Synthesis, polymerisation and degradation of poly(lactide-co-propylene glycol) dimethacrylate adhesives

Abstract

Fluid ABA triblock poly(lactide-co-propylene glycol-co-lactide)s with 7, 17 or 34 propylene glycol and 2, 4, or 8 lactic acid units in each B and A block, respectively, end capped with methacrylate groups were prepared and polymerisation rates upon blue light exposure for 60, 120 or 240 s using 0.5, 1 or 2 wt.% initiators determined. The shortest monomer formulation, with 0.5 wt.% initiators, was most promising as an injectable degradable adhesive for biomedical applications, achieving 96% polymerisation by 120 s after the start of 60 s illumination, forming then a semi-rigid polymer that in water released linearly with time poly(methacrylic-co-lactic) acid degradation products. Over 14 weeks, 2 mm thick specimens largely maintained their dimensions as water sorption balanced the 19 wt.% material loss. Raising initiator concentration or monomer length reduced polymerisation rate on the lower surface of samples. Increasing the number of lactic acid units in each A block from 2 to 8 also enhanced photocrosslinked polymer water sorption and increased average total mass loss to 60 wt.% over 14 weeks but acid product release rate decreased with time. Monomers produced with longer polypropylene glycol B blocks required longer periods of light exposure for full cure and the final polymers exhibited slower non-linear hydrolytic degradation.