2011
DOI: 10.1021/ja2074517
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Mechanically Induced Scission and Subsequent Thermal Remending of Perfluorocyclobutane Polymers

Abstract: Perfluorocyclobutane (PFCB) polymer solutions were subjected to pulsed ultrasound, leading to mechanically induced chain scission and molecular weight degradation. 19F NMR revealed that the new, mechanically generated end groups are trifluorovinyl ethers formed by cycloreversion of the PFCB groups, a process that differs from thermal degradation pathways. One consequence of the mechanochemical process is that the trifluorovinyl ether end groups can be remended simply by subjecting the polymer solution to the o… Show more

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Cited by 129 publications
(117 citation statements)
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References 43 publications
(79 reference statements)
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“…Such force-dependent reactivity is thought to account for the behaviour of polymeric materials, melts and solutions under load, may be exploited to yield new stress-responsive, actuating and energy transducing materials [1][2][3][4][5][6][7][8][9][10] and may even allow characterization of transition states. 11 Considerable theoretical, 3,[12][13][14][15][16][17][18][19] computational 13,[20][21][22][23][24][25][26] and experimental [27][28][29][30][31][32][33][34] effort has been devoted to refine and validate a model of forcedependent kinetics for elementary (single-barrier) reactions.…”
mentioning
confidence: 99%
“…Such force-dependent reactivity is thought to account for the behaviour of polymeric materials, melts and solutions under load, may be exploited to yield new stress-responsive, actuating and energy transducing materials [1][2][3][4][5][6][7][8][9][10] and may even allow characterization of transition states. 11 Considerable theoretical, 3,[12][13][14][15][16][17][18][19] computational 13,[20][21][22][23][24][25][26] and experimental [27][28][29][30][31][32][33][34] effort has been devoted to refine and validate a model of forcedependent kinetics for elementary (single-barrier) reactions.…”
mentioning
confidence: 99%
“…On sonicating perfluorocyclobutane-containing polymers, trifluorovinylethers were found to form from the cycloreversion of the cyclobutanes, in a decomposition process significantly different under thermal activation [53]. The perfluorocyclobutane groups can be regenerated by heating the polymer solution to above 150 C (Fig.…”
Section: Mechanically-induced Bond Creationmentioning
confidence: 99%
“…In another example, mechanical force can induce chain cleavage of perfluorocyclobutane (PFCB), shown in Fig. 14, generating trifluorovinyl esters (TFVE), which are also reformed by cycloreversion [61]. The chain cleavage proceeds via a stepwise mechanism with 1,4-diradical intermediates.…”
Section: Thermoresponsive Cycloaddition-based Polymeric Smart Materialsmentioning
confidence: 99%