Poly(carbonate‐urea‐urethane) networks exhibiting high‐strain shape‐memory effect

Abstract

A challenge in the design of shape‐memory polymers (SMPs) is to achieve high deformability with a simultaneous high shape recovery ratio. Here we explored, whether SMPs featuring large deformation capability and high shape recovery ratios can be created as polymer networks providing two kinds of netpoints based on covalent bonds and physical interactions. As a model system, we selected poly(carbonate‐urea‐urethane)s (PCUUs) synthesized by a precursor route, based on oligo(alkylene carbonate) diols, isophorone diisocyanate (IPDI), and water vapor. The PCUU networks exhibited a one‐way shape‐memory effect (1W‐SME) with programmed strains up to εprog = 1000% whereby they provided excellent shape fixity (92–97%) and shape recovery (≥99%) ratios. The switching temperatures (Tsw) varied between 36 and 65 °C and increased with the increasing molecular weight of the oligo(alkylene carbonate) diol and length of the hydrocarbon chain between the carbonate linkages. Tsw was also influenced by the strain applied during programming (εprog). Poly(carbonate‐urethane)s have been reported to have good biocompatibility and biostability, which in the combination of high‐strain capacity and high Young's modulus makes the obtained PCUUs interesting candidate materials suitable for medical devices such as medical sutures or vascular stents. Copyright © 2016 John Wiley & Sons, Ltd.

Synthesis of Shape-Memory Polyurethanes: Combined Experimental and Simulation Studies

“…The materials were used without any further purification. The alkylene bis(methylcarbonate)s (BMCs) were synthesized according to previously published procedures [20]. Briefly, in a 2000 cm 3 reactor equipped with a magnetic stirrer, Vigreux column, distillation condenser, and thermometer, 250.0 g (1.43 mol) of 1,10-decanediol and 1000.0 g (11.1 mol) of DMC were placed in the presence of potassium carbonate (3 mol.% referred to 1,10-decanediol), used as a catalyst.…”

“…Recently, we proposed the method of preparation of SMPs that involved the utilization of OCDs containing long hydrocarbon chains between the carbonate linkages. Obtained poly(carbonate-urea-urethane) networks (PCUUs) exhibited a high-strain shape-memory effect with excellent shape recovery and temporary shape fixation ratios [19,20], as well as a superb reversible bidirectional shape-memory effect [21].…”

Biobased polyurethanes for biomedical applications

“…Biobased PLA [ 299 , 300 ]- and vegetable oil [ 297 , 301 , 302 ]-based polyols are pertinent choices to synthesize renewable SMPUs. Moreover, polysaccharides have also been studied as multi-branched polyols [ 303 ], as well as biobased polycarbonate diol [ 304 ] and polyester polyols like PGS diol [ 295 ], PEA and PBA diols [ 305 ]. Important SMPUs properties of the previously mentioned studies and regarding their potential uses in the biomedical area reported in Table 6 .…”

Polymeric Materials Based on Carbon Dioxide: A Brief Review of Studies Carried Out at the Faculty of Chemistry, Warsaw University of Technology

“…The studies carried out in the CCTP show that highly crystallizable oligo(alkylene carbonate) diols with long hydrocarbon chains between carbonate linkages form temporary netpoints, whereas the permanent shape is defined by the small amount of hydrogen bonds, as well as covalent linkages within their hard segments (allophanate and biuret groups). Two types of isocyanate were used: IPDI [28] and lysine diisocyanate (LDI) [29]. The PCUU networks exhibited 1W-SME with programmed strains up to 1000%, whereby they provided excellent shape fixity (92-97% and 99% in the case of IPDI-and LDI-based PCUUs, respectively) and shape recovery (≥99%) ratios.…”