Journal ArticleDOI
Rate Constants for the Addition of 2-Hydroxy-2-propyl Radicals to Alkenes in Solution studied by laser flash photolysis
TLDR
In this article, the absolute rate constants for the addition of the highly nucleophilic 2-hydroxy-2-propyl radical to eight fast-reacting 1-and 1,1-disubstituted alkenes in MeOH at room temperature have been determined by laser flash photolysis.Abstract:
Absolute rate constants for the addition of the highly nucleophilic 2-hydroxy-2-propyl radical to eight fast-reacting 1- and 1,1-disubstituted alkenes in MeOH at room temperature have been determined by laser flash photolysis. Also the absorption spectra of the 2-hydroxy-2-propyl and the benzylic and alkyl-type adduct radicals are presented. The rate constants were obtained using various methods for the analysis of the kinetic traces and support earlier findings.read more
Citations
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Journal ArticleDOI
Initiator Addition to Methyl Methacrylate Studied in Liquid and Supercritical Carbon Dioxide
TL;DR: In this paper, a specially modified time-resolved electron paramagnetic resonance (TREPR) apparatus was used to detect free radicals produced from the triplet states of dimethoxyphenylacetophenone (DMPA) and trimethylbenzoyldiphenylphosphine oxide (TMDPO) after excitation of the parent compounds using a 308 nm excimer laser.
Journal ArticleDOI
Addition Rate Constants of Phosphorus- and Carbon-Centered Radicals to Double Bond of Monomers as Studied by a Pulsed Electron Paramagnetic Resonance Method.
TL;DR: The quantum chemical calculation shows that the rate constants for the addition reactions are well-explained by introducing two factors of "enthalpy effect" and "polar effect" to control the activation barrier height.
Journal ArticleDOI
Photocopying Living Chains. 1. Steady-State
TL;DR: The first ever measurements of living chain molecular weight distributions (MWDs), ψo(N), in free radical polymerization (FRP), are presented using a new technique, the “photocopy method”, which converts the living population to a labeled inert one by “photoinhibitor” molecules activated by a short laser pulse.
Journal ArticleDOI
Photocopying living chains. 2. Time-dependent measurements
TL;DR: The issue of photoinhibitor radical addition to monomer (at rate ), which creates new unwanted labeled living chains that distort the labeled living MWD measurements, is addressed.
Journal ArticleDOI
The reactivity of initiator radicals: V. The application of the revised patterns scheme
TL;DR: In this article, the reaction of initiator radicals with monomers has been used to forecast monomer reactivity ratios with a much greater precision than heretofore, and it has been shown that a parameter denoting radical polarity can be easily deduced from polymerisation data, and that these 2 parameters can be used quantitatively to characterise the behaviour of that radical in copolymerisations in general.
References
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Journal ArticleDOI
Which Factors Determine the Reactivity and Regioselectivity of Free Radical Substitution and Addition Reactions
TL;DR: In this paper, the relative importance of bond strength, steric effects, and polarity in determining the rate and orientation of free radical subsitution and free radical addition reaction is considered.
Journal ArticleDOI
Transmission Filters for the Ultraviolet
TL;DR: A set of band pass filters for the 2400–3800A region of the ultraviolet is developed, which have a half-width of 200A and a maximum transmission of 30 percent, on the average.
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