Sequence-Controlled Polyhydroxyurethanes with Tunable Regioregularity Obtained from Sugar-Based Vicinal Bis-cyclic Carbonates

Abstract

The carbonation of biosourced 1,2-diols is a sustainable avenue for the synthesis bis-five-membered cyclic carbonates (bis-5CCs), the precursors of a valuable class of polymers, for example, polyhydroxyurethanes (PHUs). In this work, we performed the direct carbonation of optically pure sugar-based butadiene tetraols, namely, (i) meso-erythritol and (ii) its (S,S) diastereoisomer, (L)-threitol. The corresponding vicinal bis-5CCs, erythritol dicarbonate (EDC) and threitol dicarbonate (TDC), respectively, retain the stereochemistry of the starting tetraols. The comprehensive study of their aminolysis reaction, in DMSO and at room temperature, indicates that the kinetics and the regio-orientation of the ring opening of the 5CC are very much dependent on their stereochemistry. The total aminolysis of EDC results in the formation of hydroxyurethanes with an excess of secondary hydroxyl groups, (OH) II , of about 85%, against 60% for TDC. Moreover, when considering the two consecutive aminolyses of EDC (and TDC, respectively), the kinetic rate constant of the first aminolysis k 1,EDC (and k 1,TDC , respectively) is 1 order of magnitude higher than that of the second aminolysis, k 2,EDC ∼ k 1,EDC /10 (and k 2,TDC ∼ k 1,TDC /10, respectively). We used this feature to develop a onepot, two-step polymerization procedure, offering sequence-controlled PHUs. All the experimental results are well supported by density functional theory calculations. In the end, the comparative study of these two diastereoisomers of simple sugar-based vicinal bis-5CCs provides a new family of PHUs with tunable sequence-and regioregularities.

Bio-Based Poly(hydroxy urethane)s for Efficient Organic High-Power Energy Storage

“…18 Bio-based polymers synthesized from erythritol dicarbonate (EDC) look especially promising, as EDC is low-cost, is highly reactive, and can be produced on a large scale, with high conversion yields and in soft conditions from a natural sugar alcohol (i.e., erythritol). 17,19 In this paper, we demonstrate the potential of bio-based PHUs for energy storage. A series of 100% bio-based PHUs is synthesized from reacting EDC with bio-based diamines (H 2 N-(CH 2 ) n -NH 2 ) by polyaddition in DMSO at 80 °C.…”

Bio-based poly(hydroxy urethane)s for efficient organic high-power energy storage

“…1a. 15 In addition to being isocyanate-free, these PHUs provide a high density of polar groups with two hydroxyl and two carbamate functions per repeating unit, which is expected to result in significant dielectric properties. Three different PHUs were synthesised, with various α,ω-diamine alkyl chain lengths, namely n = 6, 8 and 12, referred to as PHU6, PHU8 and PH12, respectively.…”

“…As expected, the ratios of secondary to primary alcohols are of about 85 : 15 for the three polymers. 13,15 The number average molecular weight, Mn, and the dispersity, Ð, were determined by size exclusion chromatography in DMF (SEC, Fig. S2) and found to be Mn = 8.6, 4.4 and 3.4 kg•mol -1 and Ð = 2.2, 3.1 and 2.8, for n = 6, 8 and 12, respectively.…”

“…erythritol). 13,15 In this paper, we demonstrate the potential of bio-based PHUs for energy storage. A series of 100% biobased PHUs is synthesised from reacting EDC with bio-based diamines (H2N-(CH2)n-NH2) by polyaddition in DMSO at 80 °C.…”

Unveiling the reactivity of epoxides in carbonated epoxidized soybean oil and application in the stepwise synthesis of hybrid poly(hydroxyurethane) thermosets

“…Among the different non-isocyanate polyurethane (NIPU) synthetic pathways, the cyclic carbonate–amine reaction leading to polyhydroxyurethanes (PHUs) has been the most developed; it is a polyaddition reaction, thus releasing no by-product, moreover the reactants are innocuous and can be obtained from biobased building blocks. 4–6 In this sense, different biobased compounds such as vegetable oils and fatty acids, 7–13 glycerol, 14–16 sugar-derived molecules 17–20 or terpenes 21–23 and lignin 24 have been derivatized to prepare either cyclic carbonates or amines to design PHUs with a large set of thermomechanical properties. Vegetable oils are particularly interesting as they are readily available in large amounts, and they usually contain unsaturations that can be easily modified to obtain polyfunctional monomers.…”