Polylactones, 11. Cationic copolymerization of glycolide with L,L‐dilactide

Copolymerizations of glycolide with L,L-dilactide were conducted in chloroform, 1,2-dichloroethane and nitrobenzene. Chlorosulfonic acid, triflic acid, boron trifluoride, triethyloxonium tetrafluoroborate, but mainly methyl triflate, were used as initiators. 50°C was found to be an optimum reaction temperature, because higher temperatures resulted in dark coloured products of low viscosities. The composition of the copolyesters was determined by 1H NMR spectroscopy and the sequences by 13C NMR spectroscopy. Dyad splitting of the carbonyl signals allowed an accurate calculation of average block lengths. Under all circumstances glycolide showed a higher rate of incorporation, and truely random sequences were never obtained. However, the relative reactivities of both monomers largely depend on the nature of the initiator. The best results with regard to random sequences were obtained in 1,2-dichloroethane with methyl triflate (rG = 10,5 and rL = 0,9) and with triflic acid (rG = 14,0 and rL = 0,5). DSC measurements revealed that most samples possess crystalline domains of polyglycolide blocks. Nonetheless, many samples are soluble in hexafluoro-2-propanol and the amorphous samples also in dichloromethane or chloroform.