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Publication numberUS3141905 A
Publication typeGrant
Publication dateJul 21, 1964
Filing dateApr 29, 1963
Priority dateApr 29, 1963
Publication numberUS 3141905 A, US 3141905A, US-A-3141905, US3141905 A, US3141905A
InventorsLongley Kermit
Original AssigneeWitco Chemical Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Cation-active surface active quaternary ammonium compounds
US 3141905 A
Abstract  available in
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Description  (OCR text may contain errors)

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

The specific cation-active surface active agents of my present invention are of the quaternary ammonium type and they are characterized by particularly advantageous properties, simplicity of production and markedly low cost. Certain of them, for instance, derived from lower dialkyl monoalkanolamines, can be represented by the formula where R and R are the same or dissimilar alkyl radicals each containing from 1 to 3 carbon atoms R2 iS-CHz- |7HO H a where R is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C H O) to R is not greater than 1 to 4, X is a member selected from the group consisting of 1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, (2) lower aliphatic-monocyclic aryl hydrocarbon radicals, (3) sulfo-aromatic hydrocarbon radicals, (4) chloro-aromatic hydrocarbon radicals; and A is an anion.

Again, various of the quaternary ammonium compounds of my invention which are derived from lower monoalkyl dialkanolamines can be represented by the formula A (C2H4O) R2 where R, R X, A and v have the same meanings as referred to under Formula I.

Still others of the quaternary ammonium compounds of my invention can be represented by the formulae (III) R a;

A. R4O-R5 where R, R X and A have the same meanings as referred to under Formula I, and R -OR is a polyoxyethylene-polyoxypropylene radical containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene radical to the polyoxypropylene radical is not greater than 1 to 4, the total number of oxypropylene groups not exceeding 60.

3,t4l,95 Patented July 21, 1954 Still others of the quaternary ammonium compounds of my invention can be represented by the formula X Rt Rai/ where R, R X, A and v have the meanings set forth above, and R has the same meaning as R the sum of the ns not exceeding 60 and the total number of carbon atoms in the sum of R and R being at least 18.

Various others of the quaternary ammonium compounds of the present invention can be represented by the formula and R is an alkyl radical containing from 1 to 4 carbon atoms, and n totals a number not exceeding 60 with the proviso that the number of carbon atoms in the total of the R radicals is at least 18, v is a number at least 1 with the proviso that the weight ratio of (C H O) to R is not greater than 1 to 4, X is a member selected from the group consisting of 1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, (2) lower aliphaticmonocyclic aryl hydrocarbon radicals, (3) sulfo-aromatic hydrocarbon radicals, (4) chloro-aromatic hydrocarbon radicals; and A is an anion.

In those cases where R for instance, is derived from propyleneoxide, there will be at least 6, and there may be up to 60 or more, of such propyleneoxide groups in R but, particularly, it is desired that R contain from 8 to 25 or 30 oxypropylene groups. Where R for instance, is derived from a-epoxides containing more than 3 carbon atoms, a lesser number of such oxyalkylene groups can be present, subject to the limitation that R if it is the only polyoxyalkylene radical present in which the oxyalkylene group contains 3 or more carbon atoms, contains at least 18 carbon atoms. The R and R alkyl radicals may be the same or dissimilar and each contains from 1 to 3 carbon atoms. X is a lower alkyl or alkenyl radical containing from 1 to 4 carbon atoms, or is an aliphatic-aryl radical containing from 7 to 9 carbon atoms, notably an alkaryl radical; and A is an anion such as chlorine or bromine. The term a-epoxide, as used herein, is intended to cover those compounds, of the type here involved, where there are two vicinal carbon atoms connected to one oxygen atom independently of the position of such group in the molecule.

The terms polyoxyalkylene, polyoxypropylene and polyoxyethylene, to the extent that they are used herein or in the claims, are employed in their usual or conventional manner. Thus, in the case of the polyoxyalkylene radical derived from a-epoxides containing from 3 to 6 carbon atoms, to wit, R in the above formulae, the same may be represented by oxypropylene and n is at least 3 in the case of the polyoxyalkylene radical being polyoxyhexylene. Where the polyoxyalkylene radical is polyoxypropylene, it may be represented by the formula 11 being from 6 to 60.

The foregoing illustrate the polyoxyalkylene and polyoxypropylene radicals where the vicinal carbons are terminal. of my invention, however, the vicinal carbons need not be terminal. A typical illustration of the latter is a polyoxyalkylene radical derived from 2,3-butylene oxide.

Most of the quaternary ammonium compounds of the present invention fall into the category of or correspond to reaction products of quaternizing esters having a hydrocarbon alkyl or alkenyl radical containing from 1 to 4 carbon atoms or a benzyl radical or a dimethylbenzyl radical or a lower alkyl substituted or chloro or nitro substituted benzyl radical, and an anion, with adducts of (a) aliphatic mono-lower alkyl hydroxyalkyl amines or di-lower alkyl hydroxyalkyl amines in which no single alkyl radical contains more than 3 carbon atoms, with (b) an a-epoxide containing at least 3 and advantageously from 3 to 8 carbon atoms, the molal ratio of (a) to (b) being 1 of (a) to at least 6 of (b) when said a-epoxide contains 3 carbon atoms and ranging down to at least 2.5 of (b) when said a-epom'de contains 8 carbon atoms.

While, as indicated, many of the novel and useful cation-active surface active agents of my invention can be represented by the above formulae, in certain cases they may be described in the form of reaction products of identified ingredients, as hereafter pointed out, since the active constituent or constituents thereof need not be separated out and recovered as such, the reaction products being usable as such for many purposes without the necessity for resorting to concentration, purification or recovery steps. Thus, for example, although this will be pointed out and described in more detail hereafter, quaternary ammonium compounds which are particularly useful and which may simply and inexpensively be pro duced are reaction products of aromatic quaternizing esters in the form of alkyl and alkenyl halides, sulfates and sulfonates containing from 1 to 4 carbon atoms, exemplified by methyl chloride, allyl chloride, methyl chloracetate, and 1 and 2 carbon atom alkyl sulfates; or quaternizing esters in the form of halides, sulfates and sulfonates advantageously containing from 7 to 9 carbon atoms exemplified by benzyl chloride, dimethylbenzyl chloride, and phenyl ethyl chloride, with adducts of (a) hydroxy alkyl amines in which any alkyl radical contains from 1 to 3 carbon atoms, such as ethyl diethanolamine or diethyl ethanolamine, with (b) propyleneoxide or butyleneoxides, said adducts containing 1 mol of (a) to from 6, and preferably from 8, to 30 mols of (b). Purification steps can, if desired, be employed as, for instance, separating unreacted tertiary amines by distillation, etc.

It is important to note that it is critical to my present invention that there be present in the molecule oxyalkylene groups derived from an m-epoxide containing at least 3 carbon atoms. Ethylene oxide, for instance, as such, is not operative in the practice of my invention since it produces compounds whose properties are radically different from those obtained in accordance with my invention and which would be useless for many of the purposes for which the cation-active surface active agents of my invention are adapted and intended. The most important embodiment of the a-epoxides whose use is contemplated by my invention in the production of the cationactive surface active agents is propyleneoxide The u-epoxides containing 4, 5, 6 or more carbon atoms can be used, but, for general reasons of lack of economy or commercial availability, are not preferred. Typical of In the broader, but less preferred, embodiments 10 such latter m-epoxides are butylene oxides such as 1,2- butylene oxide, pentylene epoxides, heXylene epoxides, heptylene epoxides, octylene epoxides, dodecylene epoxides, and C C olefin oxides or epoxides, and, as well, styrene epoxides. It will be seen that most of those of the a-epoxides in which the vicinal carbons are terminal can conveniently be represented by the formula where R is an alkyl radical. In the case of propylene oxide, R is CH and in the representation of the group of propylene oxide, butylene oxides, pentylene oxide and hexylene oxide R contains from 1 to 4 carbon atoms. In the higher molecular weight alkylene oxides, R may contain as high as 16 carbon atoms.

While, as I have stated above, the use of ethyleneoxide as the sole alkylene oxide is inoperative for my purposes, small proportions thereof,'not to exceed 25% and better still not to exceed 20% by weight of the propyleneoxide or other a-epoxides employed, can be utilized as here after described. Mixtures of two or more of the a-epoxides containing at least 3 carbons can, of course, be used as such, as well as in conjunction with ethyleneoxide, subject to the limitation that the ethyleneoxide must not exceed the aforesaid 20% to 25% of the weight of said a-epoxides.

The cation-active surface active agents of my invention are advantageously prepared by initially condensing, for instance, a monoalltyl or monoalkenyl di-hydroxyalkyl amine in which each alkyl radical or alkenyl radical contains from 1 to 3 carbon atoms, for example, monoethyl diethanolamine or monomethyl diisopropanolamine; or a dialkyl or dialkenyl mono-hydroxyalkyl amine in which each alkyl radical or alkenyl radical contains from 1 to 3 carbon atoms, for example, diethyl monoethanolamine or dimethyl isopropanolamine; with propyleneoxide or other a-epoxide containing at least 3 carbon atoms, advantageously in the presence of a conventional oxyalkylating catalyst such as sodium hydroxide or potassium hydroxide, whereby to produce an intermediate or adduct containing at least 6 oxypropylene groups. The resulting adduct is then reacted with a quaternizing ester in the form of lower alkyl or alkenyl halides, lower alkyl esters of sulfuric acid, lower alkyl esters of sulfonic acids, lower alkyl and alkenyl haloacetates, or aromatic or lower aliphaticaromatic quaternizing esters, to convert said adduct into the cation-active surface active agents of my present invention. Illustrative examples of such quaternizing esters are methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, allyl chloride, allyl bromide, methyl chloracetate, ethyl chloracetate, vinyl chloracetate, dimethyl sulfate, diethyl sulfate, benzyl chloride and dimethylbenzyl chloride, as well as their corresponding bromides; methylbenzyl chloride and bromide; phenylmethyl halides such as the chloride and bromide; phenylethyl chloride and bromide; substituted phenyl lower alkyl (from 1 to 4 carbon atoms) halides as, for example, 0- chlorbenzyl chloride and -nitrobenzyl chloride and bromide; and monocyclic arylsulfonic acid lower alkyl esters such as the methyl and ethyl esters of benzene sulfonic acid, -toluene sulfonic acid, and o-toluene sulfonic acid.

Where the quaternizing esters are in the form of lower alkyl or alkenyl halides, lower alkyl esters, etc., as described above, the alkyl and alkenyl groups should contain not more than 4 carbon atoms and, better still, should contain only 1 or 2 carbon atoms. Where said quaternizing agents contain an aryl radical, it is particularly advantageous that such aryl radical be a benzene radical which is connected to a divalent hydrocarbon radical such as -CH or CH CH or to a lower alkyl radical, that is One containing not more than 4 carbon atoms, especially CH or C H The aromatic or lower aliphatic-aromatic quaternizing esters, for best results, should contain from 7 to 9 carbon atoms. The speed of quaternization in any given instance will be governed by the reactants and the reaction conditions including the temperature and solvent medium utilized.

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

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

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

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

(d) Condensation products of 1 mol of phenylethanolamine with 10 to mols of propyleneoxide.

(e) Condensation products of /2 mol of diethylethanolamine and /2 mol of monoethyldiethanolamine with 6 to mols of propyleneoxide.

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

(g) Condensation products of 1 mol of phenyldiethanolamine with 6 to 25 mols of propyleneoxide.

(h) Condensation products of 1 mol of diethylethanok amine with 1 to 2 mols of ethyleneoxide, reacted with 20 mols of propyleneoxide.

(i) Condensation products of 1 mol of diethylethanolamine with 30 to 40 mols of propyleneoxide.

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

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

(l) Condensation products of 1 mol of diethylethanolamine with 6 to 10 mols of butyleneoxide.

The amines which are utilized in the production of the intermediate adducts or condensation products with the propylene oxide or other a-epoxides are particularly advantageously of aliphatic or acyclic character. They contain at least one reactive hydrogen in an hydroxy group which is linked to the quaternary ammonium nitrogen through an alkylene group containing from 1 to 3 carbon atoms. Illustrative examples of such amines are alkyl hydroxy amines, e.g., monomethylethanolamine, monoethylethanolamine, monomethyldiethanolamine, dimethylethanolamine, diethylethanolamine, diallylethanolamine, hydroxyethyl ethylenediamine, and N,N-dimethyl- N, N'-diisopropanol propylenediamine-l,3. Such amines may contain nonreactive substituents such as nitro groups, ether and thioether groups, CN groups, and the like, but, in general, best results will be obtained with the unsubstituted amines. Compatible mixtures of any two or more of said amines, in various proportions, can, of course, be utilized in the production of the intermediate condensation products.

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

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

Example 1 (a) 93 grains (1 mol) of dimethylethanolamine are placed in an autoclave from which the air is displaced by nitrogen. Then 74 grams (1 mol) of propylene oxide are pumped into the dimethylethanolamine in said autoclave and reacted while maintaining the temperature below 25 degrees C. The resulting reaction mixture is heated to about 150 degrees C. and 1406 (19 mols) of propylene oxide are added to the autoclave over a period of 6 hours while maintaining a nitrogen pressure in the autoclave, said reaction being advantageously carried out in the presence of 2 to 3 grams of potassium hydroxide as a catalyst. The rate of addition of the propylene oxide is controlled so that the pressure in the autoclave does not exceed 2 atmospheres and the temperature is controlled so as not to exceed about 150 degrees C. Upon completion of the reaction, the reaction mixture is cooled to below 100 degrees C. and flushed out with gaseous nitrogen.

(b) To 50 grams of the intermediate condensation product or adduct of part (a) hereof there are added 5 grams of butyl chloride in 10 grams of methanol and the resulting mixture is refluxed, with stirring, for 5 hours. A yield in excess of of theoretical of the following product is obtained:

0Q CH2CH2ORz where R is a polyoxypropylene radical containing approximately 20 oxypropylene groups.

Example 2 (a) 119 grams (1 mol) of monomethyldiethanolamine are reacted first with 74 grams (1 mol) and then with an additional 1036 grams (14 mols) of propylene oxide in the manner described in part (a) of Example 1.

(b) grams of the adduct of part (a) of this Example 2 are reacted with 8 grams of ethyl chloride in 16 grams of methanol, in the manner described in part (b) of Example 1. The final reaction product, in a yield of the order of 90%, comprises the following product:

where R are polyoxypropylene radicals the total of which contains approximately 15 oxypropylene groups.

Example 3 (a) 117 grams (1 mol) of diethylethanolamine are reacted with a total of 740 grams (10- mols) of propylene oxide in the manner described in part (a) of Example 1.

(b) 100 grams of the adduct of part (a) of this Example 3 are reacted with 7 grams of dimethylbenzyl chloride in 15 grams of methanol, in the manner described in part (b) of Example 1. The final reaction product, in a yield of the order of 90%, comprises the following product:

CH 02H, 01 CH-. :2

h CH3 where R is a polyoxypropylene radical containing approximately 10 oxypropylene groups.

Example 4 (a) 131 grams (1 mol) of diethylmonoisopropanolamine are reacted with a total of 888 grams (12 mols) of propylene oxide in the manner described in part (a) of Example 1.

(b) 50 grams of the adduct of part (a) of this Example 4 are reacted with 6 grams of benzyl chloride in 7 12 grams of methanol, in the manner described in part (b) of Example 1. The final reaction product, in a yield in excess of 80%, comprises the following product:

cant 01 mp 0,4 oIr -oH-om where R is a polyoxypropylene radical containing approximately 12 oxypropylene groups.

Example 5 where R is a polyoxypropylene radical containing approximately oxypropylene groups.

7 This application is a continuation-in-part of my applications Serial Nos. 22,099 and 22,115, each filed April 14. 1960.

What I claim as new and desire to protect by Letters 7 Patent of the United States is:

l. A quaternary ammonium compound corresponding to the formula R A where R and R are the same or dissimilar alkyl radicals each containing from 1 to 3 carbon atoms, R is where R is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total ntnnber of carbon atoms is R being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C ]i-I O) to R is not greater than 1 to 4, X is a member selected from the group consisting of (1) alkyl and alkenyl radicals containing from "1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

2. A quaternary ammonium compound corresponding to the formula CH X and R is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number" of carbon atoms is R being at least 18, X is a member selected from the group consisting of 8 member selected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

3. A quaternary ammonium compound corresponding to the formula X (OzH4O)vRz R1 I A (CZHO)VRQ where R is an alkyl radical containing from 1 to 3 carbon where R is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C H O) to R is not greater than 1 to 4, X is a (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

4. A quaternary ammonium compound corresponding to the formula ;selected from the group consisting of (1) alkyl and ,alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

5. A quaternary ammonium compound corresponding to the formula A R4O-R5 where R is an alkyl radical containing from 1 to 3 carbon atoms, R -OR is a polyoxyethylene-polyoxypropylene radical containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene radical to the polyoxypropylene radical is not greater than 1 to 4, the total number of oxypropylene groups not exceeding 60, X is a member selected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

where R is an alkyl radical containing from 1 to 3 carbon atoms, R is where R is an alkyl radical containing from 1 to 4 carbon atoms, 11 and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in the sum of R and R being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C H O) to the sum of R and R is not greater than 1 to 4, X is a member selected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

7. A quaternary ammonium compound corresponding to the formula l/ TK A CZH4OR2 where R is an alkyl radical containing from 1 to 3 carbon atoms, R is -LOH;,-OHO H K CH3 n and n totals a number from 8 to 30, X is a member selected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

8. A quaternary ammonium compound corresponding to the formula where R is an alkyl radical containing from 1 to 3 carbon and n totals a number from 8 to 30, X is a member selected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

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

and R is an alkyl radical containing from 1 to 4 carbon atoms, and n totals'a number not exceeding 60 with the proviso that the number of carbon atoms in the total of the R radicals is at least 18, v is a number at least 1 with the proviso that the Weight ratio of (C H -O-) to R is not greater than 1 to 4, X is a member slected from the group consisting of (1) alkyl and alkenyl radicals containing from 1 to 4 carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl radicals contain from 1 to 4 carbon atoms,

References Cited in the file of this patent UNITED STATES PATENTS Chiddix et a1 Aug. 21, 1956 Mark Mar. 3, 1959

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2759975 *May 28, 1952Aug 21, 1956Gen Aniline & Film CorpMixed alkyl-benzyl-alkylol quaternary ammonium salts
US2876263 *Dec 31, 1952Mar 3, 1959Universal Oil Prod CoPolyoxyalkylene cyclic hydrocarbon substituted amines and their ammonium salt derivatives
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3517045 *Jun 7, 1968Jun 23, 1970American Cyanamid CoHydroxyalkyl quaternary ammonium ethers as antistatic agents
US3668136 *Jul 7, 1969Jun 6, 1972Witco Chemical CorpCompatible anionic-catonic surfactant compositions
US4179396 *Feb 23, 1978Dec 18, 1979Nalco Chemical CompanySingle addition organic-inorganic blend emulsion breaking composition
US4281196 *Oct 11, 1979Jul 28, 1981Henkel Kommanditgesellschaft Auf AktienQuaternary ammonium compounds, their preparation, and their use as softening agents
US4540521 *Jan 16, 1984Sep 10, 1985National Distillers And Chemical CorporationLiquid quaternary ammonium antistatic compositions
US5317003 *Jul 16, 1992May 31, 1994Monsanto CompanyHerbicidal compositions comprising glyphosate salts and alkoxylated quaternary amine surfactants
US5354565 *Apr 15, 1992Oct 11, 1994Kao CorporationBiocide activator
US5464807 *Sep 23, 1994Nov 7, 1995Monsanto CompanyMethods of using glyphosate compositions comprising alkoxylated quaternary ammonium surfactants
US5492875 *Jul 19, 1994Feb 20, 1996Hoechst AgCatalyst for nucleophilic aromatic substitutions
US5652197 *Aug 9, 1996Jul 29, 1997Monsanto CompanyGlyphosate compositions
US5798310 *Mar 19, 1996Aug 25, 1998Monsanto Europe S.A.Glyphosate compositions and their use
US6339054Dec 15, 1999Jan 15, 2002Ecolab, Inc.Composition and method for road-film removal
US6350725Apr 20, 1999Feb 26, 2002Ecolab, Inc.Composition and method for road-film removal
US6551974Jun 23, 2000Apr 22, 2003Ecolab Inc.Polish compositions for gloss enhancement, and method
US6602350Nov 30, 2001Aug 5, 2003Ecolab Inc.Composition and method for road-film removal
US6686325Mar 15, 2002Feb 3, 2004Ecolab Inc.Alkaline sensitive metal cleaning composition, method for cleaning an alkaline sensitive metal surface, and washing facility
US6864220Nov 30, 2001Mar 8, 2005Ecolab Inc.Composition and method for road-film removal
US7140405Jun 28, 2004Nov 28, 2006Relevant Engineering DevelopmentMixing apparatus
US7223722Mar 14, 2003May 29, 2007Ecolab Inc.Polish compositions for gloss enhancement, and method
US7482315Mar 7, 2005Jan 27, 2009Ecolab Inc.Composition and method for road-film removal
US7530373Jun 28, 2004May 12, 2009R. Lewis Technologies, Inc.Mixing apparatus and methods using the same
US7951245May 31, 2011Ecolab Usa Inc.Composition and method for road-film removal
US8110537Jan 14, 2003Feb 7, 2012Ecolab Usa Inc.Liquid detergent composition and methods for using
US8210215Dec 11, 2008Jul 3, 2012R. Lewis Technologies, Inc.Mixing apparatus and methods of using the same
US8905088Jun 5, 2012Dec 9, 2014R. Lewis Technologies, Inc.Mixing apparatus and methods of using the same
US20040138084 *Jan 14, 2003Jul 15, 2004Gohl David W.Liquid detergent composition and methods for using
US20040261887 *Jun 28, 2004Dec 30, 2004William LewisMixing apparatus and methods using the same
US20040264295 *Jun 28, 2004Dec 30, 2004William LewisMixing apparatus
US20040266658 *Jun 28, 2004Dec 30, 2004Lenhart John G.Cleaning formulations and methods for manufacturing the same
US20050199272 *Mar 7, 2005Sep 15, 2005Ecolab Inc.Composition and method for road-film removal
US20060223736 *Mar 30, 2006Oct 5, 2006R. Lewis Technologies, Inc.Dye and scent pouches and methods of making the same
US20090188533 *Jan 26, 2009Jul 30, 2009Ecolab Inc.Composition and method for road-film removal
EP0207713A2 *Jun 24, 1986Jan 7, 1987Texaco Development CorporationCorrosion inhibiting system containing alkoxylated amines
EP0441764A1 *Jan 30, 1991Aug 14, 1991Monsanto Europe S.A.Glyphosate compositions and their use
EP0509346A1 *Apr 3, 1992Oct 21, 1992Kao CorporationBiocide activator
EP0733305A1 *Mar 24, 1995Sep 25, 1996Monsanto Europe S.A.Improved glyphosate compositions and their use
WO1996029873A1 *Mar 19, 1996Oct 3, 1996Monsanto Europe S.A.Improved glyphosate compositions and their use
Classifications
U.S. Classification562/66, 558/27, 564/292, 510/515, 564/284, 564/294, 564/285
International ClassificationA01N33/12, C23F11/10, A01N25/30, C09K3/16
Cooperative ClassificationC23F11/10, A01N33/12, A01N25/30, C09K3/16
European ClassificationA01N33/12, C09K3/16, A01N25/30, C23F11/10