Chemo‐ and Regioselective Additions of Nucleophiles to Cyclic Carbonates for the Preparation of Self‐Blowing Non‐Isocyanate Polyurethane Foams

Abstract

Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving (for example, thermal insulation). Today, greener routes for their production are intensively searched for to avoid the use of toxic isocyanates. An easily scalable process for the simple construction of self‐blown isocyanate‐free PU foams by exploiting the organocatalyzed chemo‐ and regioselective additions of amines and thiols to easily accessible cyclic carbonates is described. These reactions are first validated on model compounds and rationalized by DFT calculations. Various foams are then prepared and characterized in terms of morphology and mechanical properties, and the scope of the process is illustrated by modulating the composition of the reactive formulation. With impressive diversity and accessibility of the main components of the formulations, this new robust and solvent‐free process could open avenues for construction of more sustainable PU foams, and offers the first realistic alternative to the traditional isocyanate route.

Synthesis and characteristics of nonisocyanate polyurethane composed of bio‐based dimer diamine for supercritical CO2 foaming applications

“…[12][13][14][15][16][17] Industrial production of nonisocyanate polyurethane (NIPU) has commenced in recent years and has been studied in many fields. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Their synthesis methods can be divided into four categories: condensation polymerization, rearrangement polymerization, ring-opening polymerization, and addition polymerization. 13 The addition of polymerization by cyclic carbonate with a diamine is the most promising synthesis route at present.…”

“…Industrial production of nonisocyanate polyurethane (NIPU) has commenced in recent years and has been studied in many fields 18–34 . Their synthesis methods can be divided into four categories: condensation polymerization, rearrangement polymerization, ring‐opening polymerization, and addition polymerization 13 .…”

Synthesis of reactive phosphorus-based carbonate for flame retardant polyhydroxyurethane foams

“…It helped to determine the interconnection of the pores. 38 When the ratio is close to 1 it corresponds to a foam with an open cell structure or interconnected cells. However, when the ratio is close to zero it means that the cells are not interconnected, which corresponds to a closed cell structure.…”

“…[30][31][32][33][34][35] Hence, PHU foams are also the most promising alternative to replace PUFs and until now, only a handful of works have been reported. 23,27,29,[36][37][38] Only few carbonate monomers are commercially available and most of them are very expensive. Fortunately, they can be easily obtained by direct carbonation of oxiranes with carbon dioxide (CO 2 ).…”

Cycloaddition of CO2 to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations

“…Cyclic organic carbonates are a class of compounds with multiple remarkable applications such as solvents [1][2][3][4] and chemical intermediates for the synthesis of fine chemicals [5][6][7] and polymers. [8][9][10][11][12] Importantly, the synthesis of cyclic carbonates via cycloaddition reaction of CO2 to epoxides offers the highly sought-after [13][14][15][16] opportunity to recycle CO2 as C1 source for the synthesis of commodity chemicals. ADD here: Bruno Grignard, Sandro Gennen, Christine Jérôme, Arjan W. Kleij Catalyst-free fixation of carbon dioxide into value-added chemicals: a review.…”