Synthesis, curing, and degradation kinetics of polyurethanes based on poly(ethylene glycol), isosorbide, and pentamethylene diisocyanate

Abstract

Polyurethane (PU) synthesis based on poly(ethylene glycol) (PEG) with isosorbide (ISO) and pentamethylene diisocyanate (PDI), named (ISOPUs) was carried out targeting PUs from renewable sources. The cross-linked ISOPUs were produced and the details of the curing kinetics were determined via Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). DSC scans displayed exotherms between 100 and 200 C, related to cross-linking. ISO addition accelerated the curing and the maximum curing rate (Cmax), with 91 C and 0.2964 min À1 for the compound with 70% ISO. FTIR spectra confirmed the interaction between OH (ISO/PEG) and NCO (PDI) groups, with total NCO consumption (band at 2267 cm À1 ).Through the thermogravimetric analyses (TGA), the PU/70% ISO presented weight loss at 146 C due to the degradation of ISO. ISOPUs displayed a decreased activation energy (Ea) during curing over a range of 100 to 42 kJ/mol for 0 < α < 5%, as demonstrated using the Friedman model, and higher thermal stability as evidenced through TG analyses. Curing and degradation kinetics were modeled using Friedman (FR), Kissinger-Akahira-Sunose (KAS), and Ozawa-Flynn-Wall (OFW). Overall, ISO accelerated the curing rate and increased the degradation Ea, suggesting high thermal stability for PUs with intermediate ISO contents, that is, 30%-50%. K E Y W O R D S biobased polyurethane, curing and degradation kinetics, Isosorbide, pentamethylene diisocyanate, poly(ethylene glycol) 1 | INTRODUCTION Polyurethanes (PU) based on renewable sources, such as bio-based polyols and diisocyanates are being synthesized with the objective to replace PUs from non-renewable sources, such as petroleum, and to reduce the use of toxic isocyanates. The synthesis of bio-based PUs from alternative resources, such as glucose has been growing considerably due to its potential to modify the mechanisms of curing and degradation, providing greater chemical, and physical stability. 1-4 In this context, Wang et al. 5 successfully cross-linked thermosetting PUs through the reaction of a bio-based diol with a monocyclic acetal structure and a trifunctional isocyanate reinforced with carbon fibers.The resulting material presented higher performance for application in the automotive, aerospace, and sports equipment industries.Polyurethanes synthesis takes place through urethane bonds by the polymerization of flexible segments (polyether or polyester), known as polyols, which have one or more OH groups, and rigid segments (diisocyanates) which have two or more NCO groups.