Cationic copolymerization of isosorbide towards value-added poly(vinyl ethers)

Abstract

Biomass-derived isosorbide (IS) was converted into a mono-glycal (i.e. vinyl ether) derivative (Gly-IS) to investigate its efficacy for cationic polymerization.

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

“…However, it readily undergoes cationic copolymerization with IBVE in the presence of Lewis acids, giving up to 42 mol% of isosorbide derivative incorporated into the copolymer structure (Scheme 37) [205]. Conventional cationic copolymerization promoted a competing process of ring-opening polymerization and rearrangement, whereas photo-driven cationic polymerization protocol with a RAFT agent facilitated chain propagation against the rearrangement.…”

Rapid Synthesis of Chemically Recyclable Polycarbonates from Renewable Feedstocks

“…Isosorbide is a rigid bicyclic diol derived from glucose that has been used as a greener alternative in several commercial step-growth polymers over the past decade . Although there have been improvements in step-growth polymerization strategies, − recent advances have seen isosorbide incorporated as a vinyl and (meth)­acrylic pendant group ,− as well as derivatives amenable to cationic polymerization. , Lauryl alcohol and ethanol derived pendant groupswhich can be produced from vegetable oils and agricultural wastehave been shown to exhibit softer polymer properties (e.g., acrylic thermoplastic elastomers − ). Unfortunately, most of these materials do not have a sustainable end-of-life process available.…”

Polar Thermoplastics with Tunable Physical Properties Enabled by the Stereoselective Copolymerization of Vinyl Ethers

“…When copolymerized with isobutyl vinyl ether (iBVE), this approach yielded materials with tunable melting temperatures up to a maximum T m of 43 °C . Copolymerization of ODVE with the water-soluble monomer methoxy ethyl vinyl ether (MOVE) resulted in materials which form hydrogels cross-linked by semicrystalline ODVE-rich phases. − Similarly, Kennemur and co-workers recently copolymerized iBVE with a rigid, isosorbide-derived vinyl ether monomer in order to modulate the T g of the resulting PVE copolymers over a 25 °C range . Aoshima and co-workers sought to influence the relative hydrophobicity of PVEs by copolymerizing a tert -butyldimethylsilyl (TBDMS)-protected hydroxyethyl vinyl ether comonomer with iBVE .…”

“…11−13 Similarly, Kennemur and coworkers recently copolymerized iBVE with a rigid, isosorbide-derived vinyl ether monomer in order to modulate the T g of the resulting PVE copolymers over a 25 °C range. 14 Aoshima and co-workers sought to influence the relative hydrophobicity of PVEs by copolymerizing a tert-butyldimethylsilyl (TBDMS)-protected hydroxyethyl vinyl ether comonomer with iBVE. 15 Upon deprotection to reveal an alcoholfunctional comonomer, the relative incorporation of a hydrophilic comonomer enabled rational tuning of the aqueous lower critical solution temperature (LCST).…”