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

Abstract

Monomers derived from glucose and galactose, which contain an endocyclic alkene (in the sugar ring) and a terminal alkyne, underwent a cascade polymerization to prepare new polymers with the ringopened sugar incorporated into the polymer backbone. Polymerizations were well-controlled, as demonstrated by a linear increase in molecular weight with monomer-toinitiator ratio and generally narrow molecular weight dispersity values. The living nature of the polymerization was supported by the preparation of a block copolymer from two different sugar-based monomers. The resulting polymers were also fully degradable. They underwent fast and complete depolymerization to small molecules under acidic conditions.

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

“…Enyne monomers with an unstrained cyclohexene ring polymerized rapidly with the 3 rd generation Grubbs initiator (G3) due to the facile addition across the terminal alkyne followed by rapid intramolecular ring‐opening. While this polymer featured an all carbon backbone, Hawker recognized the potential to expand the ring size to macrocycles for preparation of sequence‐defined polyesters . This strategy was effective but the monomer synthesis required lengthy reaction sequences and suffered chain transfer at high conversions.…”

Organocatalysis for versatile polymer degradation

“…2,3 In response to this there has been a resurgence into research into bio-derived materials including poly(lactic acid) (PLA) and poly (ethylene furanoate) (PEF) among others. [4][5][6][7][8][9][10][11][12] (B) The second issue relates to the extended lifetime of plastics and end-of-life mismanagement causing leaking and persistence in the environment leading to land and sea pollution. [13][14][15][16] While biodegradable materials are being sought to reduce this issue, 17 compostable materials are not compatible with the circular economy as immediate value is lost from the life-cycle and some plastic applications require robust properties.…”

Sustainable polymer reaction engineering: Are we there yet?

“…[82][83][84][85] Many other sugar-based monomers such as aldonic acids, lactones, and anhydroalditols have also been studied to produce polycarbonates, polyesters, polyethers, and so on. [67,[86][87][88] Vegetable oil-based monomers and their derivatives are also good candidates to produce bio-based polymers for a variety of applications. [66,[89][90][91] For example, fatty acids can be polymerized directly via free radical or cationic polymerization, while saturated fatty acids can be used directly to produce polyurethane, or as a precursor of bio-based acrylic monomers.…”