A solid poly(2-methoxyethyl acrylate) (PMEA)-based polyurethane (PU) has been synthesized through reversible addition−fragmentation chain transfer (RAFT) polymerization followed by polyaddition. PMEA with four hydroxyl-groups (PMEA-(OH)4) synthesized using RAFT reagents with 4 hydroxyl groups works as an effective prepolymer and crosslinker. The thermoset PMEA-based PU can be obtained by mixing PMEA-(OH)4 and diisocyanate without additional agents for the synthesis. The temperature-independent mechanical property of the thermoset PMEA-based PU due to the chemical crosslinking points is confirmed by dynamic mechanical analysis (DMA) at temperatures ranging from 25 °C to 110 °C. The mechanical property at room temperature is also evaluated by tensile testing: The Young's modulus of PMEA-based PU increased from 454 ± 31 kPa to 574 ± 54 kPa by decreasing Mn of the PMEA prepolymer from 14,000 to 7,600. It is concluded that our synthesized PMEA-based PU exhibits sufficiently elastomeric characteristics as compared with conventional crosslinked PMEA, which may be used as a durable and more stretchable biomedical material.
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