Rate Constants in the Free-Radical Polymerization of Perdeuterated Styrene

Clouet, G.; Chaffanjon, Pierre

doi:10.1080/10601329008544723

Cited by 9 publications

(10 citation statements)

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“…[ 50 ] Deuteration may increase k p due to the secondary isotope effect: With styrene, a factor of 1.2 has been reported for k p (Sty-d8)/ k p (Sty-H8). [ 51 ] Almost the same factor has been reported for deuterated and non-deuterated methyl methacrylate. [ 52,53 ] To the best of our knowledge, k p (VAc-d6) is not known so far.…”

Section: Chain-length-dependent Termination Kinetics Of Vacsupporting

confidence: 61%

Chain‐Length‐Dependent Termination of Vinyl Acetate and Vinyl Pivalate Bulk Homopolymerizations Studied by SP‐PLP‐EPR

Kattner

Buback

2014

Macro Chemistry & Physics

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Bulk homopolymerizations of vinyl acetate and vinyl pivalate are studied by EPR experiments between −65 °C and 60 °C with dicumyl peroxide acting as the photoinitiator. No midchain radicals are seen, which demonstrates that backbiting plays no role. The chain-length dependence of the termination rate coeffi cients measured up to 13% monomer conversion is adequately represented by the composite model. The power-law exponents α s and α l for short-chain and long-chain radicals are: α s (VAc) = 0.57 ± 0.05, α s (VPi) = 0.67 ± 0.15, α l (VAc) = 0.16 ± 0.07, and α l (VPi) = 0.16 ± 0.07. The crossover chain lengths differ largely: i c (VAc) = 20 ± 10 and i c (VPi) = 110 ± 30. The rate coeffi cient for termination of two radicals of chain length unity, k t 1,1 , which is the fourth composite-model parameter, depends on temperature, as does the monomer fl uidity.

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Section: Chain-length-dependent Termination Kinetics Of Vacsupporting

confidence: 61%

Chain‐Length‐Dependent Termination of Vinyl Acetate and Vinyl Pivalate Bulk Homopolymerizations Studied by SP‐PLP‐EPR

Kattner

Buback

2014

Macro Chemistry & Physics

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“…The slower latter polymerization is consistent with literature inverse isotope effects for polymerizations of deuterated St monomers (higher rates of reaction for isotopically substituted St) [34,35]. The use of r St-d 3 Fig.…”

Section: Determination Of Reactivity Ratiosupporting

confidence: 85%

Nitroxide-mediated controlled/living radical copolymerizations with macromonomers

Ryan

Aldabbagh

Zetterlund

et al. 2008

Reactive and Functional Polymers

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“…It is not to be expected that the kinetics of polymerization in D 2 O differs significantly from the one in H 2 O solution . For bulk styrene polymerization, k p has been reported to be by 20% higher for the fully deuterated system …”

Section: Methodsmentioning

confidence: 99%

Novel Access to Propagation Rate Coefficients of Radical Polymerization by the SP-PLP-EPR Method

Kattner

Drawe

Buback

2015

Macromol. Chem. Phys.

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A novel method for kp measurement is presented, in which time‐resolved electron paramagnetic resonance detection of radical concentration after applying a single laser pulse (SP−PLP−EPR) is carried out in conjunction with measuring monomer conversion induced by the laser pulse. The method is particularly useful for the study of fully ionized monomers, as will be outlined by experiments on trimethylaminoethyl methacrylate chloride (TMAEMA, 2‐(methacryloyloxy)‐N,N,N‐trimethylethan‐1‐aminium chloride, 20 wt% in aqueous solution) at 60 °C. In addition to kp, the method provides termination rate coefficient data. The reliability of the so‐obtained rate coefficients is demonstrated by chemically induced experiments and by measuring TMAEMA conversion after single‐pulse initiation via near‐infrared (NIR) spectroscopy.

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Rate Constants in the Free-Radical Polymerization of Perdeuterated Styrene

Cited by 9 publications

References 0 publications

Chain‐Length‐Dependent Termination of Vinyl Acetate and Vinyl Pivalate Bulk Homopolymerizations Studied by SP‐PLP‐EPR

Chain‐Length‐Dependent Termination of Vinyl Acetate and Vinyl Pivalate Bulk Homopolymerizations Studied by SP‐PLP‐EPR

Nitroxide-mediated controlled/living radical copolymerizations with macromonomers

Novel Access to Propagation Rate Coefficients of Radical Polymerization by the SP-PLP-EPR Method

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