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

Leonardo Bueno Bronzeri (1) , Cony Gauche (1) , Leslie Gudimard (2) , Edwin-Joffrey Courtial (2) , Christophe Marquette (2) , Maria Isabel Felisberti (1)

1 UNICAMP - Universidade Estadual de Campinas = University of Campinas
2 ICBMS - Institut de Chimie et Biochimie Moléculaires et Supramoléculaires

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(e-caprolactone) (PCL) and poly(2-ethyl-2-oxazoline) (PEtOx) as polyols 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 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 showed that the polyurethanes are compatible with biomedical applications.

Mots clés: AMPHIPHILIC; POLYURETHANE; SYNTHESIS; PROPERTIES; 3D PRINTING; BIOCOMPATIBILITY

Domaines: Polymères; Biomatériaux

Leonardo Bueno Bronzeri, Cony Gauche, Leslie Gudimard, Edwin-Joffrey Courtial, Christophe Marquette, et al.. 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. European Polymer Journal, 2021, 151, pp.110449. ⟨10.1016/j.eurpolymj.2021.110449⟩. ⟨hal-03364503⟩