Shape-memory properties of hydrogels having a poly(ε-caprolactone) crosslinker and switching segment in an aqueous environment

The dual-shape capability of grafted multiphase copolymer networks containing crystallisable poly(ε-caprolactone) switching domains were explored in an aqueous environment. The shape-memory effect of such hydrogels is controlled by the orientation of the crystalline domains as assessed in situ by small and wide angle X-ray scattering experiments. [Display omitted] ► Shape-memory hydrogels with crystallizable poly(ε-caprolactone) switching domains. ► The shape-memory effect was explored in an aqueous environment. ► The crystallization was studied by in situ X-ray scattering experiments. ► The orientation of the crystalline domains controlled the shape-memory effect. Multiphase copolymer networks are of great relevance as their thermal and mechanical as well as shape-memory properties can be adjusted by the variation of the composition and crosslink density. In this context recently grafted copolymer networks (named CLEG), prepared by thermal free-radical polymerization with different ratios of the hydrophobic telechelic crosslinker poly(ε-caprolactone) diisocyanoethyl methacrylate (PCLDIMA, Tm,PCL=55°C) and hydrophilic poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMA, Tm,PEG=38°C) as co-monomer, were introduced, which additionally allow the alteration of the overall elastic properties via controlled water uptake. Here we study the thermomechanical properties as well as the shape-memory behavior of a series of CLEG copolymer networks in an aqueous environment. The mechanical properties of the networks at 25°C in aqueous environment were found to increase from 4MPa to 77MPa with increasing crosslink density. The shape-memory properties of the copolymer networks were examined in an aqueous environment by both bending as well as uniaxial elongation experiments. Excellent dual-shape properties with high shape fixity ratios around Rf=79–100% and shape recovery ratios in the range of Rr=59% to Rr=100% were obtained for copolymers with a PCLDIMA weight fraction ⩾50wt% in the starting composition. The swelling of CLEG in H2O resulted in a reduction of the switching temperature. Furthermore the structural changes during programming of CLEG were assessed in situ by small and wide angle X-ray scattering (SAXS, WAXS) experiments, which confirmed that the overall degree of crystallinity as well as the orientation of the crystalline domains controlled the dual-shape performance. We have found that an appropriate switching segment should result in a degree of