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
Hsin-Wei Su, Junfeng Zhou, Seiyoung Yoon, Junpeng Wang
Summary: Chemically recyclable polymers offer a solution to the unsustainable use of plastics by enabling circular economy. The identification of appropriate monomers for polymerization and depolymerization is crucial in developing chemically recyclable polymers. The study shows that introducing an additional benzene ring favors polymerization and disfavors depolymerization, and the effect is predominantly entropic. The benzo-effect can be leveraged to facilitate the chemical recycling of polymers.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This study reports the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB) through ring-opening polymerization. The reactions proceed rapidly in the presence of various metal-based catalysts, and high selectivity can be achieved by manipulating reaction conditions and catalyst systems. The topology and stereochemistry of the resulting polymer have been characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Michael Lalanne-Tisne, Audrey Favrelle-Huret, Wim Thielemans, Joao P. Prates Ramalho, Philippe Zinck
Summary: Organocatalysts are important in polymerization reactions. This study used Density Functional Theory to investigate the ring-opening polymerization of trimethylene carbonate, revealing a dual mechanism and confirming TBD as a more efficient catalyst.
Editorial Material
Chemistry, Multidisciplinary
Xiaofang Li
Summary: Xiaofang completed her undergraduate studies at Wenzhou University and continued with her master's degree there with Prof. Xingguo Zhang. Currently, Xiaofang is pursuing her PhD degree at Donghua University under the supervision of Prof. Lingling Chu. Her research focuses on nickel metallaphotoredox catalysis and the development of asymmetric radical multi-component coupling. She is eager to explore more interesting catalytic processes. Outside of the lab, she enjoys playing badminton and listening to music.
Article
Polymer Science
Masato Kawamoto, Yasuyuki Mori, Akihiko Tsuge, Takeshi Endo
Summary: In this study, the anionic ring-opening polymerization (ROP) behavior of trans-cyclohexene carbonate (CHC) using metal alkoxides as initiators was investigated. The results showed that the ROP process could be controlled under low temperature, high monomer concentration, and appropriate feed ratio conditions, while side reactions were suppressed.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Chemistry, Applied
Stephan Schandl, Thomas Koch, Juergen Stampfl, Katharina Ehrmann, Robert Liska
Summary: Aliphatic polycarbonates are highly regarded for being sustainable, biodegradable, and biocompatible. Recently, photobase generators have made cyclic carbonates available for light-induced anionic ring-opening polymerization, leading to the formation of pure aliphatic polycarbonate networks. The polymerization mechanism was investigated using photo-DSC and photorheology on synthesized cyclic carbonates. Different ratios of reactive diluent to crosslinker were tested to obtain materials with tunable mechanical properties.
REACTIVE & FUNCTIONAL POLYMERS
(2023)
Review
Chemistry, Multidisciplinary
Xiaoqian Wang, Ziyu Huo, Xiaoyu Xie, Narasimhamurthy Shanaiah, Rong Tong
Summary: The demand to replace unsustainable polyolefins drives the transformation of renewable resources into functional and degradable polymers. However, the properties of many degradable homopolymers are inferior to commodity polyolefins, limiting their utility. One-pot synthesis of sequence-defined copolymers from cyclic monomer mixtures is attractive in terms of concept and economics, as it maximizes materials usage and improves polymer performance. Recent advances in one-pot, sequence-controlled polymerizations of cyclic monomer mixtures using a single catalytic system that combines multiple catalytic cycles are highlighted, including the scopes of cyclic monomers, catalysts, and polymerization mechanisms.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Polymer Science
Wangmeng Hou, Xiuzhe Yin, Yao Chen, Jianzhong Du, Yongming Chen, Yi Shi
Summary: A novel aqueous ring-opening metathesis polymerization method named ME-ROMP is proposed. It involves injecting a small amount of a CH2Cl2 solution of the Grubbs' third-generation catalyst into the aqueous solution of water-soluble monomers, allowing high efficiency and controlled polymerization without deoxygenation. This method enables the synthesis of well-defined water-soluble polynorbornenes with various compositions and architectures.
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
Chemistry, Physical
Tatsuki Nagata, Shunsuke Aratani, Moegi Nomura, Maito Fuji, Taichi Sotani, Hiromitsu Sogawa, Fumio Sanda, Tatsuo Yajima, Yasushi Obora
Summary: The ring-opening metathesis polymerization (ROMP) of cyclic olefins with niobium(V) pentaalkoxide catalysts was investigated, and the presence of zinc, benzylidene dichloride, and chlorotrimethylsilane led to the formation of in situ niobium species and the successful ROMP reaction. Among the niobium pentaalkoxide group, Nb(OEt)5 exhibited the smallest polymer dispersity value and provided trans selective polynorbornene. This paper discussed the role of additives and elucidated the synthesis process of the polymer using the Nb(OEt)5/TMSCl/Zn/PhCHCl2 system, along with the characterization of the intermediate species using various measurements.
MOLECULAR CATALYSIS
(2023)
Review
Polymer Science
Jiaxi Xu, Nikos Hadjichristidis
Summary: The incorporation of heteroatom-containing weak bonds along polymer backbones has become a popular tool to accelerate degradation. Many methods have been reported for the synthesis of degradable heteroatom-containing polymers based on step-growth polymerization and chain-growth ring-opening polymerization. Ring-opening metathesis polymerization has emerged as an approach for the synthesis of various types of degradable polymers. This review covers the synthesis of different heteroatom-containing degradable polymers via ring-opening metathesis polymerization and their degradation mechanisms under different conditions.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Bingxin Qu, Yanan Zhao, Ping Song, Yanshan Gao, You-Yun Zhou, Xiu-Li Sun, Qiang Fu, Xiaoshan Ning, Junfang Li, Xiaokang Kuang, Yong Tang
Summary: Chain walking is a unique process that allows control over polyolefin branch type, density, topology, branch stereochemistry, and more. By introducing a ring strained monomer like norbornene, the chain walking process can be perturbed to produce copolymers with unique microstructures.
Article
Chemistry, Organic
Uladzimir S. Masiuk, Yaroslav V. Faletrov, Dzmitry G. Kananovich, Iryna Mineyeva
Summary: The stereodivergent synthesis of cis- and trans-2,6-disubstituted tetrahydropyrans (THPs) has been achieved through the oxa-Michael cyclization of (E)-zeta-hydroxy alpha,beta- unsaturated esters promoted by sodium hexamethyldisilazide. The reaction at low temperature (-78 degrees C) yields the thermodynamically favored trans-THPs with high stereoselectivity, while the reaction at room temperature does not produce the desired cis-THPs as major products and has poor stereocontrol. The addition of tetramethylethylenediamine significantly improves the stereochemical outcome of the room-temperature cyclization and allows for high cis-selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Jongho So, Eun Seon Cho, Sang Youl Kim
Summary: Epoxy functionalized cycloolefin polymers (COPs) were synthesized through ring-opening metathesis polymerization (ROMP) and subsequent hydrogenation. The controlled polymerization process resulted in high transparency and a high glass transition temperature for the hydrogenated COPs. Post-polymerization modification allowed for the transformation of epoxy functional groups to hydroxy ester functional groups, providing a versatile and efficient route for the synthesis of functionalized COPs.
Article
Chemistry, Physical
Weronika Gruszka, Haopeng Sha, Antoine Buchard, Jennifer A. Garden
Summary: The study reports the first heterobimetallic LA ROP catalysts featuring only divalent metals, with Mg/Zn and Ca/Zn complexes showing high activity in LA and ε-CL ROP, and the Ca/Zn complex exhibiting the highest activity. The enhanced activity is attributed to Lewis acidic metals enhancing monomer coordination.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Frances N. Singer, Arron C. Deacy, Thomas M. McGuire, Charlotte K. Williams, Antoine Buchard
Summary: A catalyzed chemical recycling method for the widely investigated polymer poly(cyclohexene carbonate) is reported, which can convert it into useful monomers. The method exhibits high selectivity and activity, and achieves depolymerization through chain-end catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
James Boden, Chris R. Bowen, Antoine Buchard, Matthew G. Davidson, Chris Norris
Summary: The demand for self-healing elastomers is increasing due to their potential to reduce down-time and cost by extending product lifetimes and reducing waste. However, further research is needed to understand the self-healing mechanisms and develop commercially applicable materials. This study investigates the effect of cross-linking on the self-healing performance of ENR and NR, providing a foundation for modifying ENR for future applications.
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Arron C. Deacy, Antoine Buchard, Charlotte K. Williams
Summary: The study demonstrates the chemical recycling of aliphatic polycarbonates using a heterodinuclear [Mg(II)Co(II)] catalyst under solid-state conditions, showing high activity and selectivity. This approach is not only efficient but also allows for multiple reuses of the catalyst.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Arron C. Deacy, Andreas Phanopoulos, Wouter Lindeboom, Antoine Buchard, Charlotte K. Williams
Summary: A combined computational and experimental investigation was conducted on the catalytic cycle of carbon dioxide and propylene oxide ring-opening copolymerization. The study revealed the role of a Co(III)K(I) heterodinuclear complex in activating and stabilizing the intermediates, as well as the transient carbonate nucleophile provided by potassium. The results provided insights into the key steps and selectivity limitations of the catalytic cycle, aiding future catalyst design and optimization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Craig Hardy, Gabriele Kociok-Kohn, Antoine Buchard
Summary: Introducing sulfur atoms into polymer backbones can utilize abundant chemical industry by-products and adjust polymerization thermodynamics for polymer recycling. By replacing oxygen with sulfur atoms in bio-derived polymers, their properties can be fine-tuned and application scope widened. This study reports the synthesis and characterization of cyclic carbonate and thiocarbonate monomers made from carbohydrate derivative d-glucal, varying the number and position of sulfur atoms in the polymerizable ring. The influence of sulfur on polymer properties such as ring strain, monomer conversion, crystallinity, thermal degradation, and glass transition temperature is examined, providing insights for the design of sulfur-containing renewable polymeric materials in the future.
Article
Chemistry, Physical
Antoine Buchard, Christopher J. Chuck, Matthew G. Davidson, Gerrit Gobius du Sart, Matthew D. Jones, Strachan N. McCormick, Andrew D. Russell
Summary: We have developed a zirconium-based catalytic system for the industrial production of high-molecular-weight poly(lactic acid) (PLA). We were able to prepare high-molecular-weight PLA under both laboratory and industrial conditions, with the catalyst activity comparable to that of conventional tin catalysts.
Article
Chemistry, Physical
Emma L. Daniels, James R. Runge, Matthew Oshinowo, Hannah S. Leese, Antoine Buchard
Summary: This study describes the synthesis and characterization of organogels by reacting a diol-containing polyether derived from D-xylose with 1,4-phenylenediboronic acid. The concentration of polymer and the amount of PDBA crosslinker were found to affect the gel or viscoelastic behavior of the materials. Furthermore, the incorporation of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the cross-linked matrix resulted in high ionic conductivity and electrochemical stability. This research provides a promising platform for the production of self-healing gel polymer electrolytes derived from renewable feedstocks for battery applications.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
Antoine Buchard, Matthew G. Davidson, Gerrit Gobius du Sart, Matthew D. Jones, Gabriele Kociok-Kohn, Strachan N. Mccormick, Paul Mckeown
Summary: We have reported three niobium-based initiators for the catalytic ring-opening polymerization (ROP) of epsilon-caprolactone, exhibiting good activity and molecular weight control. Among them, a monometallic cationic alkoxo-Nb(V) epsilon-caprolactone adduct has been prepared on the gram-scale and characterized, which represents an unprecedented example of a metal complex with an intact lactone monomer and a functional ROP-initiating group simultaneously coordinated at the metal center. At 80 degrees C, all three systems initiate the immortal solution-state ROP of epsilon-caprolactone via a coordination-insertion mechanism, which has been confirmed through experimental studies, and is supported by computational data. Natural bond orbital calculations further indicate that polymerization may necessitate isomerization about the metal center between the alkoxide chain and the coordinated monomer. The observations made in this work are expected to inform mechanistic understanding both of amine tris(phenolate)-supported metal alkoxide ROP initiators, including various highly stereoselective systems for the polymerization of lactides and of coordination-insertion-type ROP protocols more broadly.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Antoine Buchard, Charlotte Williams
Summary: This study presents an efficient method for chemical recycling of waste Poly(L-lactic acid) (PLLA) using a commercial Sn(II) catalyst and nonvolatile commercial alcohol. The depolymerization of PLLA to yield pure L-lactide (L-LA) can be achieved at low temperatures, and the catalyst system shows outstanding activity and selectivity. Furthermore, the catalyst system can be recycled multiple times without loss of its catalytic productivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Ella F. Clark, Gabriele Kociok-Kohn, Matthew G. Davidson, Antoine Buchard
Summary: In this study, d-xylose 3,5-anyhydrosugar (d-Ox) was used in the ring-opening copolymerisation (ROCOP) with isothiocyanates to form alternating AB-type copolymers with imidothiocarbonate linkages. The use of an Al(iii)-based aminotrisphenolate complex as catalyst allowed the synthesis of thermally robust polymers with high glass-transition temperatures. The reactivity can be tailored by using an Al(iii) porphyrin complex as catalyst, enabling the formation of a non-polymerisable cyclic thionocarbamate byproduct. The polymers exhibited degradation under acidic and basic conditions, as well as photodegradation.
Article
Materials Science, Multidisciplinary
J. C. Lightfoot, B. Castro-Dominguez, A. Buchard, S. C. Parker
Summary: Poly(lactic acid), PLA, is a sustainable alternative to single-use plastics for packaging applications, with clay fillers being explored to enhance its barrier performance. Atom-level molecular dynamics and Monte Carlo simulation techniques can accurately predict gas diffusion in polymer nanoclay composite systems, overcoming the limitations of mathematical models. The relationship between penetrant diffusion and free volume in PLA composites is investigated for the first time, providing valuable insights for the development of superior sustainable packaging materials through directed experimental research.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Multidisciplinary
Thomas M. McGuire, Antoine Buchard, Charlotte Williams
Summary: A commercial Sn(II) catalyst combined with a commercial alcohol has been found to efficiently convert waste PLLA plastic into pure L-lactic acid at low temperatures. This catalyst system exhibits not only excellent catalytic activity and yield, but also significantly lower usage compared to previous catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
