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Publication numberUS3123640 A
Publication typeGrant
Publication dateMar 3, 1964
Filing dateApr 14, 1960
Publication numberUS 3123640 A, US 3123640A, US-A-3123640, US3123640 A, US3123640A
InventorsKermit Longley
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Cation-active surface active aryldi-
US 3123640 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Ofifice My invention relates to the production of novel cationactive surface active chemical compounds which are useful for bactericidal, germicidal, antiseptic, algtaecidal, fungicidal, textile softening, corrosion inhibition, antistatic, emulsifying, foam modifying, ore beneficiation, and vari- 0118 other purposesfor which certain heretofore known cationic surface active agents have been employed or suggested for use. 7

The specific cation-active surface active agents of my present invention are of the quaternary ammonium type and they are characterized by panticuiarly advantageous properties, simplicity of production and markedly low cost. Certain of them, for instance, those derived from low molecular Weight alkyl secondary amines and cyclic amines, can be represented by the formula (I) R\ /R2 wherein R is an alkyl radical containing from 1 to 3 and more particularly from 1 to 2 carbon atoms, R, is

an alkyl radical containing firom l to 3 carbon atoms, or

a? may be a radical or .a cyclic amine containing not more than 6 carbon atoms, R is a polyoxyalltylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing at least 3 carbon atoms, especially propyleneoxide. In those cases where R is derived from propyleneoxide, there will be at least 6 of such propyleneoxide groups in R and, more particularly, it is desired that R contain from 8 to 30* oaypropylene groups. Where R is derived from e-epoxides containing more than 3 carbon atoms, a lesser number of such oxyalkylene groups can be present, subject to the limitation of R containing at least 18 atoms. R is advantageously a lower aliphaticaryl radical containing 7 to 9 carbon atoms, notably an alharyl radical, and A is an anion. It is important, for the achievements of the results to which my invention is directed, that the R radical, Where it is alkyl, contain not more than 3 carbon atoms and especially that it contain from 1 to 2 carbon atoms and, hence, that it be methyl or ethyl. Likewise, except where a is derived from a cyclic amine, as hereafter pointed out, it is important that the R radical does not contain over 3 carbon atoms, and, in any event, the maximum number of carbon atoms in R and R does not exceed a total of more than 6, and more particularly does not exceed a total of '4 or 5. While R may contain a minimum of 6 of the aforesaid oxyalkylene, particularly oxypropy-lene, groups, and may contain 40, 50 or 60 or even 100 or more of said groups, it is especially advantageous that the minimum number of said groups be 8 and the preferred range is 8 to 25 or 30 of said groups. The term m-epoxide, as used herein, is intended to cover those 3,123,646 Patented Mar. 3, 1&64

2 compounds, of the type here involved, where there are two vlcinal carbon atoms connected to one oxygen atom mdependently of the position of such group in the molecule.

The terms polyoxyallcylene, polyoxypropylene and polyoxyethylene, to the extent that they are used herein or in the claims, are employed in their usual or conventional manner. Thus, in the case of the polyoxyalkylene radical derived from a-epoxides containing from 3 to 6 carbon atoms, to wit, R in the above iormtula, the same may be represented by where R, is an alkyl radical containing from 1 to 4 carbon atoms, and, .as indicated above, since R contains a. of l8 carbon atoms, n is at least 6 in the case of the polyoxyalkylene radical being polyoxypnopylene and n s at least 3 in the case of the polyoxyalkylene radical being polyoxyhexylene. As indicated above, 11 is usually up to 60 or more. Where the polyoxyalkylene radical is polyoxypnopylene, it may be represented by the formula n advantageously being from 6 to 30.

The foregoing illustrate the polyoxyalkylene and polyoxypropylene radicals Where the vicinal carbons are terminal. In the broader, but less preferred, embodiments of my invention, however, the vicinal carbons need not be terminal. A typical illustration of the latter is g polyoxyalkylene radical derived from 2,3-buty1ene on e.

At least most of those of the particularly preferred quaternary ammonium compounds of my invention which are derived from lower monoalkyl amines can be represented by the afonrnula where R is an alkyl radical containing from 1 to 3, and especially from 1 to 2, carbon atoms, R, is

where R, is an alkyl radical containing from 1 to 4 carbon atoms, 11 and n are numbers the sum of which does not exceedbO, the total number of carbon atoms in R and R being at least 18; R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.

Various of those particularly preferred quaternary ammonium compounds of my invention .which are derived from lower dialkyl monoalkanolamines can be represented by the formula where R is an alkyl radical containing from 1 to 3, and 7 3 radical containing from 1 to 3 carbon atoms; alkylene contains not more than 3 carbon atoms, R O is where R; is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18; R is a hydrocarbon lower aliphatic-aromatic hydrocarbon radical containing from 7 to 9 carbon atoms; and A is an anion.

Again, various of those of the particularly preferred quaternary ammonium compounds of my invention which are derived from lower monoalkyl dialkanolamines can be represented by the formula (IV) Ra R O-alkyleneN R O-alky1ene A where R is an alkyl radical containing from 1 to 3, and especially from '1 to 2, carbon atoms, alkylene contains not more than 3 carbon atoms, R O is where alkylene contains not more than 3 carbon atoms, R-O is in which R, is an alkyl radical containing from 1 to 4 carbon atoms, n, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, R and R being at least 18; R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.

Most of the quaternary compounds of the present invention fall into the category of or correspond to reaction products of quaternizing esters having a benzyl radical or a dimethylbenzyl radical or a lower alkyl substituted or chloro or nitro substituted benzyl radical, and an anion, with adducts of (a) aliphatic amines or cyclic amines containing a reactive hydrogen and a total of not more than 6 carbon atoms and in which no single aliphatic radical contains more than 3 carbon atoms, with (b) an ot-epoxide containing at least 3 and advantageously from 3 to 8 carbon atoms, the molar ratio of (a) to (b) being 1 of (a) to at least 6 cl (b) when said a-epoxide contains 3 carbon atoms and ranging down to at least 2.5 of (b) when said cs-fiPGXidfl contains 8 carbon atoms.

While, as indicated, many of the novel and useful cation-active surface active agents of my invention can be represented by the above formulae, they may, in general, best be described in the form of reaction products of identified ingredients, as hereafter pointed out, since the active constituent or constituents thereof need not be separated out and recovered as such, the reaction products being usable as such for many purposes without the necessity for resorting to concentration, purification or recovery steps. Thus, for example, although this will be pointed out and described in more detail hereafter, quaternary ammonium cornpounds which are particularly use- 121 and which may simply and inexpensively be produced are reaction products of aromatic quaternizing esters in the form of halides, sulfates and sulfonates advantageously containing from 7 to 9 carbon atoms exemplified by benzyl chloride, dimethylbe-nzyl chloride, and phenyl ethyl chloride, with adducts of (a) alkyl amines having a reactive hydrogen and containing from 1 to 4 carbon atoms, such as dimethylamine and diethylamine, with (b) propylenewtide or butyleneoxides, said adducts containing 1 mol or (d) to from 6, and preferably from 8, to 30 mols of (b). Purification steps can, if desired, be employed as, for instance, separating unreacted tertiary amines by distillation, etc.

It is important to note that it is critical to my present invention that the oxyalkylene groups be derived from an u-epoxide conaining at least 3 carbon atoms. Ethyleneoxide, for instance, is not operative in the practice of my invention since it produces compounds Whose properties are radically different from those obtained in accord-ance with my invention and which would be useless for the purposes for which the cation-active surface active agents of my invention are adapted and intended. The most important embodiment of the ot-epoxides Whose use is contemplated by my invention in the production of the cation-active surface active agents is propyleneoxide butylene oxide, pentylene epoxides, hexylene epoxides,

heptylene epoxides, octylene epoxides, dodecylene epoxides, rand C ,-C olefin oxides or epoxides, and, as Well, styrene epoxide. It will be seen that most of those of the ot-epoxides in which the vioinal carbons are terminal can conveniently be represented by the formula Where R is an alkyl radical. In the case of propylene oxide, R is CH and in the representation of the group of propylene oxide, butylcne oxides, pentylene oxide and hexylene oxide R contains from 1 to 4 carbon atoms. In the higher molecular weight alkylene oxides, R may contain as high as 16 carbon atoms.

While, as lhave stated above, the use of ethyleneoxide as the sole alkylene oxide is inoperative for my purposes, small proportions thereof, not to exceed 25% and better still not to exceed 20% by Weight of the propyleneoxide or other ot-epoxide employed, can be utilized as hereafter described. Mixtures of two or more of the lat-epoxides containing at least 3 carbons can, of course, be used as such, as Well as in conjunction with ethylene-oxide,

subject to the limitation that the ethyleneoxide must not exceed the aforesaid 20% to 25% of the weight of said a-epoxides.

The cation-active surface active agents of my invention are advantageously prepared by initially condensing a lower molecular weight amine, for instance, one containing at least one allsyl radical having from 1 to 3 carbon atoms and no radical containing more than 3 carbon atoms linked to the nitrogen atom of the amine, or be initially condensing a cyclic amine such as piperidine containing not more than 6 carbon atoms, with propyleneoxide or other a-epoxide containing at least 3 carbon atoms, advantageously in the presence of a conventional oxyalkylating catalyst such as sodium hydroxide or potassium hydroxide, whereby to produce an intermediate or adduct containing at least 6 oxypropylene groups. The amines used in the reaction to produce said adducts must contain a reactive hydrogen, which may be hydrogen directly attached to the nitrogen of the amine or which may be in the form of hydroxyl hydrogen, secondary alkyl amines being especially desirable, particularly dimethylamine, diethylamine and methylethylamine. The resulting adduct is then reacted with an aromatic or lower aliphatic-aromatic quaternizing ester to convert said adduct into the cation-active surface active agents of my present invention. Illustrative examples of such quaternizing al'karyl halides, etc. are, as pointed out above, benzyl chloride and dimethylbenzyl chloride, as well as their corresponding bromides; methylbenzyl chloride and bromide; phenylrnethyl halides such as the chloride and bromide; phenylethyl chloride and bromide; substituted phenyl lower alkyl (from 1 to 4 carbon atoms) halides as, for example, o-chlorhenzyl chloride and p-nitrobenzyl chloride and bromide; and monocyclic arylsulfonic acid lower alkyl esters such as the methyl and ethyl esters of benzene sulfonic acid, p-toluene sulfonic acid, and otoluene sulfonic acid. It will be seen that all of the quaternizing esters which are utilized pursuant to the present invention contain an aryl radical, more particularly a benzene radical which is connected to a divalent hydrocarbon radical such as -CH or CH -CH or to a lower alkyl radical, that is one containing not more than 4 carbon atoms, especially CH or C H In order to obtain cation-active surface active agents having the required properties in accordance with my invention, the aromatic or lower aliphatic-aromatic quaternizing esters, for best results should contain from 7 to 9 carbon atoms. The speed of quaternization in any given instance will be governed by the reactants and the reaction conditions including the temperature and solvent medium utilized.

Illustrative examples of the intermediate condensation products or adducts which are subsequently converted into the cation-active surface active agents or quaternary ammonium compounds encompassed by my present invention are the following:

(a) Condensation products of 1 mol of dimethylamine with 6 to 10 mols of propyleneoxide.

(b) Condensation products of 1 mol of dimethylamine with mols of propyleneoxide.

(c) Condensation products of 1 mol of dimethylamine with a mixture of mols of propyleneoxide and 5 mols of ethyleneoxide.

(d) Condensation products of 1 mol of dimethylamine with 1 to 2 mols of ethyleneoxide, reacted with 20 rriols of propyleneoxide.

(e) Condensation products of 1 mol of methylamine with to mols of propyleneoxide.

(f) Condensation products of 1 mol of methylethylamine with 10 to mols of propyleneoxide.

, (g) Condensation products of 1 mol of diethylamine with 30 mols of propyleneoxide.

(h) Condensation products of 1 mol of dimethylarnine with 10 to 20 mols of propyleneoxide and then with 1 mol of ethyleneoxide.

(i) Condensation products of 1 mol of methylpropylamine with 10 to 25 mols of propyleneoxide.

(j) Condensation products of 1 mol of dirnethylamine with 10 to 15 mols of butyleneoxide.

(k) Condensation products of 1 mol of diethylamine with 10 to 18 mols of butyleneoxide.

(l) Condensation products of 1 mol of piperidine with 10 to 25 mols of propyleneoxide.

(m-) Condensation products of 1 mol of methylpiperidine with 10 to 25 mols of propyleneoxide.

(n) Condensation products of 1 mol of pyrrolidine with 10 to 25 mols of propyleneoxide.

(0) Condensation products of /2 mol of methylamine and /2 mol of diethylamine with 6 to 30 mols of propyleneoxide.

(p) Condensation products of mol of dimethylamine and /3 mol of diethylamine with 10 to 25 mols of propyleneoxide.

(q) Condensation products of 1 mol of morpholine with from 6 to 30 mols of propyleneoxide.

(r) Condensation products of 1 mol of diethylethanolamine with 8 to 20 mols of propyleneoxide.

(s) Condensation products of 1 mol of diallylethanolamine with 8 to 25 mols of propyleneoxide.

(t) Condensation products of 1 mol of furfurylamine with 8 to 25 mols of propyleneoxide.

(u) Condensation products of 1 mol of 2-amino-1,3- propanediol with 8 to 25 mols of propyleneoxide.

(v) Condensation products of 1 mol of diethylamine with 6 to 25 mols of propyleneoxide.

The amines which are utilized in the production of the intermediate adducts or condensation products with the propylene oxide or other ec-epoxides are particularly advantageously of aliphatic or acyclic character, although they also include cyclic secondary amines. In all cases, they contain at least one reactive hydrogen directly attached to nitrogen or in a hydroxy group. Illustrative examples of such amines are alkyl amines, e.g., methylamine, dimethylarnine, ethylamine, diethylamine, methylethylarnine, propyl amine, dipropylamine; alkyl hydroxy amines, e. g., monomethylethanolamine, monoethylethamol-amine, monomethyldiethanolamine, dimethylethanolamine, diethylethanolamine and diallylethanolamine; polyamines such as ethylenediamine, diethylenetriarnine and triethylenetetraamine and higher polyamines in which there is at least one short chain alkyl group, as for instance, monomethyl ethylenediamine, dimethyl ethylenediamine and trimethyl ethylenediamine; N,N-dimethyl-N,N'-diisopropanol propylenediamine-l,3; furfurylamine; cyclic secondary amines containing not more than 6 carbon atoms, typical examples of which are morpholine, piperidine, methylpiperidine, and pyrrolidine. Such amines may contain nonreactive substituents such as nitro groups, ether and thioether groups, CN groups, and the like, but, in general, best results will be obtained with the unsubstituted amines. Compatible mixtures of any two or more of said amines, in various proportions, can, of course, be utilized in the production of the intermediate condensation products.

The radical A can be any negative or salt-forming radical as, for instance, halogen such as chlorine, bromine and iodine; hydroxy; sulfate; nitrate; phosphate; acetate; formate; sulfonic acids; and the like. Of particular importance are those of the cation-active surface active agents of any invention in which the anion is chlorine or bromine. Various of said anionic radicals can he introduced directly into the molecules; and, in the case of others, they can be made, for instance, by substitution for halogen in the cation-active surface active agents of my present invention by known techniques as, for instance, by metathesis procedures.

The following examples are illustrative of the production of typical cation-active surface active agents in accordance with my invention. It will be understood that other reactants can be utilized, proportions modified, temperature and other conditions, and concentration or purification procedures employed, all within the guiding principles taught herein, without departing from the essential teachings disclosed herein.

Example 1 (a) 46 grams (1 mol) of dimethylamine were placed in an autoclave from which the air was displaced by nitrogen. 58 grams (1 mol) of propyleneoxide were pumped into the dimethylamine in said autoclave and reacted while maintaining the temperature below 25 degrees C. The resulting compound was admixed with an alkaline catalyst, say 2 to 3 grams of KOH, and was heated to about 150 degrees C. and 25 mols of propyleneoxide were added to the autoclave over a period of 6 hours while maintaining a nitrogen pressure in the autoclave. The rate of addition of the propylene-oxide was controlled so that the pressure in the autoclave did not exceed 2 atmospheres and the temperature controlled so as not to exceed 200 degrees C. and preferably at about 150 degrees C. Upon completion of the reaction, the reaction mixture was cooled to below 100 degrees C. and flushed out with gaseous nitrogen.

(b) To 77 grams of the intermediate condensation product or adduct of part (a) hereof there were added 8 grams of methanol and 8 grams of benzyl chloride and the resulting mixture was refluxed, with stirring, for hours. During this period, the temperature of reflux rose somewhat and the viscosity of the reaction mixture increased appreciably. A yield of 96% of theoretical of the following product was obtained:

0 H3 0 lag-O C R Cl wherein R is a polyoxypropylene radical containing about 25 oxypropylene groups.

Example 2 50 grams of the adduct of part (a) of Example 1 were reacted with 3 grams of dimethyl benzyl chloride in the manner described in part (b) of Example 1 to produce a product having the following formula:

CH3 R Cl where R is a polyoxypropylene radical containing about 25 oxypropylene groups.

Example 3 wherein R is an alkyl radical containing from 1 to 3 carbon atoms, R is a member selected from the group consisting of an alkyl radical containing from 1 to 3 carbon atoms and and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is where R is an alkyl radical containing from 1 to 4 carbon atoms, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R being at least 18; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;

wherein R is methyl; R is an alkyl radical containing from 1 to 3 carbon atoms; R is wherein n is a number from 6 to 30; R is a dimethylbenzyl radical; and A is an anion.

4. A quaternary ammonium compound having the formula R R: 3.21% Ra \A wherein R and R are each ethyl; R is {CH2(|3H-O):I

wherein n is a number from 6 to 30; R is a benzyl radical; and A is chlorine.

5. A quaternary ammonium compound in accordance with claim 1 wherein up to 20% by weight of R is replaced by a polyoxyethylene radical.

6. A quaternary ammonium compound having the formula wherein R is an alkyl radical containing from 1 t0 3 carbon atoms, R; is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is a polyoxypropylene-poiyoxyethylene radical in which the number of oxypropylene groups is from 6 to 60 and in which the ethylene oxide constitutes not more than 20% by weight of said radical; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an anion.

7. A quaternary ammonium compound having the formula where R is an alkyl radical containing from 1 to 3 carbon atoms, R is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a cyclic amine radical containing not more than 6 carbon atoms, with the proviso that the total number of carbon atoms in R and R does not exceed 6; R is a polyoxyalkylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing from 3 to 6 carbon atoms, said oc-BpOXidG consisting of carbon, hydrogen and oxygen, and the total number of oxyalkylene groups in said polyoxyalkylene radical not exceeding 60; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitr c nuclearly substituted derivatives of the foregoing; and A is an anion.

8. A quaternary ammonium compound having the formula B3 A wherein R is methyl; R is an alkyl radical containing from 1 to 3 carbon atoms; R is wherein n is a number from 6 to 30; R is an aralkyl radical containing from 7 to 9 carbon atoms, and A is an anion.

9. A quaternary ammonium compound having the formula Rr-N where R and R are each methyl; R is -CHz-C H-O nH CH3 wherein n is a number from 6 to 30; R is benzyl; and A is chlorine.

10. A quaternary ammonium compound having the formula I where R and R are each methyl; R is wherein n is a number from 6 to 30; R is methylbenzyl; and A is chlorine.

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Classifications
U.S. Classification564/285, 504/156, 252/390, 516/DIG.700, 516/68, 504/157, 548/574, 564/284, 504/160, 504/153, 504/155, 516/71, 516/15, 361/212, 546/248
International ClassificationC07D295/088, A01N25/30
Cooperative ClassificationA01N25/30, C07D295/088, Y10S516/07
European ClassificationA01N25/30, C07D295/088