Macromolecules, Vol.42, No.19, 7285-7291, 2009
Novel Biodegradable Poly(ester-ether)s: Copolymers from 1,4-Dioxan-2-one and D,L-3-Methyl-1,4-dioxan-2-one
Synthesis of random copolymers by the nonsequential polymerization of 1,4-dioxan-2-one With D,L,-3-methyl-1,4-dioxan-2-one was first investigated using a range of classical initiators. Experimental conditions such as temperature and initiator concentrations were varied to achieve reasonable monomer conversions and molar masses. In general, copolymers were slightly enriched in 1,4-dioxan-2-one. On the basis of block lengths of the respective (co)monomer sequences, it is proposed that the copolymer consists of longer blocks of dioxanone units and a pseudoperiodic pattern with a random distribution of MeDX units. The thermal properties of the copolymer changed significantly with the percentage of MeDX units incorporated. A copolymer with 8% mole percent of MeDX units exhibits a T-m of 95.5 degrees C, which is about 15 degrees lower than PDX homopolymer. A range of (PEG)(m)-b-[(PDX)-co-(PMeDX)](n) block copolymers was also successfully prepared using alpha-methoxy-omega-hydroxy-PEG as macroinitiator. The amphiphilic character of these copolymers is also here demonstrated with spherical core-shell micelles having an average size of 25-30 run as determined by TEM. The tunable biodegradability characteristics of the hydrophobic core make these polymers interesting candidates as nanocarriers in controlled drug delivery.