A broad scope of aliphatic polyesters prepared by elimination of small molecules from sustainable 1,3-dioxolan-4-ones

Abstract

We report a family of monomers that are built from renewable resources and use the elimination of small molecules to access aliphatic polyesters, circumventing challenging monomer syntheses to make these functionalism polymers.

Cross‐metathesis functionalized exo‐olefin derivatives of lactide

“…While reaction with SCHEME 1 Top: previous work, synthesis of compound 1 and subsequent Diels Alder and thiol addition. [17][18][19] Bottom: this work using compound 1 for olefin cross-metathesis and hydrogenation and synthesis of compound 2 from the methylenation of lactide using Tebbe's reagent followed by olefin cross-metathesis. Type II olefin, methyl acrylate, was unsuccessful, reaction with Type I olefin hex-1-ene produced 5 in 85% yield, confirming 2 is a Type III olefin of low reactivity.…”

“…This includes using upcycled CO 2 in copolymerizations with epoxides, synthesis of fatty amide derivatives from plant oils for use as platform chemicals for polymers, synthesis of a novel bio‐based isosorbide derivative for the development of block copolymers and the use of carbohydrates in the biosynthesis of poly(hydroxyalkanoate) . Yet, the pursuit to modify the properties of PLA is still an area of current interest, including blending, plasticizer incorporation, surface modification and copolymerization …”

“… Top: previous work, synthesis of compound 1 and subsequent Diels Alder and thiol addition . Bottom: this work using compound 1 for olefin cross‐ metathesis and hydrogenation and synthesis of compound 2 from the methylenation of lactide using Tebbe's reagent followed by olefin cross‐metathesis.…”

“…11 Yet, the pursuit to modify the properties of PLA is still an area of current interest, including blending, plasticizer incorporation, surface modification and copolymerization. [12][13][14][15][16][17] While research into these post-polymerization and copolymerization strategies has been extensive, modification of the lactide monomer itself has been limited. Functional derivatives of lactide have been prepared by Baker et al through condensation of substituted a-hydroxy acids, 18 producing polymers with tunable thermal properties.…”

Ring‐Opening Polymerization of a New Diester Cyclic Dimer of Mandelic and Glycolic Acid: An Efficient Synthesis Method for Derivatives of Amorphous Polyglycolide with High Tg

“…It is prepared by ROP of O‐ carboxyanhydride (OCA), exhibiting an outstanding T m of 316 °C. A crystallizable PMA by ROP of 5‐phenyl‐1,3‐dioxolan‐4‐one (Ph‐DXO) has also been reported. Although, the ROP of Ph‐DXO is managed under milder conditions than the ROP of OCA, it results in occurring racemization to produce atactic tacticity to attain amorphous characteristics.…”