Entropically Driven Macrolide Polymerizations for the Synthesis of Aliphatic Polyester Copolymers Using Titanium Isopropoxide

Adrian G. Amador, Annabelle Watts, Angelika E. Neitzel, Marc A. Hillmyer

Research output: Contribution to journalArticle

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Abstract

Thermal and mechanical properties of sustainable aliphatic polyesters can be tuned through the synthesis of copolymers. The synthesis of two 14-membered macrolides are reported: a cyclic tetraester with alternating lactic acid (LA) and 3-hydroxypropionic acid (3HP) units and a cyclic diester with alternating glycolic acid (GA) and 2-methyl-1,3-propanediol (2MD) units. Ring-opening transesterification polymerization (ROTEP) of these macrolides to yield poly(LA-stat-3HP) and poly(GA-alt-2MD), respectively, were found to be modestly endothermic (ΔHp ° = 2.0 and 0.5 kJ mol -1 , respectively) and endoentropic (ΔSp ° = 27 and 23 J mol -1 K -1 , respectively). Inexpensive and nontoxic titanium isopropoxide Ti(Oi-Pr) 4 functions as an active catalyst for these entropically driven ROTEPs, achieving high conversions (>90%) in under 1 h. The polymerizations exhibit control over molar mass with dispersity values <1.7. poly(GA-alt-2MD) is an amorphous polymer with a low glass transition temperature near -30 °C. poly(LA-co-3HP) exhibits a glass transition temperature up to 13 °C and, depending on the regioregularity, exhibits a melting temperature up to 96 °C.

Original languageEnglish (US)
Pages (from-to)2371-2383
Number of pages13
JournalMacromolecules
Volume52
Issue number6
DOIs
StatePublished - Mar 26 2019

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