Article
Multidisciplinary Sciences
Lei Wang, Yupo Xu, Quan Zuo, Haojie Dai, Lei Huang, Meng Zhang, Yongli Zheng, Chunyang Yu, Shaodong Zhang, Yongfeng Zhou
Summary: The authors have developed a novel decolorable, metal-free and visible light-controlled living cationic polymerization system. This system exhibits predictable molar mass, low dispersity and sequential polymerization capability, and shows the longest off period of 36 hours. Furthermore, the residual photocatalyst can be easily deactivated and decolored.
NATURE COMMUNICATIONS
(2022)
Article
Polymer Science
Xia Lin, Qianxi Gu, Jiajia Li, Jian Zhu
Summary: In this study, a facile and robust method for living cationic polymerization using zinc wire as a catalyst precursor was developed. Well-defined poly(vinyl ether)s with various molecular weights and narrow molecular weight distributions were obtained at room temperature. The in situ generation of trace zinc ions was found to be the key to the mild conditions of the polymerization. The utilization of zinc wire offered advantages of reusability, easy separation, and low metal residue. Moreover, the method was successfully applied in continuous flow polymerization, showing potential for scalable and efficient industrial production under mild conditions.
Review
Chemistry, Multidisciplinary
Cansu Aydogan, Gorkem Yilmaz, Ataulla Shegiwal, David M. Haddleton, Yusuf Yagci
Summary: The application of photochemistry in polymer synthesis offers unique advantages compared to thermochemistry, allowing for precise control over macromolecular structure and chain length while also being environmentally friendly. Recent research has focused on utilizing photocontrolled living radical and cationic polymerizations for polymer synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bowen Zhao, Jiajia Li, Guangliang Li, Xinrui Yang, Shaopu Lu, Xiangqiang Pan, Jian Zhu
Summary: The application of reversible deactivation radical polymerization techniques in 3D printing allows for the creation of living polymer networks with various functionalities. However, the speed at which these systems can build objects is still limited. This article presents a digital light processing (DLP)-based 3D printing system that uses photoinduced free radical-promoted cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers to build living objects at a relatively fast speed (12.99 cm h(-1)) using a commercial DLP 3D printer. The polymerization behavior and printing conditions are studied, and the livingness of the printed objects is demonstrated through spatially controlled postmodification with a fluorescent monomer.
Review
Polymer Science
Chris William Anderson Bainbridge, Andika Wangsadijaya, Neil Broderick, Jianyong Jin
Summary: Controlled radical polymerization techniques are widely used in polymer research and development. However, their application in crosslinked polymer networks, which allows versatile post-production modifications, has received less attention. These living polymer networks can be classified into parent and daughter networks, and the use of atom transfer radical polymerization and reversible addition fragmentation chain-transfer polymerization has been most common. The future potential of living polymer networks is also discussed.
Article
Polymer Science
Xia Lin, Jiajia Li, Xiangqiang Pan, Zhengbiao Zhang, Jian Zhu
Summary: In this study, a new class of catalysts, selenonium cations, were used in living cationic polymerization under ambient conditions. The polymerization reactions showed good control and resulted in poly(vinyl ether)s with controlled molecular weights and narrow molecular weight distributions. The catalysts were successfully loaded on polystyrene microspheres, enabling heterogeneous catalysis and recyclability.
Article
Polymer Science
Kazuya Maruyama, Arihiro Kanazawa, Sadahito Aoshima
Summary: This study demonstrated the synthesis of sequence-controlled copolymers with controllable molecular weights and chain ends composed of alcohols, cyclic enol ethers, and vinyl ethers. The synthesis was achieved through selective monomer generation and subsequent alternating copolymerization. The copolymers obtained had periodically arranged alcohol-derived side chain-containing cyclic enol ether and VE moieties in the repeating units, confirmed by complete degradation into a single compound by alcoholysis. The use of specific alcohols was found to be effective for the synthesis of well-defined polymers.
Article
Polymer Science
Filip Petko, Mariusz Galek, Emilia Hola, Roman Popielarz, Joanna Ortyl
Summary: This paper presents a novel method for synthesizing benzylidene iodonium salts as photoinitiators and investigates their properties, showing efficient decomposition under UV to visible light and potential application in 3D printing.
Article
Polymer Science
Filip Petko, Andrzej Swiezy, Magdalena Jankowska, Pawel Stalmach, Joanna Ortyl
Summary: In this article, a new group of cationic photoinitiators is introduced and their photophysical properties and photoinitiating activity are analyzed with respect to the arrangement of electron-donating substituents in the coumarin chromophore. The authors observed two patterns of D-pi-A structure in the five new coumarin-based iodonium salts, which differ in the strength of the push-pull effect that determines their properties. These photoinitiators show excellent activity at 365 nm, 405 nm, and 415 nm and exhibit increased activity at elevated temperatures due to thermal reactions with monomers. This photo-thermal initiating activity makes them excellent photoinitiators for nanocomposite DLP 3D-VAT printing, overcoming scattering and shadowing problems.
Article
Materials Science, Multidisciplinary
Xia Lin, Jiajia Li, Wenjing Shu, Xiangqiang Pan, Jian Zhu
Summary: Polyselenonium salt was synthesized and used as a heterogeneous catalyst for the living/controlled cationic polymerization of various vinyl ethers. The combination of the polyselenonium salt and cationic RAFT agents allows for controlled polymerization under mild conditions, resulting in well-defined polymers.
ACS APPLIED POLYMER MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Renee J. Sifri, Yuting Ma, Brett P. Fors
Summary: Advancements in photocontrolled polymerizations have expanded the range of polymer structures that can be synthesized, however, most research has focused on radical processes, limiting monomer diversity. Recent developments in photo-controlled cationic polymerizations have increased the palette of monomers that can be used, enabling the synthesis of previously inaccessible structures.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Xiangke Li, Shi-Yang Tang, Yang Zhang, Jiayuan Zhu, Helen Forgham, Chun-Xia Zhao, Cheng Zhang, Thomas P. Davis, Ruirui Qiao
Summary: Droplet-based microfluidics is a significant technology that can be improved by using fluoropolymer-based surfactants to enhance stability and biocompatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Loic Buchon, Jean-Michel Becht, Laurent Rubatat, Wei Wang, Hua Wei, Pu Xiao, Jacques Lalevee
Summary: This research synthesized and characterized four potential phosphine oxide photoinitiators and evaluated their efficiency in photopolymerization at 405 nm wavelength. Two of the obtained photoinitiators showed better performance than the widely used commercial photoinitiator. Additionally, one of the synthesized photoinitiators was successfully used in 3D printing of thermoplastics and exhibited lower cytotoxicity compared to the benchmark structure.
JOURNAL OF APPLIED POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Anthony Keyes, Huong Dau, Krzysztof Matyjaszewski, Eva Harth
Summary: A new orthogonal radical/spin coupling technique has been identified in this study, which enables living insertion and controlled radical polymerization of polyolefins. This technique shows broad tolerance for different radical/spin traps and can be used for the synthesis of polyolefin-polyvinyl block copolymers with various segments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Roland Taschner, Robert Liska, Patrick Knaack
Summary: Iodonium antimonates and borates are widely used initiators in polymerization, while cyanide-ligated borane B2 is a new type of initiator with high reactivity and cost-effectiveness.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Polymer Science
Gizem Kaya, Baris Kiskan, Recep Isci, Mehmet S. Eroglu, Turan Ozturk, Yusuf Yagci
Summary: The study presents a novel strategy for fabricating electro-responsive polybenzoxazine based high-performance thermoset surfaces. Three structurally different benzoxazines were coated as thin films on ITO electrodes and cured by thermal activation. Structural characteristics, thermal behavior, electrochemical properties, and surface properties were evaluated using various techniques. This work demonstrates a straightforward electrochemical method for tuning surface morphology and hydrophilicity through redox processes and hydrogen bonding interactions.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Polymer Science
Semira Bener, Cansu Aydogan, Yusuf Yagci
Summary: A novel approach for the synthesis of hyperbranched polymers using photoinduced self-condensing vinyl polymerization has been explored, leading to successful production of HBPs with different branching densities. This method has potential applications in various fields, especially in bio-related systems requiring highly branched structures without contamination of low-molar mass photoinitiator fragments.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2021)
Article
Chemistry, Physical
Semira Bener, Gorkem Yilmaz, Yusuf Yagci
Summary: This study investigated the cationic ring opening polymerization of epsilon-caprolactone using directly and indirectly acting photoinitiating systems. It was found that the polymerization proceeds in a controlled manner through an activated monomer mechanism. The applicability of photoinitiation to other lactone monomers was also validated.
Review
Chemistry, Multidisciplinary
Cansu Aydogan, Gorkem Yilmaz, Ataulla Shegiwal, David M. Haddleton, Yusuf Yagci
Summary: The application of photochemistry in polymer synthesis offers unique advantages compared to thermochemistry, allowing for precise control over macromolecular structure and chain length while also being environmentally friendly. Recent research has focused on utilizing photocontrolled living radical and cationic polymerizations for polymer synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Zeynep Deliballi, Rezan Demir-Cakan, Baris Kiskan, Yusuf Yagci
Summary: A new approach to vulcanize commercial PVC at room temperature using elemental sulfur and an initiator is reported. The obtained crosslinked polymer with polysulfide linkages shows potential for recycling/self-healing and as cathode material for Li-S battery.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Polymer Science
Huseyin Cem Kiliclar, Emirhan Gencosman, Yusuf Yagci
Summary: This study presents a novel visible light induced step-growth polymerization mechanism and demonstrates the potential for grafting onto polymers containing epoxide at their side chains. By changing the molar ratios of the monomers, higher molecular weight polymers can be obtained, showing the effectiveness of the chain-growth condensation polymerization mechanism.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Polymer Science
Bahar T. Ercan, Sirin S. Gultekin, Tamer Yesil, Haluk Dincalp, Sermet Koyuncu, Yusuf Yagci, Ceylan Zafer
Summary: This study reports the photoinitiated cationic polymerization of epoxy resins using four new chromophoric dyes and diphenyliodonium hexafluorophosphate under sunlight. It is shown that ISOVIII and TPDC6, which have carbazole groups, exhibited higher initiation efficiency.
POLYMER INTERNATIONAL
(2022)
Article
Polymer Science
Cansu Aydogan, F. Simal Aykac, Gorkem Yilmaz, Ye Qiu Chew, Atsushi Goto, Yusuf Yagci
Summary: A versatile strategy for the fabrication of block copolymers using a combination of two discrete living polymerization techniques has been reported. The strategy involves reversible complexation mediated living radical polymerization (RCMP) and photoinduced radical oxidation addition deactivation (PROAD) processes. The formation of the block copolymers was confirmed through various characterization techniques.
Article
Polymer Science
Mehmet Bilgehan Bilgic, Kerem Kaya, Nermin Orakdogen, Yusuf Yagci
Summary: Hydrogels, with high water absorption, biocompatibility, and non-toxic characteristics, are important polymers for various technologies. In this study, a facile synthesis of clickable polyacrylamide hydrogel was reported using photopolymerization. The gel's properties were affected by the irradiation time.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Analytical
Tugba Celiker, Faezeh Ghorbanizamani, Hichem Moulahoum, Emine Guler Celik, Kerem Tok, Figen Zihnioglu, Candan Cicek, Ruchan Sertoz, Bilgin Arda, Tuncay Goksel, Kutsal Turhan, Suna Timur, Yusuf Yagci
Summary: A rapid and easy immunofluorescence bioassay for SARS-CoV-2 detection was developed using a one-pot synthetic approach for the production of a graft fluorescent copolymer PPy-g-PCL. The assay showed a detection range of 6.03-8.7 LOG viral copy mL(-1) and a high correlation with RT-PCR data. This study provides new insights for simplified synthesis procedures of reporter molecules and their potential applications in sensing and diagnosis.
Article
Chemistry, Multidisciplinary
Azra Kocaarslan, Kerem Kaya, Steffen Jockusch, Yusuf Yagci
Summary: In this study, a single component near UV-responsive photopolymerization system using phenacyl bromide (PAB) is reported for step-growth polymerization of N-methylpyrrole (MPyr) and N-methylindole (MIn). The polymerization process proceeds through photoinduced cleavage of PAB, followed by electron transfer, proton release, and coupling processes. Chain growth continues even after photolysis in daylight or dark.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Cansin Birsen Buldum, Sevinc Gulyuz, Yusuf Yagci, Baris Kiskan
Summary: Siloxane bearing benzoxazines derived from renewable phenolics such as vanillin and coumarin have been prepared and reacted with glycerol to form processable, soft, and curable bio-hybrid gels. The presence of hydroxyl groups on glycerol moieties facilitates curing, resulting in bio-hybrid polybenzoxazines at temperatures below 200°C.
EUROPEAN POLYMER JOURNAL
(2022)
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
Sevinc Gulyuz, Yusuf Yagci, Baris Kiskan
Summary: A new strategy for the synthesis of self-healable/recyclable polybenzoxazine networks by exploiting dynamic B-O bond exchanges is presented in this work. The obtained films exhibit good self-healing properties and hydrolysis stability under mild conditions.
Article
Polymer Science
Kamer Bayram, Baris Kiskan, Yusuf Yagci
Summary: Benzoxazines with thioamide linkages were successfully prepared through a specific synthetic route, further converted into polybenzoxazines. The curing behavior and thermal stability were studied, revealing that thioamide groups can reduce curing temperatures and possibly generate thiols during heating.
