Non-Isocyanate Polyurethanes from Carbonated Soybean Oil Using Monomeric or Oligomeric Diamines To Achieve Thermosets or Thermoplastics

Abstract

Fully bio-and CO 2 -sourced non-isocyanate polyurethanes (NIPUs) were synthesized by reaction of carbonated soybean oil (CSBO) either with biobased short diamines or amino-telechelic oligoamides derived from fatty acids to achieve respectively thermoset or thermoplastic NIPUs. Biobased carbonated vegetable oils were first obtained by metal-free coupling reactions of CO 2 with epoxidized soybean oils under supercritical conditions (120 °C, 100 bar) before complete characterization by FTIR, 1 H NMR, and electrospray ionization mass spectroscopy (ESI-MS). In a second step, biobased NIPUs were produced by melt-blending of the so-produced cyclocarbonated oil with the biobased aminated derivatives. The thermal and mechanical properties of resulting polymers were found to be depending on the cyclocarbonated vegetable oil/amine ratio. More precisely, short diamines and CSBO led to the formation of cross-linked NIPUs, and the resulting tensile and thermal properties were poor. In contrast, elastomeric NIPUs derived from oligoamides and CSBO exhibited a better rigidity, an improved elongation at break (ε r up to 400%), and a higher thermal stability (T 95 wt % > 350 °C) than those of starting oligoamides. These results are impressive and highlight the potentiality of this environmental friendly approach to prepare renewable NIPU materials of high performances.

Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO2 Utilization

“…Vegetable oils are renewable sources of internal olefins and thus represent industrially attractive substrates. [181] 6c-ESBO prepared under such conditions was recently applied as ap recursor in the preparation of bio-based poly(hydroxyurethane) gluesf or metal substrates. The use of these substrates in PHUs chemistry is regarded as valuable strategy to preparep artially or entirely bio-based polymers, depending on the origin of the diamines employed.…”

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

“…Compared to traditional PUs, these new PUs have hydroxyl groups, so they are called polyhydroxyurethanes (PHUs). [13][14][15][16][17][18][19][20][21] Fleischer et al 15 investigated catalytic carbon dioxide fixation by carbonation of glycerol, trimethylolpropane, and pentaerythritol glycidyl ether, followed by curing with citric acid amino amides in the presence of cellulose carbonate. [10][11][12] Among all the cyclic carbonates, fivemembered bis(cyclic carbonate)s have stable performance and are the most widely studied.…”

CO2‐Sourced Non‐Isocyanate Poly(Urethane)s with pH‐Sensitive Imine Linkages

“…Exposure to isocyanates may cause skin irritation [12] and occupational asthma. [15,16,18,21] Among these examples, the latter technique is certainly one of the most investigated and gives NIPUs that showed great promises as PU alternatives for thermosets, [22,23] foams, [24,25] coatings, [26] adhesives/glues [27] and hydrogels. [14] Hence, several isocyanate-free alternatives to the conventional synthesis of PUs were developed, and provide the so-called non-isocyanate polyurethanes (NIPUs).…”

“…[15,16] They mainly include the CO 2 /aziridine copolymerization, [17] the melt transurethanization, [15,18,19] the ring-opening polymerization of cyclic urethanes, [20] and the polyaddition of polycyclic carbonates with polyamines. [22,24,30] Despite the successful preparation of various materials based on NIPUs, their application in fields requiring their hydrolytic degradation has not been developed, and their (bio)degradation has been rarely explored. [28] Importantly, polycyclic carbonates can be produced by the (organo)catalyzed coupling of CO 2 with epoxides.…”