From hydroxyurethane methacrylates to hybrid nonisocyanate polyurethanes

Abstract

New hybrid polyhydroxyurethane networks were quantitatively synthesized by radical polymerization of new hydroxyurethane methacrylate (HUMA) prepolymers. These HUMAs were synthesized in several steps. First, bis(cyclic carbonate) poly(propylene oxide) was reacted with two different diamines (ethylene diamine and 2,2 0 -(ethylenedioxy)diethylamine) in excess. Then, these end-functionalized hydroxyurethane prepolymers were converted into end-functionalized hydroxyl prepolymers by ring opening of ethylene carbonate. Finally, a methacrylate function was grafted to the hydroxyl functions. All these steps were performed at room temperature. These prepolymers were thermally either homopolymerized or copolymerized using benzylmethacrylate or poly(ethylene oxide) bisphenol A dimethacrylate as comonomers, leading to new hybrid nonisocyanate polyurethane networks with various properties.Polyurethane acrylates are currently widely used for coating applications and are notably obtained by ultraviolet (UV)-light processes. They exhibit excellent mechanical and chemical properties such as high abrasion resistance, toughness, or tear strength. [18][19][20][21][22] Moreover, thanks to various reactive diluents, their properties can be easily adjusted depending on the desired requests. Furthermore, the microphase separation of the urethane segments, mainly governed by the soft segment, enables the control of the mechanical properties of the thermosets. 23 Additionally, polyurethane methacrylates were also developed in order to obtain high glass transition temperatures and to improve the stability of the prepolymers. 24 Polyurethane methacrylates are major curing agents providing solvent-resistance, mechanical strength, and UV or thermal curing ability. 22,25,26 When moving to NIPU, few literature is provided for hydroxyurethane methacrylate (HUMA) monomers having only one HU unit. They are synthesized from the ring-opening reaction of ethylene carbonate by an amine followed by the grafting of methacrylic moiety. For example, these methacrylate monomers were investigated for their ability to react under UV Additional supporting information may be found in the online version of this article.M. Decostanzi and C. Bonneaud contributed equally to this article.

Functionalized acrylic polyhydroxy urethanes as molecular tool box for photocurable thermosets and 3D printing

“…These can subsequently react with polyfunctional acrylates via Michael addition or by reaction with acrylate-functionalized epoxides, methacryloylchloride or methacrylic anhydride to form acrylic oligourethanes. [13][14][15][16] In a recent advance, our group introduced a noniscocyanate route to difunctional hydroxyurethane methacrylates (HUMA) prepared by reacting difunctional amines with cyclic carbonate methacrylate, which is readily available via the chemical fixation of carbon dioxide with glycidyl methacrylate (see Figures 1, 2). The ring opening of the cyclic carbonate with amine accounts for the formation of both primary and secondary hydroxy groups in β-position to the urethane group.…”

Developing non-isocyanate urethane-methacrylate photo-monomers for 3D printing application

“…methacrylation. 7,23,24,28,29 On this subject, Wang et al 28 synthesized urethane-methylates through the mentioned non-isocyanate route as reactive diluents for UV-curable polyurethane coatings. Meng et al 23,24 prepared also urethane-methylates via the same route for emulsion polymerization.…”

Progress in hybrid non‐isocyanate polyurethanes

“…The hydroxyl groups are transformed to methacrylate groups, which form thermosets via radical crosslinking. 36 Zareanshahraki et al and Assumption and Mathias also described UV-curable hybrid PHUs via methacrylated amine-and alcohol-terminated NIPUs. 37,38 Schimpf et al synthesized methacrylate-terminated resins by reacting multifunctional amines with methacrylated glycerol carbonate.…”