US2087506A - Quaternary ammonium salts of high molecular weight acids - Google Patents

Description

Patented July 20, 1931 UNITED STATES QUATERNARY AMIMONIUM SALTS OF HIGH MOLECULAR WEIGHT ACIDS,

Melvin De Groote, St. Louis, Mo., assignor to Tretolite Company, Webster Groves, Mo., a 1

corporation of Missouri No Drawing. Application August 21, 1936, Serial No. 97,221

15 Claims.

This invention relates to a novel composition of matter, and more particularly, to certain quaternary ammonium salts derived from acids of high molecular weight and of the kind hereinafter described. Such materials may be employed as wetting, washing, frothing, emulsifying, dispersing, softening, leveling, and plasticizing agents, and they also may be employed as assistants in the textile industry and various other industries.

It is well known that various high molecular weight acids, and more particularly, their salts, such as ammonium, potassium, sodium salts, etc., are the kind which exhibit surface-active properties. They give a typical colloidal sol in water or in hydrophobe solvents, in which they happen to be miscible, depending upon the specific agents selected. Examples of such materials include the following: Salts of higher fatty acids, resinates, rosinates, naphthenates, sulfoabietenes and the like, petroleum sulfonates of both the oil-soluble and oil-insoluble type, sulfated and sulfonated higher alcohols, substituted aromatic sulfonic acids, alkylated polycyclic sulfonic acids, cycloaromatic sulfonic acids, sulfated fatty acids, sulfonated fatty acids, the various cogeners which accompany the sulfo or sulfated fatty acids or sulfonated fatty acids obtained in sulfation or sulfonation processes, and are produced by the hydrolysis of sulfo-fatty acids, followed, in some instances, by condensation; fatty acids of the kind obtained by oxidation, particularly the oxidation of ricinoleic acid, i. e., blown oil, or blown oil fatty acids, fatty acid esters in which a sulfoaromatic or sulfo-aliphatic residue has replaced the carboxylic hydrogen; sulfonated fatty amides, sulfo-amides, in which a sulfonated or sulfated alkyl group, or sulfonated or sulfated aryl group has replaced an amino hydrogen in the fatty amide residue; materials of the kind in which the hydroxyl of a fatty acid or of a glyceride has combined with a polybasic carboxy acid, such as phthalated, oxalated, succinated, or maleated esters of ricinoleic acid, triricinolein, monoricinolein, di-ricinolein, mono-olein, di-olein, mono-stearin, di-stearin, mono-naphthenine, etc. Sulfo-aromatic fatty acids of the Twitchell reagent type, such as sulfo-naphthalene stearic acid, sulfo-benzene stearic acid, sulfo-phenol stearic acid, etc. represent additional examples. In the case that a maleic acid residue is present, it may, of course, be treated with a bisulfite, so as to be converted into a sulfo-succinic acid residue. In some instances, two moles of a dibasic carboxy acid, for example, such as oxalic acid, may combine with two moles of triricinolein. Generally speaking, the properties are exhibited by materials having at least 8 carbon atoms in the molecule, and not over 120, as in the case of materials where two moles of di-ricinolein have been combined by mean-s of a dibasic acid, as previously pointed out. All these materials referred to are' well known compositions of matter, and the method of manufacturing the same is well known. They have been used in a variety of industries. Some reagents find application in a number of industries, whereas, other reagents are limited to employment, perhaps, in one or two industries,

or even employment for a single purpose in a 15 particular industry.

It is to be noted that all the chemical compounds above referred to are characterized by the presence of an acid radical, which is either a carboxy acid radical, a sulfonic acid radical, or an acid sulfate radical, as in the case of fatty acid sulfates or alcohol sulfates. The acids themselves may be characterized by the formula T.X.OH, in which T is a high molecular weight residue consisting principally of carbon atoms and hydrogen atoms, and X.OH is the acid radi cal in which X is CO or S02 or S03. In-some instances T is a hydrocarbon residue without any other concomitant atoms or radicals being present, for instance, in the case of propylated naphthalene sulfonic acid, or in the case of oleic acid, or in the case of petroleum sulfonic acid. In other instances, there may be a hydroxyl group attached to T, as in the case ofderivatives of ricinoleic acid, or derivatives of alkylated naphthol sulfonic acids. In other instances, T may contain a halogen atom, such as in the case of chlorinated or brominated oleic acid, alkylated chlornaphthalene sulfonic acid, etc. In still other instances, T may have an acid group attached thereto, as in the case of phthalated castor oil, oxylated ricinoleic acid, sulfo-naphthalene stearic acid, etc. In each case, however, T is a high molecular weight hydrocarbon residue or its til BaN[ (OH) nD].C1,

in which the various characters have their previous significance. If such material is dissolved in alcohol and reacted with an alcoholic solution -of the sodium salt of acids of the kind previously described, there occurs a precipitation of sodium chloride with the formation of the corresponding salt, which may be indicated by the formula BaNE (OH) nD] .O.X.T.

in which the various characters have their previous significance. The materials so obtained from the high molecular weight surface-active acids are much more efiective for various industrial purposes than the corresponding metallic salts or corresponding simpler amine salts. I have also found that such materials are very effective softening agents, cleansing agents, detergent agents, emulsifying agents, wetting agents, and

leveling agents, and that they can be employed as auxiliary agents for the same purpose. I do not contend that any single one of. the said materials will serve for all of the purposes mentioned, but it is believed that no particular difficulty is involved in their application. Each one of the said materials or products is derived from a high molecular weight surface-active acid, whose application in various industries in the form of simple metallic salts is well known. In substantially all instances, it will be found that reagents of the kind described in which one employs the alkylated alkylol or alkylol-oxy-alkylol quaternary ammonium compounds, instead of the simpler compounds, will result in a more effective compound for the particular purpose for which the product is employed, or a compound which will accomplish the same result at a lower cost.

It is to be noted that the high molecular weight surface-active acids or theirsimpler salts may be described as being polar" compounds, in the sense that the word polar was used by Harkins in about 1917. The meaning of the word "polar" in this sense is intended to indicate that into the hydrophobe group or body there has been introduced a hydrophile group, such as a carboxyl group, or a sulfate group, or a sulfonic acid group, which tends to make the material dissolve in water or to spread out on water, or to be wetted by water. Such polarity tends to make the materials orient at interfaces. It is to be noted that the quaternary ammonium bases themselves, if they be of the kind described, exhibit this same polar property, due to the presence of the hydrocarbon residue, indicated by B, as contributing the hydrophobe portion, and due to the nitrogen atom and the alkylol or alkylol-oxy-alkylol residue introducing' the hydrophile residue. Indeed, in some instances, such quaternary ammonium bases or simple salts, even in their simplest form, such as the chlorides, may show marked surface-active properties and produce a colloidal sol of the kind comparable to that produced by high molecular weight surface-active acids of the kind previously described. Briefly stated, then, such materials of the kind herein contemplated are characterized by the fact that one might consider both the anion and the cation as being polar, when considered as an integral part, and without consideration to the natural polar relationship to each other. The relationship is comparable to a compound in which both the anion and cation have hydrophobe and hydrophile components bound covalently, whereas, the anion and cation per se are bound electrovalently.

The quaternary ammonium compounds employed to produce the desired salts may be prepared in various manners. Glycerol may be converted by customary procedure into the chlorhydrin, or may be converted into glycidol. Similarly, a glycol, such as ethylene glycol, may be converted into the corresponding chlorhydrin. Instead of the chlorhydrin one may employ the alkylene oxide. It is to be noted that reactions involving glycidol or the alkylene oxides result in the formation of the quaternary base and not in the formation of the chloride. Naturally, such a quaternary base may be used directly to neutralize a high molecular weight surface-active acid of the kind previously described. Polyhydric alcohols can be converted into ether alcohols, such as di-glycerol ether or di-ethylene glycol ether. Such polyhydric alcohol ethers can be converted into chlorhydrins in the same manner that glycerol or ethylene glycol can be converted into a chlorhydrin. Such chlorhydrins are entirely satisfactory for reaction with tertiary amines to produce a suitable quaternary ammonium compound. For purpose of illustration, the following examples are presented:

CHQOH CH2.0H

CHaCl Reactions need not be limited to the simpler tertiary amines, but one may select a secondary amine, such as diamyl-amine, and react it with glycerol chlorhydrin, for example, to produce 1- diamyl amino propane-2,3-diol (l-diamyl amino 2-hydroxy normal propanol). Such product is in reality a substituted tertiary amine and may be indicated by the formula:

Such a tertiary amine may be reacted further with another mole of the chlorhydrin derived from glycerol, ethylene glycol, or in fact, higher glycols, such as propylene glycol, butylene glycol, hydroxylated glycol, amylene glycol, non-amethylene glycol, decamethylene glycol, etc., or it may be reacted with the alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, in the presence of water, etc.

Two molecules of glycerol mono-chlorhydrin can be reacted with one mole of mono-amylamine to yield a product of the following type:

This product can also be considered a tertiary amine, andmay be reacted in the manner previously described in regard to l-diamyl amino propane-2,3-diol. Thus, in the reactions previously described, it has been indicated that a primary amine can be reacted with two moles of a suitable chlorhydrin or its functional derivative, such'as'twomoles of an alkylene oxide to give a product of the kind indicated immediately above. However, instead of using mono-amylamine, one can employ an aralkyl amine, such as benzylamine, or a cyclic amine, such as cyclohexylamine, or their homologues. Piperidine is also satisfactory for reaction with a chlorhydrin to produce a tertiary amine. Incidentally, pyridine or its homologues are satisfactory as tertiary alkyl amines for reactions of the kind described. For purposes of classification, pyridine and its homologues will be considered as trialkylated amines in which the Cal-I5 radical or the like is equivalent to three alkyl radicals. Such tertiary amines are reacted with halohydrins of the kind described to form the quaternary ammonium compound.

It has been pointed out that the various reactions above referred to may result in the formation of a quaternary ammonium compound in the form of a chloride. Such chloride can, of course, be reacted with a salt of the high molecular weight surface-active acid in a non-aqueous" solvent, so that an inorganic chloride, such as sodium chloride, potassium chloride, or ammonium chloride is precipitated with the formation of thequaternary ammonium salt of the high molecular weight surface-active acid. On the other hand, it is simpler, as a rule, to convert the quaternary ammonium chloride into the corresponding base by treatment-with an excess of concentrated caustic soda or caustic potash, so as to yield the base itself and to employ the base for neutralization.

My preferred reagent is prepared by employing tri-amylamine or pyridine as the tertiary base and using glycidol for the reaction in which the quaternary ammonium compound is produced. 1,000 lbs. of tri-amylamine or the equivalent amount of pyridine are reacted with 350 lbs. of glycidol in presence of about 75 lbs. of water, until a complete reaction has taken place. The tri-amyl propane diol ammonium hydroxide or corresponding pyridinium hydroxide, so produced, is used to neutralize various materials of the kind previously described, and particularly materials derived by the sulfation of castor oil, or by the sulfonation of oleic' acid, inpresence of a molecular amount of naphthalene, so as to produce sulfo-naphthaiene stearic acid, or for the neutralization of propylated or amylated naphthalene sulfonic acids, or for the neutralization of oxalated, phthalated, succinated or maleated tri-ricinolein." I, have found that if the material is used for the neutralization of products obtained by the sulfation of castor oil, that one obtains a new kind of Turkey red oil having unusual properties as a dye bath assistant and as a wetting agent or leveling agent in the textile industry. I have found that if mahogany acids of the kind derived in the refining of petroleum, as in the manufacture of white oil or medicinal oil, are neutralized with the above product, that one obtains materials of unusual value in various processes involving emulsification, such as the production of cutting oils for use in connection with lathes and the like. I have found that if sulfo-aromatic fatty acids of the kind previously referred to are neutralized with this material, that one obtains an emulsifying agent of unusual effectiveness for producing oilin-water emulsions. I have found that if monophthalated or di-phthalated ricinolein is neutralized with the above material, that one obtains a plasticizer of unusual value in the manufacture of various plastics, or in the manufacture of varnishes or lacquers derived from resinous materials or cellulose bodies. I have found that all the various materials and all the various types previously mentioned are effective in the resolution of oil field emulsions. In each instance where the high molecular weight surface-active fatty acids or its simpler salts are employed in a particular industry, one can invariably find applica- "tion of the new quaternary ammonium compounds, so as to obtain increased efliciency or reduced cost.

For purpose of simplicity, the early discussion 3 in the present instance has been limited to products derived from the simplest quaternary compounds, such as indicated by the formulas B3N[(OH)1|.D].C1 or B3N[(OH1;D].OH. It has been previously indicated that a secondary amine irived from a glycerol ether, or from a glycol ether, the residue not only would contain one 'or more hydroxyl radicals, but might also con tain an oxygen atom, due to the ether group. In such instances, the (OH) nD group might be designated as an alkylol-oxy-alkylol group.

For reasons just indicated, the quaternary ammonium compound maybe indicated as being of the type BmN[(0H)nD]1 n'-OH, in which the various characters have their previous significance, 'with the qualification that B is preferably an alkyl radical having at least two carbon atoms, and m and m represent the numerals 'i, 2 or 3, and m and m' total 4. It is possible that the radical D(OH)1:, where it appears more than one time (in other words, where m has the value of 2 or 3) may #be dissimilar. It has been previously pointed out that any suitable tertiary amine may serve, such as tertiary propyl amine, tertiary butyl amine, tertiary amyl amine, tertiary hexylamine, etc. Mixed alkyl amines, such as tertiary amines, in which the alkyl groups are dissimilar, may be employed. It has been previously indicated how the corresponding primary or secondary amines may be converted into tertiary amines having at least one alkyl group or the like. Such amines may be employed for reaction with halohydrins. It is also interesting as tri-amylamine, or two moles of pyridine, that one obtains corresponding diammonium salts, which are also valuable for neutralization of the high molecular weight surface-active materials of the kind herein described.

The properties of the acids herein described which indicates their surface activity are well known. They are apt to produce a colloidal sol, particularly if dispersed in water. They tend to adsorb at interfaces; they tend to produce froths or foams; they tend to produce emulsions; they tend to lower the surface tension of the solvent in which they are dissolved; they tend to dissolve in, be wetted by, or spread out on water. In some instances, these properties in regard to water are best observed by dissolving the material in alcohol and adding the alcohol extract to a larger volume of water. The materials tend to have a high molecular weight, etc. It is not necessary that each of the selected acids exhibit the various surface-active characteristics to the optimum degree, but all of these materials exhibit one or more of the enumerated characteristics surface-active properties to a-greater or lesser degree, or else, some other obvious surface-active property. All these materials are of the kind which are conventionally understood to'be surface-active, or have surface-active properties.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is:

1. A new composition of matter, consisting of a quaternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized by the presence of at least one hydrocarbon radical, and at least one radical selected from the class consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

2. A new composition of matter, consisting of a quaternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized by the presence of at least one aralkyl radical, and at least one radical selected from the class consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

3. A new composition of matter, consisting of a quaternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized by the presence of at least one cyclohexyl radical, and at least one radical selected from the class consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

4. A new composition of matter, consisting of a quaternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized by the presence of at least one alkyl radical, and at least one radical selected from the class consisting of alkylol-oxy-alkylol radicals and alkylol radicals.

5. A'new composition of matter, consisting of a quarternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized. by the presence of at least one alkyl radical and at least one alkylol radical.

6. A new composition of matter, consisting of a quaternary ammonium salt of a high molecular weight surface-active acid of the kind in which the substituted ammonium radical is characterized by the presence of at least one alkyl radical, said alkyl radical having at least two carbon atoms, and at least one alkylol radical.

'7. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and not having more than six carbon atoms; m and m are the numerals 1, 2 or 3, and m and m total 4; [(OH)nD] is an alkylol group, n denotes the numeral 1, 2 or 3, and O.X.T represents an oil-soluble petroleum sulfonic acid radical.

9. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and not having more than six carbon atoms; m and m are the numerals 1, 2 or 3, and m and m total 4; [(OHMD] is an alkylol group, n denotes the numeral 1, 2 or 3, and O.X.T represents an alkylated naphthalene sulfonic acid radical.

10. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and not having more than six carbon atoms; m and m are the numerals 1, 2 or 3, and m and m total 4; [(OH) 1D] is an alkylol group, n denotes the numeral 1, 2 or 3, and O.X.T represents an acid radical derived by esterfication of a hydroxylated fatty body with a dibasic carboxy acid.

11. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and not having more than six carbon atoms; m and m are the numerals 1, 2 or 3, and m and m total 4; [(H)1.D] is ar. alkylol group, n denotes the numeral 1, 2 or 3, and O.X.T represents an acid radical derived by esterification of triricinolein with a dibasic carboxy acid.

12. A new composition of matter indicated by the type formula:

in which B is an alkyl radical having at least two carbon atoms and not having more than six carbon atoms; m and m are the numerals 1, 2 or 3, and m and m total 4; [(OHMD] is an alkylol group; n denotes the numeral 1, 2 or 3, and O.X.T represents an acid radical derived by esterification of triricinolein with phthalic acid.

13. A new composition of matter indicated by the type formula:

in which B is an amyl radical; m and m are the numerals 1, 2 or 3, and m and m total 4; HOHMD] is an aikylol group; n denotes the numeral 1, 2 or 3, and O.X.T represents an acid radical derived by esterification of triricinolein with phthalic acid.

14. A new composition of matter indicated by the type formula:

in which Bis an amyl radical; m is the numeral 3 a and m is the numeral 1; [(OH) "D1 is an alkylol group; n denotes the numeral 1, 2 or 3, and O.X.T

represents an acid radical derived by esterification of triricinolein with phthalic acid.

15. A new composition of matter indicated by the type formula:

in which B is an amyl radical; m is the numeral 3 and m is the numeral 1; [(OH)nD] is the C3H5 (OH)2 radical; n denotes the numeral 1, 2 or 3, and O.X.'I represents an acid radical derived by esterification of triricinoiein with phthalic acid.

MELVIN DE GROO'IE.