Polycarbamate synthesis via chain-growth copolymerization

A method of making a polycarbamate copolymer, comprising:

• contacting, in the presence of a Lewis acid, a first reactant comprising an oxirane or thiirane moiety and one or more additional reactants including a first heteroallene;
• wherein the Lewis acid is an alkylborane, trialkylborane, triethylborane, triphenylborane, triisobutylborane, tris(pentafluorophenyl)borane, alkylaluminum, trialklyaluminum, trimethylaluminum, triethlyaluminum, triisobutylaluminum, triphenylaluminum, trioctylaluminum, dimethylzinc, diethylzinc, diphenylzinc, or di-n-butylmagnesium;
• and
• wherein the first heteroallene is an isocyanate selected from the group consisting of trichloroacetyl isocyanate (TCAI), chlorosulfonyl isocyanate (CSI), benzenesulfonyl isocyanate (BSI), p-toluenesulfonyl isocyanate (TSI), 4-chlorobenzenesulfonyl isocyanate (CBSI), 4-nitrophenyl isocyanate (NPI), 4-trifluoromethylphenyl isocyanate (TFMPI), 4-fluorophenyl isocyanate (FPI), pentafluorophenyl isocyanate (PFPI), and 3,5-bis(trifluoromethyl)-phenyl isocyanate (BTFMPI).

A composition for synthesizing a polycarbamate by chain-growth copolymerization comprising:

• a Lewis acid, wherein the Lewis acid is an alkylborane, trialkylborane, triethylborane, triphenylborane, triisobutylborane, tris(pentafluorophenyl)borane, alkylaluminum, trialklyaluminum, trimethylaluminum, triethlyaluminum, triisobutylaluminum, triphenylaluminum, trioctylaluminum, dimethylzine, diethylzine, diphenylzine, or di-n-butylmagnesium;
• a first reactant comprising an oxirane or thiirane moiety;
• and
• one or more additional reactants selected from heteroallenes, including a first heteroallene and a second heteroallene, wherein the first heteroallene is selected from the group consisting of isocyanates and isothiocyanates, and wherein the second heteroallene is selected from the group consisting of carbon dioxide, carbon disulfide, and carbonyl sulfide.