Rigid diol bearing 6‐6‐6 fused ring system derived from naturally occurring myo‐inositol and its polyaddition with diisocyanates

Abstract

Naturally occurring myo‐inositol was developed into a highly rigid diol by converting its 3,4‐ and 1,6‐vicinal diols in trans configuration into the corresponding butane‐2,3‐diacetals. The resulting diol bearing 6‐6‐6 fused ring system, in which conformational change is strictly suppressed, was combined with diisocyanates to perform polyadditions. The resulting polyurethanes were analyzed by differential scanning calorimetry, and it was found that their glass transition temperatures were much higher than those of the previously reported myo‐inositol‐derived polyurethanes, which were synthesized from a myo‐inositol‐derived diol bearing 5‐6‐5 fused ring system. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3798–3803

Rigid diols bearing two adamantane‐like components: Synthesis from naturally occurring myo‐inositol and application to the synthesis of high‐Tg polyurethanes

“…Some protocols for the regioselective reactions of the hydroxyl groups of myoinositol enable the synthesis of highly rigid derivatives, such as cyclic acetals and orthoesters, 23 which we have used as rigid monomers. [24][25][26] Orthoester 1, a triol with a rigid adamantane-like motif, is a useful precursor for rigid monomers (Scheme 1). [26][27][28] For example, the reaction of 1 with phenyl isocyanate affords a diol-type monomer 26 : Polyaddition of the diol with HMDI gives a linear polyurethane.…”

“…To date, we have focused on using naturally occurring myo ‐inositol as a renewable resource for polymer synthesis: myo ‐Inositol is obtained from nonedible bioresources, such as rice bran and bean skin. Some protocols for the regioselective reactions of the hydroxyl groups of myo ‐inositol enable the synthesis of highly rigid derivatives, such as cyclic acetals and orthoesters, 23 which we have used as rigid monomers 24–26 . Orthoester 1, a triol with a rigid adamantane‐like motif, is a useful precursor for rigid monomers (Scheme 1).…”

Synthesis of hydroxyl‐bearing polyurethanes from naturally occurring myo‐inositol

“…Consequently, myo ‐inositol can be produced from rice bran, which is often wasted because of its current lack of applications . So far, we and other research groups have demonstrated some efficient uses of myo ‐inositol as a starting material for the synthesis of polymers with repeating units bearing cyclic components. Examples include polyurethane synthesis based on the derivatization of myo ‐inositol into a rigid diol, 1 , and its polyaddition with diisocyanates (Scheme ) .…”