UNITED STATES PATENT Office PROCESS of PREPARNG QUATERNIZED SALTS of RESNOUS ORGANCPOLYMERS GENCONTAINING ATOM a BASIC TERTARY NTBO Louis M
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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.