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
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)
Article
Polymer Science
Ryoya Kamiki, Tomohiro Kubo, Kotaro Satoh
Summary: This study aims to synthesize novel degradable polymers by copolymerizing bio-based thiocarbonyl compounds with various vinyl monomers using radical addition-fragmentation ring-opening reaction. The obtained polymers have degradable functional groups that can be cleaved under specific conditions with different chemical stimuli.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Hui Li, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This review introduces the synthesis methods and applications of polythioesters (PTEs) in polymer research. With the introduction of sulfur atoms, PTEs have different thermal, optical, and mechanical properties compared to conventional plastics, making them a focus of research. The emphasis is on the synthesis of different cyclic thioesters and thiolactones, as well as the effects of catalysts and initiating systems on the quality, molecular weight, and microstructure of the products.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Xing Yang, Hua-Zhong Fan, Zhongzheng Cai, Qi Zhang, Jian-Bo Zhu
Summary: Monomer design strategy is a powerful tool for synthesizing polymers with desired functionalities. In this study, a novel monomer BTO was designed and synthesized. The resulting polymer exhibited living polymerization characteristics and high molecular weight with narrow dispersity. The polymer displayed elastomeric behavior at room temperature and its mechanical properties were modulated by copolymerization. Furthermore, oxidation and debenzylation reactions allowed the adjustment of the glass transition temperature and introduction of hydroxyl groups. Ultimately, the polymer could be hydrolyzed and converted back to the monomer, completing a closed-loop cycle.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Polymer Science
Huining Ding, Xianmin Wu, Bing Han, Ning Liu, Binyuan Liu, Il Kim
Summary: Highly regioselective ring-opening copolymerizations of 5-norbornene-2,3-dicarboxylic anhydride (NA) and epoxide monomers have been achieved using Cr-III catalysts and specific ligands, allowing for the control of cis/trans regioselectivity in the resulting polyesters by adjusting feed ratio and monomer structure. The resulting polyesters from the copolymerization of NA and epichlorohydrin provide a robust platform for post-modification, with the ring-strained C=C double bonds in the norbornene units facilitating further functionalization through azide-alkene 1,3-dipolar cycloaddition reactions based on desired targets.
Article
Chemistry, Physical
Federica Tufano, Federica Santulli, Fabia Grisi, Marina Lamberti
Summary: Two zinc complexes with NHC ligands were synthesized and studied for their behavior in the Ring-Opening Polymerization of lactides, showing efficiency as initiators with molecular weights dependent on cocatalysts. Microstructural analysis revealed enriched heterotactic PLA, with kinetic parameters compared between different conditions and reactions showing pseudo-first-order dependence on monomer concentration. Reactivity studies aimed to uncover the active species in polymerization processes with different catalytic systems, including zinc complexes alone or in combination with neutral or ionic cocatalysts.
Article
Chemistry, Multidisciplinary
Emily A. Prebihalo, Anna M. Luke, Yernaidu Reddi, Christopher J. LaSalle, Vijay M. Shah, Christopher J. Cramer, Theresa M. Reineke
Summary: In this study, we report the synthesis, characterization, and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone that undergoes homopolymerization under free radical conditions without the need for a dormant comonomer or repeated initiation. The resulting polymer is fully degradable under mild, basic conditions.
Article
Polymer Science
Motoki Higuchi, Arihiro Kanazawa, Sadahito Aoshima
Summary: A temperature change-dependent sequence transformation method was demonstrated in the copolymerization of cyclic acetals and cyclic esters, where the position of the polymerization-depolymerization equilibrium was controlled by reaction temperature. The study optimized the conditions for efficient copolymerization, resulting in the generation of an alternating-like copolymer through a cycle of unzipping and scrambling reactions. The possibility of reversible sequence transformation upon heating and cooling was also observed.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Alex J. Plajer, Charlotte K. Williams
Summary: A new catalyst class demonstrates exceptional selectivity and the ability to switch between different polymerization cycles, allowing for precise control of CO2 placement in polymers and access to new polymer chemistries. The best catalyst is a trinuclear dizinc(II)sodium(I) complex with excellent reaction rates and no need for additives or co-catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Alex J. Plajer, Charlotte K. Williams
Summary: Heteroatom-containing polymers have potential as sustainable replacements for petrochemicals, offering a wide range of properties for various applications. Catalysed ring-opening copolymerisation (ROCOP) provides a route to create precise new polymer structures, leading to a renaissance in research and commercial products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Porfirio Lopez-Dominguez, Nathalie Michelle Carranco-Hernandez, Eduardo Vivaldo-Lima
Summary: A kinetic study was conducted on the mathematical modeling of polymerization rate and molar mass development in the ring opening bulk polymerization of lactones under microwave irradiation. Two modeling approaches were compared, with one focusing on average properties and the other on full molar mass distributions. The enhancement of polymerization rate under microwave irradiation was captured well by a non-thermal microwave effect modeling approach.
MACROMOLECULAR REACTION ENGINEERING
(2022)
Review
Polymer Science
Isha Jain, Payal Malik
Summary: Metal-N-heterocyclic carbene complexes (M-NHCs) have shown great potential as a catalytic system for the synthesis of various biodegradable polymers via ring opening polymerization. This review provides an overview of the field's major achievements and developments from 2004 to 2020, with a focus on the structure-activity relationship of M-NHC complexes.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Polymer Science
Michael R. Buchmeiser, Patrick Probst, Dongren Wang, Philipp Hauser
Summary: A series of cationic tungsten sulfido alkylidene N-heterocyclic carbene complexes were used as initiators in ROMP, achieving high stereocontrol and varying percentages of syndiotactic sequences. Mechanistic investigations suggest that the unique reactivity of the initiators contributes to the predominant trans-isospecifity observed in the polymerization.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Review
Chemistry, Multidisciplinary
Xue Liang, Fei Tan, Yunqing Zhu
Summary: The biomedical applications of polyesters and polycarbonates hold great potential but face challenges, with ring-opening copolymerization offering new possibilities to overcome these challenges, while advancements in catalyst development and post-polymerization modification methods have also been made in this field.
FRONTIERS IN CHEMISTRY
(2021)
