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

Abstract

New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Nonisocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU's urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post-functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding.

Lignin-derivable alternatives to petroleum-derived non-isocyanate polyurethane thermosets with enhanced toughness

“…For example, aromatic building blocks provide the required rigidity to networks for high-performance applications, while aliphatic building blocks offer weather and ultraviolet light resistance. 4,5,[15][16][17] Although NIPU thermosets derived from biobased feedstocks have been reported in the literature, 1,18,19 many of these approaches have been primarily limited to aliphatic/cycloaliphatic, bifunctional or multifunctional cyclic carbonates derived from soybean oil, [20][21][22] linseed oil, 23 glycerol, pentaerythritol, trimethylolpropane, 24 or limonene. 25 The aliphatic or cycloaliphatic backbones present in most biobased NIPUs result in thermosets with relatively low moduli and tensile strengths.…”

“…25 The aliphatic or cycloaliphatic backbones present in most biobased NIPUs result in thermosets with relatively low moduli and tensile strengths. 1,[18][19][20][22][23][24][25] In contrast, petroleumbased bisphenol A (BPA)-derived cyclic carbonate (BPACC), prepared from the dicarbonation of BPA diglycidyl ether (BADGE), is often employed to make higher-moduli NIPU networks. 15,16,26 Unfortunately, BPA is considered non-sustainable 27,28 and is a suspected endocrine disruptor, as it can potentially bind to estrogen receptors.…”

Biodegradable isocyanate-free polyurethane films via a noncatalytic route: facile modified polycaprolactone triol and biobased diamine as precursors

“…22 Five-, six-, seven-and eight-membered cyclic carbonate rings tend to afford PU, where the vemembered ring precursor has been noted to function as optimal ring size, reaction feasibility and facile reactivity with various amines. [23][24][25][26] Despite being a greenhouse gas, CO 2 has been used to form cyclic carbonates via the transformation of an epoxy group into a cyclic carbonate with the aid of a catalyst under high pressure. Moreover, CO 2 xation at atmospheric pressure has been reported recently.…”

Recent Progress of Non-Isocyanate Polyurethane Foam and Their Challenges

“…Recent reviews have reported sustainable routes for the preparation of NIPUs via several methods as well as starting monomers [ 15 , 21 , 22 , 23 ]. Here, we report the synthesis procedures and the remaining challenges of NIPUFs using both an external blowing agent or self-blowing reactions.…”