The basic principle for the operation of a thermally stimulated shape memory polymer (SMP) is a drastic change in elastic modulus above the glass transition temperature (Tg). This change from glassy modulus to rubbery modulus allows the material to be deformed above the Tg and retain the deformed shape when cooled below the Tg. The material will recover its original shape when heated above the Tg again. However, thermal activation is not the only possibility for a polymer to exhibit this shape memory effect or change of modulus. This paper discusses results of an alternative approach to SMP activation.

It is well known that the Tg of a thermosetting polymer is proportional to its crosslinking density. It is possible for the crosslinking density of a room temperature elastomer to be modified through photo-crosslinking special photo-reactive monomer groups incorporated into the material system in order to increase its Tg. Correspondingly, the modulus will be increased from the rubbery state to the glassy state. As a result, the material is transformed from an elastomer to a rigid glassy photoset, depending on the crosslinking density achieved during exposure to the proper wavelength of light. This crosslinking process is reversible by irradiation with a different wavelength, thus making it possible to produce light-activated SMP materials that could be deformed at room temperature, held in deformed shape by photo-irradiation using one wavelength, and recovered to the original shape by irradiation with a different wavelength.

In this work, monomers which contain photo-crosslinkable groups in addition to the primary polymerizable groups were synthesized. These monomers were formulated and cured with other monomers to form photo-responsive polymers. The mechanical properties of these materials, the kinetics, and the reversibility of the photo-activated shape memory effect were studied to demonstrate the effectiveness of using photo-irradiation to effect change in modulus (and thus shape memory effect).