Understanding differences in rate <i>versus</i> product determining steps to enhance sequence control in epoxide/cyclic anhydride copolymers

Wood, Zachary A.; Fieser, Megan E.

doi:10.1039/d3py00048f

Cited by 3 publications

(6 citation statements)

References 28 publications

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“…These data are consistent with a bias towards the chromophore being incorporated at the start of the reaction. Addition of the AAQ monomer presumably has a lower activation energy than CHO in this case, and a bias towards early/late incorporation is expected if the activation Polymer Chemistry Paper energies are unequal, 37 since epoxide opening is reported to be the rate-limiting step. 38,39 Physical properties DSC measurements were obtained for all polymers (S3.3), from which glass transition temperatures (T g ) were obtained.…”

Section: Papermentioning

confidence: 90%

Chemically recyclable fluorescent polyesters via the ring-opening copolymerization of epoxides and anhydrides

et al. 2023

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Section: Papermentioning

confidence: 90%

Chemically recyclable fluorescent polyesters via the ring-opening copolymerization of epoxides and anhydrides

et al. 2023

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“…Catalyst design has centered on the use of metal-based catalysts with designer ligands to identify the desired fast rates (often determined through single-point turnover frequencies (TOF)), dispersity control, and the ability to acquire high-molar mass polymers. These design successes are often due to tethering two cocatalysts together, allowing rates to be maintained even at low catalyst loading, as advanced by the Coates and Williams groups (Figure A). − We recently identified that simple rare earth metal salts, in combination with a cocatalyst, were able to maintain fast polymerization rates and excellent polymerization control, without the need for a designer ligand (Figure B). , It is evident that these catalysts could be air-stable, with the presence of water aiding in the increase of the rate of polymerization for most monomer pairs. However, the presence of water can also be detrimental, as it leads to lower polymer molar masses than desired.…”

Section: Introductionmentioning

confidence: 99%

“…51 In another study with Meng and co-workers, a thiourea catalyst with [PPN]Cl attained a TOF of 456 h −1 at 110 °C in 10 min for CHO and PA. 54 These advances in organocatalyst design for 24,26 (B) Simple salt catalyst. 29,30 (C) Organoboron catalyst. 43 The [catalyst]/[anhydride]/[epoxide] was 1:100:500.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Previously used catalysts for ROCOP of epoxides and cyclic anhydrides. (A) Heterodinuclear catalyst. , (B) Simple salt catalyst. , (C) Organoboron catalyst . (D) This work used deep eutectic solvents as a catalyst.…”

Section: Introductionmentioning

confidence: 99%

“… 24 − 28 We recently identified that simple rare earth metal salts, in combination with a cocatalyst, were able to maintain fast polymerization rates and excellent polymerization control, without the need for a designer ligand ( Figure 1 B). 29 , 30 It is evident that these catalysts could be air-stable, with the presence of water aiding in the increase of the rate of polymerization for most monomer pairs. However, the presence of water can also be detrimental, as it leads to lower polymer molar masses than desired.…”

Section: Introductionmentioning

confidence: 99%

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Choline Halide-Based Deep Eutectic Solvents as Biocompatible Catalysts for the Alternating Copolymerization of Epoxides and Cyclic Anhydrides

Cheng-Tan,

Nguyen,

Gordon

et al. 2024

ACS Sustainable Chem. Eng.

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Aliphatic polyesters have received considerable attention in recent years due to their biodegradability and biocompatible, mechanical, and thermal properties that can make them a suitable alternative to today's commercialized polymers. The ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is a route to synthesize a diverse array of polyesters that could be useful in many applications. However, the catalysts used rarely consider biocompatible catalysts in the case that any are left in the polymer. To the best of our knowledge, we report the first example of using deep eutectic solvents (DESs) as biocompatible catalysts for this target ROCOP with polymerization activity for at least six diverse monomer pairs. Choline halide salts are active for this polymerization, with dried salts showing polymerization slower than that of those conducted in air. Hydrogen bonding with water is hypothesized to enhance the ratedetermining step of epoxide ring opening. While the presence of water improves the rate of polymerization, it also acts as a chain transfer agent, leading to smaller molar mass polymers than intended. Combining the choline halide salts with urea or ethylene glycol hydrogen bond donors in air led to DES catalysts that reacted similarly to the salts exposed to air. However, when generating these DESs in air-free conditions, they showed similar rates of polymerization without a drop in polymer molar mass. The hydrogen bonding provided by urea and ethylene glycol seems to promote the rate increase without serving as a chain transfer agent. Results reported herein display the promising potential of biocompatible catalyst systems for this ROCOP process as well as introducing the use of hydrogen bonding to enhance polymerization rates.

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Alkali Metal Carboxylates: Simple, Efficient, and Industrial Relevant Catalysts for Controlled Polymer Synthesis

Li,

Suzuki,

Gao

et al. 2023

Bulletin of the Chemical Society of Japan

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Polymer materials play a pivotal role in shaping modern society. The continuous development of polymer materials can be largely attributed to innovations in polymerization methods, especially in the development of new catalysts. When pursuing high-performance catalysts, it is crucial to consider their cost and safety for practical applications. Alkali metal carboxylates (AMCs) are widely available simple chemicals, and some of them are used as food additives. In the past few years, our group has demonstrated the ability of such simple compounds to catalyze the ring-opening polymerization of cyclic esters, cyclic carbonates, epoxides, and episulfides. Additionally, AMCs have demonstrated their efficacy in facilitating the ring-opening alternating copolymerization of cyclic anhydrides and cyclic ethers, resulting in the production of polyesters in a well-controlled manner. Moreover, AMCs can also catalyze the complicated self-switchable polymerization of a mixture of at least three monomers, yielding block copolymers with well-controlled block components and architectures. This account summarizes these successful examples, offering mechanistic insights and an outlook.

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Understanding differences in rate versus product determining steps to enhance sequence control in epoxide/cyclic anhydride copolymers

Abstract: One-pot synthesis of random, gradient, and block polyesters via the ring opening copolymerization of epoxides and cyclic anhydrides is investigated using simple yttrium salt catalysts. Impact of rate versus product determining steps is discussed.

Cited by 3 publications

References 28 publications

Chemically recyclable fluorescent polyesters via the ring-opening copolymerization of epoxides and anhydrides

Chemically recyclable fluorescent polyesters via the ring-opening copolymerization of epoxides and anhydrides

Choline Halide-Based Deep Eutectic Solvents as Biocompatible Catalysts for the Alternating Copolymerization of Epoxides and Cyclic Anhydrides

Alkali Metal Carboxylates: Simple, Efficient, and Industrial Relevant Catalysts for Controlled Polymer Synthesis

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