Review
Chemistry, Multidisciplinary
Bokun Li, Chenyang Hu, Xuan Pang, Xuesi Chen
Summary: This Review provides an overview of a redox-controlled switchable strategy for controlled synthesis of polymers. By developing valence-variable metal-based catalysts, high sequence-control and easy-handling in ring-opening (co)polymerizations can be achieved, resulting in polymer products with desired microstructures and practical performances.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Bokun Li, Chenyang Hu, Zhenjie Yang, Xuan Pang, Xuesi Chen
Summary: This study successfully developed biaryl-linked bimetallic Salen-Mn catalysts for the ring-opening polymerization of lactide and epsilon-caprolactone. The activity and iso-selective tendency towards lactide are determined by the conformation and Mn-Mn separation of the catalysts. Finally, the CO2-controlled switchable polymerization succeeded in this catalytic system, and the reversibility of the on-off switch is related to the combination between active species and CO2 molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(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
Nicholas M. M. Shawver, Alicia M. M. Doerr, Brian K. K. Long
Summary: A polymer's properties are determined by the monomers used and the way they are assembled. Polyesters have gained attention as biodegradable alternatives to other petrochemical-based polymers. Researchers have developed redox-switchable catalysts that can alter chemoselectivity and kinetic modulation in ring-opening polymerizations.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Materials Science, Multidisciplinary
Siping Hu, Jianxu Chen, Xun Zhang, Yuying Zhang, Saihu Liao
Summary: Visible light-regulated organocatalytic polymerization has received significant attention in recent years due to its mild, metal-free reaction conditions and the ability to mediate polymerization with spatial and temporal control. In this study, hydroxybenzophenones (BPOHs) were successfully identified as an effective class of photoacid catalysts for the ring-opening polymerization of lactones, resulting in biodegradable polyester products with predictable molecular mass and low dispersity under visible light irradiation.
ACS APPLIED POLYMER MATERIALS
(2022)
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
Chemistry, Multidisciplinary
Jiadong Tang, Maosheng Li, Xianhong Wang, Youhua Tao
Summary: We have achieved the one-pot production of sequence-controlled block copolymer from mixed monomers using a switchable catalyst. The method allows for chemoselective and efficient polymerization reactions, resulting in a high conversion rate of CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Tobias A. Bauer, Christian Muhl, Dieter Schollmeyer, Matthias Barz
Summary: The use of racemic mixtures of NCAs can improve reaction rates and monomer conversion, the controlled living nature of polypeptide ring-opening polymerization enables the synthesis of high DP polypeptides and triblock copolymers with symmetric molecular weight distributions through sequential monomer addition.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Review
Polymer Science
Zhaowei Jia, Yuju Li, Jincai Wu
Summary: The hydrolysis behavior of copolyester is significantly influenced by its sequence structure, making sequence-controlled copolyesters an attractive material class. Through living ring-opening polymerization (ROP), both the molecular weight and sequence structure of copolyesters can be easily controlled. The development of metal-based initiators has greatly advanced research in this field.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2021)
Article
Multidisciplinary Sciences
Yali Hu, Zi-You Tian, Wei Xiong, Dedao Wang, Ruichi Zhao, Yan Xie, Yu-Qin Song, Jun Zhu, Hua Lu
Summary: This study presents a water-assisted controlled ring-opening polymerization method for ProNCA, which enables the rapid synthesis of well-defined PLP in a short time. The use of water facilitates proton shift and lowers the energy barrier, leading to fast and efficient reactions. The protein-mediated ROP of ProNCA offers a convenient approach for the synthesis of various protein-PLP conjugates with enhanced properties.
NATIONAL SCIENCE REVIEW
(2022)
Article
Polymer Science
Jian-Qun Wang, Xian-Hong Wang, You-Hua Tao
Summary: This study successfully synthesized sustainable aliphatic polyamides with controlled features by converting renewable resource 4-hydroxyproline into bicyclic bridged lactam monomers. The resulting polyamides exhibited high molecular weight and low molecular weight distribution, showing potential applications.
CHINESE JOURNAL OF POLYMER SCIENCE
(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
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)
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
Ao Chen, Daohong Liao, Changle Chen
Summary: A novel diaryl-methyl aniline with multiple tert-butyl groups and its derivatives were prepared in this study, showing excellent solubility and catalytic properties with nickel catalysts in aliphatic hydrocarbon solvents, potentially bridging academic research with practical applications in polymerization.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Chen Tan, Chen Zou, Changle Chen
Summary: The study introduces an ionic cluster strategy for controlling product morphology and improving catalytic copolymerization performance in the synthesis of polar-functionalized polyolefins. This strategy is versatile, enhancing thermal stability of catalysts at high temperatures and enabling the homopolymerization of polar-functionalized olefins. It also results in polyolefin composites with tunable mechanical properties, showing potential as compatibilizing agents for polyolefin mixtures with other polymers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Multidisciplinary Sciences
Min Chen, Changle Chen
Summary: This article introduces the methods for controlling the introduction of polar functional groups in polyolefin materials and the recent developments in copolymerization reactions using nickel catalysts. The article focuses on the design and development of different types of nickel catalyst systems for copolymerization reactions between polyolefins and polar monomers and summarizes the catalytic properties of these reactions. Additionally, the article discusses the application of heterogeneous catalysts in copolymerization reactions between polyolefins and polar monomers. Furthermore, the article mentions the properties of polar-functionalized polyolefin materials and the challenges and problems in this field, and proposes future research directions.
CHINESE SCIENCE BULLETIN-CHINESE
(2022)
Article
Chemistry, Multidisciplinary
Changwen Hong, Zihao Wang, Hui Jiang, Guifu Si, Maoping Song, Changle Chen
Summary: Brookhart-type α-diimine nickel and palladium catalysts have been extensively studied, but their heterogenization has received less attention. In this study, a trifluoroborate potassium substituent was introduced on an α-diimine framework. The ionic nature of trifluoroborate potassium strengthened the interaction between the α-diimine nickel complex and SiO2 support, while its electron-donating property enhanced the catalyst stability and polyethylene molecular weight.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Zhanshan Ma, Mengli Xu, Ningning Zhu, Chen Tan, Changle Chen
Summary: Heterogenization can improve the thermal stability and product morphology control of olefin polymerization catalysts, which are important parameters for industrial polyethylene production. In this study, alpha-diimine nickel catalysts with -OH or -ONa anchoring groups were designed and prepared to enable facile heterogenization on silica. The heterogeneous catalysts exhibited enhanced thermal stabilities and high catalytic activity, resulting in improvements in polymer morphology control, catalytic activity, and polyethylene molecular weight.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Shi-Yu Chen, Yu-Hang Song, Shuang Jiao, Chen Zou, Shi-Huan Li, Changle Chen, Xiao-Bing Lu, Ye Liu
Summary: Polyethylenes are widely used synthetic polymers, and introducing functional groups into polyethylene backbone can improve environmental persistence and compatibility with other materials. However, this process is hindered by the formation of alternating polyketones. By reducing the carbonyl density in polyketones, their properties become closer to polyethylene. In this study, Ni and Pd-coordinated cationic catalysts were used for nonalternating carbonylative copolymerization of ethylene, resulting in car-bonyl functionalized polyethylenes with similar properties to commercial high-density polyethylene.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jie Li, Dan Peng, Chen Tan, Changle Chen
Summary: In this contribution, an outer-shell self-supporting strategy was designed to heterogenize nickel catalysts on different fillers via precipitation homopolymerization of ionic cluster type polar monomer. These catalysts demonstrated high activity, good product morphology control, and stable performances in ethylene polymerization and copolymerization. Moreover, various polyolefin composites with great mechanical and customized properties can be efficiently synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Yan-Bing Wang, Chenlong Nan, Weize Zhuo, Chen Zou, Hui Jiang, Xin-Qi Hao, Changle Chen, Mao-Ping Song
Summary: The introduction of O-donor groups on amine-imine ligands leads to the synthesis of a series of nickel complexes, which exhibit high catalytic activities and produce polyethylene elastomers with high molecular weight. Moreover, these nickel complexes can also catalyze the copolymerization of ethylene with various functional monomers to prepare functionalized polyolefins.
INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Somayyeh Sadat Afi Kheljani, Khadijeh Didehban, Mohammad Atai, Changle Chen, Naeimeh Bahri-Laleh
Summary: In this research, the functionalization of easily available polyalphaolefin (PAO) based resins was achieved through copolymerization and further modification. The microstructure of the synthesized and modified resins was analyzed using various analytical methods. The resulting macromer showed a hydrophilic nature and had potential applications in tissue engineering.
JOURNAL OF POLYMER RESEARCH
(2023)
Article
Polymer Science
Dan Peng, Menghe Xu, Chen Tan, Changle Chen
Summary: In this study, an emulsion polymerization strategy was used to heterogenize imino-based nickel olefin polymerization catalysts on solid supports. Polymeric microspheres were prepared through emulsion copolymerization, and the resulting heterogeneous nickel catalysts exhibited excellent properties in ethylene polymerization and copolymerization. The catalytic properties could be controlled by adjusting the comonomer type, composition, and particle size. This strategy allowed for product morphology control, avoided reactor fouling, and generated polyethylene products with minimal inorganic contamination. Furthermore, the introduction of polymer microspheres improved the mechanical and surface properties of polyolefin products.
Article
Polymer Science
Menghe Xu, Ao Chen, Wu Li, Yougui Li, Chen Zou, Changle Chen
Summary: Introducing polar biomass groups into polyolefins improves their nonpolar nature and aligns with sustainable development. Researchers have developed an efficient method to produce polar functionalized polyolefins with high biomass content. By utilizing phosphine-sulfonate palladium-catalyzed copolymerization reactions, bioresourced comonomers with oleyl and cinnamyl groups are inserted into the polyolefins.
Article
Chemistry, Physical
Jie Xu, Changle Chen, Xiangkai Kong
Summary: Controlled alloying, structure design, phase exploration, and carbon support modulation strategies are used for efficient Ru-based catalyst synthesis. A stepped annealing approach is employed to create Ru active sites, where Ru nanocrystals are in-situ formed on CuO surface and strong interaction at the interface is generated. The resultant Ru-CuO-SA catalyst exhibits high overpotential, low Tafel slope, and high turnover frequency, surpassing most reported materials. The creation of Ru-O-Cu bonds enhances surface oxophilicity and provides moderate hydrogen binding, resulting in improved hydrogen production efficiency.
Review
Chemistry, Multidisciplinary
Chen Tan, Min Chen, Changle Chen
Summary: Transition metal-catalyzed olefin-polar monomer copolymerization has the potential to synthesize polar group-functionalized polyolefin materials. However, the traditional trial-and-error approach is challenging and time-consuming. Recent 'catalyst + X' strategies have emerged, which utilize the interactions between the catalyst and other components in the copolymerization system to influence the reaction and resulting material properties. This review summarizes selected examples of these strategies and discusses future perspectives.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chen Zou, Chen Tan, Changle Chen
Summary: Polyolefins are commonly used synthetic polymers, but their limited compatibility with polar materials has hindered their application in certain fields. Transition-metal-catalyzed copolymerization of olefin and polar functionalized monomers allows for the synthesis of polar-functionalized polyolefin materials with improved properties. Heterogenization strategies for the synthesis of high-performance heterogeneous nickel catalysts have been developed, offering better control over product morphology and improved polymerization processes.
ACCOUNTS OF MATERIALS RESEARCH
(2023)
Article
Multidisciplinary Sciences
Chen Zou, Quan Wang, Guifu Si, Changle Chen
Summary: Polar bimodal polyethylene is demonstrated as a potential solution to the trade-off between catalytic activity and polymer molecular weight caused by polar groups in catalysts. Three synthetic routes are investigated to achieve high miscibility between the polar and non-polar fractions, with the co-anchoring strategy being the most effective. This produces polyolefin materials with excellent properties for various applications.
NATURE COMMUNICATIONS
(2023)
