It is suggested that copper chloride will generally catalyse the decomposition of sulphonyl chloride into alkyl or aryl chloride and sulphur dioxide, thereby allowing a more selective reaction than the uncatalysed, purely thermal process. With styrene, on the other hand, an adduct with undecomposed sulphonyl chloride is formed. Chloromethanesulphonyl chloride, in the presence of excess of oct-1-ene and one mole-% of cupric chloride, is largely decomposed into methylene chloride and sulphur dioxide. An uncatalysed, slower cis-transisomerisation of but-2-ene takes place concurrently. With increasing catalyst concentrations, the rate of isomerisation falls, while that of adduct formation is increased, which is in accord with the suggested mechanism. The reversibility of addition of sulphonyl radicals to unconjugated olefins is demonstrated for the case of but-2-ene, where cis-trans-isomerisation of the olefin accompanies addition. A free-radical chain-mechanism is suggested for the reaction, which is similar to that of addition of carbon tetrachloride and chloroform to olefins, and in which the catalyst participates in the propagation as a chlorine-atom transfer agent (redox-transfer). The copper chloride-catalysed addition of sulphonylchlorides to vinylic monomers and other olefins provides a general and convenient synthesis of β-chloro-sulphones. Finally, SEM studies were conducted and clearly showed that surface morphology of functional latexes hardly altered with a low degree of oxidation but became aggregates when highly oxidized latexes were formed. Electrolyte stability of functionalized latexes was also examined with regard to their critical coagulation concentrations in various salt solutions. Furthermore, the amounts of surface aldehyde and carboxylic acid groups were determined by conductometric and potentiometric titrations. The concentration of the catalyst, however, was found to have little affect on the rate of oxidation.
Our investigation of the effect of oxidant concentration, reaction time, and temperature demonstrated that controlling the surface concentration of aldehyde and carboxylic acid groups was readily accomplished by altering these three reaction parameters.
Irritating to skin and mucous membranes.Ĭontrolled synthesis of aldehyde-functional poly(methystyrene) (PMS) latexes in an emulsifier-free system was achieved via an emulsifier-free emulsion polymerization of methylstyrene using V-50 as an initiator, followed by an in-situ surface oxidation catalyzed by copper(II) chloride and tert-butyl hydroperoxide. Analysis of Reagent Purity: by iodometric titration.70 Purification: cryst from hot dil aq HCl (0.6 mL g−1) by cooling in a CaCl2–ice bath.71 Handling, Storage, and Precautions: the anhydrous solid should be stored in the absence of moisture, since the dihydrate is formed in moist air. Form Supplied in: anhydrous: hygroscopic yellow to brown microcrystalline powder dihydrate: green to blue powder or crystals also supplied as reagent adsorbed on alumina (approx.
Solubility: anhydrous: sol water, alcohol, and acetone dihydrate: sol water, methanol, ethanol mod sol acetone, ethyl acetate sl sol Et2O. CuCl2 (MW 134.45) InChI = 1S/2ClH.Cu/h2*1H /q +2/p-2 InChIKey = ORTQZVOHEJQUHG-UHFFFAOYSA-L (♲H2O) Cl2CuH4O2 (MW 170.48) InChI = 1S/2ClH.Cu.2H2O/h2*1H 2*1H2/q +2 /p-2 InChIKey = MPTQRFCYZCXJFQ-UHFFFAOYSA-L (chlorinating agent oxidizing agent Lewis acid) Physical Data: anhydrous: d 3.386 g cm−3 mp 620 ☌ (reported mp of 498 ☌ actually describes a mixture of CuCl2 and CuCl) partially decomposes above 300 ☌ to CuCl and Cl2 dihydrate d 2.51 g cm−3 mp 100 ☌.