One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

Abstract

We report here an efficient one‐port synthesis of terpolymers from PO, CO2, and l‐lactide (LLA) with long LLA rich sequence using the cheapest zinc adipate as catalyst. The copolymerizations were carried out under various experimental conditions to find out the optimal conditions. The terpolymer yields increase significantly from 151 to 417 (g polymer per g zinc) by the introduction of LLA as a third monomer. The polycarbonate moiety selectivity increases by nearly 60% at relatively high polymerization temperature (80 °C). Moreover, the differences in reaction kinetic of polycarbonate and polyester moieties were observed by in situ infrared monitoring. As confirmed by XRD and DSC, the synthesized terpolymers are a kind of semicrystalline polymer in which the crystalline PLA segment function as strong noncovalent crosslinking domains. Consequently, it exhibits much better thermal properties as well as remarkable higher mechanical strength compared with amorphous polycarbonate PPC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1734–1741

One‐pot regioselective and stereoselective terpolymerization of rac‐lactide, CO2 and rac‐propylene oxide with TPPMCl (M = Cr, Co, Al)/PPNCl binary catalyst

“…Overall we have prepared various PPC‐PLA‐PPO block copolymers (various PLA:PPC:PPO values), which will display a different hydrolysis period relative to PLA and PPC due to the difference of hydrophilicity between PLA and PPC. Thus a potential biomaterial with a broad bandwidth of thermal, mechanical and bio‐degradable performance was prepared and will find a broad bandwidth of application fields, e.g. for biomedical applications.…”

“…Among these monomers, lactide shows much potential for it comes from a biomass resource, and PLA has a number of favorable properties including zero toxicity, biocompatibility, high mechanical strength, thermal plasticity and good compostability; it has been approved for use in medical fields and food‐packaging fields by the Food and Drug Administration of the USA . To date, one‐pot terpolymerization of CO 2 , PO and lactide has been realized with polymer‐loaded bi‐metal catalyst, rare earth coordination catalyst and zinc adipate, and remarkable improvements either in bio‐degradability or thermal resistance performance of the terpolymer were developed relative to PPC. However, due to the heterogeneous nature of the previous catalysts used, less concern was given to the main chain structure of the copolymer of CO 2 , PO and lactide (PPCLA) thus formed.…”

Mechanistic Insights into the Synthesis of Fully Condensed Polyhedral Octaphenylsilsesquioxane

“…Real time infrared (RTIR) spectroscopy has been proven to be an efficient tool for monitoring chemical changes in reacting systems . RTIR can track the concentration change of key species, capture transient reaction information, infer mechanism and kinetic measurement, reveal the main process of reaction, and optimize the process in real time.…”

Synthesis of CO2‐based functional poly(carbonate‐co‐lactide)

“…One‐pot selective synthesis of block copolymer from LA, CO 2 and PO was also achieved using a “switch catalysis” strategy 10 : Using carbon dioxide/N 2 as a switching agent, salen metal catalyst could initiate ring opening copolymerization of epoxide and CO 2 to produce a perfectly alternating polycarbonate block, and once carbon dioxide was consumed/removed, the system was filled with N 2, the same catalyst would selectively polymerize lactide by ring opening polymerization, ultimately producing block copoly(ester‐carbonates) with controllable chain structure. One‐pot/one‐step ter‐polymerization of CO 2 , EPO, and LA was also realized to form poly(aliphatic carbonate‐co‐lactide) copolymer (simplified as APCLA) with polymer‐loaded bi‐metal catalyst (PBM), 11 rare earth coordination catalyst, 12 zinc adipate, 13 and salenCo catalysts, 14 remarkable improvements either in biodegradability or thermal resistance performance of the ter‐polymer were developed relative to APC. However, due to the inherent hydrophobicity and inertness of APC block and PLA block, APCLA has poor hydrolysis and post‐polymerization modification performance, which confined its use in value‐added fields such as functional materials, 15 drug‐loading in biomedicine, 16 and nanotechnologies 17 .…”