Nitrogen-containing organic compounds

Patented Sept. 6,1938

2,129,264

UNITED STATES PATENT OFFICE

2,129,264

NITROGEN-CONTAINING ORGANIC COMPOUNDS

Frederick Baxter Downing, Carneys Point, and Frank Willard Johnson, Penns Grove, N. J., assignors to E. I. da Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware

No Drawing. Application March 29, 1935, Serial No. 13,664

Claims. (CL 260—501)

This invention relates to new quaternary ammonium compounds, and more particularly refers to pentavalent nitrogen compounds wherein four· of the nitrogen valences are connected to sub5 stituent groups through carbon, and wherein the fifth nitrogen valence is connected to an anion or is connected through oxygen to one of the other substituent groups.

It is an object of this invention to produce an 10 entirely new class of quaternary ammonium derivatives. A further object is to produce pentavalent nitrogen compounds, many of which may be converted to their inner salts or anhydrides. A still further object is to produce a 15 class of compounds which is related to betaine, but which differs therefrom in a manner to be described hereafter. A still further object is to produce wetting, detergent, emulsifying and dispersing agents. A still further object is to pro20 duce surface active materials which are particularly adapted for the production of self-emulsifying oils, etc. A still further object is to produce compounds which may be used in place of or in admixture with soap and soap-like products in 25 the various processes wherein such products have previously been used or are capable of use. Additional objects will become apparent from a consideration of the following description and claims.

These objects are attained according to the 30 herein described invention wherein nitrogenous compounds are reacted with hydrocarbon derivatives in order to produce pentavalent nitrogen compounds, four of the nitrogen valences of which are bound to substituent groups through carbon, 35 and wherein one of the substituent groups contains at least six carbon atoms. In a more limited sense this invention pertains to pentavalent nitrogen compounds having the following general formula:

⁴⁰ Ri Rj

Ri-N—R<

wherein X represents a non-hydrocarbon radical such as a halogen or hydroxyl group, Ri represents a hydrocarbon radical containing at least six carbon atoms, and R2, R3 and R4 represent hydrocarbon-containing substituents which are con50 nected to the nitrogen atom through carbon, at least one of the substituents (Ri—R2—Ra—R4) being further substituted by at least one non-hydrocarbon radical. A non-hydrocarbon radical may be defined as a group which is not entirely 56 composed of hydrogen and carbon atoms, as, for example, hydroxyl, halogen, amino, carboxyl, sulfonic acid, etc., groups.

In its preferred embodiment this invention pertains to quaternary ammonium salts having the following general formula: 6

Rs Rs Ri—N—R₍i wherein X represents a halogen group, Ri represents an aliphatic hydrocarbon radical containing from twelve to eighteen carbon atoms, R2, R3 and R« represent aliphatic hydrocarbon radicals each of which contains less than eight carbon atoms, and in addition, at least one of the groups represented by Ri, R2, R3 and R4 has substituted thereon at least one group containing an acid hydrogen or a derivative thereof, particularly a single carboxyl or sulfonic acid group. „θ This preferred embodiment is also intended to embrace inner salts or anhydrides of the aforementioned compounds wherein the halogen atom is removed from the nitrogen nucleus and wherein the hydrogen atom or its equivalent is removed from the salt-forming substituent, the resuiting compounds having a nitrogen nucleus bound through oxygen to one of the substituents represented by Ri, R2, R3 and Ra.

The invention may be more readily understood __ by a consideration of the following illustrative examples, in which the quantities are stated in parts by weight:

Example 1

Into a pressure vessel provided with brine cool- 35 ing were charged 300 parts by weight of liquid trimethylamine. To this were added 50 parts of alpha brom stearic acid (prepared as described by C. Hell and J. Sadomsky, Ber. 24,2391 (1891)), and the vessel was closed and warmed to about 40 40° C. The brom stearic acid first dissolved in the trimethylamine and then as the quaternary ammonium derivative was formed, a solid deposits. The exact temperature was not important, the reaction proceeding more rapidly with increased 46 temperature but at high temperatures decomposition of the product sets in. When the reaction had proceeded as far as it would, as indicated by the fact that no more solid was formed and that a representative sample showed no further In- 60 crease in ionizable bromine, the trimethylamine was distilled off. This product may be used as such in certain applications but in general it was preferable to dissolve it in about 100 parts of warm alcohol and then add 5.5 parts of sodium 55

2,128,264 hydroxide dissolved in 100 parts of alcohol. The alcohol and trimethylamine were then distilled off. The product may be freed from sodium bromide by dissolving in a suitable solvent such 5 as dry benzene and filtering.

A solution of this material in water, containing 0.075% of the active ingredient, showed remarkable detergent power in the washing of badly soiled mixed wool and cotton fabric. It was par10 ticularly valuable for this purpose because of its insensitivity toward hard water. Excellent emulsions can be prepared by the use of one or two per cent of this material based on the weight of the dispersed phase.

1® Example 2

A mixture of 50 parts by weight of alpha brom stearic acid and 35 parts of dimethyl cyclohexylamine was warmed gently until a clear liquid was ₂θ obtained. This was maintained at 60° until no further increase in ionizable bromine occurred. The product was dissolved in 150 parts alcohol and a solution of 5.5 parts of sodium hydroxide in 100 parts of alcohol was added. The alcohol and amine were removed at 50° under reduced pressure.

Example 3

757 parts of octadecylene chlorsulfonate (obtained, for example, by addition of chlorsulfonic 30 acid to octadecylene) were added to 4500 parts of liquid trimethylamine, cooled to prevent loss of the latter. The mixture was kept under pressure at 30-50° until no more solid was deposited. The amine was evaporated and the product dis35 solved in 1000 parts of alcohol. A solution of 50 parts of sodium in 1000 parts of alcohol was then added and the sodium chloride Altered out. The alcohol was removed under reduced pressure.

Example 4 ⁴⁰ A mixture of 95 parts sodium chloracetate, 297 parts of dimethyl octadecylamine and 5000 parts of alcohol was kept at 40-50° for 12 hours and the temperature then raised to 70-80° until the reaction was complete as shown by the fact that ⁴⁰ a sample was wholly soluble in dilute alkali. The product was Altered and the alcohol removed under reduced pressure.

Example 5

To a solution of 757 parts of octadecylene chlorsulfonate in 2500 parts of ethylene dichloride were added 750 parts of triethanolamine. The mixture was maintained at 60-70° for 48 hours and 1500 parts of alcohol were added. Hydrogen 55 chloride was then passed through the mixture until in excess to precipitate the excess triethanolamine. The hydrochloride was Altered out and ' the excess hydrogen chloride removed under reduced pressure. The alcohol may be removed 60 under reduced pressure and the product used as it is or it may be neutralized to Brilliant Yellow before drying.

Example 6 »- A mixture of 211 parts of brom ethane sodium sulfonate and 297 parts of dimethyl octadecylamine in 5000 parts of alcohol was heated at 70° until no further increase in ionizable halogen occurred. The product was Altered and the alcohoi removed under reduced pressure.

Example 7

21.8 parts of ethylene chlorhydrine (10% excess) and 31 parts of “lorol” dimethylamine were heated together under an air condenser at 95-100° 75 C. for 24 hours or until a test drop showed com plete solubility in water. (Note: By “lorol” Is meant a mixture of C10, C12, Cm, Cie and Cie carbon length chains with the C12 chain predominating. The “lorol” dimethylamine was made from lorol chloride and dimethylamine.) The 5 product, the quaternary ammonium salt of “lorol” dimethylamine and ethylene chlorhydrine, was a white waxy solid and had the following formula:

ci “Lorol”—N—CH,CHaOH CHj ^CHa

In place of relatively dry ethylene chlorhydrine, an equeous solution of ethylene chlorhydrine has been found to work equally well. 15

In place of the “lorol” dimethylamine, 39 parts of “stenyl” dimethylamine have been used. (Note: By “stenyl” is meant a mixture of essentially Cie and Cie carbon length chains with some C12, Cm and C20 carbon length chains also being present. ²® The “stenyl” dimethylamine was made from “stenyl” chloride and dimethylamine.) In this case the mixture was heated at 125-150° c. for 16 hours to effect complete solubility in water. The product of this reaction was the quaternary ²⁵ammonium salt of “stenyl” dimethylamine and ethylene chlorhydrine.

In place of “lorol” dimethylamine, 42 parts of octadecyl dimethylamine have been used. In this case, the mixture was heated at 120-135° c. for ³⁰20 hours to effect complete solubility in water. This gave as a product the quaternary ammonium salt of octadecyl dimethylamine and ethylene chlorhydrine. The “stenyl” and octadecyl derivatives possessed properties which were similar ³⁵to those of the “lorol” derivative.

Example 8

100 parts of “stenyl” dimethylamine (see Ex- _4nample 7) and 42 parts of glycerol-mono-chlorhy- ^4υdrine (10% excess) were heated under an air condenser at 140-155° C. for 12 hours or until a test drop showed complete solubility in water. This reaction gave the quaternary ammonium salt of “stenyl” dimethylamine and mono-chlor- ⁴⁵hydrine, a waxy solid and had the formula:

ci “Stenyl”—N—CH2CHOHCH2OH

CEi \hi ⁵⁰

In place of glycerol-mono-chlorhydrine, 25 parts of glycerol-di-chlorhydrine (10% excess) has been used. The product, the di-quaternary ammonium salt of “stenyl” dimethylamine and 55 glycerol-di-chlorhydrine, a waxy solid, has the formula:

“Stenyl”—N—CH2CHOHCH2—N—Stenyl”

CHa ^CHa CHa '''''CHa ₆₀

Alsu in place of glycerol-mono-chlorhydrine, 35 parts of epichlorhydrine (10% excess) has been used. The reaction was exothermic but was heated at 145—155° C. for 7 hours. The product, the quaternary ammonium salt of “stenyl” di- ⁶⁵methylamine and epichlorhydrine, a semi-hard waxy solid, has the formula:

Cl j—0—1

Stenyl—N—CHaCH CHj 70

CHa ^CHa

The quaternary ammonium compounds in Examples 7 and 8 that possess an hydroxyl group in a side chain may be sulfated with the usual re- 75

8,188,864 agents to give detergent bodies of interest and for other uses as surface active bodies.

Example 9 parts of hexadecyl bromide and 86 parts of “stenyl” dimethylamine (see Example 7) were heated under an air condenser at 125-150° C. for 7 hours. The product, the quaternary ammonium salt of “stenyl” dimethylamine and hexadecyl bromide, was a semi-hard waxy solid, and had the formula:

Br

Stenyl—N—ChHm CHi ^CHs

In place of hexadecyl bromide, 83 parts of “stenyl” chloride or 97 parts of “stenyl” bromide or 111 parts of “stenyl” iodide have each been heated with 86 parts of “stenyl” dimethylamine at temperatures of 95-175° C. for 12 to 24 hours to form the corresponding quaternary ammonium salts. They were all waxy solids.

Example 10 parts of “stenyl” dimethylamine (see Example 7) and 45 parts of chlorpropanol sulfonate sodium salt in 100 parts of water were refluxed for 6 hours or until the amine has gone completely into solution. The aqueous solution of the product was almost water white.

It is to be understood that the aforementioned examples are illustrative merely of a representative few of the many means of carrying into practical operation the present invention. The processes utilized, the reactants entering into such processes, the proportions of reactants, and the conditions of reaction, may be varied widely without departing from the scope of this invention. In general, it may be stated that the desired pentavalent compounds may conveniently be obtained by reacting a tertiary amine with a hydrocarbon· containing a replaceable anion. Where one of the substituents also contains an acid hydrogen or a derivative thereof the resulting pentavalent nitrogen'compounds may ordinarily be converted to inner salts or anhydrides, for example, by treatment with an alkali.

The majority of compounds comprised within the scope of this Invention, in their uncondensed form, may be represented by the following general formula:

wherein X represents a non-hydrocarbon radical such as chlorine, bromine, iodine or hydroxyl groups, and Ri, Rs, Rs and R4 represent hydrocarbon groups or derivatives thereof connected to the nitrogen nucleus through carbon, at least one of said groups containing at least six carbon atoms. One or more of the aforementioned hydrocarbon groups may have substituted thereon one or more non-hydrocarbon radicals, as, for instance, hydroxyl, halogen, amino, benzoylamino, trifluormethyl, carboxyl, acetyl, borate, alkoxy, sulfonic acid, sulfuric acid, phosphoric acid, etc. groups. The hydrocarbon radicals represented by Ri, Rs, R3 and R« may be of open chain or cyclic derivation and may be saturated or unsaturated. For example, they may be derived from hydrocarbons of the aliphatic, aralkyl, aromatic, or cycloaliphatic series. A few of the radicals coming within this category are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, amyl, hexyl, octyl, decyl, lauryl, myristyl, cetyl, stearyl, oleyl, rlcinoleyl, linoleyl, —CH1CH1OH, — CH1CHCH,, —OHjCHOHC&OH, —CHjCHt-OSOjNa, - CHjCHOHCHiSOiNa, —CHiCHOHCHiOSOiNa, —CHiCHOHCHi—if—Bi. R / ^Xr>

The aforementioned and related groups may be used as such, or may be further substituted with non-hydrocarbon radicals such as those mentioned previously, substitution taking place either before or after preparation of the quaternary ammonium compounds. Moreover, these radicals may be externally joined in such manner that the nitrogen nucleus becomes an integral portion of a heterocyclic ring. In other words, the nitrogen nucleus may be a component of a heterocyclic compound of the pyridine, piperi- ₂θ dine, quinoline, acridine, etc. series. It is to be understood that the aforementioned hydrocarbon radicals or derivatives thereof may be the same or dissimilar to one another, and one or more should contain at least six carbon atoms. „_g

Since this invention is particularly directed to compounds of the betaine type it is to be understood that the following instructions which pertain to such compounds are the preferred embodiment thereof. As is well known, betaine ₃₀is a trimethyl-amino-acetic acid inner salt. It has the following configuration:

CHs

N-CHj ³⁵ \lo .

In accordance with the present Invention it has been found that an entirely new class of com- ._ pounds may be obtained by substituting for a hydrogen atom of the CH2 group or for the CHa group itself, in the above identified betaine formula, a hydrocarbon group or derivative containing at least six and preferably from twelve to eighteen carbon atoms. It is also contemplated that the aforementioned higher hydrocarbon group may be substituted for one or more of the methyl groups, rather than for the CHs group. Furthermore, in place of one or more of the methyl groups, shown in said formula, other sub- ⁵⁰stituents, as, for instance, other alkyl groups or aralkyl, aryl or cycloaliphatic groups may be substituted. In the same manner, the nitrogen nucleus may form an integral part of a heterocyclic ring, such as a pyridine or piperidine ring. Like- ⁸⁵wise, the carbonyl group may be the residue of other salt-forming groups than the carboxyl group. For instance, it may be the residue of a sulfonic acid, a sulfuric acid ester, a phosphoric „θ acid or a phosphoric acid ester group. This carbonyl group, or other salt-forming group, may, moreover, be substituted on some other substituent of the compound rather than upon the substituent which contains, or is, a long chain hydrocarbon group. In other words, the salt-forming ⁰⁸group may be substituted on one of the methyl groups, referred to in the above formula, or it may be substituted on the group which replaces such methyl group or which Is substituted thereon. The aforementioned compounds are herein ⁷⁰designated as inner salts or anhydrides. It should be borne in mind, however, that the quaternary ammonium derivatives which give rise to such inner salts or anhydrides are themselves of considerable merit in the industrial arts. ⁷⁵

2,128,264 “Betaine type” compounds referred to herein may conveniently be produced by reacting a hydrocarbon derivative of at least six carbon atoms, which in addition contains both an acid hydro5 gen or its equivalent and a replaceable anion, with a tertiary amine. Hydrocarbon derivatives which are well adapted for use in this connection may be obtained from a variety of compounds, both naturally occurring and synthetic, 10 for example, from petroleum or vegetable and animal oils, fats and waxes. Such derivatives, as is clear from the preceding description, are’ higher hydrocarbons which preferably contain from twelve to eighteen carbon atoms. Hydro15 carbons of open chain series, and in particular straight chain hydrocarbons, are of optimum value for use herein under a wide variety of conditions. These hydrocarbons may be derived from heptane, octadecane, octane, decane, tetra20 decane, hexadecane, dodecane and the intermediate homologues thereof. Moreover, they may be unsaturate members of the aforementioned series, such as hexylene, octylene, decylene, tetradecylene, dodecylene, hexadecylene, octadecylene 25 and didecylene, etc. Salt-forming groups which may be substituted thereon prior to use herein are, for example, carboxyl, sulfonic acid, sulfuric acid ester, phosphoric acid, phosphoric acid ester, and the like. Replaceable anions which may 30 also be substituted thereon prior to use heroin are acid residues such as chlorine, bromine, and the like.

Tertiary amines with which the hydrocarbon derivatives described supra may be reacted are 35 exceedingly great in number, and since they are well known no attempt will be made herein to describe them in detail. For purposes of illustration, however, reference may be made to amines such as trimethylamine, trialkylamines 40 generally, cyclohexyl dimethylamines, dialkylcyclohexylamine generally, dicyclohexyl alkylamines, ethanol dialkylamines generally, tertiary amines containing one to three alkylol groups, triethanolamine, pyridine, alkyl piperi45 dine, alkylol piperidine, etc. It is to be understood that these tertiary amines may contain additional non-hydrocarbon radicals. As such radicals are well known and have been referred to herein previously, they need not be further 50 described.

Quaternary ammonium compounds formed by reacting the above described higher hydrocarbon derivatives with the described tertiary amines may be used as such, or may be converted into 55 their inner salts or anhydrides, these latter compounds being of the betaine type. The examples hereof describe several methods of converting the quaternary ammonium compounds to derivatives of the betaine type. Such methods briefly com60 prise treating the quaternary ammonium compounds with an alkali. This treatment probably results in the removal of the anion from the nitrogen nucleus, and removal of acid hydrogen from the salt-forming group. The resulting com65 pound has the nitrogen group bound through the oxygen of the salt-forming group to the higher hydrocarbon substituent. In its secondary embodiment it is contemplated that the saltforming group or substituent containing an acid 70 hydrogen may be present on a lower hydrocar„ bon radical.

The aforementioned quaternary ammonium compounds may likewise be formed by alkylation, aralkylation or similar treatment of an 75 amino fatty acid. In place of the amino fatty acid other amino compounds containing a saltforming group might be substituted. Moreover, an unsaturated tertiary amine might be reacted in known manner to add on a salt-forming group, for example, by treating with cold con- r centrated sulfuric acid.

Quaternary ammonium compounds made in accordance with the instructions just referred to as preferred may for the most part be designated by the following general formula:

Ri—N—R_f

I X wherein X represents an anion, preferably chlo- 15 nne or bromine; Ri represents an aliphatic hydrocarbon radical containing at least six carbon atoms, preferably a straight chain aliphatic hydrocarbon radical containing from twelve to eighteen carbon atoms, and also containing a 20 salt-forming group, preferably carboxylic or sulfonic acid; R2, R3, and R$ represent hydrocarbon radicals, preferably aliphatic hydrocarbon radicals containing less than eight carbon atoms

As previously mentioned, instead of substitut- 25 mg the salt-forming group upon the radical represented by Ri in the above formula it may be substituted upon one of the radicals represented ^by ^³. R·⁴' same manner, the following instructions with respect to inner salts 30 or anhydrides may be varied by attaching the residue of the salt-forming group, represented by ~^Y · ^{to one} °f the radicals represented by Ra R3 and R4.

Inner salts or anhydrides of the aforemen- 35 tioned preferred quaternary ammonium compounds, in general, conform to the following illustrative formula:

Rj Rj

1—0 wherein Ri represents the residue of a higher hydrocarbon radical which contains at least six carbon atoms and is preferably an aliphatic hydrocarbon radical containing from twelve to eighteen ’ carbon atoms; Rz, R3 and R4 represent hydrocarbon radicals, preferably aliphatic hydrocarbon radicals of less than eight carbon atoms; Y represents the residue of a salt-forming group nreferably CO or SO2. In this formula Ri, r₂ R₃⁵⁰and/or R4 may be further substituted by nonhydrocarbon radicals. Each of the aforementioned substituents represented by R is connected ^the “^trogen nucleus through a carbon atom.

Where these compounds are to be used as sub- ⁵⁵statutes for soap and soap-like products it is usually advisable to have the salt-forming group and the pentavalent nitrogen atom quite close together. In other words, they should preferably _anbe separated by no more than about four carbon ⁶QrAYVIC **

It is contemplated that the compounds described herein may be made by various additional processes. For example, a refined petroleum fraction may be chlorinated and converted to a ⁶⁵tertiary amine. This amine, which contains a long hydrocarbon radical, may then be converted to a quaternary ammonium compound by reaction with a chlorinated hydrocarbon containing an acid hydrogen, such as a halogen acid. The ‘° resulting compound may, if desired, be converted to an inner salt by treatment with an alkali. The position of the carboxyl, or other group containing an acid hydrogen, in the halogen acid ₇₆

9,129,264 determines its position in the resulting product, whether alpha-, beta-, gamma-, etc.

Another illustrative method of obtaining these compounds is to oxidize a refined petroleum 5 fraction to the acid. This acid is then halogenated and converted to a quaternary ammonium salt by reaction with a tertiary amine. The resulting product may, if desired, be converted to an inner salt by treatment with sodium hydrox10 ide. While petroleum from practically any source may be used herein it is ordinarily advisable to select an oil predominating in paraffin hydrocarbons. It is to be understood, however, that naphthenic and asphaltic base oils are also suit15 able for use herein.

a representative few of the many “betainetype” compounds which may be made in accordance with the instructions given supra are:

1. Alpha-betaines:

(a) N-stenyl-alpha-betaine

CuHn (CH_s)_J=N-CH_i-C=O J—o--125 (b) N-lorol-alpha-betaine

CuHu (ΟΗί)ί=Ν—CHt-C=O J---o---* „_n (c) N-stenyl-methyl-alpha-betalne ⁰⁰ Ci«Ha OH>

(ch»)2=n—in—c=o

L—o—। (d) N-distenyl-alpha-betaine

CHs ( C1 sHs?) f=N— C Hr— C=O I—o—I

2. Beta-betaines:

(a) N-stenyl-beta-betaine-sulfate

Inner salt of N-stenyl-choline-sulfate (0H_!)f=N—CHi— CHr-O— S Oj ⁴⁰ (b) N-lorol-beta-betaine-sulfate

Inner salt of N-stenyl-choline-sulfate

CiaHis (CH₃)i=A—CHj—CHi—O—S Os

1------O-------1 (c) N-stenyl-beta-betaine

C18HS7 (OHa)a=N-—CHr-CHr-C=O v

3. Gamma-betaines:

(a) N-stenyl-beta-hydroxy-gamma-betaine-i sulfonate

CisHjt

CO (CHs)s=l!r—CHs-CHOH—CHs-SOs

I-------------------------o---------.1 (b) N-stenyl-beta-hydroxy-gaxnma-betainesulfate

CuHss

G5| (CHs)s=N—CHs-CHOH—CHs—O—S Os

I----------------o-1

In one of its secondary embodiments this invention is concerned with the production of non70 condensed or uncondensible compounds having the following general formula:

Ri Rs

R1-N-R4 wherein X represents a non-hydrocarbon radical such as hydroxyl, chlorine, bromine or iodine groups, Ri represents a hydrocarbon radical of at least six carbon atoms, and Ra, Rs and B* represent hydrocarbon radicals having one or more carbon atoms present therein. The radicals represented by R may be unsubstituted, or one or more of them may contain one or more nonhydrocarbon substituents in accordance with the preceding instructions. These radicals may be of open chain or cyclic character, and may be saturated or unsaturated. For example, Rs, Rs and Ri may each represent methyl or ethyl groups or higher alkyl groups, Ri may represent a hexyl, octyl, decyl, lauryl or myristyl group, and X may represent a hydroxyl, chlorine, bromine or iodine group. Compounds of this type are of considerable value for use as wetting agents, particularly when Ri represents the lower alkyl groups specified. If these compounds are to be used as detergents it is advisable to substitute groups such as stearyl, oleyl and higher members of the same series for Ri, the remainder of the molecule being the same as before. The substitution of nonhydrocarbon radicals upon one or more of the substituents designated by R is also contemplated, substituents such as hydroxyl, halogen, ether and ester groups being quite satisfactory.

Quaternary ammonium salts described herein, and their described derivatives are capable of use for innumerable purposes. One of their chief uses is for wetting, detergent, emulsifying and dispersing purposes. In this connection it may be stated that they are capable of use either in admixture with one another and/or in admixture with soap or soap-like products for utilization in all the processes where soap or soap-like products have heretofore been used or are capable of use. A relative few of these uses will now be given merely for purposes of illustration:

A. Treatment for the processing and improvement of natural or synthetic textile materials involving:

Cleansing vegetable and animal fibers when removing fatty or oily materials.

Carbonization.

As an addition to flax retting baths.

Fulling.

Sizing.

As an addition when sizing is removed from textile materials.

Impregnating.

Bleaching.

Mordanting.

As an addition to soap in an acid or hard water bath.

Mercerizing lye liquors.

Improvement of absorption capability of fibrous materials particularly when subjected to a treatment for finishing, softening, stiffening, coloring or special chemical treatment such as waterproofing or mildewprooflng.

Delustering or lustering.

Degumming.

Kier boiling.

Scouring.

Stripping.

Felting.

Oiling or lubricating.

Weighting or loading.

2,129,264

B. Dyeing processes:

Dyeing in neutral, acid or alkaline baths.

Reserving cotton in acid baths.

Dyeing with developed dyes.

4 Dyeing of animal fibers with vat dyes.

Dyeing cellulose acetate fibers with Insoluble dyes.

Dyeing and printing with aniline black. • 7 Dyeing of leather.

8 In printing pastes to assist in the dispersion of the dye or dye component and in the penetration into the natural or synthetic fiber.

C. Dyes and coloring material:

1 For making pastes of dyes or dye components.

For the production of pigments of azo, basic, acid, vat, and sulfur dyes in a finely divided condition.

3 For the production of finely divided inorganic pigments.

D. Miscellaneous uses:

For converting liquid or solid substances normally insoluble in water, such as 25 hydrocarbons, higher alcohols, other oxygen containing compounds, fats, oils, waxes, resins, pitches and pitchy substances into clear solutions or stable emulsions or dispersions.

2 As cleansing agents particularly in hard water and where a fatty or oily film resists the ordinary cleansing media.

In tanning.

In softening and treating baths for hides 35 and skins, particularly the fat liquor treatment.

In flotation processes including minerals and oils such as the recovery of fixed oil from the oil sands.

E. General:

The reagents may be used in pure or standardized form.

May be used in conjunction with the known processing or treating agents.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not lim₅₀ ited to the specific embodiments thereof except as defined in the appended claims.