Ring‐Opening Metathesis Polymerization of Biomass‐Derived Levoglucosenol

Abstract

The readily available cellulose-derived bicyclic compound levoglucosenol was polymerizedt hrough ringopening metathesis polymerization (ROMP) to yield polylevoglucosenol as an ovel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides,c ontains cyclic as well as linear segments in its main chain. Highmolar-mass polyacetals with apparent weight-average molar masses of up to 100 kg mol À1 and dispersities of approximately 2were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends.T he resulting highly functionalizedp olyacetals are glassy in bulk with ag lass transition temperature of around 100 8 8C. In analogy to polysaccharides,p olylevoglucosenol degrades slowlyi na n acidic environment.

Polymers from sugars and unsaturated fatty acids: ADMET polymerisation of monomers derived from d-xylose, d-mannose and castor oil

“…Besides ADMET, ring opening metathesis polymerisation (ROMP) was also reported for the polymerisation of lactonic sophorolipids [37][38][39][40] and levoglucosenol. 41 Inspired by these previous works, we herein exploit ADMET polymerisation for the synthesis of renewable polymers incorporating both monosaccharides and fatty acid moieties in the main polymer chain. Previously mentioned 10-undecenoic acid was employed as it is known to confer flexibility to polymer backbonesin contrast with previously reported purely sugar-based polymers, characterised by elevated glass transition temperatures (T g ) but brittle behaviour.…”

Controlled Living Cascade Polymerization To Make Fully Degradable Sugar-Based Polymers from d-Glucose and d-Galactose

“…Of note, there are several reports on ADMET polymerization or ROMP of biomassderived monomers, that do not contain sugars, but are still derived from carbohydrate feedstocks, such as glucose, 40,41 mannitol, 38 pentose, 42−44 and cellulose. 45 Unfortunately, the majority of these monomers did not enable controlled polymerizations.…”

Synthesis of Functionally and Stereochemically Diverse Polymers via Ring-Opening Metathesis Polymerization of Derivatives of the Biomass-Derived Platform Molecule Levoglucosenone Produced at Industrial Scale

“…When one considers the potential for multiple variations of the simple chemical manipulations deployed in this study, including the nature of the dienes that compounds 2 and 3 could react with, it would appear that a very large class of novel (bio)­polymeric materials is now available from the biomass-derived and abundant platform molecule levoglucosenone ( 2 ). As such, and given the recent report of the Schlaad group, LGO clearly warrants further attention as an important new building block for polymer synthesis.…”