Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature

Carbon dioxide is inexpensive and abundant, and its prevalence as waste makes it attractive as a sustainable chemical feedstock. Although there are examples of copolymerizations of CO2 with high-energy monomers, the direct copolymerization of CO2 with olefins has not been reported. Herein, an alternate route to tunable, recyclable polyesters derived from CO2 and butadiene via an intermediary lactone, 3-ethyl-6-vinyltetrahydro-2H-pyran-2-one, is described. Catalytic ring-opening polymerization of the lactone by 1,5,7-triazabicyclo[4.4.0]dec-5-ene yields polyesters with molar masses up to 13.6 kg/mol and pendent vinyl sidechains that can undergo post-polymerization functionalization. The polymer has a low ceiling temperature of 138 ºC, allowing for facile chemical recycling. These results mark the first example of a well-defined polyester derived solely from CO2 and olefins, expanding access to new feedstocks that were once considered unfeasible.

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Lipase-catalyzed synthesis of aliphatic polyesters in supercritical carbon dioxide

e-Polymers ◽

10.1515/epoly.2001.1.1.19 ◽

2001 ◽

Vol 1 (1) ◽

Cited By ~ 10

Author(s):

Tetsufumi Takamoto ◽

Hiroshi Uyama ◽

Shiro Kobayashi

Keyword(s):

Carbon Dioxide ◽

Molecular Weight ◽

Supercritical Carbon Dioxide ◽

Ring Opening ◽

Monomer Concentration ◽

Random Copolymer ◽

Ring Opening Polymerization ◽

Reaction Parameters ◽

Aliphatic Polyesters ◽

Supercritical Carbon

AbstractSynthesis of aliphatic polyesters has been examined using Candidaantarctica lipase in supercritical carbon dioxide (scCO2). The enzymatic ring-opening polymerization of ε-caprolactone (ε-CL) proceeded in scCO2 to give a polymer with molecular weight higher than 104. Effects of reaction parameters such as the monomer concentration, enzyme amount and pressure have been systematically investigated. Copolymerization of ε-CL with 12-docecanolide afforded the random copolymer. The enzymatic polycondensation of divinyl adipate and 1,4-butanediol also proceeded in scCO2 to produce the corresponding polyester.

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Ring-opening polymerization

AccessScience ◽

10.1036/1097-8542.801760 ◽

2015 ◽

Keyword(s):

Ring Opening ◽

Ring Opening Polymerization

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A Recommender System for Inverse Design of Polycarbonates and Polyesters

10.26434/chemrxiv.12679031 ◽

2020 ◽

Author(s):

Nathaniel Park ◽

Dmitry Yu. Zubarev ◽

James L. Hedrick ◽

Vivien Kiyek ◽

Christiaan Corbet ◽

...

Keyword(s):

Ring Opening ◽

High Performance ◽

Recommendation System ◽

Polymeric Materials ◽

Monomer Conversion ◽

Design Strategy ◽

Ring Opening Polymerization ◽

Inverse Design ◽

False Negatives ◽

Accelerate Development

The convergence of artificial intelligence and machine learning with material science holds significant promise to rapidly accelerate development timelines of new high-performance polymeric materials. Within this context, we report an inverse design strategy for polycarbonate and polyester discovery based on a recommendation system that proposes polymerization experiments that are likely to produce materials with targeted properties. Following recommendations of the system driven by the historical ring-opening polymerization results, we carried out experiments targeting specific ranges of monomer conversion and dispersity of the polymers obtained from cyclic lactones and carbonates. The results of the experiments were in close agreement with the recommendation targets with few false negatives or positives obtained for each class.<br>

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