Review
Chemistry, Applied
Nina Guy, Olivia Giani, Sebastien Blanquer, Julien Pinaud, Jean-Jacques Robin
Summary: Photopolymerization is gaining interest in both industrial and academic fields due to its high reaction kinetics, low emissions of organic solvents, and reduced shrinking stress. This method has mainly been developed for radical polymerization of vinyl monomers and to a lesser extent for ring-opening polymerization (ROP). With the emergence of new initiating systems, the photopolymerization of various cyclic monomers has expanded beyond epoxides, which were the first monomers polymerized by cationic ring-opening polymerization (CROP).
PROGRESS IN ORGANIC COATINGS
(2021)
Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Narumi Miyasako, Shin-ichi Matsuoka, Masato Suzuki
Summary: New ester-functionalized bicyclic aliphatic polymers were successfully synthesized through ring-opening metathesis polymerization (ROMP) of various norbornene lactones and their analogues, followed by hydrogenation. The comparison and discussion of polymerizability and thermal properties between different monomers before and after hydrogenation were conducted. The obtained polymers showed excellent thermal stability and processing deformation suitable for transparent resin materials.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Taeyang An, Hanseul Ryu, Tae-Lim Choi
Summary: This study presents a versatile approach to improve the alternation and degradability of 2,3-dihydrofuran (DHF) copolymers by carefully controlling the reactivity of both the Ru initiators and the monomers. The DHF copolymers showed outstanding A, B-alternation and could be broken down to a single repeat unit level under acidic conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Polymer Science
Chengjian Zhang, Xiaowei Geng, Xinghong Zhang, Yves Gnanou, Xiaoshuang Feng
Summary: Sensitivity to environmental concerns and the demand for metal-free polymeric materials have driven research towards breakthroughs in organocatalytic polymerizations. Triethyl borane (TEB) has been discovered as an exceptional Lewis acid, serving to generate ate complexes and activate epoxides. Lewis pairs consisting of alkyl boranes combined with onium salts or organic bases have demonstrated unprecedented versatility for (co)polymerizations of oxygenated monomers, producing various oxygenated polymers. This review summarizes the progress made in TEB-mediated polymerization systems and proposes future challenges in organocatalytic synthesis.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Phuong T. T. Do, Berwyck L. J. Poad, Hendrik Frisch
Summary: This study presents a strategy to program photodegradability into vinylic polymers by utilizing the wavelength selectivity of photocycloadditions for radical ring-opening polymerization (rROP). Coumarin terminated allylic sulfides were irradiated with UVA light to initiate intramolecular [2+2] photocycloaddition, generating cyclic macromonomers. Copolymers with photoreactivity inherited from the cyclic parent monomer were synthesized through subsequent RAFT-mediated rROP with methyl acrylate. Efficient photocycloreversion of the coumarin dimers upon UVB irradiation led to polymer degradation within minutes under UVB light or days under sunlight. This synthetic strategy enables the incorporation of photolabile linkages into vinylic polymers, tuning degradation for specific wavelengths.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xuejin Yang, Sean R. Gitter, Allison G. Roessler, Paul M. Zimmerman, Andrew J. Boydston
Summary: Research has found a simple method to control alkene stereochemistry in photoredox mediated metal-free ring-opening metathesis polymerization. Ion-pairing, initiator sterics, and solvation effects each have a profound impact on polynorbornene's stereochemistry. By adjusting reaction conditions, it is possible to control the cis or trans alkene content of PNB.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Hongyuan Bai, Li Han, Xuefei Wang, Hong Yan, Haitao Leng, Siwei Chen, Hongwei Ma
Summary: In this study, a strategy to synthesize unique C7 and C8 skeleton polymers through living anionic polymerization was proposed. The polymerization behavior of two diene monomers with high ring strain substituents was investigated. It was found that the content of C4 and C7/C8 skeleton structures in the chain can be controlled by adjusting the mode of monomer additions.
Article
Polymer Science
Yujin Cha, JiHyeon Hwang, Luis Ramos, Huina Lin, Tianyu Zhu, Chuanbing Tang
Summary: The synthesis of cyclic cobaltocenium and its application in the synthesis of high-performance copolymers have been reported.
Article
Biochemistry & Molecular Biology
Ervin Kovacs, Bence Balterer, Nguyen Anh Duc, Gyorgyi Szarka, Michael C. Owen, Attila Domjan, Bela Ivan
Summary: A large number of organic solvents contaminate the environment on a daily basis worldwide. This study demonstrates that benzotrifluoride can be used as a suitable solvent for olefin metathesis reactions, providing high yields and similar or even higher reaction rates compared to dichloromethane.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Review
Polymer Science
Yiyi Deng, Fabian Mehner, Jens Gaitzsch
Summary: Radical Ring-opening polymerization (RROP) of cyclic ketene acetals (CKAs) is a valuable polymerization technique. This review discusses the progress made in the field, including the synthesis of available CKAs and the understanding of the polymerization mechanism. The potential of producing fully biodegradable polymers through CKAs without vinylenes is highlighted. The control of side reactions, the impact on polymer properties, and the expanded application range of materials from RROP are also explored.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yening Xia, Georg M. Scheutz, Charles P. Easterling, Junpeng Zhao, Brent S. Sumerlin
Summary: This study introduces a method for synthesizing well-defined polyacrylamido-b-polyether block copolymers by combining photoiniferter polymerization and organocatalytic ring-opening polymerization. The compatibility between the two polymerization systems is demonstrated, allowing for the tailored synthesis of block copolymers from chemically distinct monomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Dmitry S. Belov, Logesh Mathivathanan, Melanie J. Beazley, William Blake Martin, Konstantin V. Bukhryakov
Summary: The study explores the capability of an iron-based catalyst in performing ring-opening metathesis polymerization of olefins, demonstrating that the use of in situ prepared heteroleptic iron catalysts significantly enhances polymerization rate and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Mohammad Yasir, Andreas F. M. Kilbinger
Summary: Norbornene and cyclohexene show different polymerization behaviors using Grubbs' catalysts due to their varying ring strain energy levels; a sequence-selective cascade polymerization of a monomer containing both rings resulted in polymers with moderate molecular weight dispersities and good control over molecular weight.
Article
Chemistry, Multidisciplinary
Yanchao Wang, Maosheng Li, Shixue Wang, Youhua Tao, Xianhong Wang
Summary: SCA monomers derived from amino acids are more reactive than thiolactones for ultrafast and selective ROP, resulting in controlled molecular weight, low dispersities, and retained stereoregularity of the synthesized polythioesters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Dylan J. Walsh, Devin A. Schinski, Robert A. Schneider, Damien Guironnet
NATURE COMMUNICATIONS
(2020)
Article
Multidisciplinary Sciences
Bijal B. Patel, Dylan J. Walsh, Do Hoon Kim, Justin Kwok, Byeongdu Lee, Damien Guironnet, Ying Diao
Article
Polymer Science
Dylan J. Walsh, Matthew A. Wade, Simon A. Rogers, Damien Guironnet
Article
Polymer Science
Tianyuan Pan, Bijal B. Patel, Dylan J. Walsh, Sarit Dutta, Damien Guironnet, Ying Diao, Charles E. Sing
Summary: Bottlebrush polymers have unique physical properties suitable for photonic crystals, and a simulation model has been developed to predict their self-assembly in solution and compare with experimental results.
Article
Chemistry, Physical
Bijal B. Patel, Dylan J. Walsh, Kush Patel, Do Hoon Kim, Justin J. Kwok, Damien Guironnet, Ying Diao
Summary: This study investigates the properties of brush-like block copolymer films using surface-induced ordering techniques. The results show that the depth of surface-induced ordering decreases with increasing film thickness, possibly due to the competition between heterogeneously nucleated grains at the surface and homogeneously nucleated grains throughout the bulk. This work demonstrates the potential of brush-like block copolymers in rapid fabrication processes and provides a reference for future applications of directed self-assembly.
Article
Polymer Science
Yash Laxman Kamble, Dylan J. Walsh, Damien Guironnet
Summary: In this study, a Monte Carlo method is developed to explore the precision of noncylindrical bottlebrush polymer synthesis and generate design rules. The research highlights the importance of low brush density and narrow backbone dispersity for achieving high precision in architecture control of bottlebrush polymers.
Article
Chemistry, Multidisciplinary
Dylan J. Walsh, Timo N. Schneider, Bradley D. Olsen, Klavs F. Jensen
Summary: This paper presents a design of a versatile, uniform light platform for photochemistry to improve the performance and reproducibility of high throughput experiments. The design is based on the development of an open-source ray tracing light simulation package and is experimentally validated using radiometry. The usefulness of the platform is demonstrated through its application in photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization of methyl acrylate.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Michael E. Deagen, Dylan J. Walsh, Debra J. Audus, Kenneth Kroenlein, Juan J. de Pablo, Kaoru Aou, Kyle Chard, Klavs F. Jensen, Bradley D. Olsen
Summary: Autonomous experimental systems provide an intriguing glimpse into the future of materials research and development, where machines guided by AI and ML play a vital role. The development of networks and interfaces in polymer science can accelerate innovation and address societal challenges. The introduction of CRIPT as a novel polymer data ecosystem facilitates innovation in polymer technology.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Multidisciplinary Sciences
Katharina A. Fransen, Sarah H. M. Av-Ron, Tess R. Buchanan, Dylan J. Walsh, Dechen T. Rota, Lana Van Note, Bradley D. Olsen
Summary: The development of biodegradable plastics has been driven by the increasing plastic pollution. However, limited research on polymer biodegradation has hindered innovation due to costly and slow measurement methods. To tackle this issue, a high-throughput polymer synthesis and biodegradation method were utilized to generate a dataset for 642 chemically distinct polyesters and polycarbonates. The results showed that biodegradability depended on the length of the aliphatic repeat unit, with shorter chains and side chains improving biodegradability. Aromatic backbone groups generally hindered biodegradability, but ortho- and para-substituted benzene rings were more degradable than meta-substituted rings. In addition, ether groups in the backbone improved biodegradability.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Multidisciplinary
Dylan J. Walsh, Weizhong Zou, Ludwig Schneider, Reid Mello, Michael E. Deagen, Joshua Mysona, Tzyy-Shyang Lin, Juan J. de Pablo, Klavs F. Jensen, Debra J. Audus, Bradley D. Olsen
Summary: This article presents the design of a general material data model that supports the application of polymer materials in nearly every aspect of modern life.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Ludwig Schneider, Dylan Walsh, Bradley Olsen, Juan de Pablo
Summary: The enhanced version of BigSMILES notation, called generative BigSMILES, provides a foundational tool for automated polymeric material design. By integrating additional data and utilizing a generative graph algorithm, the notation allows for efficient specification of complex molecular ensembles. The combination of generative BigSMILES with advanced machine learning techniques has the potential to accelerate materials design processes and advance the field of polymer science.
Article
Polymer Science
Bijal B. Patel, Tianyuan Pan, Yilong Chang, Dylan J. Walsh, Justin J. Kwok, Kyung Sun Park, Kush Patel, Damien Guironnet, Charles E. Sing, Ying Diao
Summary: Bottlebrush polymers, with their unique potential for structure-property design, can self-assemble into ordered phases that exhibit photonic band gaps. The self-assembly behavior in solution matches the results from experiments, demonstrating the tunability of the photonic band gap by varying the polymer concentration.
Article
Polymer Science
Bijal B. Patel, Yilong Chang, Sang Kyu Park, Siqing Wang, John Rosheck, Kush Patel, Dylan Walsh, Damien Guironnet, Ying Diao
Summary: This article presents a versatile hardware and software platform for melt and solution-phase benchtop AM, demonstrating successful patterning and post-deposition processing of a series of non-filament forming functional polymers. PolyChemPrint, a free Python module, serves as a research-optimized AM control software for researchers without extensive computer programming experience.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Chemistry, Physical
Matthew A. Wade, Dylan Walsh, Johnny Ching-Wei Lee, Elizabeth Kelley, Katie Weigandt, Damien Guironnet, Simon A. Rogers
Meeting Abstract
Chemistry, Multidisciplinary
Damien Guironnet, Dylan Walsh, Charles Sing, Simon Rogers, Matthew Wade, Sarit Dutta
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY
(2019)
