Enzymatic synthesis of carbonate monomers and polycarbonates.
Diphenyl carbonate is an attractive monomer for copolymerization with Bisphenol-A to produce the strong, high melting polycarbonate, Bisphenol-A Polycarbonate. Diphenyl carbonate is an ideal candidate for this polymerization as the phenols constitute good leaving groups during polymerization. Industrially, diphenyl carbonate is produced via the phosgenation of a phenolic sodium salt. Using phosgene creates additional safety hazards as well as concerns in treating or disposing of the reaction by-products. The enzymatic synthesis of diphenyl carbonate via alcoholysis of dimethyl carbonate by phenol is presented. While the process is environmentally benign and eliminates the considerable safety issues related to the use of phosgene, phenol is a poor nucleophile and conversion to diphenyl carbonate is limited. Enzyme catalyzed condensation polymerization of carbonate monomers and diols is a more feasible and direct enzymatic route to polycarbonate. We describe an AA-BB condensation polymerization to make polycarbonates using enzymes at ambient conditions. Molecular weights of up to 8, 500 MW are achieved. Unlike the industrial polymerization, this process is performed without the use of acid catalysts, significant energy input, or high temperature or pressure.
Rodney
R L
RL
Department of Chemical and Petroleum Engineering & Center for Biotechnology and Bioengineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, USA.
Stagno
J L
JL
Beckman
E J
EJ
Russell
A J
AJ
D002254:Carbonates / Q000737:chemistry / Q000378:metabolism*; D004798:Enzymes / Q000378:metabolism*; D005561:Formates / Q000737:chemistry / Q000378:metabolism; D006867:Hydrolases; D019800:Phenol / Q000737:chemistry / Q000378:metabolism; D011076:Polycarboxylate Cement / Q000737:chemistry / Q000378:metabolism*; D011108:Polymers; D013379:Substrate Specificity
D002254:Carbonates; D004798:Enzymes; D005561:Formates; D011076:Polycarboxylate Cement; D011108:Polymers; C005506:polycarbonate; D019800:Phenol; D006867:Hydrolases; C023025:methyl carbonate