Nonisocyanate Poly(Hydroxyl Urethane)-Based Green Polymer Hybrid Coating Systems: Tailoring of Biomacromolecular Compound Architecture Using APTMS-ZnO/TEMPO-Oxidized Cellulose Nanoparticles

Abstract

Hybrid bionanocomposite coating systems (HBCSs) are green polymer materials consisting of an interface between a coating matrix and nanoparticles. The coating matrix was prepared by using a nonisocyanate poly­(hydroxyl urethane) (NIPHU) prepolymer crosslinked via 1,3-diaminopropane and epoxidized Jatropha curcas oil. TEMPO-oxidized cellulose nanoparticles (TARC) were prepared from microcrystalline cellulose, and (3-aminopropyl)­trimethoxysilane (APTMS)-coated ZnO nanoparticles (APTMS-ZnO) and their suspensions were synthesized separately. The suspensions at different weight ratios were incorporated into the coating matrix to prepare a series of HBCSs. FT-IR, 1H-NMR, 13C-NMR, XRD, SEM, and TEM were used to confirm the chemical structures, morphology, and elements of the coating matrix, nanomaterials, and HBCSs. The thermomechanical properties of the HBCSs were investigated by TGA-DTG and pencil hardness analyses. The UV and IR absorption spectra of the HBCSs were obtained using UV–vis spectroscopy and FTIR spectroscopy, respectively. The HBCSs exhibited good thermal stability at about 200 °C. The degradation temperature at 5% mass loss of all samples was over around 280 °C. The HBCSs exhibited excellent UV block and IR active properties with a stoichiometric ratio of the NIPHU prepolymer and EJCO of 1:1 (wt/wt) containing 5 wt % TARC and 15 wt % APTMS-ZnO nanoparticles. It was observed that the sample with 5 wt % TARC and 15 wt % APTMS-ZnO (HBCS-2) exhibited a uniform crosslinking and reinforcement network with a T onset of 282 °C. This sample has successfully achieved good coating hardness and excellent UV and IR absorption.

Bio‐based Poly(hydroxy urethane)s: Synthesis and Pre/Post‐Functionalization

“…Malonization of methyl 10‐undecenoate was used to create a monomer with a terminal double bond. Since the first study on the synthesis of thermoplastic BPHUs published in 2010 by Boyer et al., various fatty acid derivatives‐based CC synthesis routes have been introduced in the BPHUs synthesis [8,9b,15a,25] …”

“…In general, pre‐functionalization of BPHU is an in situ polymerization where crosslinking and functionalization occur at the same time between the starting monomers and the reactive functional moieties. Three steps synthesis of a multicomponent BPHU based nanocomposite system has been reported recently [9b] . In a typical procedure, firstly polycarbonate JCO and 1,3‐diaminopropane were used as starting monomers to synthesis BPHU.…”

“…Dangling −OH groups of the BPHU were targeted to make In situ polymerization via ring‐opening reaction of epoxidized JCO in the presence of H 2 SO 4 . Finally, the reactive functional moieties such as −COOH and −NH groups of TEMPO‐oxidized cellulose nanocrystals (TARC) and (3‐Aminopropyl)trimethoxysilane (APTMS) coated ZnO NPs were built covalent and hydrogen bonds with −OH groups formed in the system [9b] …”

“…It was found that the samples exhibited good thermal resilience, excellent UV block and IR absorption, good hardness of the coating with a uniformed crosslinking and reinforcing network (Scheme 9). [9b] Bisphenol A oligocyclocarbonate, polycarbonate and cyclosiloxanes have also been used as a starting monomer for this kind of pre‐functionalization to generate isocyanate‐free poly(arylenesiloxane) [15a,49] (Scheme 10). The resultant polymer displayed strong adhesion and better mechanical properties with −Si−(OR)n groups that could later react with hydroxyl groups in many types of matrices.…”

“… Pre‐functionalization of JCO based PHU using TEMPO‐oxidized cellulose nanocrystals and APTMS coated ZnO nanoparticles [9b,1b] …”