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Che, G.*; Tang, X.*; Liu, J.*; Lang, P.*; Fei, Y.*; Yang, X.*; Wang, Y.*; Gao, D.*; Wang, X.*; Ju, J.*; et al.
Nano Letters, 25(39), p.14467 - 14472, 2025/09
Times Cited Count：0 Percentile：0.00(Chemistry, Multidisciplinary)Mechanochemical radical polymerization has unique advantages in the synthesis of polymer due to its reduced solvent consumption and adaptability of insoluble monomers. However, it suffers from the uncontrollable degradation of the formed polymers during reaction and new synthetic strategy with precise controllability needs to be developed. Here, by employing high static pressure up to 30 GPa, we found 1,3,5-trifluorobenzene undergoes radical polymerization by breaking the conjugated 
-bonds, and forms a carbon nanothread with high selectivity (Polymer-I polymorph). Based on the crystal structure at the threshold pressure and the calculated energy barriers for the bonding pathway, we concluded that the benzene-rings react via a 1-2 radical polymerization pathway. Our work highlights high pressure is a robust method to initiate the solid-state radical polymerization, even for very stable aromatics, and offers fresh insights for the synthesis of polymeric carbon-based materials with high selectivity.
Enomoto, Kazuyuki*; Narita, Tadashi*; Maekawa, Yasunari; Yoshida, Masaru; Hamana, Hiroshi*
Journal of Fluorine Chemistry, 125(7), p.1153 - 1158, 2004/07
Times Cited Count：3 Percentile：10.46(Chemistry, Inorganic & Nuclear)Radical polyaddition of bis(
-trifluoromethyl-
,-difluorovinyl) terephthalate (BFP) with 1,4-dioxane (DOX) afforded higher molecular weight polymers under 
-rays compared to those yielded by benzoyl peroxide initiation. More detailed study on the radiation-induced polyaddition of BFP with DOX and optimization of the reaction conditions were carried out. It was necessary to irradiate with doses of 2000, 1500, and 750 kGy, to obtain quantitative conversion of BFP at the feed molar ratio DOX/BFP of 8.0, 16, and 32, respectively. Step-growth polymerization mechanism was suggested by the measurements of molecular weights of the polymers obtained with several irradiation doses. It was concluded that the molecular weight of the polymer could be controlled by the feed molar ratio of DOX/BFP and irradiation doses. The reaction between polymers might take place after the quantitative conversion of BFP. Radiation-induced radical polyaddition mechanism of BFP with DOX was proposed.
Machi, Sueo; Takashi Sakai*; ;
Bulletin of the Chemical Society of Japan, 41(4), p.897 - 903, 1968/00
Times Cited Count：4no abstracts in English
