it underwent degradation with a quantitative elimination of isobutene at 180~190°C. The remaining polymer was confirmed to be a pure poly(fumaric acid), poly(hydroxycarbonylmethylene). Therefore, the degradation of poly(DtBF) in solution at 180~190°C was found to be a new route for synthesizing of a high molecular weight poly(fumaric acid).