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 T_g

Abstract

In this study, poly(mandelate-co-glycolate) (PMG), a modified polyglycolide (PGL), is prepared by ring-opening polymerization (ROP) of L-3-phenyl-1,4-dioxane-2,5-dione (PDD); the cyclic dimer of biobased mandelic acid and glycolic acid. The resulting polymer shows an increased glass transition temperature (T ) due to the incorporation of phenyl groups in the chain. High molecular weight PMG is obtained by bulk ROP at 150 °C, and it exhibits a glassy amorphous state with enhanced thermal properties such as a T being 35 °C higher than conventional PGL. PDD is also copolymerized with glycolide (GL) and lactide (LA), resulting in poly(mandelate-co-glycolate/glycolate) ((P(MG/GL)) with GL and poly(mandelate-co-glycolate/lactide) ((P(MG/LA)) with LA. The thermal properties of P(MG/GL) and P(MG/LA) are found to be distinctly different from PMG and conventional PGL and polylactide, and they are tunable with a changing molar ratio of PDD, GL, and LA. Therefore, PDD opens an elegant way to control and tailor the properties of biobased polyesters.

Enhancement of Tg of Poly(l‐lactide) by Incorporation of Biobased Mandelic‐Acid‐Derived Phenyl Groups by Polymerization and Polymer Blending

“…In the bulk polymerization, the amount of moisture was not precisely controlled, and it was true we might have had a risk that the content of moisture was not appropriate. However, we previously reported that this polymerization approach is effective for such small scale polymerizations of lactones . The conversion of polymers from S,S‐MPDD and R,S‐MPDD, which is displayed in Table are adequately high, while the final molecular weight of PML1 from each run is not constant.…”

“…One of the practical solutions to tackle this is a moderation of thermal properties by a copolymerization of ma with other biobased α‐hydroxy aliphatic acids. Recently, we have reported that cyclic diester monomer, which consists of ma and glycolic acid and poly(mandelate‐ co ‐glycolate), was prepared by ROP of the cyclic diester . The mandelate and glycolate units are excellently miscible in the resultant polymers, and these copolymers also showed excellent amorphous properties, such as high transparency and high T g .…”

Heterodinuclear catalysts Zn(ii)/M and Mg(ii)/M, where M = Na(i), Ca(ii) or Cd(ii), for phthalic anhydride/cyclohexene oxide ring opening copolymerisation

“…9,10 Using it to make rigid, semi-aromatic or functionalised polyesters requires esoteric monomer syntheses, many showing low yields and multiple steps, and reactions requiring optimisation to overcome ring strain on a case-by-case basis. 9,[11][12][13][14] The ring-opening copolymerisation (ROCOP) of cyclic anhydrides and epoxides is a useful alternative to lactone ROP. 5,15 It is well controlled, applies monomers (epoxides/ anhydrides) already made and used at scale by the polymer industry and produces high yields of functionalised, rigid and/or semi-aromatic polyesters.…”

Exploration of mandelicacid‐basedpolymethacrylates: Synthesis, properties, and stereochemical effects

“…Therefore, PMA has a higher T g (100 C) than amorphous PLA (60 C) which has led to multiple studies of blended biodegradable PLA/PMA systems to improve thermal properties. 33,[38][39][40][41][42][43][44] While the use of MA to produce PMA has shown utility as a sustainable polymer, to the best of our knowledge it has only been researched as a biodegradable polyester. We envisioned that MA may serve as a valuable biomass component in acrylics and that an investigation on the potential stereochemical effects from MA pendants is warranted.…”

“…PMA is structurally similar to poly(lactide) or poly(lactic acid) (PLA) but with two chiral phenyl substituents in lieu of methyls. Therefore, PMA has a higher T g (100°C) than amorphous PLA (60°C) which has led to multiple studies of blended biodegradable PLA/PMA systems to improve thermal properties 33,38–44 …”