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Fully Aromatic High Performance Thermoset via Sydnone–Alkyne Cycloaddition

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Mitsubishi Chemical Center for Advanced Materials, §Department of Chemistry and Biochemistry, Materials Department, and Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States
Mitsubishi Chemical USA, Inc., Chesapeake, Virginia 23320, United States
# Mitsubishi Chemical Group Science and Technology Research Center, Inc., Yokohama 227-8502, Japan
Institute of Pharmacy, Freie Universität Berlin, Königin-Luise-Str. 2-4, 14195 Berlin, Germany
Cite this: J. Am. Chem. Soc. 2016, 138, 20, 6400–6403
Publication Date (Web):May 16, 2016
Copyright © 2016 American Chemical Society

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    We have developed an efficient synthetic platform for the preparation of a new class of high performance thermosets based on the 1,3-dipolar cycloaddition of a bifunctional sydnone with a trifunctional alkyne. These processable materials possess outstanding thermal stability, with Td5% of 520 °C and a weight loss of <0.1% per day at 225 °C (both in air). Key to this performance is the stability of the starting functional groups that allows for reactive B-staging via simple thermal activation to give fully aromatic and highly cross-linked polypyrazole-based thermosets.

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    9. Xiaojuan Tang, Chao Zheng, Yizhao Chen, Zujin Zhao, Anjun Qin, Rongrong Hu, and Ben Zhong Tang . Multicomponent Tandem Polymerizations of Aromatic Diynes, Terephthaloyl Chloride, and Hydrazines toward Functional Conjugated Polypyrazoles. Macromolecules 2016, 49 (24) , 9291-9300.
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    11. Zhaorun Hou, Chunxia Zhao, Jinbo Cheng, Zhuo Chen, Jixuan Wei, Hui Li, Dong Xiang, Yuanpeng Wu. Preparation and Properties of Fiber-Reinforced Polybenzoxazine Composite Aerogels based on Freeze Drying and Ambient Pressure Drying Methods. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2024, 8 , 133510.
    12. Qian Chen, Dayong Ren, Weichen Sheng, Kan Zhang. Synthesis, polymerization and thermal properties of bio‐based benzoxazine resins containing imide or amide functionality. Journal of Applied Polymer Science 2024, 141 (2)
    13. Lei Li, Rui Yuan, Sucheng Yang, Li Yang, Guanjun Chang, Ying Huang. A facile strategy to improve the strength and toughness of high-performance polymers and recycling by dynamic Ni-coordination crosslinking. High Performance Polymers 2023, 35 (10) , 1035-1041.
    14. Ryan Dol, Srini Vemulapalli, Oyin Azeez, Travis Dudding. A catalytic one-pot synthesis of sydnone heterocycles with mechanistic insights. Tetrahedron 2023, 148 , 133704.
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    18. Souad Zerbib, Mostafa Khouili, Marco Catto, Latifa Bouissane. Sydnone: Synthesis, Reactivity and Biological Activities. Current Medicinal Chemistry 2023, 30 (10) , 1122-1144.
    19. Xia Song, Kelin Wang, Xinying Zhang, Xuesen Fan. Unsymmetrical relay C–H alkenylation and [2 + 2] cycloaddition of N -arylsydnones with allenyl acetates leading to quinoline-fused cyclobutanes. Organic Chemistry Frontiers 2023, 10 (5) , 1191-1197.
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    24. Yingying Liu, Fei Lu, Junjun Wan, Lei Yang, Yudong Huang, Zhen Hu. Recyclable tough thermosets with an imide-hexahydrotriazine structure. Polymer Chemistry 2022, 13 (21) , 3063-3075.
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    28. William Fraser. 1,2,3-Oxadiazoles. 2022, 122-146.
    29. Zhengzhu Zhu, Xian He, Wei Tan, Jinlang Hong, Shenjun Liao, Jiangbo Lv, Ke Zeng, Jianghuai Hu, Gang Yang. A new class of high-performance thermoset resins using dicyanoimidazole (DCI) as crosslinking group: A key demo of synthesis, curing behavior and thermal properties. Polymer 2021, 235 , 124264.
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    36. Uroš Grošelj, Jurij Svete, . [3 + 2] Cycloadditions of Azomethine Imines. 2020, 529-930.
    37. Qian Liu, Shouhai Zhang, Zhaoqi Wang, Yuning Chen, Xigao Jian. Effect of pendent phenyl and bis-phthalazinone moieties on the properties of N-heterocyclic poly(aryl ether ketone ketone)s. Polymer 2020, 198 , 122525.
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    40. Il’ya A. Cherepanov, Sergey K. Moiseev. Recent developments in the chemistry of sydnones and sydnone imines. 2020, 49-164.
    41. Xianfeng Liu, Lue Xiang, Jiayi Li, Ying Wu, Ke Zhang. Stoichiometric imbalance-promoted step-growth polymerization based on self-accelerating 1,3-dipolar cycloaddition click reactions. Polymer Chemistry 2020, 11 (1) , 125-134.
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    45. Yuan Zu, Guiyang Li, Lishuai Zong, Liyuan Qiao, Jinyan Wang, Xigao Jian. Branched phenyl‐ s ‐triazine moieties to enhance thermal properties of phthalonitrile thermosets. Polymer International 2018, 67 (2) , 189-196.
    46. Andrew W. Brown. Recent Developments in the Chemistry of Pyrazoles. 2018, 55-107.
    47. Jing Zhang, Qingzhong Zhang, Shuaifeng Zhou, Yuping Liu, Wei Huang. Synthesis and characterization of amphiphilic miktoarm star polymers based on sydnone-maleimide double cycloaddition. Polymer Chemistry 2018, 9 (2) , 203-212.
    48. Q. Yin, Y. Peng, S. Zhang, F. Zhu, W. Li, K. Du. Recyclable heat-resisting polymer poly(ether azaindole ketone)-H + via hydrogen bonding crosslinking. Polymer Chemistry 2018, 9 (10) , 1164-1167.
    49. Huimin Tao, Fang Liu, Ruxin Zeng, Zhuzhou Shao, Lufeng Zou, Yang Cao, Jennifer M. Murphy, K. N. Houk, Yong Liang. Origins of halogen effects in bioorthogonal sydnone cycloadditions. Chemical Communications 2018, 54 (40) , 5082-5085.
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    51. Veronika Hladíková, Jiří Váňa, Jiří Hanusek. [3 + 2]-Cycloaddition reaction of sydnones with alkynes. Beilstein Journal of Organic Chemistry 2018, 14 , 1317-1348.
    52. Zijie Qiu, Ting Han, Jacky W. Y. Lam, Ben Zhong Tang. Recent New Methodologies for Acetylenic Polymers with Advanced Functionalities. Topics in Current Chemistry 2017, 375 (4)
    53. Huseyin Erguven, David C. Leitch, Evan N. Keyzer, Bruce A. Arndtsen. Development and Cycloaddition Reactivity of a New Class of Pyridine‐Based Mesoionic 1,3‐Dipole. Angewandte Chemie 2017, 129 (22) , 6174-6178.
    54. Huseyin Erguven, David C. Leitch, Evan N. Keyzer, Bruce A. Arndtsen. Development and Cycloaddition Reactivity of a New Class of Pyridine‐Based Mesoionic 1,3‐Dipole. Angewandte Chemie International Edition 2017, 56 (22) , 6078-6082.
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