Effects of sensitizer length on radiation crosslinked shape-memory polymers

Shape-memory polymers (SMPs) are smart materials that can be designed to retain a metastable state and upon activation, recover a preprogrammed shape. In this study, poly(methyl acrylate) (PMA) is blended with poly(ethylene glycol) diacrylate (PEGDA) of various molecular weights in various concentrations and subsequently exposed to ionizing radiation. PEGDA sensitizes the radiation crosslinking of PMA, lowering the minimum absorbed dose for gelation and increasing the rubbery modulus, after crosslinking. Minimum dose for gelation, as determined by the Charlesby-Pinner equation, decreases from 25.57 kGy for unblended PMA to 2.06 kGy for PMA blended with 10.00 mole% PEGDA. Moreover, increase in the blend concentration of PEGDA increases the crosslinking density of the resulting networks. Sensitizer length, namely Mn of PEGDA, also affects crosslinking and final mechanical properties. Increase in the length of the PEGDA molecule at a constant molar ratio increases the efficacy of the molecule as a radiation sensitizer as determined by the increase in gel fraction and rubbery modulus across doses. However, at a constant weight ratio of PEGDA to PMA, shorter PEGDA chains sensitize more crosslinking because they have more reactive ends per weight fraction. Sensitized samples of PMA with PEGDA were tested for shape-memory properties and showed shape fixity of greater than 99%. Samples had a glass transition temperature near 28 deg. C and recovered between 97% and 99% of the induced strain when strained to 50%.