US2169976A - Process of producing assistants in the textile and related industries - Google Patents

Process of producing assistants in the textile and related industries Download PDF

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US2169976A
US2169976A US2224A US222435A US2169976A US 2169976 A US2169976 A US 2169976A US 2224 A US2224 A US 2224A US 222435 A US222435 A US 222435A US 2169976 A US2169976 A US 2169976A
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parts
product
amines
oxidation
aliphatic
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Guenther Fritz
Saftien Karl
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IG Farbenindustrie AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

Definitions

  • Patented Aim. i5 193% STATES Fritz (member and Karl Saftien. Ludwigshaienon-the-Rhine, Germany, asslgnors to I. G. Farb'enind'ustrie Aktlenge'sellschaft, Frankfort-onthe-Main,
  • the present invention relates to' new assistants in the textile and related industries especially wetting, cleansing, dispersing and like nts and a process for producing same.
  • organic compounds which contain in the molecule at least one nitro en atom, at least two organic radicles directly attached to said nitrogen atom, in which the said nitrogen atom is present in a higher oxidation stage than in organic ammonia substances" and which contain at least one aliphatic (i. e, open chain aliphatic or cycloaliphatic) radicle with at least 8 carbon atoms, are valuable assistants in the textile and related industries, especially wetting, cleansing, dispersing and like agents.
  • organic ammonia substances is intended to mean for the purposes of the present invention amines and ammonium compounds containing organic radicles including quaternary ammonium compounds.
  • Wetting, cleansing, dispersing andv like agents of the kind defined above can be obtained by treating amines containing at most one hydrogen atom directly attached to nitrogen with oxidizing agents, while taking care that no degradation of the amines but a combination of oxygen on the amino nitrogen atom takes place and introducing at any time an aliphatic radicle with at least 8 carbon atoms.
  • the introduction of the latter may either consist in selecting such amines as already contain such a radicle or, if this is not the case, by reacting the amine before or after the oxidation with a compound capable of introducing an aliphatic radicle of the said kind. If desired, further radicles of any desired kind may be introduced.
  • R K R -N 0, or N-OH (Amineoxide ioi'm) (Hydroxylamine form)
  • Open chain aliphatic or cycloaliph'aticradicles suitable for the purposes of the present invention are for example those of lauric, stearic, palmitic, oleic and rici'noleic acids, the hydrocarbon radicles corresponding to the montanic acids, resinic and naphthenic acids and to the alcohols and carboxylic acids obtainable by the oxidation of paraffin wax.
  • the term is intended to include radicles of hydrogenated aromatic hydrocarbons of high molecular weight, as for example decahydronaphthalene.
  • aliphatic radicals as employed in the claims covers both open chain aliphatlc radicals and cyclo-aliphatic radicals and radicals in which 2 open ch'ain radicals are joined. together as for example in compounds of, the type obtained when a piperidine compound is employed as the amine.
  • the said organic radicles containing at least eight carbon atoms are connected to a. nitrogen atom either directly or by means of other atoms or atomic groups, such as oxygen atoms or sulphur atoms or carbonyl, carboxylic acid ester, carboxylic acid amide, sulphonic or sulphonamide groups, or of organic rings.
  • the chains of radicles of high molecular weight may also be'interrupted by one or more of the said atoms or atomic groups.
  • Secondary and tertiary amines suitable as initial materials are for example octyl propylamine, cetyl butylamine, dodecyl naphthylamine, decyl dimethylamine, dodecyl dimethylamine, hexadecyl diethylamine, oleyl dimethylamine, and amines obtainable by the reaction of primary or secondary amines of low molecular weight with higher molecular halogen-parafiin hydrocarbons.
  • Suitable amines are N-dimethyldecahydronaphthylamine,N-dodecylethylaniline, N-octylpiperidine, N-dialkylethylenediamines which are acylated on one side by fatty acid radicles of high molecular weight, the dodecyl ether of para-dimethylaminephenol, the dodecyl ester of N-dimethylaminoethyl alcohol, N-monomethyl-C-dodecylaniline, N-dimethyl-C-dodecylaniline and the cetyl amide of dimethylamlnoacetic acid.
  • Amines of the said kind which contain any desired substituents, as for example halogen atoms, hydroxy, carboxyl, ester, ether,
  • the said amines may be subjected to the oxidizing treatment alone or in admixture with each other.
  • oxidizing agents may be employed, as for example hydrogen peroxide, sodium peroxide, permoncsulphurlc acid, benzoyl peroxide, sodium hypochlorite and oxygen or mixtures containing oxygen or other gas mixtures having an oxidizing action preferably in the presence of oxidizing catalysts, the oxidation is advantageously carried out in aqueous solution or suspension and/or while employing organic solvents or diluents, such as ethyl alcohol, acetone or benzene, at ordinary or elevated temperature, advantageously between 0 and 100 C. or between 20 and 100 C.
  • the resulting oxidation product contains only two' organic radicles attached to nitrogen it is advantageous to introduce further organic radicles; this may be efl'ected in known manner by alkylation, arylation or aralkylation.
  • the oxidation product of dodecylmethylamine may be converted into an oxidation product of a tertiary amine by treatment with benzyl chloride or an alkyl iodide.
  • the compounds thus obtainable which contain halogen may be converted into the corresponding amine oxides by means of silver oxide; if instead of the alkyliodides alkyl sulphates are employed, the conversion into the amine oxides may be effected by means of barium hydroxide.
  • the amines em-' ployed as initial materials contain no aliphatic or cycloaliphatic radicles containing at least eight carbon atoms. It is preferable during the conversion of the oxidation product into the oxidation product of a tertiary amine to introduce into the molecule a radicle of high molecular weight.
  • the oxidation product of dimethylamine may be converted by reaction with cetyl iodide into an oxidation product of a weight into oxidation products of tertiary amines,
  • the latter or oxidation products of tertiary amines of low molecular weight being then directly condensed with correspoding compounds of high molecular weight.
  • the oxidation products it is advantageous for the oxidation products to contain atoms or atomic groups which permit of a subsequent introduction of aliphatic or cycloaliphatic radicles of high molecular weight;
  • a secondary amine of low molecular weight may be'caused to react with chloracetic acid; then before or after the oxidation an aliphatic radicle of high molecular weight may be introduced into the carboxylic acid group contained in the reaction product, for example by esteriilcation.
  • the oxidation product of dimethylglycine may be caused to react for example with dodecylamine.
  • Oxidation products of tertiary amines of low molecular weight which contain no reactive atoms or atomic groups in the organic radicles are also suitable for the preparation of the said compounds.
  • the introduction of aliphatic radicles of high molecular weightv (R4) may be effected by adding organic compounds R4X (wherein X may be OH or the radicle of any acid such as Cl, -HSO4, CH3.COO and the like) on the amineoxide, the double bond between the oxygen atom and the nitrogen atom being removed in the said reaction.
  • R4X organic compounds
  • X may be OH or the radicle of any acid such as Cl, -HSO4, CH3.COO and the like
  • the addition of a high molecular alkylhalide on a tertiary alkylamine oxide proceeds according to the following equation.
  • the oxidation product of trimethylamine may be converted into a product of the desired kind by reaction with dodecyl iodide.
  • the introduction of the radicles of high molecular weight or the conversion of secondary amines into tertiary amines and the oxidation may thus be carried out in any desired sequence. It is immaterial in what manner the oxidation products of the amines are prepared.
  • the oxidation products of secondary amines obtainable by the action of metallo-organic compounds on nitroparaflln hydrocarbons may be converted into oxidation products of tertiary amines containing radicles of high molecular weight according to this invention.
  • organic radicles as for example by the action of alkylene oxides or by reaction with diazomethane, into oxidation products of tertiary amines already containing aliphatic radicles of high molecular weight is advantageous in many cases.
  • organic radicles of low molecular weight in the oxidation products may be replaced with advantage by radicles of high molecular weight, as for example by replacing carbomethoxy groups by carbonamido groups of high molecular weight.
  • Oxida tion products of primary and secondary amines substituted by halogen, nitro, sulphonic, carboxylic and amino groups may also be obtained according to this invention by introducing such atoms or atomic groups into the initial materials or subsequently into the reaction products.
  • the products obtainable according to this invention have a high solubility in neutral and alkaline baths. Their basicity is less as compared with the initial materials so that they may be employed for purposes for which the amines themselves are unsuitable by reason of their strongly basic properties. For the greater part they are, however, still capable of forming watersoluble salts with inorganic or organic acids, and these salts may frequently be employed for the same purposes as the oxidation products themselves.
  • the aqueous solutions of the products have a high stability to acids, alkalies and salts and are furthermore stable to the sub stances forming the hardness in water.
  • the products may be employed with great advantage as wetting, washing, cleansing and dispersing agents in the textile, leather, paper and other industries. They are especially suitable as additions to any dyebath in which they frequently effect an increase in the solubility or dispersion of the dyestuif and a thorough dyeing and levelling. Eventhe undesirable precipitation of calcium salts when employing hard water is to a great extent suppressed by reason of the high protective colloid action of the products.
  • the said products may also be employed with advantage for stripping and after-seeping and for improving the iastness to rubbing of many dyeings. They are also suitable as additions to printing pastes and as preserving agents and also as valuable additions to mercerizing and bucking liquors and as softening agents for textile materials.
  • the said products may also be employed with advantage as substitutes for soaps; in the presence of soaps they prevent the precipitation of calcium soaps to a large extent when using hard water by reason of their high protective colloid action.
  • the products may be employed alone, in admixture with each other or together with other usual wetting, washing, dispersing and like agents, as for example Turkey red oil, sulphuric acid esters of aliphatic alcohols of high molecular weight, true sulphonic acids of aliphatic or aromatic compounds of high molecular weight, as for example reaction products of fatty acids with hydroxyalkyl or aminoalkyl sulphonic acids.
  • solvents such as carbon tetrachloride, cyclohexanol, or benzyl alcohol
  • salts as for example Glauber's salt, perborates, waterglass, or with protective colloids, such as glue, gelatine, or dextrlne.
  • Example 1 21 parts of dimethyidodecylamine are dissolved in 120 parts of ethyl alcohol and heated for nine hours at about 60 C. after the addition of 60 parts of 6 per cent hydrogen peroxide: A solution, capable of dilution with water to give a clear solution, is obtained from which the oxidation product formed may beisolated in solid form by evaporation.
  • the product dissolves very readily in water; the aqueous solution has, inter alia, an excellent wetting, foaming and washing power; it has a practically neutral reaction.
  • Example 2 60 parts of 6 percent hydrogen peroxide are added to a solution of 30 parts of cetyldiethylamide in 350 parts of of ethyl alcohol and the whole heated for ten hours at about 60 C. After evaporation of the solution, the oxidation product may be obtained in solid form. It has properties similar to those of the product obtainable according to Example 1.
  • Example 3 30 parts of 6 per cent hydrogen peroxide are added to a solution of 92 parts of decyldimethylamine in 600 parts of ethyl alcohol and the whole is heated for several hours to about 60 C.
  • Example 4 12 parts of 30 percent hydrogen peroxide are added to a solution of 62 parts of octodecenyldimethylamine in a mixture of 100 parts of water and 250 parts of ethyl alcohol. After heating the mass for three hours to about 60 C. another 12 parts or" hydrogen peroxide are added and the mixture is then heated to about 60 C. until the solution obtained, when diluted with water, remains clear. In the manner described above a product having good cleansing and dispersing properties is obtained. By evaporation of the water the new product may be obtained in "in anhydrous form.
  • octodecyldimethylamine or dodecyldibutylamine or chlorstearyldimethylamine (obtainable by adding hydrogen chloride on octodecenyldimethyl amine) can be converted into valuable cleansing and dispersing agents by treating with hydrogen peroxide.
  • Example 5 A mixture of 54 parts of the dodecylamide of dlmethylamino acetic acid 100 parts of water, 250 parts of ethyl alcohol and 30 parts of 30 per cent hydrogen peroxide is heated for several hours to about 60 C. In this manner a valuable wetting and cleansing agent is obtained.
  • a product having similar properties can be obtained by treating oleyl-N-diethyl-ethylenedlamine with hydrogen peroxide in the manner described above.
  • Example 6 40 parts of dodecylmonomethylamine are dissolved in 300 parts of ethyl alcohol, 125 parts of 6 per cent hydrogen peroxide are added and the mixture is heated for about 20 hours at 60 C. The ethyl alcohol and the water are evaporated at ordinary temperature in vacuo and methyldodecylhydroxylamine is obtained in the form of a slightly yellow colored oil. The product yields strongly foaming emulsions with water and possesses an excellent washing and softening power.
  • the product may be alkylated, for example by means of ethyl bromide, whereby a product is obtained which is also soluble in water and has a good washing and wetting power.
  • Example 7 20 parts of C-dodecyl-N-dimethylani1ine are dissolved in 700 parts of ethyl alcohol and the solution obtained is heated with 40 parts of 15 per cent hydrogen peroxide so that it boils slightly until a sample is clearly soluble in water. The ethyl alcohol and the water are evaporated in vacuo. The amine-oxide formed is water-soluble and possesses an excellent washing, wetting and foaming power.
  • Example 8 70 parts of cyclohexylmethyldodecylamine are dissolved in 350 parts of ethyl alcohol, 150 parts of 6 per cent hydrogen peroxide are added and the mixture is warmed for about hours at 60 C. After evaporating the solvent a clearly watersoluble product of excellent washing, wetting and foaming power is obtained.
  • Example 9 60 parts of a mixture of tertiary amines each of which corresponds to the formula wherein the radicle -(CH2) :rCH3 is a radicle of one of the alcohols corresponding to the fatty acids of palm kernel oil are introduced into 550 parts of an aqueous solution of permonosulphuric acid containing 4.4 parts of active oxygen, the addition being effected slowly while cooling with ice and shaking.
  • the reaction product is allowed to stand for some hours in the cold and then rendered distinctly alkaline whereby the amineoxide is separated out.
  • the product is filtered oil. If desired, it may be'redissolved in water, shaken with dieth lether in order to remove unconverted amine an It has similar properties as the product obtained according to Example 1.
  • Example 10 24 parts of dodecyl-dimethylamineoxide and 30 parts of methyl iodide are dissolved in 20 parts of ethyl alcohol and the solution is allowed to stand in a closed vessel for about 48 hours. The solvent and non-reacted methyl iodide are distilled OE and a yellow crystalline powder is obtained which is readily soluble in water and possesses an excellent foaming, wetting and washing power.
  • a valuable product is also obtained by oxidizing trimethylamine to trimethylamine oxide and reacting the latter with dodecyl iodide by heating the two components in the presence of methyl alcohol in a closed vessel for about 8 hours at from 100 to 110 C.
  • Example 11 22 parts of methyldodecylhydroxylamine (ob tainable for example according to Example 6) are heated together with 20 parts of benzyl chloride for 1 hour on a water-bath. Water is added to the reaction product, non-reacted benzyl chloride is removed by shaking with diethyl ether and the remaining aqueous solution is evaporated to dryness. A clearly water-soluble product of high wetting and washing power is obtained.
  • R1, R2, R3 and R4 stand for radicals selected from the group consisting of aliphatic and aromatic radicals, at least one of which radicals contains an aliphatic chain of at least 8 carbon atoms.
  • the process for producing assistants in the .textile and related industries which comprises treating an amine containing at least one allphatic radicle with at least 8 carbon atoms and at most one hydrogen atom directlyv attached to nitrogen with an oxidizing agent at a temperature between about 0 and about 100 C.
  • R1 stands for a member selected from the group consisting of hydrogen and aliphatic and aromatic radicals
  • R: and Re stand for radicals selected from the group consisting of aliphatic and aromatic radicals, at least one of said radicals containing an aliphatic chain of at least 8 carbon atoms.
  • Rr-N drogen peroxide a tertiary amine having the formula Rr-N in which R1 is one of the group consisting of a straight-chain alk-yl radical of more than 7 carbon atoms and mono-alkylated-aryl radical of the benzene series in which the alkyl portion is a straight chain radical of more than 7 carbon atoms. and R: and R3 are both one of the group consisting of a lower alkyl and, jointly, a cyclic polymethylene group.
  • R is an alkyl straight chain radical of more than 7 carbon atoms and R4 and R5 are lower alkyl straight-chain radicals.
  • Il -N wherein R1 represents a radical linked to the N-atom through carbon and containing a straight aliphatic chain having at least 10 carbon atoms, which chain is not directly linked to the nitrogen atom, R2 and Rs each represent methyl radicals.
  • R1 represents a radical linked to the N-atom through carbon and containing nitrogen and a straight aliphatic chain having at least 10 carbon atoms. which chain is not directly linked to the nitrogen atom N, R2 and Ra each represent methyl radicals.
  • R1 represents a radical linked to the N-atom through carbon and containing an allphatic chain consisting of at least 6 carbon atoms
  • R: and R3 each represent alkyls of low molecular weight the number of carbon atoms of which does not exceed 6, which products have a fatty aspect, and are liquid to semi-solid and solid masses soluble in water, both in the presence of acids and alkalies,- and in organic solvents and lipoids, and whose dilute aqueous solutions possess excellent properties of capillary activity.
  • tertiary amine oxides which comprises reacting with an oxidizing agent containing the -OO-group a tertiary amine having the formula in which R is an organic hydrocarbon radical containing an alkyl radical having more than 7 carbon atoms, and R2 and R3 are both one of the group consisting of a lower alkyl and, jointly, a cyclic poiymethylene group.

Description

Patented Aim. i5, 193% STATES Fritz (member and Karl Saftien. Ludwigshaienon-the-Rhine, Germany, asslgnors to I. G. Farb'enind'ustrie Aktlenge'sellschaft, Frankfort-onthe-Main,
NoDrawin'g. Application January 17, 1935, Se-
rial No. 2,224. In Germany January 26, 1934 15 Claims.
The present invention relates to' new assistants in the textile and related industries especially wetting, cleansing, dispersing and like nts and a process for producing same.
We have found that organic compounds which contain in the molecule at least one nitro en atom, at least two organic radicles directly attached to said nitrogen atom, in which the said nitrogen atom is present in a higher oxidation stage than in organic ammonia substances" and which contain at least one aliphatic (i. e, open chain aliphatic or cycloaliphatic) radicle with at least 8 carbon atoms, are valuable assistants in the textile and related industries, especially wetting, cleansing, dispersing and like agents. The term organic ammonia substances is intended to mean for the purposes of the present invention amines and ammonium compounds containing organic radicles including quaternary ammonium compounds.
Wetting, cleansing, dispersing andv like agents of the kind defined above can be obtained by treating amines containing at most one hydrogen atom directly attached to nitrogen with oxidizing agents, while taking care that no degradation of the amines but a combination of oxygen on the amino nitrogen atom takes place and introducing at any time an aliphatic radicle with at least 8 carbon atoms. The introduction of the latter may either consist in selecting such amines as already contain such a radicle or, if this is not the case, by reacting the amine before or after the oxidation with a compound capable of introducing an aliphatic radicle of the said kind. If desired, further radicles of any desired kind may be introduced.
By carrying out the said oxidation with tertiary amines R N- Ra R7N=O, or, in the hydrated form, R3
If, however, secondary amines R1--NH-R2 are oxidized in the said manner amineoxides are obtained which are tautomeric with the correspond ing hydroxylamines. These compounds may be represented by the i'ollowing formulae:
R K R -N=0, or N-OH (Amineoxide ioi'm) (Hydroxylamine form) Open chain aliphatic or cycloaliph'aticradicles suitable for the purposes of the present invention are for example those of lauric, stearic, palmitic, oleic and rici'noleic acids, the hydrocarbon radicles corresponding to the montanic acids, resinic and naphthenic acids and to the alcohols and carboxylic acids obtainable by the oxidation of paraffin wax. Furthermore the term is intended to include radicles of hydrogenated aromatic hydrocarbons of high molecular weight, as for example decahydronaphthalene. The expression aliphatic radicals as employed in the claims covers both open chain aliphatlc radicals and cyclo-aliphatic radicals and radicals in which 2 open ch'ain radicals are joined. together as for example in compounds of, the type obtained when a piperidine compound is employed as the amine.
In the said wetting, cleansing, dispersing and like agents the said organic radicles containing at least eight carbon atoms are connected to a. nitrogen atom either directly or by means of other atoms or atomic groups, such as oxygen atoms or sulphur atoms or carbonyl, carboxylic acid ester, carboxylic acid amide, sulphonic or sulphonamide groups, or of organic rings. The chains of radicles of high molecular weight may also be'interrupted by one or more of the said atoms or atomic groups.
Secondary and tertiary amines suitable as initial materials are for example octyl propylamine, cetyl butylamine, dodecyl naphthylamine, decyl dimethylamine, dodecyl dimethylamine, hexadecyl diethylamine, oleyl dimethylamine, and amines obtainable by the reaction of primary or secondary amines of low molecular weight with higher molecular halogen-parafiin hydrocarbons. Other suitable amines are N-dimethyldecahydronaphthylamine,N-dodecylethylaniline, N-octylpiperidine, N-dialkylethylenediamines which are acylated on one side by fatty acid radicles of high molecular weight, the dodecyl ether of para-dimethylaminephenol, the dodecyl ester of N-dimethylaminoethyl alcohol, N-monomethyl-C-dodecylaniline, N-dimethyl-C-dodecylaniline and the cetyl amide of dimethylamlnoacetic acid. Amines of the said kind which contain any desired substituents, as for example halogen atoms, hydroxy, carboxyl, ester, ether,
The said amines may be subjected to the oxidizing treatment alone or in admixture with each other. A great variety of oxidizing agents may be employed, as for example hydrogen peroxide, sodium peroxide, permoncsulphurlc acid, benzoyl peroxide, sodium hypochlorite and oxygen or mixtures containing oxygen or other gas mixtures having an oxidizing action preferably in the presence of oxidizing catalysts, the oxidation is advantageously carried out in aqueous solution or suspension and/or while employing organic solvents or diluents, such as ethyl alcohol, acetone or benzene, at ordinary or elevated temperature, advantageously between 0 and 100 C. or between 20 and 100 C.
When the resulting oxidation product contains only two' organic radicles attached to nitrogen it is advantageous to introduce further organic radicles; this may be efl'ected in known manner by alkylation, arylation or aralkylation. For example the oxidation product of dodecylmethylamine may be converted into an oxidation product of a tertiary amine by treatment with benzyl chloride or an alkyl iodide. The compounds thus obtainable which contain halogen may be converted into the corresponding amine oxides by means of silver oxide; if instead of the alkyliodides alkyl sulphates are employed, the conversion into the amine oxides may be effected by means of barium hydroxide. If the amines em-' ployed as initial materials contain no aliphatic or cycloaliphatic radicles containing at least eight carbon atoms. it is preferable during the conversion of the oxidation product into the oxidation product of a tertiary amine to introduce into the molecule a radicle of high molecular weight. Thus for example the oxidation product of dimethylamine may be converted by reaction with cetyl iodide into an oxidation product of a weight into oxidation products of tertiary amines,
the latter or oxidation products of tertiary amines of low molecular weight being then directly condensed with correspoding compounds of high molecular weight. In this case it is advantageous for the oxidation products to contain atoms or atomic groups which permit of a subsequent introduction of aliphatic or cycloaliphatic radicles of high molecular weight; For example a secondary amine of low molecular weight may be'caused to react with chloracetic acid; then before or after the oxidation an aliphatic radicle of high molecular weight may be introduced into the carboxylic acid group contained in the reaction product, for example by esteriilcation. Furthermore the oxidation product of dimethylglycine may be caused to react for example with dodecylamine.
Oxidation products of tertiary amines of low molecular weight which contain no reactive atoms or atomic groups in the organic radicles are also suitable for the preparation of the said compounds. In this case the introduction of aliphatic radicles of high molecular weightv (R4) may be effected by adding organic compounds R4X (wherein X may be OH or the radicle of any acid such as Cl, -HSO4, CH3.COO and the like) on the amineoxide, the double bond between the oxygen atom and the nitrogen atom being removed in the said reaction. For example the addition of a high molecular alkylhalide on a tertiary alkylamine oxide proceeds according to the following equation.
Thus the oxidation product of trimethylamine may be converted into a product of the desired kind by reaction with dodecyl iodide.
The introduction of the radicles of high molecular weight or the conversion of secondary amines into tertiary amines and the oxidation may thus be carried out in any desired sequence. It is immaterial in what manner the oxidation products of the amines are prepared. For example the oxidation products of secondary amines obtainable by the action of metallo-organic compounds on nitroparaflln hydrocarbons may be converted into oxidation products of tertiary amines containing radicles of high molecular weight according to this invention. The introduction of further organic radicles, as for example by the action of alkylene oxides or by reaction with diazomethane, into oxidation products of tertiary amines already containing aliphatic radicles of high molecular weight is advantageous in many cases. Frequently organic radicles of low molecular weight in the oxidation products may be replaced with advantage by radicles of high molecular weight, as for example by replacing carbomethoxy groups by carbonamido groups of high molecular weight. Oxida tion products of primary and secondary amines substituted by halogen, nitro, sulphonic, carboxylic and amino groups may also be obtained according to this invention by introducing such atoms or atomic groups into the initial materials or subsequently into the reaction products.
The products obtainable according to this invention have a high solubility in neutral and alkaline baths. Their basicity is less as compared with the initial materials so that they may be employed for purposes for which the amines themselves are unsuitable by reason of their strongly basic properties. For the greater part they are, however, still capable of forming watersoluble salts with inorganic or organic acids, and these salts may frequently be employed for the same purposes as the oxidation products themselves. The aqueous solutions of the products have a high stability to acids, alkalies and salts and are furthermore stable to the sub stances forming the hardness in water.
The products may be employed with great advantage as wetting, washing, cleansing and dispersing agents in the textile, leather, paper and other industries. They are especially suitable as additions to any dyebath in which they frequently effect an increase in the solubility or dispersion of the dyestuif and a thorough dyeing and levelling. Eventhe undesirable precipitation of calcium salts when employing hard water is to a great extent suppressed by reason of the high protective colloid action of the products. The said products may also be employed with advantage for stripping and after-seeping and for improving the iastness to rubbing of many dyeings. They are also suitable as additions to printing pastes and as preserving agents and also as valuable additions to mercerizing and bucking liquors and as softening agents for textile materials.
no formation of a precipitate takes place.
The said products may also be employed with advantage as substitutes for soaps; in the presence of soaps they prevent the precipitation of calcium soaps to a large extent when using hard water by reason of their high protective colloid action. The products may be employed alone, in admixture with each other or together with other usual wetting, washing, dispersing and like agents, as for example Turkey red oil, sulphuric acid esters of aliphatic alcohols of high molecular weight, true sulphonic acids of aliphatic or aromatic compounds of high molecular weight, as for example reaction products of fatty acids with hydroxyalkyl or aminoalkyl sulphonic acids. They may also be employed in admixture with solvents, such as carbon tetrachloride, cyclohexanol, or benzyl alcohol, or together with salts, as for example Glauber's salt, perborates, waterglass, or with protective colloids, such as glue, gelatine, or dextrlne.
The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.
Example 1 21 parts of dimethyidodecylamine are dissolved in 120 parts of ethyl alcohol and heated for nine hours at about 60 C. after the addition of 60 parts of 6 per cent hydrogen peroxide: A solution, capable of dilution with water to give a clear solution, is obtained from which the oxidation product formed may beisolated in solid form by evaporation.
The product dissolves very readily in water; the aqueous solution has, inter alia, an excellent wetting, foaming and washing power; it has a practically neutral reaction.
Example 2 60 parts of 6 percent hydrogen peroxide are added to a solution of 30 parts of cetyldiethylamide in 350 parts of of ethyl alcohol and the whole heated for ten hours at about 60 C. After evaporation of the solution, the oxidation product may be obtained in solid form. It has properties similar to those of the product obtainable according to Example 1.
Example 3 30 parts of 6 per cent hydrogen peroxide are added to a solution of 92 parts of decyldimethylamine in 600 parts of ethyl alcohol and the whole is heated for several hours to about 60 C.
if the solution obtained be diluted with water y evaporation of the water a product is obtained which has excellent wetting and foaming properties.
Example 4 12 parts of 30 percent hydrogen peroxide are added to a solution of 62 parts of octodecenyldimethylamine in a mixture of 100 parts of water and 250 parts of ethyl alcohol. After heating the mass for three hours to about 60 C. another 12 parts or" hydrogen peroxide are added and the mixture is then heated to about 60 C. until the solution obtained, when diluted with water, remains clear. In the manner described above a product having good cleansing and dispersing properties is obtained. By evaporation of the water the new product may be obtained in "in anhydrous form.
In an analogous manner octodecyldimethylamine or dodecyldibutylamine or chlorstearyldimethylamine (obtainable by adding hydrogen chloride on octodecenyldimethyl amine) can be converted into valuable cleansing and dispersing agents by treating with hydrogen peroxide.
Example 5 A mixture of 54 parts of the dodecylamide of dlmethylamino acetic acid 100 parts of water, 250 parts of ethyl alcohol and 30 parts of 30 per cent hydrogen peroxide is heated for several hours to about 60 C. In this manner a valuable wetting and cleansing agent is obtained.
A product having similar properties can be obtained by treating oleyl-N-diethyl-ethylenedlamine with hydrogen peroxide in the manner described above.
Example 6 40 parts of dodecylmonomethylamine are dissolved in 300 parts of ethyl alcohol, 125 parts of 6 per cent hydrogen peroxide are added and the mixture is heated for about 20 hours at 60 C. The ethyl alcohol and the water are evaporated at ordinary temperature in vacuo and methyldodecylhydroxylamine is obtained in the form of a slightly yellow colored oil. The product yields strongly foaming emulsions with water and possesses an excellent washing and softening power.
The product may be alkylated, for example by means of ethyl bromide, whereby a product is obtained which is also soluble in water and has a good washing and wetting power.-
Example 7 20 parts of C-dodecyl-N-dimethylani1ine are dissolved in 700 parts of ethyl alcohol and the solution obtained is heated with 40 parts of 15 per cent hydrogen peroxide so that it boils slightly until a sample is clearly soluble in water. The ethyl alcohol and the water are evaporated in vacuo. The amine-oxide formed is water-soluble and possesses an excellent washing, wetting and foaming power.
Example 8 70 parts of cyclohexylmethyldodecylamine are dissolved in 350 parts of ethyl alcohol, 150 parts of 6 per cent hydrogen peroxide are added and the mixture is warmed for about hours at 60 C. After evaporating the solvent a clearly watersoluble product of excellent washing, wetting and foaming power is obtained.
Example 9 60 parts of a mixture of tertiary amines each of which corresponds to the formula wherein the radicle -(CH2) :rCH3 is a radicle of one of the alcohols corresponding to the fatty acids of palm kernel oil are introduced into 550 parts of an aqueous solution of permonosulphuric acid containing 4.4 parts of active oxygen, the addition being effected slowly while cooling with ice and shaking. The reaction product is allowed to stand for some hours in the cold and then rendered distinctly alkaline whereby the amineoxide is separated out. The product is filtered oil. If desired, it may be'redissolved in water, shaken with dieth lether in order to remove unconverted amine an It has similar properties as the product obtained according to Example 1.
Example 10 24 parts of dodecyl-dimethylamineoxide and 30 parts of methyl iodide are dissolved in 20 parts of ethyl alcohol and the solution is allowed to stand in a closed vessel for about 48 hours. The solvent and non-reacted methyl iodide are distilled OE and a yellow crystalline powder is obtained which is readily soluble in water and possesses an excellent foaming, wetting and washing power.
A valuable product is also obtained by oxidizing trimethylamine to trimethylamine oxide and reacting the latter with dodecyl iodide by heating the two components in the presence of methyl alcohol in a closed vessel for about 8 hours at from 100 to 110 C.
Example 11 22 parts of methyldodecylhydroxylamine (ob tainable for example according to Example 6) are heated together with 20 parts of benzyl chloride for 1 hour on a water-bath. Water is added to the reaction product, non-reacted benzyl chloride is removed by shaking with diethyl ether and the remaining aqueous solution is evaporated to dryness. A clearly water-soluble product of high wetting and washing power is obtained.
What we claim is:
1. As assistants in the textile and related industries, compounds corresponding to the general formula:
wherein R1, R2, R3 and R4 stand for radicals selected from the group consisting of aliphatic and aromatic radicals, at least one of which radicals contains an aliphatic chain of at least 8 carbon atoms.
2. The process for producing assistants in the .textile and related industries, which comprises treating an amine containing at least one allphatic radicle with at least 8 carbon atoms and at most one hydrogen atom directlyv attached to nitrogen with an oxidizing agent at a temperature between about 0 and about 100 C.
3. Assistants in the textile and related industries essentially comprising nitrogeneous compounds containing oxygen directly attached to nitrogen selected from the class consisting of compounds corresponding to the general formulae:
R: R: OH
wherein R1 stands for a member selected from the group consisting of hydrogen and aliphatic and aromatic radicals, R: and Re stand for radicals selected from the group consisting of aliphatic and aromatic radicals, at least one of said radicals containing an aliphatic chain of at least 8 carbon atoms.
4. The process for the production of tertiary amine oxides which comprises reacting with hydried in vacuo at from 60 to 70 C.
drogen peroxide a tertiary amine having the formula Rr-N in which R1 is one of the group consisting of a straight-chain alk-yl radical of more than 7 carbon atoms and mono-alkylated-aryl radical of the benzene series in which the alkyl portion is a straight chain radical of more than 7 carbon atoms. and R: and R3 are both one of the group consisting of a lower alkyl and, jointly, a cyclic polymethylene group.
5. A tertiary amine oxide having the formula in which R1 is one of the group consisting of a straight-chain alkyl radical of more than 7 carbon atoms and mono alkylated-aryl radicals of the benzene series in which the alkyl portion is a straight chain radical of more than 7 carbon atoms, and R2 and R: are both one of the group consisting of a lower alkyl and, jointly, a cyclic polymethylene group. 6. The compound R-C-N-OH:CH:N
wherein R is an alkyl straight chain radical of more than 7 carbon atoms and R4 and R5 are lower alkyl straight-chain radicals.
7. The dodecyldimethylamine-oxide of the formula which product has afatty aspect, and is a semi-- solid mass solublein water, both in the presence of acids'and alkalies, and in organic solvents and lipoids, and whose dilute aqueous solution possesses excellent properties of capillary activity.
8. Process for the manufacture of oxides of tertiary amines, consisting in reacting with oxidizing agents containing the OO-group tertiary amines of the general formula:
Il -N wherein R1 represents a radical linked to the N-atom through carbon and containing a straight aliphatic chain having at least 10 carbon atoms, which chain is not directly linked to the nitrogen atom, R2 and Rs each represent methyl radicals. 10. Process for the manufacture of oxides of tertiary amines, consisting in reacting with oxidizing agents containing the O-group tertiary amines of the general formula:
wherein R1 represents a radical linked to the N-atom through carbon and containing nitrogen and a straight aliphatic chain having at least 10 carbon atoms. which chain is not directly linked to the nitrogen atom N, R2 and Ra each represent methyl radicals.
11. Process for the manufacture of an oxide of a tertiary amine, consisting in reacting stearoyldiethylethylene-diamine with Caros acid.
12. The oxides of tertiary amines of the general formula:
Iii-N wherein R1 represents a radical linked to the N-atom through carbon and containing an allphatic chain consisting of at least 6 carbon atoms, R: and R3 each represent alkyls of low molecular weight the number of carbon atoms of which does not exceed 6, which products have a fatty aspect, and are liquid to semi-solid and solid masses soluble in water, both in the presence of acids and alkalies,- and in organic solvents and lipoids, and whose dilute aqueous solutions possess excellent properties of capillary activity.
13. The process for the production of tertiary amine oxides which comprises reacting with an oxidizing agent containing the -OO-group a tertiary amine having the formula in which R is an organic hydrocarbon radical containing an alkyl radical having more than 7 carbon atoms, and R2 and R3 are both one of the group consisting of a lower alkyl and, jointly, a cyclic poiymethylene group.
14. A tertiary amine oxide having the formula /Ra Ri-N O in which R1 is an organic hydrocarbon radical containing an alkyl radical having more than 7 carbon atoms and R2 and Rs are both one of the group consisting of a lower alkyl and, Jointly, a cyclic polymethylene group.
15. The process for the production of tertiary amine oxides which comprises reacting with an oxidizing agent containing the O0-group a tertiary amine having the formula
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US2416658A (en) * 1944-10-19 1947-02-25 Lilly Co Eli Preparation of 6-methoxyquinoline-nu-oxide
US2432126A (en) * 1943-10-06 1947-12-09 Rayonier Inc Method of improving the processing of refined chemical pulp into viscose
US2472411A (en) * 1943-11-02 1949-06-07 Merck & Co Inc Method for alkylating phenolic hydroxyl group containing alkaloids and the resultingproducts
US2862968A (en) * 1955-08-16 1958-12-02 Upjohn Co Methadone n-oxide and the acid addition salts thereof
US2995562A (en) * 1958-02-07 1961-08-08 Parke Davis & Co Higher alkylpyridine-nu-oxides
US3007784A (en) * 1960-03-28 1961-11-07 Standard Oil Co Fuel oil composition
US3062824A (en) * 1959-10-12 1962-11-06 Union Carbide Corp Preparing vinylpyridine-n-oxides and certain derivatives thereof
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US3086943A (en) * 1959-06-10 1963-04-23 Procter & Gamble Shampoo containing amine oxide
US3179598A (en) * 1961-07-03 1965-04-20 Procter & Gamble Detergent composition
US3179599A (en) * 1961-07-03 1965-04-20 Procter & Gamble Detergent composition
US3192166A (en) * 1960-11-14 1965-06-29 Procter & Gamble Liquid detergent composition
US3194767A (en) * 1961-12-18 1965-07-13 Procter & Gamble Sudsing detergent composition
US3197509A (en) * 1961-12-21 1965-07-27 Procter & Gamble Diamine dioxide compounds
US3202714A (en) * 1961-12-04 1965-08-24 Procter & Gamble Oxy containing tertiary amine oxides
US3206512A (en) * 1962-02-07 1965-09-14 Marchon Products Ltd N-dialkyl-alkyl-and-alkaryl-oxyalkylamine oxides
US3215741A (en) * 1963-01-08 1965-11-02 Du Pont Process for preparing maine oxides
DE1205221B (en) * 1961-08-21 1965-11-18 Procter & Gamble Liquid detergent
US3222287A (en) * 1962-01-23 1965-12-07 Procter & Gamble Detergent composition
US3223647A (en) * 1959-04-20 1965-12-14 Procter & Gamble Mild detergent compositions
US3228957A (en) * 1963-12-16 1966-01-11 Shell Oil Co Pyrrolidine production
US3234139A (en) * 1961-12-21 1966-02-08 Procter & Gamble Diamine dioxide detergent compositions
US3267147A (en) * 1963-03-05 1966-08-16 Du Pont Recovery of amine oxide salts by spray drying
US3270060A (en) * 1963-04-22 1966-08-30 Millmaster Ouyx Corp Amine oxides
US3275673A (en) * 1963-05-15 1966-09-27 Du Pont Extraction method for recovering amine oxide salts from aqueous solutions
US3287125A (en) * 1963-06-26 1966-11-22 Polaroid Corp Aminoalkyl hydroxylamines as photographic developers
DE1229249B (en) * 1959-08-08 1966-11-24 Therachemie Chem Therapeut Cosmetic hair treatment preparations
US3293034A (en) * 1963-06-26 1966-12-20 Polaroid Corp Alkoxy hydroxylamines as photographic developers
US3303896A (en) * 1965-08-17 1967-02-14 Procter & Gamble Process for drilling boreholes in the earth utilizing amine oxide surfactant foaming agent
US3317430A (en) * 1960-05-05 1967-05-02 Lever Brothers Ltd Detergent compositions
US3342863A (en) * 1963-04-24 1967-09-19 Du Pont N, n-dilower alkyl amino adamantane oxides
US3346495A (en) * 1964-08-20 1967-10-10 Armour & Co Water base lubricants
US3348947A (en) * 1963-12-18 1967-10-24 Ibm Diazo print process
US3356727A (en) * 1963-06-25 1967-12-05 Marchon Products Ltd Alkyl-and alkaryl-oxyalkyl-nu-hydroxyalkyl amine oxides
US3388069A (en) * 1964-01-04 1968-06-11 Henkel & Cie Gmbh Liquid active oxygen detergent bleaching concentrate
US3429914A (en) * 1964-09-03 1969-02-25 Monsanto Co Organo-phosphono-amine oxides
US3441611A (en) * 1961-12-04 1969-04-29 Procter & Gamble Hydroxyalkylamine oxide detergent compounds
US3441612A (en) * 1968-01-23 1969-04-29 Procter & Gamble Hydroxyalkylamine oxide
US3449430A (en) * 1960-07-14 1969-06-10 Henkel & Cie Gmbh Amino oxides
US3450637A (en) * 1968-05-03 1969-06-17 Procter & Gamble Detergent containing hydroxy alkyl amine oxide
US3457312A (en) * 1965-10-24 1969-07-22 Armour Ind Chem Co Amine oxides
US3470244A (en) * 1964-09-03 1969-09-30 Monsanto Co Methyl bis(dihydrogen phosphono methyl)-amine oxide and related compounds
US3470243A (en) * 1964-09-03 1969-09-30 Monsanto Co Tetrakis(dihydrogen phosphono methyl)-ethylene diamine,n,n'-dioxide and related compounds
US3474133A (en) * 1964-09-03 1969-10-21 Monsanto Co Tris(phosphono-lower alkylidene) amine oxides
US3483178A (en) * 1968-04-18 1969-12-09 Monsanto Co Esters,salts,and acids of organo-phosphono-amine oxides
US3494962A (en) * 1966-11-02 1970-02-10 Armour Ind Chem Co Aryl-substituted aliphatic amine oxides
US3957873A (en) * 1969-01-16 1976-05-18 Celanese Corporation Peracetic acid oxidation of amines to amine oxides
US4113631A (en) * 1976-08-10 1978-09-12 The Dow Chemical Company Foaming and silt suspending agent
FR2442634A1 (en) * 1978-07-12 1980-06-27 Anprosol Inc STERILIZATION SYSTEM
US4284599A (en) * 1978-07-12 1981-08-18 Anprosol Incorporated Sterilization system
US4425243A (en) 1982-10-21 1984-01-10 Millmaster Onyx Group, Inc. Foaming agents for use in drilling for oil and gas
US4845290A (en) * 1986-02-17 1989-07-04 Interox (Societe Anonyme) Process for the preparation of hydroxylamines and products thereby obtained
US4918194A (en) * 1987-10-29 1990-04-17 Montedipe S.P.A. Process for the synthesis of a N,N-dialkyl-hydroxylamine
US4970341A (en) * 1987-02-24 1990-11-13 Ethyl Corporation Amine oxide process
US5023376A (en) * 1989-07-17 1991-06-11 Interox America Reduction of nitrosamine formation
US5075501A (en) * 1989-10-02 1991-12-24 Ethyl Corporation Mixed tert-amine oxide dihydrates
US5120469A (en) * 1990-05-17 1992-06-09 Ethyl Corporation Amine oxide composition and process
US5324857A (en) * 1992-04-28 1994-06-28 Solvay Interox Inhibition of the formation of nitrosamines
EP0866058A2 (en) * 1997-03-20 1998-09-23 General Electric Company Synthesis of tertiary amine oxides
US6297278B1 (en) * 1991-03-22 2001-10-02 Biosyn Inc. (A Pennsylvania Corporation) Method for inactivating sexually transmitted enveloped viruses

Cited By (63)

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Publication number Priority date Publication date Assignee Title
US2432126A (en) * 1943-10-06 1947-12-09 Rayonier Inc Method of improving the processing of refined chemical pulp into viscose
US2472411A (en) * 1943-11-02 1949-06-07 Merck & Co Inc Method for alkylating phenolic hydroxyl group containing alkaloids and the resultingproducts
US2416658A (en) * 1944-10-19 1947-02-25 Lilly Co Eli Preparation of 6-methoxyquinoline-nu-oxide
US2862968A (en) * 1955-08-16 1958-12-02 Upjohn Co Methadone n-oxide and the acid addition salts thereof
US2995562A (en) * 1958-02-07 1961-08-08 Parke Davis & Co Higher alkylpyridine-nu-oxides
US3223647A (en) * 1959-04-20 1965-12-14 Procter & Gamble Mild detergent compositions
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
DE1150781B (en) * 1959-06-10 1963-06-27 Procter & Gamble Shampoos
US3086943A (en) * 1959-06-10 1963-04-23 Procter & Gamble Shampoo containing amine oxide
DE1229249B (en) * 1959-08-08 1966-11-24 Therachemie Chem Therapeut Cosmetic hair treatment preparations
US3062824A (en) * 1959-10-12 1962-11-06 Union Carbide Corp Preparing vinylpyridine-n-oxides and certain derivatives thereof
US3007784A (en) * 1960-03-28 1961-11-07 Standard Oil Co Fuel oil composition
US3317430A (en) * 1960-05-05 1967-05-02 Lever Brothers Ltd Detergent compositions
US3449430A (en) * 1960-07-14 1969-06-10 Henkel & Cie Gmbh Amino oxides
US3192166A (en) * 1960-11-14 1965-06-29 Procter & Gamble Liquid detergent composition
US3179599A (en) * 1961-07-03 1965-04-20 Procter & Gamble Detergent composition
US3179598A (en) * 1961-07-03 1965-04-20 Procter & Gamble Detergent composition
DE1205221B (en) * 1961-08-21 1965-11-18 Procter & Gamble Liquid detergent
US3202714A (en) * 1961-12-04 1965-08-24 Procter & Gamble Oxy containing tertiary amine oxides
US3281368A (en) * 1961-12-04 1966-10-25 Procter & Gamble Built tertiary amine oxide detergents
US3441611A (en) * 1961-12-04 1969-04-29 Procter & Gamble Hydroxyalkylamine oxide detergent compounds
US3194767A (en) * 1961-12-18 1965-07-13 Procter & Gamble Sudsing detergent composition
US3197509A (en) * 1961-12-21 1965-07-27 Procter & Gamble Diamine dioxide compounds
US3234139A (en) * 1961-12-21 1966-02-08 Procter & Gamble Diamine dioxide detergent compositions
US3222287A (en) * 1962-01-23 1965-12-07 Procter & Gamble Detergent composition
US3206512A (en) * 1962-02-07 1965-09-14 Marchon Products Ltd N-dialkyl-alkyl-and-alkaryl-oxyalkylamine oxides
US3215741A (en) * 1963-01-08 1965-11-02 Du Pont Process for preparing maine oxides
US3267147A (en) * 1963-03-05 1966-08-16 Du Pont Recovery of amine oxide salts by spray drying
US3270060A (en) * 1963-04-22 1966-08-30 Millmaster Ouyx Corp Amine oxides
US3342863A (en) * 1963-04-24 1967-09-19 Du Pont N, n-dilower alkyl amino adamantane oxides
US3275673A (en) * 1963-05-15 1966-09-27 Du Pont Extraction method for recovering amine oxide salts from aqueous solutions
US3356727A (en) * 1963-06-25 1967-12-05 Marchon Products Ltd Alkyl-and alkaryl-oxyalkyl-nu-hydroxyalkyl amine oxides
US3293034A (en) * 1963-06-26 1966-12-20 Polaroid Corp Alkoxy hydroxylamines as photographic developers
US3287125A (en) * 1963-06-26 1966-11-22 Polaroid Corp Aminoalkyl hydroxylamines as photographic developers
US3228957A (en) * 1963-12-16 1966-01-11 Shell Oil Co Pyrrolidine production
US3348947A (en) * 1963-12-18 1967-10-24 Ibm Diazo print process
US3388069A (en) * 1964-01-04 1968-06-11 Henkel & Cie Gmbh Liquid active oxygen detergent bleaching concentrate
US3346495A (en) * 1964-08-20 1967-10-10 Armour & Co Water base lubricants
US3470243A (en) * 1964-09-03 1969-09-30 Monsanto Co Tetrakis(dihydrogen phosphono methyl)-ethylene diamine,n,n'-dioxide and related compounds
US3429914A (en) * 1964-09-03 1969-02-25 Monsanto Co Organo-phosphono-amine oxides
US3474133A (en) * 1964-09-03 1969-10-21 Monsanto Co Tris(phosphono-lower alkylidene) amine oxides
US3470244A (en) * 1964-09-03 1969-09-30 Monsanto Co Methyl bis(dihydrogen phosphono methyl)-amine oxide and related compounds
US3303896A (en) * 1965-08-17 1967-02-14 Procter & Gamble Process for drilling boreholes in the earth utilizing amine oxide surfactant foaming agent
US3457312A (en) * 1965-10-24 1969-07-22 Armour Ind Chem Co Amine oxides
US3494962A (en) * 1966-11-02 1970-02-10 Armour Ind Chem Co Aryl-substituted aliphatic amine oxides
US3441612A (en) * 1968-01-23 1969-04-29 Procter & Gamble Hydroxyalkylamine oxide
US3483178A (en) * 1968-04-18 1969-12-09 Monsanto Co Esters,salts,and acids of organo-phosphono-amine oxides
US3450637A (en) * 1968-05-03 1969-06-17 Procter & Gamble Detergent containing hydroxy alkyl amine oxide
US3957873A (en) * 1969-01-16 1976-05-18 Celanese Corporation Peracetic acid oxidation of amines to amine oxides
US4113631A (en) * 1976-08-10 1978-09-12 The Dow Chemical Company Foaming and silt suspending agent
FR2442634A1 (en) * 1978-07-12 1980-06-27 Anprosol Inc STERILIZATION SYSTEM
US4284599A (en) * 1978-07-12 1981-08-18 Anprosol Incorporated Sterilization system
US4425243A (en) 1982-10-21 1984-01-10 Millmaster Onyx Group, Inc. Foaming agents for use in drilling for oil and gas
US4845290A (en) * 1986-02-17 1989-07-04 Interox (Societe Anonyme) Process for the preparation of hydroxylamines and products thereby obtained
US4970341A (en) * 1987-02-24 1990-11-13 Ethyl Corporation Amine oxide process
US4918194A (en) * 1987-10-29 1990-04-17 Montedipe S.P.A. Process for the synthesis of a N,N-dialkyl-hydroxylamine
US5023376A (en) * 1989-07-17 1991-06-11 Interox America Reduction of nitrosamine formation
US5075501A (en) * 1989-10-02 1991-12-24 Ethyl Corporation Mixed tert-amine oxide dihydrates
US5120469A (en) * 1990-05-17 1992-06-09 Ethyl Corporation Amine oxide composition and process
US6297278B1 (en) * 1991-03-22 2001-10-02 Biosyn Inc. (A Pennsylvania Corporation) Method for inactivating sexually transmitted enveloped viruses
US5324857A (en) * 1992-04-28 1994-06-28 Solvay Interox Inhibition of the formation of nitrosamines
EP0866058A2 (en) * 1997-03-20 1998-09-23 General Electric Company Synthesis of tertiary amine oxides
EP0866058A3 (en) * 1997-03-20 2002-08-14 General Electric Company Synthesis of tertiary amine oxides

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