Bioinspired All‐Polyester Diblock Copolymers Made from Poly(Pentadecalactone) and Poly(3,4‐Ethylene Furanoates): Synthesis and Polymer Film Properties

Abstract

Bio‐based, fully degradable aliphatic‐aromatic block copolymers are synthesized from ω‐pentadecalatone and cyclic oligo(3,4‐ethylene furanoates). In the first approach, the ring‐opening polymerization of the cyclic oligo(3,4‐ethylene furanoates) is initiated by a poly(pentadecalactone) macroinitiator with a terminal hydroxy group. The reaction temperatures of the melt polymerization are 210 to 230 °C due to the high melting points of the oligo(3,4‐ethylene furanoates). Under these conditions, transesterification is observed. The blockyness of the reaction products depends on the reaction temperature and on the ratio of pentadecalactone to 3,4‐ethylene furanoate repeat units, which was 50:50, 80:20 and 90:10. At lower temperatures and more pentadecalactone content, the blockyness is larger. The number average molar mass of the block copolymers remains smaller than 20,000 g mol⁻¹. In the second approach, poly(pentadecalactone) is functionalized with an alkyne group, and the OH group of the oligo(3,4‐ethylene furanoates) (molar mass 1,900 g mol⁻¹) is converted into an azide group. Connecting the two polymers in a copper‐catalyzed 1,3‐dipolar addition reaction (“click reaction”) yields block copolymers with a number average molar mass of 12,400 g mol⁻¹. The mechanical properties of the polymer films are intermediate between those of the parent homopolymers.

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