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
Polymer Science
Francisco W. M. Ribeiro, Isaac Omari, Gilian T. Thomas, Mathias Paul, Peter J. H. Williams, J. Scott McIndoe, Thiago C. Correra
Summary: This study presents a mass spectrometric evaluation of the initial step of benzoxazine polymerization and distinguishes between the phenoxy and phenolic products formed by different pathways. The findings suggest a preference for the phenoxy product in the initial stages of the reaction, while the phenolic product is observed at later stages. This information is valuable in understanding the benzoxazine polymerization process and optimizing polymerization conditions.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Zehra Gul Coban, Huseyin Cem Kiliclar, Yusuf Yagci
Summary: Photochemical techniques have seen a revival due to their adaptability and ability to produce complex macromolecular structures, although their application in the polymerization of cyclic siloxane monomers has been limited. This study investigated the cationic ring-opening polymerization of Octamethylcyclotetrasiloxane (D4) using diphenyl iodonium hexafluorophosphate (DPI) as the initiator. Both direct and indirect initiation systems were examined, using benzophenone and pyrene to generate photochemically induced protonic acids and silylium cations for the polymerization. Kinetics of the polymerization were monitored using viscosimetry and GPC analysis. This approach has potential industrial importance for polysiloxane fabrication due to its ability to overcome challenges associated with conventional methods.
Article
Polymer Science
Balazs Pasztoi, Tobias M. Trotschler, Akos Szabo, Benjamin Kerscher, Heikki Tenhu, Rolf Muelhaupt, Bela Ivan
Summary: Cationic ring-opening polymerization of EtOx in BTF and other solvents shows similar kinetics, with BTF offering the highest polymerization rates and conversions; The Arrhenius parameters indicate relatively high activation energy in BTF, but a compensation effect is observed between activation energies and frequency factors in various solvents.
Article
Chemistry, Multidisciplinary
Yongliang Xia, Pengjun Yuan, Yanping Zhang, Yangyang Sun, Miao Hong
Summary: This study reports the efficient conversion of gamma-valerolactone and its derivatives into sustainable and degradable polythioesters through the establishment of the first isomerization-driven ring-opening polymerizations (IROPs) of corresponding thionolactone intermediates. The development of a new cationic initiator [Et3O](+)[B(C6F5)(4)](-) with high activity, exclusive selectivity, living nature, and broad scope of thionolactones is the key to this success. The study also reveals the complete inversion of configuration during IROP of enantiopure gamma-thionovalerolactone and the formation of a highly crystalline supramolecular stereocomplex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Engineering, Environmental
Huiyue Wang, Zhao Jin, Xin Hu, Qiao Jin, Songwei Tan, Ali Reza Mahdavian, Ning Zhu, Kai Guo
Summary: By combining microreactor and cation pool method or carbocation stabilization, improved living cationic polymerizations can be achieved under mild conditions. This review highlights cationic addition polymerizations of vinyl monomers and cationic ring-opening polymerizations of cyclic monomers in the context of microreactor-based flow chemistry, proposing challenges and opportunities to promote the development of cationic polymerization in both academia and industry.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Polymer Science
Jinlong Chen, Yilin Dong, Chunsheng Xiao, Youhua Tao, Xianhong Wang
Summary: The research team successfully synthesized a novel class of poly(epsilon-lysine) mimics through ring-opening polymerization, avoiding tedious deprotection procedures, and exhibited high antimicrobial activities and excellent biocompatibility.
Article
Chemistry, Multidisciplinary
Ju-Hyung Chae, Minyeong Choi, Semin Son, Su-Min Ko, In-Hwan Lee
Summary: Precise control of multiple structural parameters associated with vinyl polymers is important for producing materials with the desired properties and functions. The development of living polymerization methods has provided a way to control the various structural parameters of vinyl polymers, but controlling their sequence and regioregularity remains challenging. In this study, we report a scalable and modular synthesis of cyclic monomers through a one-step protocol using readily available vinyl precursors. The living cationic ring-opening polymerization of these cyclic monomers allows for the synthesis of vinyl polymers while controlling multiple factors, such as molecular weight, dispersity, alternating sequence, regioregularity, and end-group functionality. The synthesized vinyl polymers exhibit unique thermal properties and undergo fast photodegradation even under sunlight.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Daisuke Hotta, Arihiro Kanazawa, Sadahito Aoshima
Summary: tert-Butyl esters play a crucial role as chain transfer agents in the cationic copolymerization, liberating tert-butyl cations to facilitate the chain transfer process. The chain transfer reactions by tert-butyl esters potentially occur reversibly through the reaction of the propagating cation with the ester group at the omega-end of another chain.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Materials Science, Multidisciplinary
Georgy V. Timofeev, Maksim I. Hulnik, Irina V. Vasilenko, Francois Ganachaud, Guy Jacob, Sergei V. Kostjuk
Summary: This study investigates the cationic ring-opening polymerization of epichlorohydrin initiated by BF3•Et2O. The fast synthesis of pure poly(epichlorohydrin) diols with controlled molar mass and low dispersity was successfully achieved. An innovative approach involving the generation of an initiator in situ through the reaction of BF3•Et2O with water was developed, resulting in improved solubility of the oligomers in the reaction medium. Polymerization then proceeds exclusively through the activated monomer mechanism, allowing precise control over the polymer growth. Additionally, the reasons for coloration of the polymer during polymerization and/or storage were investigated.
ACS APPLIED POLYMER MATERIALS
(2023)
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
Zhunxuan Li, Rui Chen, Ying Wang, Linlin Zhu, Wenyi Luo, Zhen Zhang, Nikos Hadjichristidis
Summary: An efficient synthetic methodology was developed for the modification of hyperbranched polyethyleneimines (PEI) using N-sulfonyl aziridines, resulting in materials with unique fluorescence properties and the ability to remove hazardous metals.
Article
Chemistry, Multidisciplinary
Ge-Ge Gu, Tian-Jun Yue, Wei-min Ren
Summary: This communication presents the synthesis of cyclic polyamines by cationic ring-opening polymerization of N-benzylaziridines initiated by tris(pentafluorophenyl)borane. The resulting polyamines were further converted into water-soluble polyethylenimine derivatives via debenzylation. Mass spectrometry and density functional theory analysis indicated that the polymerization proceeded through activated chain end intermediates.
CHEMICAL COMMUNICATIONS
(2023)
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
Polymer Science
Masato Suzuki, Aya Watanabe, Raimu Kawai, Ryo Sato, Shin-ichi Matsuoka, Susumu Kawauchi
Summary: This study reports the ring-opening polymerization of thiolactide, where thiolactic acid undergoes cyclic condensation to form rac-thiolactide, which is then polymerized using a combination of thiol as initiator and DBU as catalyst. The polymerization process was found to be in equilibrium and displayed different structural characteristics and degradability compared to polylactide.
