Macromolecules, Vol.50, No.13, 5155-5164, 2017
Creating Poly(tetramethylene oxide) Glycol-Based Networks with Tunable Two-Way Shape Memory Effects via Temperature-Switched Netpoints
Polymers with two-way shape memory effect (2W-SME) are of great potential in real applications due to the reversible nature. Though 2W-SME has been already realized in some semicrystalline networks by the crystallization-induced elongation (CIE) and melting-induced contraction (MIC), more adaptable 2W-SME systems are highly expected. In this work, to achieve tunable 2W-SME with different reversible deformation ranges, we designed a semicrystalline poly(tetramethylene oxide) glycol (PTMEG) network with temperature-switched netpoints. This adaptable network was constructed by photo-cross-linking of the PTMEG-based copolymer containing amorphous poly(D,L-lactide) (PDLLA) segments in main chain and photosensitive anthracene groups in side chain. The photo-cross-linking degrees of networks were adjusted by controlling irradiation time. Remarkably, 2W-SME in the current system was realized by the CIE and MIC of PTMEG segments for the first time. Here, along with the photo-cross-links, the low content of PDLLA served as a switchable netpoint which was controlled by high temperature (T-high). Differential scanning calorimetry (DSC) analysis revealed that all the photo-cross-linked networks exhibited desirable crystallinity. Dynamic mechanical analysis (DMA) indicated that there-Were two distinct declines of storage modulus (E') when temperature crossed T-m,T-PTMEG and T-g,T-PDLLA) which guided us to choose 45 and 70 degrees C as two specific T(high)s. 2W-SME was investigated by DMA under constant stress; in detail, the effects of applied stress, T-high, and photo-cross-linking degree synergizing with the switchable netpoints structure on the characteristics of 2W-SME (epsilon(i), epsilon(Non-CIE), epsilon(CIE), R-act(sigma) and R-rec(sigma)) have been disclosed.