Mechanically Induced Scission and Subsequent Thermal Remending of Perfluorocyclobutane Polymers

Klukovich, Hope M.; Kean, Zachary S.; Iacono, Scott T.; Craig, Stephen L.

doi:10.1021/ja2074517

Cited by 129 publications

(117 citation statements)

References 43 publications

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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.…”

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confidence: 99%

Model studies of force-dependent kinetics of multi-barrier reactions

et al. 2013

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According to transition state theory, the rate of a reaction that traverses multiple energy barriers is determined by the least stable (rate-determining) transition state. The preceding ('inner') energy barriers are kinetically 'invisible' but mechanistically significant. Here we show experimentally and computationally that the reduction rate of organic disulphides by phosphines in water, which in the absence of force proceeds by an equilibrium formation of a thiophosphonium intermediate, measured as a function of force applied on the disulphide moiety yields a usefully accurate estimate of the height of the inner barrier. We apply varying stretching force to the disulphide by incorporating it into a series of increasingly strained macrocycles. This force accelerates the reduction, even though the strain-free rate-determining step is orthogonal to the pulling direction. The observed rate-force correlation is consistent with the simplest model of force-dependent kinetics of a multibarrier reaction.

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confidence: 99%

Model studies of force-dependent kinetics of multi-barrier reactions

et al. 2013

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“…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%

Mechanochemical Reactions Reporting and Repairing Bond Scission in Polymers

Clough

Balan

Sijbesma

2015

Topics in Current Chemistry

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The past 10 years have seen a resurgence of interest in the field of polymer mechanochemistry. Whilst the destructive effects of mechanical force on polymer chains have been known for decades, it was only recently that researchers tapped into these forces to realize more useful chemical transformations. The current review discusses the strategic incorporation of weak covalent bonds in polymers to create materials with stress-sensing and damage-repairing properties. Firstly, the development of mechanochromism and mechanoluminescence as stress reporters is considered. The second half focuses on the net formation of covalent bonds as a response to mechanical force, via mechanocatalysis and mechanically unmasked chemical reactivity, and concludes with perspectives for the field.

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“…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%

Responsive Polymers as Sensors, Muscles, and Self-Healing Materials

Zhang

Serpe

2015

Topics in Current Chemistry

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Responsive polymer-based materials can adapt to their surrounding environment by expanding and shrinking. This swelling and shrinking (mechanotransduction) can result in a number of functions. For example, the response can be used to lift masses, move objects, and can be used for sensing certain species in a system. Furthermore, responsive polymers can also yield materials capable of self-healing any damage affecting their mechanical properties. In this chapter we detail many examples of how mechanical responses can be triggered by external electric and/or magnetic fields, hygroscopicity, pH, temperature, and many other stimuli. We highlight how the specific responses can be used for artificial muscles, self-healing materials, and sensors, with particular focus on detailing the polymer response yielding desired effects.

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Mechanically Induced Scission and Subsequent Thermal Remending of Perfluorocyclobutane Polymers

Cited by 129 publications

References 43 publications

Model studies of force-dependent kinetics of multi-barrier reactions

Model studies of force-dependent kinetics of multi-barrier reactions

Mechanochemical Reactions Reporting and Repairing Bond Scission in Polymers

Responsive Polymers as Sensors, Muscles, and Self-Healing Materials

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