Kinetic elucidation of a novel photoproduct via irradiation of isopropylthioxanthone with maleic anhydride / Matthew E. Mullings in JOURNAL OF COATINGS TECHNOLOGY AND RESEARCH, Vol. 4, N° 3 (09/2007)  

[article]  inJOURNAL OF COATINGS TECHNOLOGY AND RESEARCH > Vol. 4, N° 3 (09/2007) . - p. 255-261 Titre : Kinetic elucidation of a novel photoproduct via irradiation of isopropylthioxanthone with maleic anhydride Type de document : texte imprimé Auteurs : Matthew E. Mullings, Auteur ; T. Brian Cavitt, Auteur ; Adam McDonough, Auteur ; Corry D. Walker, Auteur Année de publication : 2007 Article en page(s) : p. 255-261 Note générale : Bibliogr. Langues : Américain (ame) Catégories : Anhydride maléique Cinétique chimique Photoamorceurs (chimie) Photochimie Polyaddition Thioxanthone Le thioxanthone est un composé hétérocyclique qui est un soufre analogue du xanthone. Le Thioxanthone peut être synthétisé par réaction de sulfure de diphényle avec du phosgène en présence de catalyseur de chlorure d'aluminium . Cette synthèse peut être considérée comme un cas particulier de l'acylation de Friedel-Crafts . Le produit de réduction est le thioxanthène. Index. décimale : 667.9 Revêtements et enduits Résumé : Isopropylthioxanthone is a popular cosyner-gist for Type II and three-component photoinitiators used to photopolymerize ultraviolet (UV) curable coatings and can be used in the presence of maleic anhydride derivatives to efficiently cure coatings used in numerous applications. Isopropylthioxanthone (ITX) was shown via ultraviolet-visible (UV-vis) spectroscopy to yield a single photoproduct with maleic anhydride (MA) when irradiated (lambda > 350 nm). Following irradiation of ITX and MA at set time intervals, high-performance liquid chromatography (HPLC) was used to observe the formation of the photoproduct by monitoring the UV-vis absorbance spectra of the photoproduct and the reactants. Based on the consumption of ITX shown in the HPLC plots, the complete rate law was calculated based on the initial rates. Finally, a possible mechanism is proposed for the formation of the photoproduct which may provide evidence for the reduced initiation efficiency of photoinitiators incorporating ITX and a MA derivative when compared to a similar photoinitiator substituting an N-substituted maleimide for the MA derivative. DOI : 10.1007/s11998-007-9038-8 En ligne : https://link.springer.com/content/pdf/10.1007%2Fs11998-007-9038-8.pdf Format de la ressource électronique : Pdf Permalink : https://e-campus.itech.fr/pmb/opac_css/index.php?lvl=notice_display&id=3640 [article]

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Photoinitiation of multifunctional acrylates via ferrocene-alkyl chloride charge transfer complexes / Julie A. Anderson in JOURNAL OF COATINGS TECHNOLOGY AND RESEARCH, Vol. 4, N° 1 (03/2007)  

[article]  inJOURNAL OF COATINGS TECHNOLOGY AND RESEARCH > Vol. 4, N° 1 (03/2007) . - p. 43-49 Titre : Photoinitiation of multifunctional acrylates via ferrocene-alkyl chloride charge transfer complexes Type de document : texte imprimé Auteurs : Julie A. Anderson, Auteur ; Evan Hardgrove, Auteur ; T. Brian Cavitt, Auteur ; Perry C. Reeves, Auteur Année de publication : 2007 Article en page(s) : p. 43-49 Note générale : Bibliogr. Langues : Américain (ame) Catégories : Cinétique chimique Molécules -- Modèles Photoamorceurs (chimie) Photochimie Photoréticulation Polyacrylates Rayonnement électronique Rayonnement ultraviolet Simulation, Méthode de Spectroscopie ultraviolette Index. décimale : 667.9 Revêtements et enduits Résumé : The propensity for ferrocene-alkyl chloride charge transfer complexes (CTCs) to photoinitiate free-radical polymerization of multifunctional acrylates was determined using photodifferential scanning calorimetry. Also, the effects of varying ferrocene (ferrocene, methoxyferrocene, and cyanoferrocene) and alkyl chloride (dichloromethane and benzyl chloride) derivatives were evaluated with regard to the overall polymerization rate and conversion. Furthermore, relative polymerization rates of traditional free-radical Type I and Type II photoinitiators were compared to those of the ferrocene-alkyl chloride CTCs. Semi-empirical quantum mechanical analysis of the complexation reaction was performed using PM3, indicating a thermodynamic preference of complexations involving benzyl chloride, and corroborated the reported complexation mechanism. In order to explain the varying polymerization rates, the association constants for each complex were determined, whereupon complexation of each ferrocene derivative with dichloromethane was found to be more facile than similar complexation with benzyl chloride due to steric considerations. Substituent effects were more pronounced for the benzyl chloride complexes relative to those involving dichloromethane where steric constraints caused deviation from the expected effect. Thus, the cyanoferrocene-benzyl chloride CTC was determined to be the most effective photoinitiator examined with regard to semi-empirical analysis, complexation kinetics, and polymerization rate. DOI : 10.1007/s11998-007-9008-1 En ligne : https://link.springer.com/content/pdf/10.1007%2Fs11998-007-9008-1.pdf Format de la ressource électronique : Pdf Permalink : https://e-campus.itech.fr/pmb/opac_css/index.php?lvl=notice_display&id=3669 [article]

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