Biomacromolecules, Vol.8, No.3, 1018-1027, 2007
Shape-memory polymer networks from oligo[(epsilon-hydroxycaproate)-co-glycolate]dimethacrylates and butyl acrylate with adjustable hydrolytic degradation rate
Degradable shape-memory polymer networks intended for biomedical applications were synthesized from oligo[(epsilon-hydroxycaproate)-co-glycolate]dimethacrylates with glycolate contents between 0 and 30 mol % using a photopolymerization process. In addition AB copolymer networks were prepared by adding 60 wt % n-butyl acrylate as comonomer. All synthesized polymer networks are semicrystalline at room temperature. A melting transition T-m between 18 and 53 degrees C which can be used as switching transition for the shape-memory effect can be attributed to the crystalline poly(epsilon-hydroxycaproate) phase. At temperatures below T-m the elastic properties are dominated by these physical cross-links. At temperatures higher than T-m the E modulus of the amorphous polymer networks is lowered by up to 2 orders of magnitude, depending on the chemical cross-link density. Copolymer networks based on macrodimethacrylates with a M-n of up to 13 500 g center dot mol(-1) and a maximum glycolate content of 21 mol % show quantitative strain recovery rates in stress-controlled cyclic thermomechanical experiments. Hydrolytic degradation experiments of polymer networks performed in phosphate buffer solution at 37 degrees C show that the degradation rate can be accelerated by increasing the glycolate content and decelerated by the incorporation of n-butyl acrylate.