Amphiphilic and segmented polyurethanes based on poly(ε-caprolactone)diol and poly(2-ethyl-2-oxazoline)diol: Synthesis, properties, and a preliminary performance study of the 3D printing. (15th May 2021)

• Record Type: Journal Article
• Authors: Bronzeri, Leonardo Bueno; Gauche, Cony; Gudimard, Leslie; Courtial, Edwin-Joffrey; Marquette, Christophe; Felisberti, Maria Isabel
• Is Part Of: European polymer journal. Volume 151(2021)
• Publication Date: 2021-05-15
• Subjects: Amphiphilic -- Polyurethane -- Synthesis -- Properties -- 3D printing -- Biocompatibility; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2021.110449
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: Amphiphilic polyurethanes based on PCL and PEtOx were synthesized. The polyurethanes are heterogenous in solid state due to the immiscibility of PCL end PEtOx. Polyurethanes presented a LCST behaviour similar to PEtOx in aqueous medium. Polymers are applicable for 3D printing at high temperatures. The polyurethanes are biocompatible. Abstract: Polyurethanes (PU) have a wide variety of applications due to possessing tailored properties which can be imparted by composition. The combination of polyols in different ratios provide specific properties for the segmented PU, such as mechanical strength, elasticity, hydrophilicity and so on. In this work, amphiphilic and segmented polyurethanes, based on poly(ε-caprolactone)diol (PCL-diol) and poly(2-ethyl-2-oxazoline)diol (PEtOx-diol) at variable mass fractions, were synthesized by a two-step route and characterized according to composition, molar mass, thermal, dynamic mechanical, and rheological properties. Polyurethanes with molar masses ranging from 17.9 to 39.6 kDa, and a molar mass dispersity in the range of 2.0–4.0, are capable of swelling in water, with the swelling coefficient being modulated by the polyurethane composition and by the temperature because of the lower critical solubility temperature (LCST) behavior of PEtOx in an aqueous medium. PCL and PEtOx segments in the PU chains are partially miscible, therefore the polyurethanes are heterogeneous, presenting a PCL/PEtOx miscible phase dispersed in a PCL rich matrix in the solid state. PU with 50% mass fraction of PEtOx presented a gelation temperature of 69 °C, as determined by rheology, and was evaluated for Fused Deposition Modelling (FDM) 3D printing, showing promising features, although with a low resolution and fidelity to the computational project, mainly due to its high viscoelasticity which may be modulated by the molar mass of the polymer. Moreover, cell viability tests suggest that the polyurethanes are compatible with biomedical applications.