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Title: Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance

Authors:
 [1];  [1];  [1];  [2]
  1. Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder Colorado 80309 United States
  2. Department of Chemistry and Biochemistry, Materials Science and Engineering Program, University of Colorado Boulder, Boulder Colorado 80309 United States
Publication Date:
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1401302
Grant/Contract Number:
AR0000683
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Macromolecular Rapid Communications
Additional Journal Information:
Journal Volume: 38; Journal Issue: 13; Related Information: CHORUS Timestamp: 2017-10-20 16:57:39; Journal ID: ISSN 1022-1336
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Theriot, Jordan C., McCarthy, Blaine G., Lim, Chern-Hooi, and Miyake, Garret M.. Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance. Germany: N. p., 2017. Web. doi:10.1002/marc.201700040.
Theriot, Jordan C., McCarthy, Blaine G., Lim, Chern-Hooi, & Miyake, Garret M.. Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance. Germany. doi:10.1002/marc.201700040.
Theriot, Jordan C., McCarthy, Blaine G., Lim, Chern-Hooi, and Miyake, Garret M.. Mon . "Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance". Germany. doi:10.1002/marc.201700040.
@article{osti_1401302,
title = {Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance},
author = {Theriot, Jordan C. and McCarthy, Blaine G. and Lim, Chern-Hooi and Miyake, Garret M.},
abstractNote = {},
doi = {10.1002/marc.201700040},
journal = {Macromolecular Rapid Communications},
number = 13,
volume = 38,
place = {Germany},
year = {Mon Apr 03 00:00:00 EDT 2017},
month = {Mon Apr 03 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/marc.201700040

Citation Metrics:
Cited by: 11works
Citation information provided by
Web of Science

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  • Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less
  • This work reports on the grafting of methyl methacrylate polymer brushes containing spirobenzopyran pendant groups from flat silica surfaces and colloidal particles utilizing atom transfer radical polymerization (ATRP). The reaction conditions were optimized with respect to the kind of surface bound initiator, the type of halide and ligand used in the catalytic complex, the presence/absence of untethered initiator, and solvent type. This enabled synthesis of coatings up to 80 {+-} 3 nm thick with controlled spirobenzopyran content. While polymerization kinetics indicate the presence of chain termination reactions, the 'living' character of the process is confirmed by controlled formation of blockmore » copolymer brushes. UV/vis spectroscopy was used to characterize the UV-induced isomerization of spirobenzopyran to zwitterionic merocyanine and the thermal back-reaction. Spectral and kinetic analyses of this latter bleaching process points to the existence of free and associated merocyanines in the polymeric brush in both tetrahydrofuran and toluene. However, stabilization of merocyanine species by the polymer matrix is considerably greater in toluene with thermal back-reaction rates approaching those determined for solid dry films.« less