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
Polymer Science
Jingjing Liu, Yves Gnanou, Xiaoshuang Feng
Summary: The value and merit of triethylborane (TEB)-based ate complexes for the synthesis of various oxygenated polymers have been demonstrated. This study expanded the scope of TEB-based initiating systems to anionically polymerize cyclic esters and to copolymerize them with propylene oxide (PO). The addition of hydrogen-bonding donors promoted a fast and controlled ring-opening polymerization (ROP) of cyclic esters. The controlled nature of the polymerization was confirmed by characterization techniques. These borane-based ate complexes showed great potential for the synthesis of copolymers.
Article
Polymer Science
Chong-Min Chen, Xiaowei Xu, He-Yuan Ji, Bin Wang, Li Pan, Yi Luo, Yue-Sheng Li
Summary: In this study, the ring-opening alternating copolymerization of cyclic anhydride and epoxide was thoroughly investigated using alkali metal carboxylates as initiators. The coordination effects of epoxide on the alkali metal carboxylate were verified using FT-IR spectroscopy and DFT calculations. Alkali metal carboxylates were found to effectively catalyze the copolymerization of cyclic anhydride and epoxide, leading to the synthesis of polyesters with alternating structures. The use of potassium acetate was particularly noteworthy as it allowed for the copolymerization of different cyclic anhydrides and epoxides, including the high molar feed ratio synthesis of poly(PA-alt-PO) with a molecular weight exceeding 100 kDa.
Article
Polymer Science
Guofei Feng, Ximin Feng, Xiong Liu, Wenqi Guo, Chengjian Zhang, Xinghong Zhang
Summary: This article introduces a method to convert the pollutant CS2 into valuable sulfur-containing polymers using a cooperative organocatalyst system. The copolymerization reaction is highly efficient, avoids small-molecule byproducts, and produces polythiocarbonates with highly regular sequences. The polythiocarbonates demonstrate desirable thermal and mechanical properties.
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
Chemistry, Multidisciplinary
Xiaoxian Lu, Xun Zhang, Chengjian Zhang, Xinghong Zhang
Summary: The alternating copolymerization of cyclic anhydride and o-phthalaldehyde is reported for the synthesis of cyclic and recyclable polyesters. The method is efficient and utilizes common catalysts at room temperature, producing high yields within a short time. The resulting polyesters have well-defined alternating sequences and high-purity cyclic topology, and can be easily recycled to their monomers through chemical reactions.
Article
Chemistry, Inorganic & Nuclear
Quanyou Yao, Yaorong Wang, Bei Zhao, Xuehua Zhu, Yunjie Luo, Dan Yuan, Yingming Yao
Summary: A series of Nd-Zn heterometallic complexes with o-phenylenediamine-bridged tris(phenolato) ligands were synthesized. Among them, a highly active Nd-Zn heterometallic complex 12 was found to be effective for the copolymerization of CO2 and cyclohexene oxide (CHO), resulting in alternating poly-(cyclohexene carbonate) with a high turnover frequency. Kinetic studies revealed that the copolymerization reaction catalyzed by 12 exhibited first-order dependence on 12 and CHO concentration, and zero-order dependence on CO2 pressure. A plausible synergistic polymerization mechanism was proposed based on experimental evidence.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Max Hirschmann, Rachele Zunino, Sara Meninno, Laura Falivene, Tiziana Fuoco
Summary: In this study, bi-functional organocatalysts containing a (thio-)urea moiety and an iminophosphorane moiety were synthesized and optimized for the ring-opening alternating co-polymerization of phthalic anhydride with three different epoxides. The most effective catalyst showed quantitative conversion of all tested epoxides within 24 hours, with high ester-selectivities up to >97%. NMR and DFT experiments revealed that the catalysts existed as dimers in solution and dissociated during the initiation of polymerization. The catalyst coordinated to the growing chain and modulated its reactivity through reversible protonation/deprotonation, suppressing transesterification side reactions even at prolonged polymerization times without the need for a co-catalyst. The rate-determining step of the polymerization was the ring-opening of the epoxide by the carboxylate chain end, and higher temperatures and concentrations of epoxide and catalyst promoted polymerization rates.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Polymer Science
Tian-Jun Yue, Li-Yang Wang, Wei-Min Ren, Xiao-Bing Lu
Summary: The thermal performance of semiaromatic polythioesters obtained from the copolymerization of epoxides with phthalic thioanhydride (PTA) has been improved by increasing the isotacticity of the copolymers in a regioselective manner. This was achieved through the use of unsymmetrical Salcy-based Cr-complexes with modified steric hindrance around the catalytic center, resulting in highly regioselective copolymerization and the formation of isotacticity-rich polythioesters. Furthermore, semiaromatic polythioester stereocomplexes were obtained by blending equal-mass (R)- and (S)-isotactic PGE/PTA copolymers, which exhibited crystalline nature with a higher melting temperature compared to the amorphous isotactic parent copolymer.
EUROPEAN POLYMER JOURNAL
(2023)
Review
Chemistry, Physical
Claire A. L. Lidston, Sarah M. Severson, Brooks A. Abel, Geoffrey W. Coates
Summary: The ring-opening copolymerization (ROCOP) of epoxides with CO2 or cyclic anhydrides using multifunctional catalysts has been explored as a versatile route for synthesizing a wide range of polycarbonate and polyester copolymers. Covalently tethering the Lewis acid catalyst and cocatalyst together has been shown to increase both catalyst activity and selectivity in epoxide ROCOP. This review examines the development of multifunctional catalysts for copolymerization of epoxides with CO2, cyclic anhydrides, carbonyl sulfide (COS), and cyclic thioanhydrides, and evaluates how the mechanisms of these catalysts lead to improved activity and selectivity in ROCOP.
Article
Polymer Science
Xingji Zhu, Rui Wang, Xinhui Kou, Fusheng Liu, Yong Shen
Summary: In this research, an organic cyclic trimeric phosphazene base (CTPB) in combination with different ureas was utilized as a binary catalyst, showing high catalytic activities in the ring-opening alternating copolymerization (ROAC) of epoxides and cyclic anhydrides. The resulting polyesters exhibited diverse structures, well-defined chain-ends, and low dispersities.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2021)
Article
Polymer Science
Jiaojiao Qin, Xiaoyan Tang
Summary: This study presents a facile and efficient method for synthesizing cyclic poly(ester amide)s (PEAs) through copolymerization of N-substituted aziridines and phthalic anhydride. Control over the polymerization process was achieved, and PEAs with diverse structures were prepared.
Article
Polymer Science
Lanfang Hu, Xun Zhang, Xiaohan Cao, Danjing Chen, Yue Sun, Chengjian Zhang, Xinghong Zhang
Summary: The study presents an easy and efficient method to synthesize semicrystalline polyesters via copolymerization of IBO and cyclic anhydrides, yielding polymers with high alternation degree, high molecular weights, and elevated melting temperatures. Besides, by manipulating the cis/trans isomerization of the C=C bond, unsaturated polyesters can exhibit a unique crystalline-amorphous-crystalline transformation.
Review
Chemistry, Inorganic & Nuclear
Gulzar A. Bhat, Donald J. Darensbourg
Summary: The use of carbon dioxide for producing polymeric materials as an alternative feedstock has promising prospects. The synthesis of polycarbonates from CO2 and epoxides has attracted much attention, and metal coordination complexes have greatly advanced the synthetic capability and mechanistic understanding of these reactions. This review focuses on the advancements in CO2/epoxide polymerization processes using various main group and transition metal complexes as catalysts for thermoplastic preparation, while also discussing the development of organocatalysts based on their metal counterparts.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Polymer Science
Oliver J. Driscoll, Jack A. Stewart, Paul McKeown, Matthew D. Jones
Summary: A simple and organic catalytic system utilizing 14 Fe(III) complexes as catalysts for ROCOP was developed, leading to the successful synthesis of high-quality polymers and investigation of structure-activity relationships. The discovery that organic catalysts outperformed their Lewis acidic Fe(III) analogues provides hope for future sustainable polymerization research.
Article
Chemistry, Multidisciplinary
Xiaohan Cao, Hongliang Wang, Jialiang Yang, Ruiyang Wang, Xin Hong, Xinghong Zhang, Junting Xu, Hai Wang
Summary: This paper investigates the crystallization behavior and properties of poly(trimethylene monothiocarbonate) (PTMMTC) and its analogue poly(trimethylene carbonate) (PTMC). The study finds that PTMMTC exhibits stronger crystallizability and intermolecular interaction due to the presence of sulfur substitution. Additionally, the crystal structure of PTMMTC is preliminarily determined.
CHINESE CHEMICAL LETTERS
(2022)
Article
Polymer Science
Jiraya Kiriratnikom, Xun Zhang, Xiaohan Cao, Bo Chu, Chengjian Zhang, Xinghong Zhang
Summary: The facile synthesis of sulfur-rich polymers using common feedstocks such as ethylene oxide, propylene oxide, and carbonyl sulfide is highly sought after but challenging. By varying the feedstock ratio, copoly(thioether)s with tunable thermal properties and high solubility can be obtained, showing great potential for various applications.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Yanni Xia, Xinchen Yue, Yue Sun, Chengjian Zhang, Xinghong Zhang
Summary: The green revolution in plastics needs to be expedited due to growing concerns about sustainability. We have developed a series of chemically recyclable polymers using a cascade polymerization reaction of H2O, COS, and diacrylates. These polymers, with abundant feedstocks, efficient synthesis, and high molecular weights, demonstrate impressive toughness and ductility. The presence of an in-chain ester group enables chemical recycling and the versatility of our method expands the range of structures and properties. These polymers offer promising prospects as sustainable materials due to the availability of raw materials, ease of synthesis, and high performance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Munir Ullah Khan, Safir Ullah Khan, Xiaohan Cao, Muhammad Usman, Xinchen Yue, Abdul Ghaffar, Muhammad Hassan, Chengjian Zhang, Xinghong Zhang
Summary: This study shows the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate catalyst in the copolymerization of carbonyl sulfide and propylene oxide. By tuning the reaction conditions, the molecular weight and content of the copolymer can be effectively controlled.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Polymer Science
Xiaowei Geng, Ziheng Liu, Chengjian Zhang, Xinghong Zhang
Summary: This study presents a one-pot, metal-free, and switchable copolymerization method for the synthesis of sustainable polymers to replace petroleum-based plastics. The resulting copolymers exhibit impressive toughness and ductility due to the presence of isotactic polylactide fragments and high molecular weights.
Article
Chemistry, Multidisciplinary
Yanni Xia, Yue Sun, Ziheng Liu, Chengjian Zhang, Xinghong Zhang
Summary: This article introduces a novel, modular, and efficient click reaction for synthesizing recyclable polymers. The method utilizes sustainable feedstocks and releases carbonyl sulfide (COS) as industrial waste. The polymers obtained have versatile and tunable structures, and can be easily recycled due to in-chain thiocarbonate and ester polar groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Guofei Feng, Ximin Feng, Xiong Liu, Wenqi Guo, Chengjian Zhang, Xinghong Zhang
Summary: This article introduces a method to convert the pollutant CS2 into valuable sulfur-containing polymers using a cooperative organocatalyst system. The copolymerization reaction is highly efficient, avoids small-molecule byproducts, and produces polythiocarbonates with highly regular sequences. The polythiocarbonates demonstrate desirable thermal and mechanical properties.
Article
Polymer Science
Ying Wang, Ziheng Liu, Wenqi Guo, Chengjian Zhang, Xinghong Zhang
Summary: In this study, frustrated Lewis pair (FLP) composed of commercial tertiary phosphine and trialkylborane was used as a catalyst for the copolymerization of CO2 and propylene oxide (PO). The rational matching of Lewis bases and acids greatly influences the activity and controllability of CO2 copolymerization. The obtained polycarbonates showed well-defined structures with high carbonate content, tunable molecular weights, and narrow dispersities.
Article
Multidisciplinary Sciences
Xun Zhang, Wenqi Guo, Chengjian Zhang, Xinghong Zhang
Summary: Our society is seeking chemically recyclable polymers to advance the green revolution in plastics. A recyclable polyester library is developed through the alternating copolymerization of aldehyde and cyclic anhydride, demonstrating unexpected alternating characteristics.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jiafang Guo, Xiong Liu, Xiaohan Cao, Xun Zhang, Haoke Zhang, Yingying Lu, Chengjian Zhang, Xinghong Zhang
Summary: This study reports a polymer electrolyte based on poly(ester-alt-acetal), which provides stable lithium plating/stripping behavior and high oxidation potential. The electrolyte suppresses concentration polarization through interactions with Li+ and TFSI-, and exhibits good compatibility with the electrodes.
ACS ENERGY LETTERS
(2023)
Article
Chemistry, Physical
Shu Yan, Pengfei Jiang, Xinghong Zhang, Yongsheng Guo, Wenjun Fang
Summary: To enhance the extraction efficiency of crude oil emulsions, researchers have designed and synthesized n-hexadecanoyl hyperbranched poly(amido-amine) (CHPAMAM) as an amphiphilic demulsifier with hyperbranched poly(amido-amine) as the core and palmitic acid chains as the shell. Stable oil-in-water emulsions can be completely separated into two phases at low temperature with the presence of highly active CHPAMAM, resulting in a clear phase interface and a thin transition layer. By adding 80 ppm CHPAMAM to simulated emulsions and crude oils from China's oilfields, the oil removal ratios can exceed 99.9% and the water contents in the oil phase can be reduced to less than 0.01%, achieving demulsification equilibrium within 40 min at 30 degrees C. The demulsification process is monitored in real-time using laser scanning confocal microscopy (LSCM). The demulsification mechanism of CHPAMAM is studied through adsorption kinetics experiments and validated by dissipative particle dynamics simulation, demonstrating its ability to disrupt the stabilizing materials and enhance demulsification performance at low temperature.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Xiaoxian Lu, Xun Zhang, Chengjian Zhang, Xinghong Zhang
Summary: The alternating copolymerization of cyclic anhydride and o-phthalaldehyde is reported for the synthesis of cyclic and recyclable polyesters. The method is efficient and utilizes common catalysts at room temperature, producing high yields within a short time. The resulting polyesters have well-defined alternating sequences and high-purity cyclic topology, and can be easily recycled to their monomers through chemical reactions.
Article
Polymer Science
Ying Wang, Guofei Feng, Wenqi Guo, Chengjian Zhang, Xinghong Zhang
Summary: In this study, a unique method for the quantitative chemical recycling of poly(propylene carbonate) (PPC) to sulfur-containing polymers using COS was proposed. The process involves several steps facilitated by commercially available organic bases. The resulting polymers possess tunable thioether and thiocarbonate linkages and the approach is also feasible for other polymer categories.
Article
Chemistry, Physical
Yuhan Li, Kai Xi, Mingbo Ma, Shiyao Lu, Hu Wu, Xiaohan Cao, Xinghong Zhang, Shujiang Ding
Summary: A composite solid polymer electrolyte based on poly(thioether)/polyethylene oxide (PTE/PEO) was designed to enhance the conductivity and prevent the dissolution of polysulfides and the growth of lithium dendrites, leading to high capacity and safety of lithium-sulfur batteries.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Materials Science, Multidisciplinary
Kang Chen, Yaling Wang, Bo Chu, Zishan Yan, Hairu Li, Haoke Zhang, Shengliang Hu, Yongzhen Yang, Bin Liu, Xing-Hong Zhang
Summary: Non-traditional intrinsic clusteroluminescence (CL) polymers with persistent room-temperature phosphorescence (RTP) properties have been prepared in this study. Through experimental results and theoretical calculations, the researchers found that the n-pi interaction among carbonyl groups is responsible for the RTP emission.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)