- Novel dialkyl vinyl ether phosphonate monomers: Their synthesis and alternated radical copolymerizations with electron-accepting monomers
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Three new vinyl ether monomers containing phosphonate moieties were synthesized from transetherification reaction. We showed that the yield was dependent on the spacer length between the vinyl oxy group and the phosphonate moieties: when the spacer is a single methylene side reaction may occur, leading to the formation of acetal compounds. Free-radical copolymerizations of phosphonate-containing vinyl ether monomers with maleic anhydride were carried out, leading to alternated copolymers of rather low molecular weights (from 1000 to 7000 g/mol). Both gel permeation chromatography and 31P NMR analyses enhanced possible intramolecular transfer reactions occurring from the phosphonate moieties. Kinetic investigation showed that the electron-withdrawing character of the phosphonate moieties tends to decrease the rate of copolymerization. Nevertheless, almost complete monomers conversion was reached after 30 min of reaction with dimethyl vinyloxyethylphosphonate (VEC 2PMe). Then, radical copolymerization of VEC2PMe with a series of electron-accepting monomers, that is, dibutyl maleate, dibutylitaconate, itaconic anhydride, butyl maleimide, and methyl maleimide, led to a series of alternated copolymers. From kinetic investigation, we showed that the higher the electron-accepting effect, the faster the vinyl ether consumption and the higher the molecular weights.
- Iftene, Fadela,David, Ghislain,Boutevin, Bernard,Auvergne, Remi,Alaaeddine, Ali,Meghabar, Rachid
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experimental part
p. 2432 - 2443
(2012/07/28)
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This paper describes the synthesis and the characterization by 1H and 31P NMR of several monosalts and monoacids issued from phosphonates bearing alkyl groups (C1 to C18) or alkylene groups (allyl or vinyl). Functional compounds (alcohol or acetate) were also used and the results demonstrate the reaction selectivity. The method involves sodium iodide in ketones (acetone or 2-butanone) under reflux. It is very selective for monosalts, but only methyl phosphonates are very reactive. The corresponding acids were then obtained in quantitative yields with a cation exchange resin (sulfate acid).
- Boutevin,Hervaud,Jeanmaire,Boulahna,Elasri
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- Preparation of phosphorus-organic esters
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2-Hydroxyethane-phosphonic acid diesters, 2-hydroxyethylphoshinic acid esters and the corresponding thiophoshonic acid-O,O-diesters or thiophosphinic acid-O-esters of the formula EQU1 wherein R1 is alkyl having from 1 to 18 carbon atoms, R2 has the meaning of R1 or represents cycloalkyl having up to 10 carbon atoms, alkenyl having up to 18 carbon atoms, aryl having up to 14 carbon atoms or aralkyl having up to 15 carbon atoms, R3 means hydrogen, alkyl having up to 18 carbon atoms, alkenyl having up to 18 carbon atoms, cycloalkyl having up to 10 carbon atoms, aryl having up to 14 carbon atoms or aralkyl having up to 15 carbon atoms, the substituents R1 -R3 optionally being substituted, X represents oxygen or sulfur and n represents either 0 or 1, are prepared from 2-acyloxyethane-phosphonic acid diesters, 2-acyloxy-ethyl-phoshinic acid esters or the corresponding thiophoshonic acid-O,O-diesters or thiophoshinic acid-O-esters and are important intermediate products for the preparation of plant protecting agents and flame-proofing agents.
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