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Mechanophore-Linked Addition Polymers
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Champaign, Urbana, Illinois 61801 
Section:Abstract
The use of mechanical energy to increase reaction rates and alter the distribution of products has gained considerable interest of late. However, the discovery of new mechanophores (i.e., mechanochemically reactive units) is currently time-consuming, expensive, low-yielding, and a process that is not easily scaled to large quantities. Here we show that mechanophore-linked addition polymers are easily prepared using bifunctional initiators with a living radical polymerization method. The mechanophore is positioned close to the center of the polymer, where ultrasound-generated forces are the largest. Since these forces are strongly dependent on molecular weight, the use of controlled polymerization enables fine-tuning of the mechanical activity so that mechanophore reactions are initiated while minimizing chain scission. The approach is illustrated first with the synthesis and investigation of a 1,2-disubstituted benzocyclobutene mechanophore that is incorporated into the center of a polymethacrylate (PMA) chain. Selected molecular weights are probed using ultrasound to illustrate that the 4π electrocyclic ring opening of the benzocyclobutene link is stress-induced. To demonstrate the broad applicability of this method for mechanophore screening, we also report a new spiropyran-linked PMA that undergoes an ultrasound-induced 6π-electron electrocyclic ring opening. The straightforward synthesis of mechanophore-linked addition polymers presented here shows considerable promise for the investigation of new mechanophores and will lead to a greater understanding of mechanochemical reactivity within polymer systems.
Citing Articles
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This article has been cited by 19 ACS Journal articles (5 most recent appear below).
Microstructure of Copolymers Formed by the Reagentless, Mechanochemical Remodeling of Homopolymers via Pulsed Ultrasound
Ashley L. Black Ramirez, James W. Ogle, Andrew L. Schmitt, Jeremy M. Lenhardt, Matthew P. Cashion, Mahesh K. Mahanthappa, and Stephen L. CraigACS Macro Letters2012 1 (1), 23-27Microstructure of Copolymers Formed by the Reagentless, Mechanochemical Remodeling of Homopolymers via Pulsed Ultrasound
Ashley L. Black Ramirez, James W. Ogle, Andrew L. Schmitt, Jeremy M. Lenhardt, Matthew P. Cashion, Mahesh K. Mahanthappa, and Stephen L. CraigACS Macro Letters2012 1 (1), 23-27The high shear forces generated during the pulsed ultrasound of dilute polymer solutions lead to large tensile forces that are focused near the center of the polymer chain, but quantitative experimental evidence regarding the force distribution is rare. ...
Role of Mechanophore Orientation in Mechanochemical Reactions
Brett A. Beiermann, Sharlotte L.B. Kramer, Jeffrey S. Moore, Scott R. White, and Nancy R. SottosACS Macro Letters2012 1 (1), 163-166Role of Mechanophore Orientation in Mechanochemical Reactions
Brett A. Beiermann, Sharlotte L.B. Kramer, Jeffrey S. Moore, Scott R. White, and Nancy R. SottosACS Macro Letters2012 1 (1), 163-166The orientation of force-sensitive chemical species (mechanophores) in bulk polymers was measured via the anisotropy of fluorescence polarization. Orientation measurements were utilized to investigate the role of mechanophore alignment on mechanically ...
Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores
Matthew J. Kryger, Alexander M. Munaretto, and Jeffrey S. MooreJournal of the American Chemical Society2011 133 (46), 18992-18998Structure–Mechanochemical Activity Relationships for Cyclobutane Mechanophores
Matthew J. Kryger, Alexander M. Munaretto, and Jeffrey S. MooreJournal of the American Chemical Society2011 133 (46), 18992-18998Ultrasound activation of mechanophores embedded in polymer backbones has been extensively studied of late as a method for realizing chemical reactions using force. To date, however, there have been few attempts at systematically investigating the effects ...
Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations
Bryan M. Wong and Joseph G. CordaroThe Journal of Physical Chemistry C2011 115 (37), 18333-18341Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations
Bryan M. Wong and Joseph G. CordaroThe Journal of Physical Chemistry C2011 115 (37), 18333-18341The band structure and electronic properties in a series of vinylene-linked heterocyclic conducting polymers are investigated using density functional theory (DFT). In order to accurately calculate electronic band gaps, we utilize hybrid functionals with ...
Cellulose Microfibrils Grafted with PBA via Surface-Initiated Atom Transfer Radical Polymerization for Biocomposite Reinforcement
Shuzhao Li, Miaomiao Xiao, Anna Zheng, and Huining XiaoBiomacromolecules2011 12 (9), 3305-3312Cellulose Microfibrils Grafted with PBA via Surface-Initiated Atom Transfer Radical Polymerization for Biocomposite Reinforcement
Shuzhao Li, Miaomiao Xiao, Anna Zheng, and Huining XiaoBiomacromolecules2011 12 (9), 3305-3312Immobilizing poly(butyl acrylate) (PBA) on cellulose microfibrils (CMFs) by atom transfer radical polymerization (ATRP) of butyl acrylate (BA) on the surface of 2-bromoisobutyryl-functionalized CMF generated highly hydrophobic microfibrils (CMF-PBA) with ...
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- Published In Issue November 14, 2007
- Received August 16, 2007
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