Stereoregular functionalized polysaccharidesviacationic ring-opening polymerization of biomass-derived levoglucosan

Abstract

We report the facile synthesis and characterization of 1,6-α linked functional stereoregular polysaccharides from biomass-derived levoglucosan via cationic ring-opening polymerization (cROP). Levoglucosan is a bicyclic acetal with rich hydroxyl functionality,...

Biobased and degradable thiol–ene networks from levoglucosan for sustainable 3D printing

“…In our first work on levoglucosan, we identified mild functionalization routes to access a triallyl levoglucosan monomer, which could be polymerized with biocompatible catalysts to obtain a high functionality allylic scaffold. 38 The levoglucosan based allylic polymer was readily subjected to UV-mediated thiol-ene click chemistry to afford functional polymers with tunable properties and high thermal stability due to the rigid glucopyranose ring in the polymer backbone. 38 While our previous work lays the foundation for reactive levoglucosan based materials, there is still ample space for the development and characterization of levoglucosan-based ther-mosets.…”

“…38 The levoglucosan based allylic polymer was readily subjected to UV-mediated thiol-ene click chemistry to afford functional polymers with tunable properties and high thermal stability due to the rigid glucopyranose ring in the polymer backbone. 38 While our previous work lays the foundation for reactive levoglucosan based materials, there is still ample space for the development and characterization of levoglucosan-based ther-mosets. To the best of our knowledge, research on UV-assisted 3D printing of levoglucosan-based resins has not been conducted before.…”

Recent Advances in Sequence‐Controlled Ring‐Opening Copolymerizations of Monomer Mixtures

“…In addition, cyclic acetals are often found in natural products such as anhydrosugars, and therefore such acetal-containing anhydrosugars have been utilized to prepare polymers via ROP of cyclic acetals. [136][137][138][139][140][141][142] Alternating copolymerization of cyclic acetals with anhydrides was recently achieved using BF 3 • Et 2 O at 25-80 °C, affording over 40 different polyesters with M n s of 8 to 33 kDa and Đs of 1.2-1.5. [143] The obtained polyesters exhibited low T g s (À 64-À 27 °C) with relatively low absolute viscosities (Scheme 7b).…”

“…Coates and coworkers recently reported the controlled cationic polymerization of cyclic acetals could be mediated by InBr 3 /2,6‐di‐ tert ‐butyl pyridine with chloromethyl methyl ether as the initiator, which produced polyacetals with M n s ranging from 37 to 220 kDa (Scheme 7a) [46] . In addition, cyclic acetals are often found in natural products such as anhydrosugars, and therefore such acetal‐containing anhydrosugars have been utilized to prepare polymers via ROP of cyclic acetals [136–142] …”

Lipase-Catalyzed Synthesis of Biobased Polyesters Containing Levoglucosan Units

“…Yet, despite long-standing interest, no levoglucosan-based polymer was ever reported in the literature, other than synthetic polysaccharides. − As pointed out in 1993 by researchers from the Canadian company BC Research, LGA could confer hydrophilicity, biodegradability, and optical activity (chirality) to the polymeric structure . These advantages are nevertheless still hampered by the low reactivity of LGA.…”