ABSTRACT
Poly(lactide)s stereocomplex ultrathin film with controlled structure at a molecular level was able to be prepared by stepwise assembly using the stereocomplex interaction. Pure stereocomplex crystal can be easily obtained by using this technique. When the substrates pre-coated with the stereocomplex assembly were immersed into solution of poly(L-lactide) or poly(D-lactide) for a long time, each polymer was homogeneously deposited on the substrates. The enantiomer was epitaxially crystallized on the stereocomplex film. The XRD pattern of the films showed similar characteristic peaks of the stereocomplex, indicating that the crystallization was influenced by conformation of polymer at the substrate. This is the first case of the epitaxially growth of polymers on the structurally regulated surface. These films had high degree of crystallinity although the assemblies did not undergo a crystallization process. This method was considered to be a general method that can be applied to other polymers, which able to form stereocomplex.
Subject(s)
Crystallization/methods , Membranes, Artificial , Nanostructures/chemistry , Nanostructures/ultrastructure , Nanotechnology/methods , Polyesters/chemistry , Adsorption , Macromolecular Substances/chemistry , Materials Testing , Molecular Conformation , Particle Size , Stereoisomerism , Surface PropertiesABSTRACT
A mixed suspension of the enantiomeric B-A-B triblock copolymers, polyoxyethylene-block-poly(L-lactide)-block-polyoxyethylene (PEG-PLLA-PEG) and polyoxyethylene-block-poly(D-lactide)-block-polyoxyethylene (PEG-PDLA-PEG), was found to induce reversible gel-to-sol transition depending on the polymer concentration and temperature. The storage and loss moduli of the gel formed at lower temperature were much higher than those of the gel prepared from the corresponding ABA-type triblock copolymers because of the higher polymer concentration in the former. Although the stereo-complexation of the PLLA and PDLA blocks occurred at higher temperature also in the B-A-B copolymers, it was not responsible for the gelation of the mixed suspension. The PEG chains, involved in the helix formation of the PLLA and PDLA, should form helices with opposite helical senses to aggregate and lead the gelation of the system.
