Patented Oct. 11, 1949. 2484,420 UNITED STATES PATENT office PROCESS OF PREPARNG QUATERNIZED SALTS OF RESNOUS ORGANCPOLYMERS GENCONTAINING ATOM A BASIC TERTARY NTBO Louis M. Minsk and William O. Kenyon, Roch ester, N. Y., assignors to Eastman Kodak Com Jerseypany, Rochester, N. Y., a corporation of New No Drawing. Application December 31, 1946, Serial No. 719,626 8 Claims. 1. (C. 260-88.3) This invention relates to a process for the 2 preparation of quaternary salts of resinous linear and the monomethyl ether of ethylene glycol. addition-type organic polymers which contain The latter are similar in being solvents for the a basic tertiary nitrogen atom comprising heat initial reacting components, but dissimilar in ing the polymer with an alkyl sulfate or an alkyl their solvent actions on the quaternary salt prod arylsulfonate in a solvent of the group consisting lucts. In the case of 1,4-dioxane, it is a non of alcohols, ethers, alcohol-ethers and ketones. Solvent for the quaternary salts, so that the prod Monomeric quaternary ammonium salts can uct settles out of the reaction mixture as it is be prepared in mass by simply heating a mixture formed, whereas the monomethyl ether of ethyl of the tertiary nitrogen compound with the de ene glycol is a solvent for both the initial reacting sired alkyl halide. Such monomeric quater O components and the quaternary salt products, nary salts can be purified by the usual methods from which the quaternary salt must be isolated of washing, recrystallization, etc. However, in by precipitation of the reaction solution into a the case of resinous organic polymers the at non-solvent for the polymer, for example, 2 tempt to purify their quaternary salt derivatives vinylpyridine polymer metho-p-toluenesulfonate meets with considerable difficulties. It is not s formed in the monomethyl ether of ethylene possible as a rule to obtain pure polymeric com glycol was precipitated by pouring the mixture pounds by the simple process of reaction in mass into butyl acetate. Other non-solvents for the followed by the ordinary methods of purification. quaternized salts of our invention include ethers, We have now found that by controlling the acid esters of higher alcohols and higher ketones, step of quaternization of the resinous polymers, 20 for example, ethyl ether, amyl acetate, methyl products of much higher, uniform purity are ob isobutyl ketone. tainable. This marked improvement we accom The alkyl sulfates and alkyl arylsulfonates plish in our invention by carrying out the qua which can advantageously be used as quaterniz ternization in an inert liquid, which at the same ing reagents in the process of our invention in time is a solvent for the components entering in 25 clude arylsulfonates of the benzene series, for ex to the quaternizing reaction, the quaternary Salt ample, methyl p-toluenesulfonate, n-butylp-tolu product being obtained in solid form by precipi enesulfonate, isobutyl p-toluenesulfonate, methyl tating the reaction medium into a liquid which is benzenesulfonate, ethyl benzenesulfonate, n non-solvent for the salt, filtering out the salt and propyl benzenesulfonate, n-butyl benzenesulfo washing it with a non-solvent liquid. Our new 30 nate, isobutyl benzenesulfonate, or dialkyl sul proceess is advantageously adaptable to large fates, for example, dimethyl sulfate, diethyl sul scale production. Also the quaternary Salt prod fate, di-n-propyl sulfate, di-n-butyl sulfate or di lucts prepared by our new process have less color, isobutyl sulfate. Other alkyl sulfates and alkyl more homogeneity and higher compound purity arylsulfonates which can also be used in our proc than the same salt products made in mass with 5 ess are, for example, n-amyl p-toluenesulfonate, out the benefit of an inert liquid reaction solvent isoamyl p-toluenesulfonate, n-hexyl p-toluenesul medium. fonate, isohexyl p-toluenesulfonate, n-heptyl p In the practice of our invention, we prefer to toluenesulfonate, n-octyl p-toluenesulfonate, n use as the inert liquid reaction solvent medium, nonyl p-toluenesulfonate, n-decyl p-toluenesulfo a neutral oxygen containing Organic compound 40 nate, n-lauryl p-toluenesulfonate, n-amyl ben which is a solvent for the initial starting Com Zenesulfonate, isoamyl benzenesulfonate, n-hexyl ponents. While solvents such as methyl alcohol, benzenesulfonate, isohexyl benzenesulfonate, n absolute ethyl alcohol, isopropyl alcohol, butyl al heptyl benzenesulfonate, n-octyl benzenesulfo cohol, the monoethyl ether of ethylene glycol, the nate, n-nonyl benzenesulfonate, n-decyl benzene monomethyl ether of ethylene glycol, the mono Sulfonate, n-lauryl benzenesulfonate, di-n-amyl ethyl ether of diethylene-glycol, ethyl lactate, Sulfate, diisoamyl sulfate, di-n-hexyl sulfate, B-hydroxyethyl acetate, 1,4-dioxane, the formal diisohexyl Sulfate, di-n-heptyl sulfate, di-n-octyl of ethylene glycol, methyl ethyl ketone, methyl Sulfate, di-n-nonyl Sulfate, di-n-decyl sulfate, or isopropyl ketone, formamide, ethyl cyanoacetate, di-n-lauryl sulfate. The ratios in which the nitromethane, nitrobenzene, can all be used suc 50 components in the quaternizing mixtures can be cessfully, we have found that the best results are used in our process can vary quite widely from obtained with those solvents having only carbon, One to more than three molecular parts of the hydrogen and oxygen atoms in their chemical alkyl sulfate or alkyl arylsulfonate to one molec compositions, and more particularly 1,4-dioxane ular part of the resinous polymer having the tertiary nitrogen to be quaternized. The tem 2,484,420 4. 3 hour with each extraction, and finally extracted perature of the quaternization reaction mixture once with Skellysolve G, (essentially consisting can also be varied over a considerable tempera of low boiling hydrocarbons). After filtering off, ture range, depending upon the boiling point of the polymer was dried in a vacuum desiccator un the inert solvent medium, but preferably from der constant vacuum, protected from atmospheric 50° to 200° C. The quaternary salts produced by moisture by a calcium chloride tube, followed by our process as described in the preceding and in drying in an open dish at normal atmospheric the examples which follow are particularly valu pressure, at 55° C. for 2 hours. The yield was able as precipitants and mordants of acid dyes, 460 grams. The analysis gave a value for nitro as well as being useful colloidizing agents. gen content of 4.95 per cent by weight, and sul It is, accordingly, an object of the invention to O phur content of 10.64 per cent, as compared to provide a process whereby quaternary salts of calculated theoretical of 4.81 per cent and 1.01 resinous linear addition-type organic polymers per cent, respectively. This result indicates that which contain a basic tertiary nitrogen atom Substantially all of the nitrogen groups had been can be obtained. Other objects will become ap quaternized. parentThe followinghereinafter. examples will serve further to Eacample 3-Poly-2-vinylpyridine metho-p- jlustrate our invention. toluenesulfonate 100 grams of poly-2-vinylpyridine were dis Eacample 1.-Poly-2-vinylpyridine ethioethyl persed in one liter of 1,4-dioxane, 240 grams of sulfate 20 methyl p-toluene sulfonate added, and the mix 20 grams of poly-2-vinylpyridine were dissolved ture heated for a period of 16 hours on a steam in 100 c. c. of dry 1,4-dioxane. To the clear tan bath in an all-glass apparatus equipped with a colored dope obtained, there were added 40 grams calcium chloride tube for protection against mois of diethyl sulfate, and the mixture heated to re ture from the atmosphere. The polymer began flux in an all-glass apparatus for about one hour. 25 to precipitate after 10 minutes of heating. At the The quaternized polymer precipitated almost at end of the heating period the mixture was cooled once. The supernatant liquid was then poured and the Supernatant liquid decanted off. One off, and the cake remaining quickly extracted liter of absolute ethyl alcohol was added and the with 200 c. c. of 1,4-dioxane, followed by one mixture shaken until the cake had completely quick wash with 250 c. c. of absolute ethyl alco 30 dissolved. The ethyl alcohol dope was then hol. The cake was then dispersed by shaking poured in a fine stream into 75 pounds of butyl with 250 c.c. of absolute ethyl alcohol. The dope acetate and vigorously agitated by a large me obtained was filtered through paper by suction chanical stirrer. After 30 minutes of stirring, the and precipitated in a large excess of ethyl ether. product was filtered onto a Buchner funnel, The granular precipitate was extracted with three 35 stirred with two 15 pound portions of fresh butyl 2-liter changes of fresh ether and dried in a vac acetate, each with one hour of stirring followed uum desiccator under constant water pump vac by filtration onto a Buchner funnel. The prod uum. 30 grams of light tan colored friable prod uct was dried at 60° C. On a tray. A good yield of uct were obtained. This product was soluble in high purity 2-vinylpyridine polymer metho-p-tol water and no precipitation was caused, when the 40 uenesulfonate was obtained. water solution was made alkaline by addition of Eacample 4-Poly-2-vinylpyridine metho-p- sodium hydroxide. The analysis gave a nitrogen toluenesulfonate and sulfur content of 6.47 and 11.51 per cent by 100 grams of poly-2-vinylpyridine were dis weight, respectively, as compared with calculated persed in 900 grams of methyl ethyl ketone, 240 of 5.41 and 12.37 per cent. This result indicates grams of methyl p-toluene sulfonate added, and that more than 70 per cent of the nitrogen groups the mixture heated for a period of 16 hours on a had been quaternized. steam bath in an all-glass apparatus. The qua Eacample 2-Poly-2-vinylpyridine metho-p- ternized polymer precipitated in the form of a toluenesulfonzdie 50 white cake. The reaction mixture was cooled, the supernatant liquid poured off and the cake 200 grams of poly-2-vinylpyridine were dis dissolved by shaking with 1200 c. c. of absolute persed in a shaker with 1600 c.c. of dry 1,4-diox ethyl alcohol. The product was reprecipitated ane. To the dope obtained, there were added by pouring the alcohol solution into 5 gallons of 500 c. c. of methyl p-toluene sulfonate, and the 55 butyl acetate with vigorous stirring. The pre mixture heated on a steam bath for about 16 cipitated product was filtered off, washed with hours in an all-glass apparatus equipped with a two 2 gallon portions of fresh butyl acetate, each calcium chloride tube for protection against mois with one hour of stirring followed by filtration ture from the atmosphere. The quaternized pol onto a filtering funnel, washed on the funnel with ymer precipitated from the solution in the form 60 two 2 liter portions of fresh butyl acetate and of a cake. The supernatant liquid was poured off dried at 60° C., on a tray. Analysis of the product and the cake dissolved in 4 liters of absolute ethyl gave a nitrogen and sulfur content of 6.0 and 9.0 alcohol. The resulting alcoholic dope Solution was per cent, respectively, as compared to calculated filtered through paper with the aid of suction, and the resin reprecipitated by pouring the fil theoretical of 4.81 and 11.01 per cent. trate in a fine stream into 20 gallons of ethyl 65 Eacample 5.-Poly-2-vinylquinoline metho-p-tol ether under agitation by means of a large mixer. uenesulfonate The precipitate was stirred for 20 minutes and 1 gram of poly-2-vinylcquinoline was dispersed filtered onto a Buchner funnel. The polymer in 10 c. c. of 1,4-dioxane. To the dope obtained, was extracted with 2 gallons of fresh ethyl ether 70 there were added 2 C. C. of methyl p-toluene by stirring therein for one hour, filtered off once Sulfonate. The reaction mixture was heated for more, and re-dissolved in about 7 liters of abso 18 hours on a steam bath in an all-glass reflux lute ethyl alcohol. The polymer was again repre apparatus, protected from atmospheric moisture cipitated in 20 gallons of ethyl ether, followed by by means of a calcium chloride tube. The poly three extractions with 2 gallon portions of fresh mer precipitated from the solution. The reac ether, the polymer being stirred for about one 75

5 2,484,420 tion mixture was cooled, the supernatant liqui 6 poured of, and the solid dissolved in 10 c.c. of hours on a steam bath in an all-glass reflux absolute ethyl alcohol. The dope obtained was apparatus, protected from atmospheric moisture brown in color, and after filtering, it was pre by a calcium chloride tube. A clear dark tan cipitated in 200 c. c. of ethyl ether. The gran colored dope was obtained. The dope was poured ular precipitate was filtered off, washed with fresh in a fine stream into three gallons of butyl ace portions of ether and dried in a vacuum desicca tate and the precipitation mixture vigorously agi tor under constant vacuum, protected from mois tated. The suspension was stirred for 20 min ture by a calcium chloride tube. The yield was 1 utes, after which the Suspended product was gram. Analysis of this product gave 4.59 per filtered onto a Buchner funnel. The product was cent by weight of nitrogen and 7.57 per cent by stirred for 30 minutes with fresh butyl acetate, weight of Sulfur, as compared to calculated theo again filtered onto a Buchner funnel, washed On retical of 4.10 per cent and 9.40 per cent, respec the funnel with one-half gallon of fresh butyl tively. This result indicates that about 80 per acetate, removed from the funnel and dried on cent of the nitrogen groups had been quaternized. a tray at 50°-60° C. The yield was very nearly Eacample 6.-Poly-2-vinylpyridine metho-p-tolu quantitative. Analysis gave 4.67 per cent by enesulfonate weight of nitrogen and 10.94 per cent by weight 10 grams of poly-2-vinylpyridine were dispersed of sulfur, as compared with the calculated theo in 50 c.c. of nitromethane and 25 c. c. of methyl spectively.retical of 4.81 per cent and 11.01 per cent, re p-toluene sulfonate added. The reaction mixture 20 was heated on a steam bath for three hours in Eacample 9-Poly-4-vinylpyridine metho-p-tolu an all glass reflux apparatus, protected from at enesulfonate mospheric moisture by means of a calcium chlo 25 grams of poly-4-vinylpyridine were dis ride tube. The resulting clear tan dope was di persed in 330 c. c. of the monomethyl ether of luted with 50 c. c. of nitromethane and precipi ethylene glycol. To the dope, there were added tated in ethyl ether. The soft precipitate ob 60 grams of methyl p-toluene sulfonate, and the tained was extracted with fresh ether, redissolved reaction mixture heated for 16 hours on a steam in absolute ethyl alcohol and reprecipitated in bath in an all-glass reflux apparatus, equipped Skellysolve G. The latter reprecipitate was then with a calcium chloride tube for protection extracted with two one-liter portions of Skelly 30 against atmospheric moisture. The resulting solve (consisting essentially of aliphatic hydro clear tan colored dope was diluted to 800 c.c. with carbons boiling at 50-70) and dried in a vac monomethyl ether of ethylene glycol and di uum desiccator under constant water pump vac vided into two unequal portions. The larger por uum, protected from atmospheric moisture by a tion was precipitated in a large excess of butyl calcium chloride tube. The yield of product was acetate and the precipitate obtained then ex 16.5 grams. Analysis of this product gave 4.78 tracted with fresh portions of butyl acetate. The per cent by weight of nitrogen and 11.25 per cent product was dried at 60° C. in an air oven. The by weight of sulfur, as compared to calculated yield was 58.5 grams. The smaller portion of theoretical of 4.81 per cent and 11.01 per cent, the dope was precipitated in methyl isobutyl respectively. This result indicates that product 40 ketone, and the precipitate purified by extraction was substantially pure 2-vinylpyridine polymer with fresh portions of the same solvent. The metho-p-toluene sulfonate. product was then dried in an air oven at 60 Eacample 7-Poly-2-vinylpyridine metho-p-tolu C. The yield was 9 grams. Analysis for nitro enesulfonate 45 gen and sulfur on the former sample were 11.07 20 grams of poly-2-vinylpyridine were dis per cent and 4.42 per cent, respectively; on the persed in 200 c.c. of absolute ethyl alcohol. To tively.latter 4.54 per cent and 11.43 per cent, respec this were added 50 c. c. of methyl p-toluene sulfonate. The mixture was then heated on a Eacample 10-Poly-2-vinylpyridine metho-p-tol steam bath for 16 hours in an all-glass appara 50 uene sulfonate tus, protected from atmospheric moisture by a A solution composed of 104 grams of mono calcium chloride tube. The clear tan dope ob meric 2-vinylpyridine, freshly distilled in a vac tained was diluted with one liter of absolute uum, 250 c.c. of absolute ethyl alcohol and 200 ethyl alcohol and the resin precipitated by pour grams of methyl p-toluene sulfonate was heated ing the solution in a fine stream into four liters 55 to reflux in an all-glass apparatus for a period of ethyl ether, accompanied with vigorous stir of two and one-half hours. The resulting dope ring. The precipitate was given three extrac upon standing at room temperature, changed to tions with two liter portions of ethyl ether, fol a very viscous, reddish-brown, clear dope, which lowed by two extractions with Skellysolve G (con was completely soluble in water. The product sisting essentially of aliphatic hydrocarbons boil 60 was 2-vinylpyridine polymer metho-p-toluene ing at 50-70°). The product was dried in a sulfonate. vacuum desiccator under constant vacuum, pro tected by a calcium chloride tube, and finally in Ecample 11-Poly-4-vinylpyridine metho-p- an oven for 3 hours at 50° C. The yield Was 52 toluenesulfonate grams, or equivalent to about 93 per cent of theo 65 A mixture of 10.5 grams of 4-vinylpyridine retical. monomer, 18.6 grams of methyl p-toluene sul fonate and 50 c.c. of nitrobenzene Was heated in Eacample 8-Poly-2-vinylpyridine metho-p-tolu an oil bath at 190° C., for a period of about 30 enesulfonate minutes. The brown solution obtained was di 100 grams of poly-2-vinylpyridine were dis 70 luted with water and the nitrobenzene removed persed by shaking in 1000 c.c. of the monomethyl by steam distillation. The solution was decolor ether of ethylene glycol. To this dope, there ized by boiling with Norite (a decolorizing char were added 190 grams of methyl p-toluene Sull coal) for 10 minutes, filtered and concentrated fonate, and the reaction mixture heated for 16 75 wasto 400 poly-4-vinylpyridine c.c. under reduced pressure.polymer metho-p-tolThe product 2,484,420 8 7 hours. The resulting dope was diluted with ab uene sulfonate. In place of methyl p-toluene solute ethyl alcohol and the diluted dope poured sulfonate in the above example, there can into ethyl acetate to precipitate the quaternary be substituted an equivalent amount of ethyl salt. The gummy precipitate was redissolved in p-toluene sulfonate, n-propyl p-toluene sul ethyl alcohol and the quarternary Salt again fonate, n-butyl p-toluene sulfonate, isobutyl precipitated by pouring the ethyl alcoholic Solu p-toluene sulfonate, methyl benzene sulfonate, tion into diethyl ether. The quaternary Salt ethyl benzene sulfonate, n-propyl benzene Sull (now in the form of a granular product) was fonate, n-butyl benzene sulfonate, or isobutyl given 3 extractions with 1-liter portions of fresh benzene sulfonate to obtain the corresponding diethyl ether, each for 1 hour, followed by 2 ex 4-vinylpyridine polymer alko-p-arylsulfonates. 10 tractions with 1 liter portions of a hydrocarbon In similar manner there can be prepared the mixture (essentially aliphatic hydrocarbons boil corresponding quaternary salts of 2-vinylpyridine ing between 50 and 70° C.), each for A2 hour. polymer. The quaternary salt was then dried in a vacuum Eacample 12-Poly-g- diethylaminoethyla desiccator under constant water pump vacuum, methacrylate metho-p-toluenesulfonate 15 protected from moisture by a calcium chloride 15 g. of poly - B - diethylaminoethyl or - meth tube. Analysis: nitrogen found 3.14%, calculated acrylate were dispersed, by shaking, in 150 cc. 3.06%; sulfur found 6.19%, calculated 7.0%. of dry 1,4-dioxane. To the dope obtained were Eacample 14-Poly-2-vinylpyridine metho-p-tol added 37.5 c.c. of methyl p-toluenesulfonate, and 20 uenesulfonate the mixture was heated for 16 hours on a steam bath in an all-glass reflux outfit, protected from 20 g. of poly-2-vinylpyridine were dispersed, by atmospheric moisture by a calcium chloride shaking, in 200 g. of glycol formal (Delephine, tube. Within 5 minutes of heating, Separation Comp. rend. 131,745 (1900)). To the dispersion of the quaternary salt of the polymer began and 25 were added 48 g. of methyl p-toluenesulfonate after the 16-hour heating period, the quater and the mixture was heated on a steam bath in nary salt of the polymer had precipitated out as an all-glass reflux apparatus for 16 hours. At a soft cake. The reaction mixture was cooled, the end of this time, the metho-p-toluenesul the supernatant liquid poured off, and the cake fonate had precipitated as a tan cake. The was dissolved in 20 cc. of absolute ethyl alcohol. 30 supernatant liquid was poured off and replaced After filtering the resulting dope through paper with 200 cc. of absolute ethyl alcohol. Upon by suction, the dope was poured, in a fine stream, shaking, a Smooth dope was obtained. This was into 3 liters of diethyl ether and the whole Was diluted with an additional 200 cc. of absolute vigorously agitated. The precipitated quater ethyl alcohol and then poured, in a fine Stream, nary salt of the polymer was removed from the 3 5 into 3 liters of n-butyl acetate with stirring. The ether and again extracted with a fresh portion precipitated quaternary salt was extracted with 3 of diethyl ether. The quaternary salt of the liters of fresh n-butyl acetate, with stirring, for polymer was then dissolved in 250 cc. of absolute 30 minutes, filtered off and again extracted with ethyl alcohol and again precipitated by pouring 1 liter of fresh n-butyl acetate. The quaternary the ethyl alcoholic dope into 3 liters of diethyl 40 salt was then dried at 55° C. Yield 42 g. Analy ether. For further purification, the quaternary sis: nitrogen found 4.9%; sulfur found 10.8%. salt of the polymer was given 2 additional ex Eacample 15.-Metho-p-toluenesulfonate of co tractions, each of one hour with stirring, with polymer of 2-vinyl-pyridine and Styrene one liter portions of fresh diethyl ether, and then 2 extractions, each of 10 minutes with stirring, 50 g. of a 2-vinylpyridine-styrene copolymer, with 34 of a liter of a mixture of hydrocarbons containing 25% (by weight) of styrene, were dis (consisting essentially of aliphatic hydrocar persed in 500 g. of 1,4-dioxane. When Solution bons boiling at 50 to 70° C.). The quaternary was complete, 90 g. of methyl-p-toluenesulfonate salt of the polymer was then dried in a vacuum were added, and the mixture was heated for 16 desiccator under constant water pump vacuum, hours on a steam bath in an all-glass reflux ap protected from moisture by a calcium chloride paratus, protected from atmospheric moisture tube. Analysis: nitrogen found 3.51%, calcu by a calcium chloride tube. The quaternary salt lated 3.77%; sulfur found 8.29%, calculated precipitated out as a cake. The supernatant 8.63%. liquid was poured off, and 500 cc. of absolute ethyl alcohol were added. The mixture was then Eacample 13-Metho-p-toluenesulfonate of the shaken until a smooth dope was obtained. The copolymer of B -diethylamino-ethyl a-meth quaternary salt was precipitated by pouring the acrglate and a-methacrylic acid dope (diluted to 1200 cc. with absolute ethyl al A copolymer was prepared by mixing 100 g. of cohol), in a fine stream, into an excess of n-butyl ot-methacrylic anhydride, 400 c.c. of 1,4-dioxane 60 acetate, with stirring. The precipitated quater and 300 mg. of benzoyl peroxide, and heating the nary salt was extracted with four 2-liter portions mixture on a steam bath for 2 hours, then add of fresh n-butyl acetate, with 1.5 hours soaking ing 200 g. of B-diethylaminoethyl alcohol, and for each extraction. The quaternary salt was heating for 16 additional hours. At the end of filtered from the n-butyl acetate and dried at this time a little water was added and the cool 65 60° C. in an air oven. The yield was 46 g. Analy reaction mixture was poured into acetone to pre sis: nitrogen found 3.8%; sulfur found 8.0%. cipitate the copolymer. The precipitated copoly What we claim is: mer was stirred with several fresh portions of 1. A process for preparing resinous poly-2- acetone and finally dried in vacuo. 10 g. of the vinylpyridine metho-p-toluenesulfonate compris copolymer were dispersed at 90° C. in 100 cc. of ing heating resinous poly-2-vinylpyridine with ethylene glycol in an all-glass reflux apparatus, methyl p-toluenesulfonate in solution in 1,4-di protected from atmospheric moisture by a cal OX88. cium chloride tube. To the resulting dope were 2. A process for preparing resinous poly-2- added 10 cc. of methyl-p-toluenesulfonate and vinylpyridine metho-p-toluenesulfonate compris the resulting mixture was heated at 90° C. for 16 75 ing heating resinous poly-2-vinylpyridine with

9 2,484,420 methyl p-toluenesulfonate in solution in mono 10 methyl ether of ethylene glycol, 7. A process for quaternizing resinous poly-4- 3. A process for quaternizing a resinous poly vinylpyridine comprising heating the poly-4- vinylpyridine selected from those wherein the vinylpyridine with methyl p-toluensoulfonate, in vinyl group is attached to a carbon atom of the solution in a monoalkyl ether of ethylene glycol pyridine nucleus comprising heating the poly containing from 3 to 4 carbon atoms. vinylpyridine with a compound selected from the 8. A process for preparing poly-4-vinylpyridine group consisting of dialkyl sulfates and alkyl metho-p-toluenesulfonate comprising heating arylsulfonates, in solution in a neutral organic poly-4-vinylpyridine with methyl p-toluenesul compound selected from the group consisting of fonate, in Solution in monomethyl ether of ethyl saturated monohydric aliphatic alcohols, Satur () ene glycol. ated aliphatic ethers, saturated aliphatic ketones LOUIS. M. MNSK. and 1,4-dioxane. WILLIAM. O. KENYON. 4. A process for quaternizing resinous poly-2- vinylpyridine comprising heating the poly-2- REFERENCES CTED vinylpyridine with an alkyl arylsulfonate in Solu The following references are of record in the tion in a neutral organic compound selected from file of this patent: the group consisting of saturated monohydric aliphatic alcohols, saturated aliphatic ethers, Sat UNITED STATES PATENTS urated aliphatic ketones 1,4-dioxane. Number Name Date 5. A process for quaternizing resinous poly-4- 20 2,138,763 Graves ------Nov. 29, 1938 vinylpyridine comprising heating the poly-4- 2,138,762 Graves ------Nov. 29, 1938 vinylpyridine with an alkyl arylsulfonate, in solu FOREIGN PATENTS tion in a neutral organic compound Selected from the group consisting of Saturated monohydric Number Country Date aliphatic alcohols, saturated aliphatic ethers, Sat 25 849,126 France ------Aug. 7, 1939 urated aliphatic ketones and 1,4-dioxane. OTHER REFERENCES 6. A process for quaternizing resinous poly-2- . vinylpyridine comprising heating the poly-2- Shriner and Fuson, “The Systematic Identifl vinylpyridine with methyl p-toluensoufonate, in cation of Organic Compounds,’ 2nd ed., Wiley, solution in a monoalkyl ether of ethylene glycol 30 New York, 1940, pages 148-149. containing from 3 to 4 carbon atoms.