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Oleophilic ion-exchange resins are ones capable of appreciable swelling in most organic solvents, and thus they have functional ion-exchange properties in these solvents. These resins were prepared by introduction into the polymer structure of hydrophobic or oleophilic groups which reduce the polarity of an ion-exchange polymer and make f o r its swelling in organic solvents. Oleophilic ion-exchange polymers were prepared by the copolymerization of methacrylic acid and dodecyl methacrylate; by the copolymerization of styrene and isobutylene, followed b y sulfonation; by the formation of a cage polymer of polystyrene about a linear, oil-soluble polymer of isobutylene or butyl rubber, followed by cross linking (sometimes) and sulfonation; by the acylation (with lauroyl groups, as an example) of polystyrene, followed by sulfonation; by the quaternerization with long-chain alkyl halides of polyvinylimidazole; by the chloromethylation of polystyrene, followed by treatment with a long-chain tertiary amine. In this manner, polymers were prepared which had appreciable swelling in a wide range of solvents varying f r o m hexane or benzene on one hand to water on the other. The rates of exchange of certain of these oleophilic ion-exchange polymers in apolar solvents were shown to be comparable to those of conventional ion-exchange resins in aqueous media.

Polyvinylmethylglyoxime was prepared by treating polyvinyl ethyl ketone with ethyl nitrite and converting the a ketomonoxime to the glyoxime with hydroxylamine hydrochloride. The acid dissociation constants and some metallic ioii binding constants were determined in 4/1 dioxane-water solutions for the polymer and its monomeric analog, dimethylglyoxime. Using a modified Bjerrum technique, formation constants were calculated for the displacetnent of a proton from the chelate acid by the metallic cation. On this basis it was found that both the polymer and its monomeric analog bound u?i(II) to approximately the same extent; weaker binding was observed with both Nd(II1) and Pr(II1) for the polymer. Binding to Ni(I1) was weak relative to UOz++, but stronger than with the rare earth cations.Previous papers2t3 in this series discussed the chelating properties of polymers. This contribution concerns itself with the synthesis and properties of n new polychelate, polyvinylmethylglyoxime (PMG), the polymeric analog of dimethylglyoxime. ExperimentalPreparation of Polymer.-The polymer was prepared by treating polyvinyl ethyl ketone with ethyl nitrite so as to add an a-oxime group to the carbonyl, followed by the addition of hydroxylamine hydrochloride to convert the carbonyl to an oxime. First, polyvinyl ethyl ketone was obtained by free radical polymerization of vinyl ethyl ketone a t 90" using 0.5% benzoyl peroxide as a catalyst. Ethyl nitrite was prepared by slowly adding a mixture of an aqueous ethanol solution (8.5y0 by volume; 125 ml.) and 22 g. of concentrated sulfuric acid to 32 g. of sodium nitrite dissolved in 125 ml. of 8.5% ethanol in water. The gaseous ethyl nitrite was passed for a period of one hour into a solution of 35 g. of polyvinyl ethyl ketone in 120 ml. of ethanol containing 2% (by volume) concentrated hydrochloric acid. The reaction temperature was maintained a t 40-50'. The resulting reaction mixture was agitated for an additional hour, and then added slowly with constant stirring to 700 ml. of water. After suction filtering and drying the resulting precipitate, a yellow-brown powder was obtained.As a chemical analysis indicated that only half of the theoretical nitrogen content was introduced, the nitrosation procedure was repeated and the polymer t,hen was found to contain 9.11 % nitrogen. A calculation indicated that 67.4y0 of the monomeric units were converted to t8wo probable nitrosation products, I1 and I11 I L CHs An I I11( 1 ) A portion of this work is ahstracted from the Dissertatiori of Juliaii B. Andelitian to be submitted in partial fulfilliiient of the requireiiients for the degree of Doctor of Philosophy in Cheniistry, Polytechnic Institute of Brooklyn.(2) H. P. Qregor, with L. B. Liittinger and E. R1. Loehl, THla JOURNAL, 59, 34, 3Gti, 559, 990 (1055).(3) G. I<. Hoeschelc, J. B. Airdeltuan and H. P. Gregor, ibid., 62, (1958).This reaction is analogous to the nitrosation of ethyl isopropyl ketone reported by Aston, et ul.4 They found that nitrosation occurred in both positions a to the c...

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