高分子乳液修复.ppt

* Selected Topics of Polymer Materials Science Yue Zhao Sichuan University, May 2008 (3) Shape-Memory Polymers What’s a shape-memory polymer ? A polymer that can be deformed and fixed into a temporary shape, and recover its original permanent shape only on exposure to an external stimulus such heat, light, electric field and pH. From Angew. Chem. Int. Ed. 2002, 41, 2034 Is the following statement right or wrong? Any amorphous polymers can be shape-memory polymers if processed (programmed) properly! Shape-memory effect is an intrinsic property of polymers based on the rubber (entropy) elasticity stretched at TTg chain orientation relaxation before cooling to TTg heating to TTg heating to TTg stretched at TTg quenching to TTg Basic requirement for shape-memory effect: No polymer chain relaxation (slipping, contraction, flow) under stress during the programming stage. This can be achieved by polymer crosslinking (formation of a network): covalent or physical crosslinks can effectively suppress the chain relaxation of the polymer under strain. Temporary shape: ``freezing`` chain mobility and stresses (chain deformation) Recovery to permanent shape: chain mobility activated under the effect of a stimulus and stresses released Thermosensitive shape-memory polymers From Angew. Chem. Int. Ed. 2002, 41, 2034 (a) Multi-block, phase segregated polyurethanes and ABA block copolymers Hard segment for Tpermanent and soft segment for Ttransition=Tm or Tg Ttransition adjusted to be around the body temperature for biomedical applications, in addition to biocompatibility and biodegradability. Implant inserted in compressed (temporary) shape can recover to application-relevant shape upon warming in the body. (b) Chemically crosslinked polyethylene: Commercialized heat-shrinkable polymers Crosslinking by ionizing irradiation after shaping, then deformed (expansion) at TTm followed by cooling for fixation; subsequent heating to TTm for recovery (e.g. heat-shrinkable tubing)