A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s

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T1 - A rigid spirocyclic diol from fructose-based 5-hydroxymethylfurfural: synthesis, life-cycle assessment, and polymerization for renewable polyesters and poly(urethane-urea)s

AU - Warlin, Niklas

AU - Garcia Gonzalez, Nelly

AU - Mankar, Smita

AU - Valsange, Nitin

AU - Sayed Ali Sayed, Mahmoud

AU - Pyo, Sang-Hyun

AU - Rehnberg, Nicola

AU - Lundmark, Stefan

AU - Hatti-Kaul, Rajni

AU - Jannasch, Patric

AU - Zhang, Baozhong

N1 - The article was received on 30 Aug 2019, accepted on 10 Nov 2019 and first published on 13 Nov 2019

PY - 2019

Y1 - 2019

N2 - There is currently an intensive development of sugar-based building blocks toward the production of renewable high performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life cycle assessment (LCA) indicated that the spiro-diol produced 46% less CO2 emission than bio-based 1,3-propanediol. Polymerizations of the spiro-diol together with another sugar-based flexible 1,6-hexanediol for the production of polyesters and poly(urethane-urea)s were investigated, and reasonably high molecular weights were achieved when up to 20 or 60 mol% spiro-diol was used for polyesters or poly(urethane-urea)s, respectively. The glass transition temperatures (Tg) of the polyesters and poly(urethane-urea)s significantly increased upon the incorporation of the rigid spirocyclic structure. On the other hand, it was observed that the spiro-diol was heat-sensitive, which could cause coloration andpartial crosslinking when >10%(with respect to dicarboxylate) was used for the polyester synthesis at high temperatures.The results indicated that the polymerization conditions have to be carefully controlled in order to avoid coloration and side reactions during the polyester formation when >10% of the spiro-diol is used. However, when the spiro-diol was used for the synthesis of polyurethanes at lower temperature, the side reactions were insignificant. This suggests that the new spiro-diol can be potentially suitable toward the production of sustainable rigid polyurethane materials like coatings or foams, as well as renewable polyesters after further optimization of the polymerization conditions.

AB - There is currently an intensive development of sugar-based building blocks toward the production of renewable high performance plastics. In this context, we report on the synthesis of a rigid diol with a spirocyclic structure via a one-step acid-catalyzed acetalation of fructose-sourced 5-hydroxymethylfurfural and pentaerythritol. Preliminary life cycle assessment (LCA) indicated that the spiro-diol produced 46% less CO2 emission than bio-based 1,3-propanediol. Polymerizations of the spiro-diol together with another sugar-based flexible 1,6-hexanediol for the production of polyesters and poly(urethane-urea)s were investigated, and reasonably high molecular weights were achieved when up to 20 or 60 mol% spiro-diol was used for polyesters or poly(urethane-urea)s, respectively. The glass transition temperatures (Tg) of the polyesters and poly(urethane-urea)s significantly increased upon the incorporation of the rigid spirocyclic structure. On the other hand, it was observed that the spiro-diol was heat-sensitive, which could cause coloration andpartial crosslinking when >10%(with respect to dicarboxylate) was used for the polyester synthesis at high temperatures.The results indicated that the polymerization conditions have to be carefully controlled in order to avoid coloration and side reactions during the polyester formation when >10% of the spiro-diol is used. However, when the spiro-diol was used for the synthesis of polyurethanes at lower temperature, the side reactions were insignificant. This suggests that the new spiro-diol can be potentially suitable toward the production of sustainable rigid polyurethane materials like coatings or foams, as well as renewable polyesters after further optimization of the polymerization conditions.

U2 - 10.1039/C9GC03055G

DO - 10.1039/C9GC03055G

M3 - Article

VL - 21

SP - 6667

EP - 6684

JO - Green Chemistry

JF - Green Chemistry

SN - 1463-9270

IS - 24

ER -