Critically Evaluated Rate Coefficients for Free-Radical Polymerization Part 6: Propagation Rate Coefficient of Methacrylic Acid in Aqueous SolutionParts 1 to 5, cf. refs M. Buback, R. G. Gilbert, R. A. Hutchinson, B. Klumperman, F.-D. Kuchta, B. G. Manders, K. F. O’Driscoll, G. T. Russell, J. Schweer. Macromol. Chem. Phys. 196, 3267 (1995). S. Beuermann, M. Buback, T. P. Davis, R. G. Gilbert, R. A. Hutchinson, O. F. Olaj, G. T. Russell, J. Schweer, A. M. van Herk. Macromol. Chem. Phys. 198, 1545 (1997). S.

Beuermann, Sabine; Buback, Michael; Hesse, Pascal; Kuchta, Frank-Dieter; Lacı́k, Igor; Herk, Alex M. van

doi:10.1515/iupac.79.2220

Cited by 75 publications

(187 citation statements)

References 0 publications

Supporting

Mentioning

179

Contrasting

Unclassified

Order By: Relevance

“…In the present work, the interpretation of the different cases and subsequent evaluation of the different hypotheses can however be reliably done based on these inflection point data, as the error induced falls within the expected experimental uncertainty of at least 10%. 10,13,50 In addition, the same trends are obtained if the location of the peak maximum is used instead of the location of the inflection point, as shown in Fig. S19 in the ESI.…”

mentioning

confidence: 62%

“…12,13 Depending on the monomer and the experimental characteristics (e.g. the degree of SEC broadening) using the location of the peak maximum might be more accurate towards this limit, as for example demonstrated by Sarnecki and Schweer.…”

Section: Introductionmentioning

confidence: 99%

“…Such conditions although lead to less structured SEC traces with no possibility to perform a consistency check (L 2 ≈ 2L 1 ), as recommended by IUPAC. 51 …”

mentioning

confidence: 99%

See 2 more Smart Citations

Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

et al. 2017

View full text Add to dashboard Cite

The radical propagation kinetics of vinyl acetate (VAc) in pulsed laser polymerization (PLP) is studied by combining ab initio calculated rate coefficients for propagation of head, tail and mid-chain radicals, and backbiting reactions with kinetic Monte Carlo modeling of PLP spectra. The intriguing laser pulse frequency dependency of the propagation kinetics is shown to be mainly caused by the formation of stabilized mid-chain radicals via backbiting of tail radicals, originating from head-to-head propagation. These mid-chain radicals are approximately 35 times less reactive towards propagation at 323 K which, in agreement with experimental observations, results in a 15% increase of the observed propagation rate coefficient if the laser pulse frequency is increased from low (25-100 s −1

show abstract

mentioning

confidence: 62%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

et al. 2017

View full text Add to dashboard Cite

show abstract

“…For simplicity, a constant conventional radical initiator effi ciency is assumed, which is a reasonable assumption for monomer conversions below 80%. [ 47,48 ] The RAFT exchange by degenerative transfer rate coeffi cients are varied for the evaluation of the various methods for a wide range of conditions. Chain length and conversion dependent apparent termination kinetics have been implemented explicitly via the k t,app ( n , x ) surface function reported by Derboven et al [ 8 ] at 353 K via the RAFT-chain length dependent-termination (RAFT-CLD-T) technique.…”

Section: Simulation Of a "Perfect Experiment"mentioning

confidence: 99%

Chain Transfer in Degenerative RAFT Polymerization Revisited: A Comparative Study of Literature Methods

Derboven

Steenberge

Reyniers

et al. 2016

Macro Theory & Simulations

View full text Add to dashboard Cite

Under the validity of the degenerative transfer mechanism, the activation/deactivation process in reversible addition-fragmentation chain transfer (RAFT) polymerization can be formally quantifi ed by transfer coeffi cients, depending on the chemical structure of the participating radicals and dormant species. In the present work, the different literature methods to experimentally determine these RAFT transfer coeffi cients are reviewed and theoretically re-evaluated. The accuracy of each method is mapped for a broad range of reaction conditions and RAFT transfer reactivities. General guidelines on when which method should be applied are formulated.

show abstract

“…The virtual monomer reaction order can be determined by measuring the rate of polymerization, R p (t), for varying monomer concentrations up to high conversions and plotting log(R p (t)) -log([I] 0.5 ) vs log([M]) [90]. The slope of the resulting graph is the virtual monomer reaction order, which then translates directly to k * p using equation 4.8 [90,102].…”

Section: The Raft-cld-t Techniquementioning

confidence: 99%

The RAFT Process as a Kinetic Tool: Accessing Fundamental Parameters of Free Radical Polymerization

Junkers

Lovestead

Barner‐Kowollik

2008

Handbook of RAFT Polymerization

View full text Add to dashboard Cite

IntroductionLiving/controlled free radical polymerization (LFRP) techniques such as nitroxide-mediated polymerization, atom transfer polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization gave rise to new designs and syntheses of well-defined materials with respect to size, shape, polydispersity and functionality. For example, macromolecular architectures such as stars, combs, block copolymers, core-shell nanoparticles and branched structures have become feasible [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15], rendering these materials ideal for applications in biomaterials (e.g. drug delivery devices and diagnostic nanoparticles) and molecular electronics [1,8,[16][17][18][19].The reason why LFRPs give access to such a vast number of highly specific microstructure is that they yield materials with high-functionality and lowpolydispersity indices, PDI, as all radical chains nearly grow uniformly with increasing monomer consumption, i.e. polymerization time (see equation 4.1). Ideally, the chain length i depends solely on the fraction of monomer consumed, c 0 M X (where X denotes monomer conversion and c 0 M the initial monomer concentration) and c 0 LFRP , which is the concentration of the mediating agent before the reaction commenced, that is at t = 0 [1,[5][6][7][20][21][22][23][24].This feature is utilized in many ways for synthetic purposes because the chain length of the polymer product can be conveniently tuned -widely independent from the outer reaction conditions -simply by changing the monomer and mediating agent concentrations. Less realized is, however, that the correlation of equation 4.1 can also be a powerful tool in the hands of a physical chemist for the very same reason: it gives easy access to reactions and kinetic information of radicals with known, and moreover, adjustable size.

show abstract

Cited by 75 publications

References 0 publications

Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

Ab initio based kinetic Monte Carlo analysis to unravel the propagation kinetics in vinyl acetate pulsed laser polymerization

Chain Transfer in Degenerative RAFT Polymerization Revisited: A Comparative Study of Literature Methods

The RAFT Process as a Kinetic Tool: Accessing Fundamental Parameters of Free Radical Polymerization

Contact Info

Product

Resources

About