Programmable High-Throughput Platform for the Rapid and Scalable Synthesis of Polyester and Polycarbonate Libraries

Lin, Binhong; Hedrick, James L.; Park, Nathaniel H.; Waymouth, Robert M.

doi:10.1021/jacs.9b02450

Cited by 85 publications

(105 citation statements)

References 58 publications

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“…Starting from basic catalysts, such as DMAP and NHC, through the use of non-nucleophilic bases, such as DBU and phosphazenes, the researchers came to organocatalysts, providing the most gentle and energetically favourable donor-acceptor mechanism, namely, TBD-DBU/TU-thiourea and urea salts. Currently, the last group of the catalysts appears to be highly promising due to versatility [142] and knowingly lack of toxicity. The role of DFT modeling in understanding of the ROP mechanisms and in the design of the novel ROP catalysts is crucial, comparative theoretical estimations of the ROP activation barriers for zwitterionic and donor-acceptor mechanisms resulted in the development of efficient catalytic systems that are able to activate both cyclic ester molecule and chain-end fragment.…”

Section: Discussionmentioning

confidence: 99%

“…The thioimidate catalyst demonstrated good catalytic activity in lactide polymerization, but lower activity in TMC ROP and low productivity in polymerization of lactones. The novel simple and promising catalysts, the close structural analogs of TU-derived thioamidate, were studied in the few past years [138][139][140][141][142]. These catalysts, which represent the metal derivatives of disubstituted ureas, demonstrated high activities in ROP of cyclic esters of all actual structure types-lactide, lactones, TMC, and ethylene phosphates.…”

Section: Thiourea-based Catalystsmentioning

confidence: 99%

See 1 more Smart Citation

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Nifant’ev

Ivchenko

2019

Polymers

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Organocatalysis is highly efficient in the ring-opening polymerization (ROP) of cyclic esters. A variety of initiators broaden the areas of organocatalysis in polymerization of different monomers, such as lactones, cyclic carbonates, lactides or gycolides, ethylene phosphates and phosphonates, and others. The mechanisms of organocatalytic ROP are at least as diverse as the mechanisms of coordination ROP; the study of these mechanisms is critical in ensuring the polymer compositions and architectures. The use of density functional theory (DFT) methods for comparative modeling and visualization of organocatalytic ROP pathways, in line with experimental proof of the structures of the reaction intermediates, make it possible to establish these mechanisms. In the present review, which continues and complements our recent manuscript that focused on DFT modeling of coordination ROP, we summarized the results of DFT modeling of organocatalytic ROP of cyclic esters and some related organocatalytic processes, such as polyester transesterification. 4 of 49 were found to be polymerizable due to strain in the ester group. In addition, the predominance of high-energy coiled conformations in linear homopolymers the formed from PDO, εCL and GL was proportionately less than extended conformations, in comparison to the inactive monomer γBL. However, while the prevalence of coiled conformations over extended conformations was expected for poly(LA), this factor does not affected the reactivity of lactides. Very good agreement between the experimental and calculated data for ROP of GL, l-LA and (R,S)-lactide [47] should be separately noted. 4-(Dimethylamino)pyridine (DMAP) and Related CompoundsDMAP was the first employed organocatalyst in polymer synthesis. In 2001, Nederberg et al. [48] reported the "first organocatalytic living polymerization" (Ð M < 1.2) of L-lactide (l-LA) mediated by DMAP or 4-pyrrolidinopyridine in the presence of ROH initiators. Four years later [49], Feng and Dong reported polymerization of ε-caprolactone (εCL) catalyzed by DMAP in the presence of chitozane as an initiator. Bourissou et al. studied the mechanism of DMAP-catalyzed ROP of l-LA and five-membered lactic O-carboxylic anhydride (lacOCA) [50]. Two possible reaction pathways were analyzed at the B3LYP/6-31G(d) level of theory [39,40,51]; the solvent effect of dichloromethane was taken into account through the PCM/SCRF model [52]. The modeled reaction was the methanolysis of l-LA or lacOCA; alternative nucleophilic/monomer (Scheme 1a) and basic/alcohol (Scheme 1b) activation mechanisms were proposed for these reactions, and then analyzed by DFT optimization of the key reaction intermediates and transition states, if necessary. Scheme 1. Schematic representation of the nucleophilic/monomer (a) and basic/alcohol (b) mechanisms for (Dimethylamino)pyridine (DMAP)-catalyzed methanolysis of l-LA. Author Contributions: Conceptualization, P.I.; Methodology, I.N. and P.I.; Writing-Original draft preparation, P.I.; Writing-Review and editing, I.N. and P.I.; V...

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Section: Discussionmentioning

confidence: 99%

Section: Thiourea-based Catalystsmentioning

confidence: 99%

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Nifant’ev

Ivchenko

2019

Polymers

View full text Add to dashboard Cite

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“…In the future, when the material synthesis process is fully automated, it will be integrated with industrial manufacturing 4.0, such as programmable high‐throughput synthesis platform for polymers . In the early stage of this high‐throughput synthesis, ML is needed to explore the parameter space to determine how the ratio of raw materials and the rate of catalyst supply can be used to synthesize ideal organic compounds with appropriate molecular weight, narrow distribution, and few side reactions.…”

Section: Ai Applications For Materials Science and Engineeringmentioning

confidence: 99%

Artificial Intelligence to Power the Future of Materials Science and Engineering

Sha

Guo

Qing

et al. 2020

Advanced Intelligent Systems

109

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Artificial intelligence (AI) has received widespread attention over the last few decades due to its potential to increase automation and accelerate productivity. In recent years, a large number of training data, improved computing power, and advanced deep learning algorithms are conducive to the wide application of AI, including material research. The traditional trial‐and‐error method is inefficient and time‐consuming to study materials. Therefore, AI, especially machine learning, can accelerate the process by learning rules from datasets and building models to predict. This is completely different from computational chemistry where a computer is only a calculator, using hard‐coded formulas provided by human experts. Herein, the application of AI in material innovation is reviewed, including material design, performance prediction, and synthesis. The realization details of AI techniques and advantages over conventional methods are emphasized in these applications. Finally, the future development direction of AI is expounded from both algorithm and infrastructure aspects.

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“…There have been many reports on polymer fabrications by using programmable platform. [114] Microflow technology is increasingly applied in the synthesis of block polymers. [115][116][117] The spatial-temporal control and high-efficiency of mass/heat transfer properties of continuousflow chemistry enable high level control of the architectures of polymers.…”

Section: Challenge 1: Development Of Novel Synthetic Strategies To Janusmentioning

confidence: 99%

“…[115][116][117] The spatial-temporal control and high-efficiency of mass/heat transfer properties of continuousflow chemistry enable high level control of the architectures of polymers. [114,118,119] Guironnet and co-workers [120] presented a scalable strategy to synthesize bottlebrush polymers with programmable shape, size, and composition. They also prepared bottlebrush polymers by using automated continuous-flow systems.…”

Section: Challenge 1: Development Of Novel Synthetic Strategies To Janusmentioning

confidence: 99%

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

Chen

Zhu

et al. 2020

Macromol. Rapid Commun.

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in solution, [28-30] and at the interfaces [31,32] features the unique microstructures and varied applications (Figure 1C). Janus bottlebrush polymers are a class of special molecular brushes, which have two incompatible side chains on the same repeating unit of the backbone. [33] "Janus" is the god in ancient Roman religion and myth with two faces looking to the past and the future. [34] In scientific community, the phrases containing Janus, such as "Janus nanoparticles," [35-38] "Janus beads," [39,40] and "Janus polymerization," [41-43] indicate something consisting of counterparts. [44-46] The design of Janus bottlebrush polymers was inspired by Janus particles. [35,47-49] The characteristic of Janus bottlebrush polymers is that the repeating unit of the backbone possesses two immiscible side chains. [50-52] Core-shell bottlebrush polymers with block copolymers as the side chains are usually not Janus-type unless the block side chains are unsymmetrical. [6] An emerging Janus core-shell bottlebrush polymer has been developed by transferring the side chains from homo polymers to two different block copolymers. [53] Design, synthesis, and self-assembly of Janus bottlebrush polymers have arouse much interest in polymer chemistry and material science. [54,55] In general, Janus bottlebrush polymers could be prepared via backbone-first [50] (grafting-to and graftingfrom) or side-chain-first [56] (grafting-through) strategy. Most of Janus bottlebrush polymers were reported via grafting-through approach. Macromonomers are first designed and subsequently polymerizations occur to form the backbone. [23] Backbonefirst route also allows for the synthesis of Janus bottlebrush polymers by using combined grafting-to and grafting-from approach. [57] The special unsymmetrical architectures enable Janus bottlebrush polymers to achieve ideal phase separation in bulk, [58,59] in solution, [52] and at the interface. [32] The preorganized interface can promote self-assembly process and avoid the distorted phase separation. [32,33] The self-assembly of Janus bottlebrush polymers achieves small domain size and tunable bulk property, [58,59] which is challenging for the traditional linear or bottlebrush polymers. [60,61] Therefore, Janus bottlebrush polymers have great potential applications in nanolithography, [58] photonic crystals, [62] biomedicine, [53] surfactants, [63] etc. The big families of bottlebrush polymers have been nicely reviewed by Grubbs and co-workers, [64] Müllner and coworkers, [65-67] Rzayev and co-workers, [7] Verduzco and coworkers, [6] and Matyjaszewski and co-workers [2]. As a young but significant class, Janus bottlebrush polymers have achieved remarkable advances in recent years. Therefore, this review attempts to focus on Janus bottlebrush polymers, covering Janus bottlebrush polymers are a class of special molecular brushes, which have two immiscible side chains on the repeating unit of the backbone. The characteristic architectures of Janus bottlebrush polymers enable unique selfassembly properties and br...

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Programmable High-Throughput Platform for the Rapid and Scalable Synthesis of Polyester and Polycarbonate Libraries

Cited by 85 publications

References 58 publications

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

DFT Modeling of Organocatalytic Ring-Opening Polymerization of Cyclic Esters: A Crucial Role of Proton Exchange and Hydrogen Bonding

Artificial Intelligence to Power the Future of Materials Science and Engineering

Design, Synthesis, and Self‐Assembly of Janus Bottlebrush Polymers

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