The suitability of different types of telechelic poly(lactic acid) (PLA) copolymers for dilactide production and prepolymer products was evaluated. L-lactic acid (L-LA) was copolymerized with 1,4-butanediol, pentaerythritol, adipic acid, or 1,2,3,4-butanetetracarboxylic acid (1,2,3,4-BTCA). The influence of branching, the choice of catalyst, and the type of terminal groups on the properties and the thermal stability of the end product was determined. Carboxyl-termination of PLA was shown to lead to higher molar masses than hydroxyl-termination. The observed differences in the molar masses were explained by the lower thermal stability of the hydroxyl-terminated PLA, as evidenced by the faster depolymerization rate of the hydroxyl-terminated polymers and their higher tendency to undergo racemization. Sn(Oct)2 was found to be a more effective copolymerization catalyst than Fe(OAc)2 in terms of the final molar masses obtained. It was additionally found that the amount of chains not attached to the comonomers decreased toward longer polymerization times and was typically higher for the hydroxyl-terminated copolymers. The results suggest that predominant carboxyl-termination would increase the thermal stability of PLA polymers, whereas hydroxyl-termination could be utilized to increase the production speed and efficiency of dilactide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
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