Hybrid Nonisocyanate Polyurethanes (H‐NIPUs): A Pathway towards a Broad Range of Novel Materials

Abstract

The increasing demand for using less toxic and dangerous products has fostered the development of nonisocyanate polyurethanes (NIPUs). Despite several years of progress within the search for these novel materials, they are still facing difficulties to reach the market. This may be due to the low mechanical properties obtained, which can be explained by the difficult access to high molar masses polymers. The combination of NIPUs with other types of polymers, thus forming polymer-polymer hybrid-NIPUs (so called H-NIPUs) can be an interesting alternative for the valorization of NIPUs though. This review describes the latest advancements in the developments of H-NIPUs, with a specific focus on the combination with epoxy, polyacrylic, and silicium-containing polymers. Finally, the emerging field of combining NIPUs with biopolymers is discussed. A specific focus on the synthetic challenges is provided, as well as their resulting influence onto the final material properties, thus showing how the synergistic combination of NIPUs with other polymers can be a promising pathway toward the formation of novel materials.

A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications

“…Conventional petrochemical diisocyanates (Figure 15), such as MDI, TDI and others, are toxic, hazardous, nonrenewable, and synthesized from poisonous phosgene gas (Llevot et al, 2016;Sawpan, 2018). Thus, NIPUs, such as polyhydroxyurethanes (PHUs) arising from aminolysis of cyclic carbonates with diamines (Figure 28a), serve as environmentally friendly and renewable alternatives (Bizet et al, 2022;Carre et al, 2015Carre et al, , 2019Cornille et al, 2017;Gomez-Lopez et al, 2021;Kreye et al, 2013;Maisonneuve et al, 2015;Nohra et al, 2013). The presence of hydroxy groups adjacent b CTAB, cetyltrimethylammonium bromide; NMP, N-methyl-2-pyrrolidone; SiO 2 -I, silica-supported 4-pyrrolidinopyridinium iodide; TBAB, tetrabutylammonium bromide; X, Br, Cl and I. c CO 2 was continuously bubbled through a solution of reactants at atmospheric pressure.…”

A Review on CO2‐Based Polyureas and Polyurea Hybrids

“…The reduction, capture, or utilization of CO 2 discharged from industrial processes is also one of the greatest scientific and technological challenges of the 21st century. [9] Current interest in the area of CO 2 utilization is focused on the transformation of it into high value-added chemicals, [10][11][12] fuels, [13][14] and polymers [1,4,15,16] including PUs, PUas, polycarbonates and so on. Herein, the CO 2 -involved routes for PUas synthesis from either CO 2 or CO 2 -derived building blocks (e. g. carbonate polycarbonate, urea, methanol) with diamine will be reviewed firstly, including the properties of the synthesized CO 2 -based PUas.…”

Accelerating the Curing of Hybrid Poly(Hydroxy Urethane)-Epoxy Adhesives by the Thiol-Epoxy Chemistry

“…There are two main strategies for the production of PHU-epoxy hybrids: ,, (i) the one-step terpolymerization of epoxy and cyclic carbonates with amines and (ii) the chain extension of amino-terminated PHU (NH 2 –PHU–NH 2 ) prepolymer with the epoxy resin. The amino-terminated prepolymer strategy is preferable as the reaction between amines and epoxides is much faster than the one between amines and cyclic carbonates (Figure ).…”

“…12 The creation of hybrid systems through the combination with epoxy chemistry is particularly popular and has been shown to lead to PHUs with better adhesion performance 13−19 and also to improve their properties for other applications, such as coatings. 20−24 There are two main strategies for the production of PHUepoxy hybrids: 12,25,26 (i) the one-step terpolymerization of epoxy and cyclic carbonates with amines and (ii) the chain extension of amino-terminated PHU (NH 2 −PHU−NH 2 ) prepolymer with the epoxy resin. The amino-terminated prepolymer strategy is preferable as the reaction between amines and epoxides is much faster than the one between amines and cyclic carbonates (Figure 1).…”