Flexible, elastic and tear-resistant networks prepared by photo-crosslinking poly(trimethylene carbonate) macromers

Poly(trimethylene carbonate) (PTMC) macromers with molecular weights (Mn) between 1000 and 41,000 g mol−1 were prepared by ring opening polymerization and subsequent functionalization with methacrylate end groups. Flexible networks were obtained by radical photo-crosslinking reactions of these macromers. With increasing molecular weight of the macromer the networks obtained showed increasing swelling ratios in chloroform and decreasing glass transition temperatures, reaching a constant value of approximately −18 °C, which is close to that of linear high molecular weight PTMC. For all prepared networks the creep resistance was high. However, the molecular weight of the macromer strongly influenced the tensile properties of the networks. With increasing molecular weight of the macromer the E-modulus of the networks decreased from 314 MPa (lowest Mn) to 5 MPa (highest Mn), while their elongation at break continuously increased, reaching a very high value of 1200%. The maximum tensile strength values of the networks were found to first decrease with increasing Mn, but to increase again at values above approximately 10,000 g mol−1, at which the networks started to show rubber-like behavior. The toughness (area under the stress–strain curves, W) determined in tensile testing experiments, in tear propagation experiments, and in suture retention strength measurements showed that PTMC networks prepared from the higher molecular weight macromers (Mn > 10,000 g mol−1) were tenacious materials. The mechanical properties of these networks compare favorably with those of linear high molecular weight PTMC and well-known elastomeric materials like silicone rubber (poly(dimethylsiloxane)) and natural latex rubber. Additionally they also compare well with those of native blood vessels, which may be of importance in the use of these materials for the tissue engineering of small diameter blood vessels.