US3123640A - Cation-active surface active aryldi- - Google Patents

Cation-active surface active aryldi- Download PDF

Info

Publication number
US3123640A
US3123640A US3123640DA US3123640A US 3123640 A US3123640 A US 3123640A US 3123640D A US3123640D A US 3123640DA US 3123640 A US3123640 A US 3123640A
Authority
US
United States
Prior art keywords
carbon atoms
propyleneoxide
mol
radical
mols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Publication date
Application granted granted Critical
Publication of US3123640A publication Critical patent/US3123640A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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

  • United States Patent Ofifice My invention relates to the production of novel cationactive surface active chemical compounds which are useful for bactericidal, germicidal, antiseptic, algtaecidal, fungicidal, textile softening, corrosion inhibition, antistatic, emulsifying, foam modifying, ore beneficiation, and vari- 0118 other purposesfor which certain heretofore known cationic surface active agents have been employed or suggested for use. 7
  • the specific cation-active surface active agents of my present invention are of the quaternary ammonium type and they are characterized by panticuiarly advantageous properties, simplicity of production and markedly low cost. Certain of them, for instance, those derived from low molecular Weight alkyl secondary amines and cyclic amines, can be represented by the formula (I) R ⁇ /R2 wherein R is an alkyl radical containing from 1 to 3 and more particularly from 1 to 2 carbon atoms, R, is
  • a? may be a radical or .a cyclic amine containing not more than 6 carbon atoms
  • R is a polyoxyalltylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing at least 3 carbon atoms, especially propyleneoxide.
  • propyleneoxide there will be at least 6 of such propyleneoxide groups in R and, more particularly, it is desired that R contain from 8 to 30* oaypropylene groups.
  • R is derived from e-epoxides containing more than 3 carbon atoms, a lesser number of such oxyalkylene groups can be present, subject to the limitation of R containing at least 18 atoms.
  • R is advantageously a lower aliphaticaryl radical containing 7 to 9 carbon atoms, notably an alharyl radical, and A is an anion. It is important, for the achievements of the results to which my invention is directed, that the R radical, Where it is alkyl, contain not more than 3 carbon atoms and especially that it contain from 1 to 2 carbon atoms and, hence, that it be methyl or ethyl. Likewise, except where a is derived from a cyclic amine, as hereafter pointed out, it is important that the R radical does not contain over 3 carbon atoms, and, in any event, the maximum number of carbon atoms in R and R does not exceed a total of more than 6, and more particularly does not exceed a total of '4 or 5.
  • R may contain a minimum of 6 of the aforesaid oxyalkylene, particularly oxypropy-lene, groups, and may contain 40, 50 or 60 or even 100 or more of said groups, it is especially advantageous that the minimum number of said groups be 8 and the preferred range is 8 to 25 or 30 of said groups.
  • m-epoxide as used herein, is intended to cover those 3,123,646 Patented Mar. 3, 1&64
  • polyoxyallcylene, polyoxypropylene and polyoxyethylene are employed in their usual or conventional manner.
  • R is an alkyl radical containing from 1 to 4 carbon atoms, and, .as indicated above, since R contains a.
  • n is at least 6 in the case of the polyoxyalkylene radical being polyoxypnopylene and n s at least 3 in the case of the polyoxyalkylene radical being polyoxyhexylene.
  • 11 is usually up to 60 or more.
  • the polyoxyalkylene radical is polyoxypnopylene, it may be represented by the formula n advantageously being from 6 to 30.
  • At least most of those of the particularly preferred quaternary ammonium compounds of my invention which are derived from lower monoalkyl amines can be represented by the afonrnula where R is an alkyl radical containing from 1 to 3, and especially from 1 to 2, carbon atoms, R, is
  • R is an alkyl radical containing from 1 to 4 carbon atoms, 11 and n are numbers the sum of which does not exceedbO, the total number of carbon atoms in R and R being at least 18;
  • R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.
  • R is an alkyl radical containing from 1 to 3, and 7 3 radical containing from 1 to 3 carbon atoms; alkylene contains not more than 3 carbon atoms, R O is where R; is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18; R is a hydrocarbon lower aliphatic-aromatic hydrocarbon radical containing from 7 to 9 carbon atoms; and A is an anion.
  • Ra R O-alkyleneN R O-alky1ene A where R is an alkyl radical containing from 1 to 3, and especially from '1 to 2, carbon atoms, alkylene contains not more than 3 carbon atoms, R O is where alkylene contains not more than 3 carbon atoms, R-O is in which R, is an alkyl radical containing from 1 to 4 carbon atoms, n, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, R and R being at least 18; R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.
  • Most of the quaternary compounds of the present invention fall into the category of or correspond to reaction products of quaternizing esters having a benzyl radical or a dimethylbenzyl radical or a lower alkyl substituted or chloro or nitro substituted benzyl radical, and an anion, with adducts of (a) aliphatic amines or cyclic amines containing a reactive hydrogen and a total of not more than 6 carbon atoms and in which no single aliphatic radical contains more than 3 carbon atoms, with (b) an ot-epoxide containing at least 3 and advantageously from 3 to 8 carbon atoms, the molar ratio of (a) to (b) being 1 of (a) to at least 6 cl (b) when said a-epoxide contains 3 carbon atoms and ranging down to at least 2.5 of (b) when said cs-fiPGXidfl contains 8 carbon atoms.
  • quaternary ammonium cornpounds which are particularly use- 121 and which may simply and inexpensively be produced are reaction products of aromatic quaternizing esters in the form of halides, sulfates and sulfonates advantageously containing from 7 to 9 carbon atoms exemplified by benzyl chloride, dimethylbe-nzyl chloride, and phenyl ethyl chloride, with adducts of (a) alkyl amines having a reactive hydrogen and containing from 1 to 4 carbon atoms, such as dimethylamine and diethylamine, with (b) propylenewtide or butyleneoxides, said adducts containing 1 mol or (d) to from 6, and preferably from 8, to 30 mols of (b). Purification steps can, if desired, be employed as, for instance, separating unreacted tertiary amines by distillation, etc.
  • the oxyalkylene groups be derived from an u-epoxide conaining at least 3 carbon atoms.
  • Ethyleneoxide for instance, is not operative in the practice of my invention since it produces compounds Whose properties are radically different from those obtained in accord-ance with my invention and which would be useless for the purposes for which the cation-active surface active agents of my invention are adapted and intended.
  • the most important embodiment of the ot-epoxides Whose use is contemplated by my invention in the production of the cation-active surface active agents is propyleneoxide butylene oxide, pentylene epoxides, hexylene epoxides,
  • R is an alkyl radical.
  • R is CH and in the representation of the group of propylene oxide, butylcne oxides, pentylene oxide and hexylene oxide R contains from 1 to 4 carbon atoms. In the higher molecular weight alkylene oxides, R may contain as high as 16 carbon atoms.
  • ethyleneoxide as the sole alkylene oxide is inoperative for my purposes, small proportions thereof, not to exceed 25% and better still not to exceed 20% by Weight of the propyleneoxide or other ot-epoxide employed, can be utilized as hereafter described. Mixtures of two or more of the lat-epoxides containing at least 3 carbons can, of course, be used as such, as Well as in conjunction with ethylene-oxide,
  • the cation-active surface active agents of my invention are advantageously prepared by initially condensing a lower molecular weight amine, for instance, one containing at least one allsyl radical having from 1 to 3 carbon atoms and no radical containing more than 3 carbon atoms linked to the nitrogen atom of the amine, or be initially condensing a cyclic amine such as piperidine containing not more than 6 carbon atoms, with propyleneoxide or other a-epoxide containing at least 3 carbon atoms, advantageously in the presence of a conventional oxyalkylating catalyst such as sodium hydroxide or potassium hydroxide, whereby to produce an intermediate or adduct containing at least 6 oxypropylene groups.
  • a lower molecular weight amine for instance, one containing at least one allsyl radical having from 1 to 3 carbon atoms and no radical containing more than 3 carbon atoms linked to the nitrogen atom of the amine, or be initially condensing a cyclic
  • the amines used in the reaction to produce said adducts must contain a reactive hydrogen, which may be hydrogen directly attached to the nitrogen of the amine or which may be in the form of hydroxyl hydrogen, secondary alkyl amines being especially desirable, particularly dimethylamine, diethylamine and methylethylamine.
  • a reactive hydrogen which may be hydrogen directly attached to the nitrogen of the amine or which may be in the form of hydroxyl hydrogen
  • secondary alkyl amines being especially desirable, particularly dimethylamine, diethylamine and methylethylamine.
  • the resulting adduct is then reacted with an aromatic or lower aliphatic-aromatic quaternizing ester to convert said adduct into the cation-active surface active agents of my present invention.
  • an aromatic or lower aliphatic-aromatic quaternizing ester to convert said adduct into the cation-active surface active agents of my present invention.
  • benzyl chloride and dimethylbenzyl chloride are, as pointed out above, benzyl chloride and dimethylbenzyl chloride, as well as their corresponding bromides; methylbenzyl chloride and bromide; phenylrnethyl halides such as the chloride and bromide; phenylethyl chloride and bromide; substituted phenyl lower alkyl (from 1 to 4 carbon atoms) halides as, for example, o-chlorhenzyl chloride and p-nitrobenzyl chloride and bromide; and monocyclic arylsulfonic acid lower alkyl esters such as the methyl and ethyl esters of benzene sulfonic acid, p-toluene sulfonic acid, and otoluene sulfonic acid.
  • all of the quaternizing esters which are utilized pursuant to the present invention contain an aryl radical, more particularly a benzene radical which is connected to a divalent hydrocarbon radical such as -CH or CH -CH or to a lower alkyl radical, that is one containing not more than 4 carbon atoms, especially CH or C H
  • 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.
  • the amines which are utilized in the production of the intermediate adducts or condensation products with the propylene oxide or other ec-epoxides are particularly advantageously of aliphatic or acyclic character, although they also include cyclic secondary amines. In all cases, they contain at least one reactive hydrogen directly attached to nitrogen or in a hydroxy group.
  • Illustrative examples of such amines are alkyl amines, e.g., methylamine, dimethylarnine, ethylamine, diethylamine, methylethylarnine, propyl amine, dipropylamine; alkyl hydroxy amines, e.
  • 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.
  • halogen such as chlorine, bromine and iodine
  • hydroxy sulfate; nitrate; phosphate; acetate; formate; sulfonic acids; and the like.
  • anion is chlorine or bromine.
  • Various of said anionic radicals can he introduced directly into the molecules; and, in the case of others, they can be made, for instance, by substitution for halogen in the cation-active surface active agents of my present invention by known techniques as, for instance, by metathesis procedures.
  • Example 1 46 grams (1 mol) of dimethylamine were placed in an autoclave from which the air was displaced by nitrogen. 58 grams (1 mol) of propyleneoxide were pumped into the dimethylamine in said autoclave and reacted while maintaining the temperature below 25 degrees C. The resulting compound was admixed with an alkaline catalyst, say 2 to 3 grams of KOH, and was heated to about 150 degrees C. and 25 mols of propyleneoxide were added to the autoclave over a period of 6 hours while maintaining a nitrogen pressure in the autoclave. The rate of addition of the propylene-oxide was controlled so that the pressure in the autoclave did not exceed 2 atmospheres and the temperature controlled so as not to exceed 200 degrees C. and preferably at about 150 degrees C. Upon completion of the reaction, the reaction mixture was cooled to below 100 degrees C. and flushed out with gaseous nitrogen.
  • an alkaline catalyst say 2 to 3 grams of KOH
  • R is a polyoxypropylene radical containing about 25 oxypropylene groups.
  • Example 2 50 grams of the adduct of part (a) of Example 1 were reacted with 3 grams of dimethyl benzyl chloride in the manner described in part (b) of Example 1 to produce a product having the following formula:
  • R is a polyoxypropylene radical containing about 25 oxypropylene groups.
  • Example 3 wherein R is an alkyl radical containing from 1 to 3 carbon atoms, R is a member selected from the group consisting of an alkyl radical containing from 1 to 3 carbon atoms and and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is where R is an alkyl radical containing from 1 to 4 carbon atoms, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R being at least 18; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
  • R is methyl; R is an alkyl radical containing from 1 to 3 carbon atoms; R is wherein n is a number from 6 to 30; R is a dimethylbenzyl radical; and A is an anion.
  • n is a number from 6 to 30; R is a benzyl radical; and A is chlorine.
  • a quaternary ammonium compound in accordance with claim 1 wherein up to 20% by weight of R is replaced by a polyoxyethylene radical.
  • a quaternary ammonium compound having the formula wherein R is an alkyl radical containing from 1 t0 3 carbon atoms, R; is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is a polyoxypropylene-poiyoxyethylene radical in which the number of oxypropylene groups is from 6 to 60 and in which the ethylene oxide constitutes not more than 20% by weight of said radical; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
  • A is an anion.
  • a quaternary ammonium compound having the formula where R is an alkyl radical containing from 1 to 3 carbon atoms, R is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a cyclic amine radical containing not more than 6 carbon atoms, with the proviso that the total number of carbon atoms in R and R does not exceed 6;
  • R is a polyoxyalkylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing from 3 to 6 carbon atoms, said oc-BpOXidG consisting of carbon, hydrogen and oxygen, and the total number of oxyalkylene groups in said polyoxyalkylene radical not exceeding 60;
  • R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
  • A is an anion.
  • a quaternary ammonium compound having the formula Rr-N where R and R are each methyl; R is -CHz-C H-O nH CH3 wherein n is a number from 6 to 30; R is benzyl; and A is chlorine.

Description

United States Patent Ofifice My invention relates to the production of novel cationactive surface active chemical compounds which are useful for bactericidal, germicidal, antiseptic, algtaecidal, fungicidal, textile softening, corrosion inhibition, antistatic, emulsifying, foam modifying, ore beneficiation, and vari- 0118 other purposesfor which certain heretofore known cationic surface active agents have been employed or suggested for use. 7
The specific cation-active surface active agents of my present invention are of the quaternary ammonium type and they are characterized by panticuiarly advantageous properties, simplicity of production and markedly low cost. Certain of them, for instance, those derived from low molecular Weight alkyl secondary amines and cyclic amines, can be represented by the formula (I) R\ /R2 wherein R is an alkyl radical containing from 1 to 3 and more particularly from 1 to 2 carbon atoms, R, is
an alkyl radical containing firom l to 3 carbon atoms, or
a? may be a radical or .a cyclic amine containing not more than 6 carbon atoms, R is a polyoxyalltylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing at least 3 carbon atoms, especially propyleneoxide. In those cases where R is derived from propyleneoxide, there will be at least 6 of such propyleneoxide groups in R and, more particularly, it is desired that R contain from 8 to 30* oaypropylene groups. Where R is derived from e-epoxides containing more than 3 carbon atoms, a lesser number of such oxyalkylene groups can be present, subject to the limitation of R containing at least 18 atoms. R is advantageously a lower aliphaticaryl radical containing 7 to 9 carbon atoms, notably an alharyl radical, and A is an anion. It is important, for the achievements of the results to which my invention is directed, that the R radical, Where it is alkyl, contain not more than 3 carbon atoms and especially that it contain from 1 to 2 carbon atoms and, hence, that it be methyl or ethyl. Likewise, except where a is derived from a cyclic amine, as hereafter pointed out, it is important that the R radical does not contain over 3 carbon atoms, and, in any event, the maximum number of carbon atoms in R and R does not exceed a total of more than 6, and more particularly does not exceed a total of '4 or 5. While R may contain a minimum of 6 of the aforesaid oxyalkylene, particularly oxypropy-lene, groups, and may contain 40, 50 or 60 or even 100 or more of said groups, it is especially advantageous that the minimum number of said groups be 8 and the preferred range is 8 to 25 or 30 of said groups. The term m-epoxide, as used herein, is intended to cover those 3,123,646 Patented Mar. 3, 1&64
2 compounds, of the type here involved, where there are two vlcinal carbon atoms connected to one oxygen atom mdependently of the position of such group in the molecule.
The terms polyoxyallcylene, polyoxypropylene and polyoxyethylene, to the extent that they are used herein or in the claims, are employed in their usual or conventional manner. Thus, in the case of the polyoxyalkylene radical derived from a-epoxides containing from 3 to 6 carbon atoms, to wit, R in the above iormtula, the same may be represented by where R, is an alkyl radical containing from 1 to 4 carbon atoms, and, .as indicated above, since R contains a. of l8 carbon atoms, n is at least 6 in the case of the polyoxyalkylene radical being polyoxypnopylene and n s at least 3 in the case of the polyoxyalkylene radical being polyoxyhexylene. As indicated above, 11 is usually up to 60 or more. Where the polyoxyalkylene radical is polyoxypnopylene, it may be represented by the formula n advantageously being from 6 to 30.
The foregoing illustrate the polyoxyalkylene and polyoxypropylene radicals Where the vicinal carbons are terminal. In the broader, but less preferred, embodiments of my invention, however, the vicinal carbons need not be terminal. A typical illustration of the latter is g polyoxyalkylene radical derived from 2,3-buty1ene on e.
At least most of those of the particularly preferred quaternary ammonium compounds of my invention which are derived from lower monoalkyl amines can be represented by the afonrnula where R is an alkyl radical containing from 1 to 3, and especially from 1 to 2, carbon atoms, R, is
where R, is an alkyl radical containing from 1 to 4 carbon atoms, 11 and n are numbers the sum of which does not exceedbO, the total number of carbon atoms in R and R being at least 18; R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.
Various of those particularly preferred quaternary ammonium compounds of my invention .which are derived from lower dialkyl monoalkanolamines can be represented by the formula where R is an alkyl radical containing from 1 to 3, and 7 3 radical containing from 1 to 3 carbon atoms; alkylene contains not more than 3 carbon atoms, R O is where R; is an alkyl radical containing from 1 to 4 carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18; R is a hydrocarbon lower aliphatic-aromatic hydrocarbon radical containing from 7 to 9 carbon atoms; and A is an anion.
Again, various of those of the particularly preferred quaternary ammonium compounds of my invention which are derived from lower monoalkyl dialkanolamines can be represented by the formula (IV) Ra R O-alkyleneN R O-alky1ene A where R is an alkyl radical containing from 1 to 3, and especially from '1 to 2, carbon atoms, alkylene contains not more than 3 carbon atoms, R O is where alkylene contains not more than 3 carbon atoms, R-O is in which R, is an alkyl radical containing from 1 to 4 carbon atoms, n, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, R and R being at least 18; R is a hydrocarbon lower aliphatic-aromatic radical containing from 7 to 9 carbon atoms; and A is an anion.
Most of the quaternary compounds of the present invention fall into the category of or correspond to reaction products of quaternizing esters having a benzyl radical or a dimethylbenzyl radical or a lower alkyl substituted or chloro or nitro substituted benzyl radical, and an anion, with adducts of (a) aliphatic amines or cyclic amines containing a reactive hydrogen and a total of not more than 6 carbon atoms and in which no single aliphatic radical contains more than 3 carbon atoms, with (b) an ot-epoxide containing at least 3 and advantageously from 3 to 8 carbon atoms, the molar ratio of (a) to (b) being 1 of (a) to at least 6 cl (b) when said a-epoxide contains 3 carbon atoms and ranging down to at least 2.5 of (b) when said cs-fiPGXidfl contains 8 carbon atoms.
While, as indicated, many of the novel and useful cation-active surface active agents of my invention can be represented by the above formulae, they may, in general, best be described in the form of reaction products of identified ingredients, as hereafter pointed out, since the active constituent or constituents thereof need not be separated out and recovered as such, the reaction products being usable as such for many purposes without the necessity for resorting to concentration, purification or recovery steps. Thus, for example, although this will be pointed out and described in more detail hereafter, quaternary ammonium cornpounds which are particularly use- 121 and which may simply and inexpensively be produced are reaction products of aromatic quaternizing esters in the form of halides, sulfates and sulfonates advantageously containing from 7 to 9 carbon atoms exemplified by benzyl chloride, dimethylbe-nzyl chloride, and phenyl ethyl chloride, with adducts of (a) alkyl amines having a reactive hydrogen and containing from 1 to 4 carbon atoms, such as dimethylamine and diethylamine, with (b) propylenewtide or butyleneoxides, said adducts containing 1 mol or (d) to from 6, and preferably from 8, to 30 mols of (b). Purification steps can, if desired, be employed as, for instance, separating unreacted tertiary amines by distillation, etc.
It is important to note that it is critical to my present invention that the oxyalkylene groups be derived from an u-epoxide conaining at least 3 carbon atoms. Ethyleneoxide, for instance, is not operative in the practice of my invention since it produces compounds Whose properties are radically different from those obtained in accord-ance with my invention and which would be useless for the purposes for which the cation-active surface active agents of my invention are adapted and intended. The most important embodiment of the ot-epoxides Whose use is contemplated by my invention in the production of the cation-active surface active agents is propyleneoxide butylene oxide, pentylene epoxides, hexylene epoxides,
heptylene epoxides, octylene epoxides, dodecylene epoxides, rand C ,-C olefin oxides or epoxides, and, as Well, styrene epoxide. It will be seen that most of those of the ot-epoxides in which the vioinal carbons are terminal can conveniently be represented by the formula Where R is an alkyl radical. In the case of propylene oxide, R is CH and in the representation of the group of propylene oxide, butylcne oxides, pentylene oxide and hexylene oxide R contains from 1 to 4 carbon atoms. In the higher molecular weight alkylene oxides, R may contain as high as 16 carbon atoms.
While, as lhave stated above, the use of ethyleneoxide as the sole alkylene oxide is inoperative for my purposes, small proportions thereof, not to exceed 25% and better still not to exceed 20% by Weight of the propyleneoxide or other ot-epoxide employed, can be utilized as hereafter described. Mixtures of two or more of the lat-epoxides containing at least 3 carbons can, of course, be used as such, as Well as in conjunction with ethylene-oxide,
subject to the limitation that the ethyleneoxide must not exceed the aforesaid 20% to 25% of the weight of said a-epoxides.
The cation-active surface active agents of my invention are advantageously prepared by initially condensing a lower molecular weight amine, for instance, one containing at least one allsyl radical having from 1 to 3 carbon atoms and no radical containing more than 3 carbon atoms linked to the nitrogen atom of the amine, or be initially condensing a cyclic amine such as piperidine containing not more than 6 carbon atoms, with propyleneoxide or other a-epoxide containing at least 3 carbon atoms, advantageously in the presence of a conventional oxyalkylating catalyst such as sodium hydroxide or potassium hydroxide, whereby to produce an intermediate or adduct containing at least 6 oxypropylene groups. The amines used in the reaction to produce said adducts must contain a reactive hydrogen, which may be hydrogen directly attached to the nitrogen of the amine or which may be in the form of hydroxyl hydrogen, secondary alkyl amines being especially desirable, particularly dimethylamine, diethylamine and methylethylamine. The resulting adduct is then reacted with an aromatic or lower aliphatic-aromatic quaternizing ester to convert said adduct into the cation-active surface active agents of my present invention. Illustrative examples of such quaternizing al'karyl halides, etc. are, as pointed out above, benzyl chloride and dimethylbenzyl chloride, as well as their corresponding bromides; methylbenzyl chloride and bromide; phenylrnethyl halides such as the chloride and bromide; phenylethyl chloride and bromide; substituted phenyl lower alkyl (from 1 to 4 carbon atoms) halides as, for example, o-chlorhenzyl chloride and p-nitrobenzyl chloride and bromide; and monocyclic arylsulfonic acid lower alkyl esters such as the methyl and ethyl esters of benzene sulfonic acid, p-toluene sulfonic acid, and otoluene sulfonic acid. It will be seen that all of the quaternizing esters which are utilized pursuant to the present invention contain an aryl radical, more particularly a benzene radical which is connected to a divalent hydrocarbon radical such as -CH or CH -CH or to a lower alkyl radical, that is one containing not more than 4 carbon atoms, especially CH or C H In order to obtain cation-active surface active agents having the required properties in accordance with my invention, the aromatic or lower aliphatic-aromatic quaternizing esters, for best results should contain from 7 to 9 carbon atoms. The speed of quaternization in any given instance will be governed by the reactants and the reaction conditions including the temperature and solvent medium utilized.
Illustrative examples of the intermediate condensation products or adducts which are subsequently converted into the cation-active surface active agents or quaternary ammonium compounds encompassed by my present invention are the following:
(a) Condensation products of 1 mol of dimethylamine with 6 to 10 mols of propyleneoxide.
(b) Condensation products of 1 mol of dimethylamine with mols of propyleneoxide.
(c) Condensation products of 1 mol of dimethylamine with a mixture of mols of propyleneoxide and 5 mols of ethyleneoxide.
(d) Condensation products of 1 mol of dimethylamine with 1 to 2 mols of ethyleneoxide, reacted with 20 rriols of propyleneoxide.
(e) Condensation products of 1 mol of methylamine with to mols of propyleneoxide.
(f) Condensation products of 1 mol of methylethylamine with 10 to mols of propyleneoxide.
, (g) Condensation products of 1 mol of diethylamine with 30 mols of propyleneoxide.
(h) Condensation products of 1 mol of dimethylarnine with 10 to 20 mols of propyleneoxide and then with 1 mol of ethyleneoxide.
(i) Condensation products of 1 mol of methylpropylamine with 10 to 25 mols of propyleneoxide.
(j) Condensation products of 1 mol of dirnethylamine with 10 to 15 mols of butyleneoxide.
(k) Condensation products of 1 mol of diethylamine with 10 to 18 mols of butyleneoxide.
(l) Condensation products of 1 mol of piperidine with 10 to 25 mols of propyleneoxide.
(m-) Condensation products of 1 mol of methylpiperidine with 10 to 25 mols of propyleneoxide.
(n) Condensation products of 1 mol of pyrrolidine with 10 to 25 mols of propyleneoxide.
(0) Condensation products of /2 mol of methylamine and /2 mol of diethylamine with 6 to 30 mols of propyleneoxide.
(p) Condensation products of mol of dimethylamine and /3 mol of diethylamine with 10 to 25 mols of propyleneoxide.
(q) Condensation products of 1 mol of morpholine with from 6 to 30 mols of propyleneoxide.
(r) Condensation products of 1 mol of diethylethanolamine with 8 to 20 mols of propyleneoxide.
(s) Condensation products of 1 mol of diallylethanolamine with 8 to 25 mols of propyleneoxide.
(t) Condensation products of 1 mol of furfurylamine with 8 to 25 mols of propyleneoxide.
(u) Condensation products of 1 mol of 2-amino-1,3- propanediol with 8 to 25 mols of propyleneoxide.
(v) Condensation products of 1 mol of diethylamine with 6 to 25 mols of propyleneoxide.
The amines which are utilized in the production of the intermediate adducts or condensation products with the propylene oxide or other ec-epoxides are particularly advantageously of aliphatic or acyclic character, although they also include cyclic secondary amines. In all cases, they contain at least one reactive hydrogen directly attached to nitrogen or in a hydroxy group. Illustrative examples of such amines are alkyl amines, e.g., methylamine, dimethylarnine, ethylamine, diethylamine, methylethylarnine, propyl amine, dipropylamine; alkyl hydroxy amines, e. g., monomethylethanolamine, monoethylethamol-amine, monomethyldiethanolamine, dimethylethanolamine, diethylethanolamine and diallylethanolamine; polyamines such as ethylenediamine, diethylenetriarnine and triethylenetetraamine and higher polyamines in which there is at least one short chain alkyl group, as for instance, monomethyl ethylenediamine, dimethyl ethylenediamine and trimethyl ethylenediamine; N,N-dimethyl-N,N'-diisopropanol propylenediamine-l,3; furfurylamine; cyclic secondary amines containing not more than 6 carbon atoms, typical examples of which are morpholine, piperidine, methylpiperidine, and pyrrolidine. Such amines may contain nonreactive substituents such as nitro groups, ether and thioether groups, CN groups, and the like, but, in general, best results will be obtained with the unsubstituted amines. Compatible mixtures of any two or more of said amines, in various proportions, can, of course, be utilized in the production of the intermediate condensation products.
The radical A can be any negative or salt-forming radical as, for instance, halogen such as chlorine, bromine and iodine; hydroxy; sulfate; nitrate; phosphate; acetate; formate; sulfonic acids; and the like. Of particular importance are those of the cation-active surface active agents of any invention in which the anion is chlorine or bromine. Various of said anionic radicals can he introduced directly into the molecules; and, in the case of others, they can be made, for instance, by substitution for halogen in the cation-active surface active agents of my present invention by known techniques as, for instance, by metathesis procedures.
The following examples are illustrative of the production of typical cation-active surface active agents in accordance with my invention. It will be understood that other reactants can be utilized, proportions modified, temperature and other conditions, and concentration or purification procedures employed, all within the guiding principles taught herein, without departing from the essential teachings disclosed herein.
Example 1 (a) 46 grams (1 mol) of dimethylamine were placed in an autoclave from which the air was displaced by nitrogen. 58 grams (1 mol) of propyleneoxide were pumped into the dimethylamine in said autoclave and reacted while maintaining the temperature below 25 degrees C. The resulting compound was admixed with an alkaline catalyst, say 2 to 3 grams of KOH, and was heated to about 150 degrees C. and 25 mols of propyleneoxide were added to the autoclave over a period of 6 hours while maintaining a nitrogen pressure in the autoclave. The rate of addition of the propylene-oxide was controlled so that the pressure in the autoclave did not exceed 2 atmospheres and the temperature controlled so as not to exceed 200 degrees C. and preferably at about 150 degrees C. Upon completion of the reaction, the reaction mixture was cooled to below 100 degrees C. and flushed out with gaseous nitrogen.
(b) To 77 grams of the intermediate condensation product or adduct of part (a) hereof there were added 8 grams of methanol and 8 grams of benzyl chloride and the resulting mixture was refluxed, with stirring, for hours. During this period, the temperature of reflux rose somewhat and the viscosity of the reaction mixture increased appreciably. A yield of 96% of theoretical of the following product was obtained:
0 H3 0 lag-O C R Cl wherein R is a polyoxypropylene radical containing about 25 oxypropylene groups.
Example 2 50 grams of the adduct of part (a) of Example 1 were reacted with 3 grams of dimethyl benzyl chloride in the manner described in part (b) of Example 1 to produce a product having the following formula:
CH3 R Cl where R is a polyoxypropylene radical containing about 25 oxypropylene groups.
Example 3 wherein R is an alkyl radical containing from 1 to 3 carbon atoms, R is a member selected from the group consisting of an alkyl radical containing from 1 to 3 carbon atoms and and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is where R is an alkyl radical containing from 1 to 4 carbon atoms, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R being at least 18; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
wherein R is methyl; R is an alkyl radical containing from 1 to 3 carbon atoms; R is wherein n is a number from 6 to 30; R is a dimethylbenzyl radical; and A is an anion.
4. A quaternary ammonium compound having the formula R R: 3.21% Ra \A wherein R and R are each ethyl; R is {CH2(|3H-O):I
wherein n is a number from 6 to 30; R is a benzyl radical; and A is chlorine.
5. A quaternary ammonium compound in accordance with claim 1 wherein up to 20% by weight of R is replaced by a polyoxyethylene radical.
6. A quaternary ammonium compound having the formula wherein R is an alkyl radical containing from 1 t0 3 carbon atoms, R; is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine; R is a polyoxypropylene-poiyoxyethylene radical in which the number of oxypropylene groups is from 6 to 60 and in which the ethylene oxide constitutes not more than 20% by weight of said radical; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an anion.
7. A quaternary ammonium compound having the formula where R is an alkyl radical containing from 1 to 3 carbon atoms, R is an alkyl radical containing from 1 to 3 carbon atoms, and compounds wherein R and R are joined together to form with the N atom a cyclic amine radical containing not more than 6 carbon atoms, with the proviso that the total number of carbon atoms in R and R does not exceed 6; R is a polyoxyalkylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing from 3 to 6 carbon atoms, said oc-BpOXidG consisting of carbon, hydrogen and oxygen, and the total number of oxyalkylene groups in said polyoxyalkylene radical not exceeding 60; R is a member selected from the group consisting of benzene; methyl benzenes; ethyl benzenes;
and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitr c nuclearly substituted derivatives of the foregoing; and A is an anion.
8. A quaternary ammonium compound having the formula B3 A wherein R is methyl; R is an alkyl radical containing from 1 to 3 carbon atoms; R is wherein n is a number from 6 to 30; R is an aralkyl radical containing from 7 to 9 carbon atoms, and A is an anion.
9. A quaternary ammonium compound having the formula Rr-N where R and R are each methyl; R is -CHz-C H-O nH CH3 wherein n is a number from 6 to 30; R is benzyl; and A is chlorine.
10. A quaternary ammonium compound having the formula I where R and R are each methyl; R is wherein n is a number from 6 to 30; R is methylbenzyl; and A is chlorine.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A QUATERNARY AMMONIUM COMPOUND HAVING THE FORMULA
US3123640D Cation-active surface active aryldi- Expired - Lifetime US3123640A (en)

Publications (1)

Publication Number Publication Date
US3123640A true US3123640A (en) 1964-03-03

Family

ID=3453170

Family Applications (1)

Application Number Title Priority Date Filing Date
US3123640D Expired - Lifetime US3123640A (en) Cation-active surface active aryldi-

Country Status (1)

Country Link
US (1) US3123640A (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3346604A (en) * 1962-06-11 1967-10-10 American Cyanamid Co Quaternary ammonium complexes with heteropolyanions
US3365313A (en) * 1962-06-11 1968-01-23 American Cyanamid Co Anti-corrosion compositions
US3429970A (en) * 1961-02-02 1969-02-25 Hoffmann La Roche Method of hindering the metamorphosis and reproduction of arthropodes
US3668136A (en) * 1969-07-07 1972-06-06 Witco Chemical Corp Compatible anionic-catonic surfactant compositions
DE2256234A1 (en) * 1971-11-19 1973-05-24 Mo Och Domsjoe Ab CATIONIC SURFACE-ACTIVE COMPOUNDS, PROCESSES FOR THEIR PRODUCTION AND THEIR USE FOR THE TREATMENT OF TEXTILE MATERIALS
US3876760A (en) * 1969-10-23 1975-04-08 Bristol Myers Co Hair dressing compositions containing a hair substantive quaternary resin
US3959463A (en) * 1972-07-10 1976-05-25 Bristol-Myers Company Hair dressing compositions containing a hair substantive quaternary resin
US4169279A (en) * 1978-09-25 1979-09-25 Lester Laboratories, Inc. Method for neutralizing static electricity with mixed atmospheres
DE3046352A1 (en) * 1979-12-10 1981-09-10 Berol Kemi AB, 44401 Stenungsund Boundary-active quaternary ammonium compounds and their use for the treatment of textile and cellulose materials
US4314308A (en) * 1980-10-06 1982-02-02 Lester Laboratories, Inc. Increasing the rate of neutralization of static electricity
US4313895A (en) * 1980-06-24 1982-02-02 Akzona Incorporated Alkoxylated diquaternary ammonium compounds
US5430005A (en) * 1991-08-02 1995-07-04 Monsanto Company Herbicidal compositions
US5464807A (en) * 1990-02-05 1995-11-07 Monsanto Company Methods of using glyphosate compositions comprising alkoxylated quaternary ammonium surfactants
US5525261A (en) * 1994-10-18 1996-06-11 Henkel Corporation Anti-static composition and method of making the same
US6339054B1 (en) 1999-04-20 2002-01-15 Ecolab, Inc. Composition and method for road-film removal
US6350725B1 (en) 1999-04-20 2002-02-26 Ecolab, Inc. Composition and method for road-film removal
US6551974B1 (en) 1999-04-20 2003-04-22 Ecolab Inc. Polish compositions for gloss enhancement, and method
EP1320285A1 (en) * 2001-12-11 2003-06-18 Girolamo Barbieri Method and apparatus for neutralizing electrostatic charges from an electrostatically charged element
US6686325B2 (en) 2002-03-15 2004-02-03 Ecolab Inc. Alkaline sensitive metal cleaning composition, method for cleaning an alkaline sensitive metal surface, and washing facility
US20040138084A1 (en) * 2003-01-14 2004-07-15 Gohl David W. Liquid detergent composition and methods for using
US20040261887A1 (en) * 2003-06-26 2004-12-30 William Lewis Mixing apparatus and methods using the same
US20040266658A1 (en) * 2003-06-26 2004-12-30 Lenhart John G. Cleaning formulations and methods for manufacturing the same
US20050176896A1 (en) * 1997-11-06 2005-08-11 Bentley Michael D. Heterobifunctional poly (ethylene glycol) derivatives and methods for their preparation
US20060223736A1 (en) * 2005-03-30 2006-10-05 R. Lewis Technologies, Inc. Dye and scent pouches and methods of making the same
US10005983B2 (en) 2015-02-12 2018-06-26 Reuben H Chow Cleaning formulations and methods of use thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2003960A (en) * 1935-06-04 Printing
US2060850A (en) * 1932-11-08 1936-11-17 Du Pont Quaternary ammonium compounds and process for the production thereof
US2087506A (en) * 1936-08-21 1937-07-20 Tretolite Co Quaternary ammonium salts of high molecular weight acids
US2137314A (en) * 1935-05-22 1938-11-22 Ig Farbenindustrie Ag Process of producing quaternary ammonium compounds
US2161322A (en) * 1936-03-28 1939-06-06 Ig Farbenindustrie Ag C-aliphatic isocyclic amines n-substituted by oxyaliphatic radicals
US2214352A (en) * 1935-06-22 1940-09-10 Gen Aniline & Film Corp Process for the production of condensation products containing onium groups
US2677700A (en) * 1951-05-31 1954-05-04 Wyandotte Chemicals Corp Polyoxyalkylene surface active agents
US2701239A (en) * 1952-01-16 1955-02-01 Nat Aluminate Corp Steam generation and compositions for inhibiting foaming
US2759975A (en) * 1952-05-28 1956-08-21 Gen Aniline & Film Corp Mixed alkyl-benzyl-alkylol quaternary ammonium salts
US2775604A (en) * 1953-02-09 1956-12-25 Atlas Powder Co Quaternary ammonium halides
US2876263A (en) * 1952-12-31 1959-03-03 Universal Oil Prod Co Polyoxyalkylene cyclic hydrocarbon substituted amines and their ammonium salt derivatives

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2003960A (en) * 1935-06-04 Printing
US2060850A (en) * 1932-11-08 1936-11-17 Du Pont Quaternary ammonium compounds and process for the production thereof
US2137314A (en) * 1935-05-22 1938-11-22 Ig Farbenindustrie Ag Process of producing quaternary ammonium compounds
US2214352A (en) * 1935-06-22 1940-09-10 Gen Aniline & Film Corp Process for the production of condensation products containing onium groups
US2161322A (en) * 1936-03-28 1939-06-06 Ig Farbenindustrie Ag C-aliphatic isocyclic amines n-substituted by oxyaliphatic radicals
US2087506A (en) * 1936-08-21 1937-07-20 Tretolite Co Quaternary ammonium salts of high molecular weight acids
US2677700A (en) * 1951-05-31 1954-05-04 Wyandotte Chemicals Corp Polyoxyalkylene surface active agents
US2701239A (en) * 1952-01-16 1955-02-01 Nat Aluminate Corp Steam generation and compositions for inhibiting foaming
US2759975A (en) * 1952-05-28 1956-08-21 Gen Aniline & Film Corp Mixed alkyl-benzyl-alkylol quaternary ammonium salts
US2876263A (en) * 1952-12-31 1959-03-03 Universal Oil Prod Co Polyoxyalkylene cyclic hydrocarbon substituted amines and their ammonium salt derivatives
US2775604A (en) * 1953-02-09 1956-12-25 Atlas Powder Co Quaternary ammonium halides

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429970A (en) * 1961-02-02 1969-02-25 Hoffmann La Roche Method of hindering the metamorphosis and reproduction of arthropodes
US3346604A (en) * 1962-06-11 1967-10-10 American Cyanamid Co Quaternary ammonium complexes with heteropolyanions
US3365313A (en) * 1962-06-11 1968-01-23 American Cyanamid Co Anti-corrosion compositions
US3668136A (en) * 1969-07-07 1972-06-06 Witco Chemical Corp Compatible anionic-catonic surfactant compositions
US3876760A (en) * 1969-10-23 1975-04-08 Bristol Myers Co Hair dressing compositions containing a hair substantive quaternary resin
DE2256234A1 (en) * 1971-11-19 1973-05-24 Mo Och Domsjoe Ab CATIONIC SURFACE-ACTIVE COMPOUNDS, PROCESSES FOR THEIR PRODUCTION AND THEIR USE FOR THE TREATMENT OF TEXTILE MATERIALS
US3959463A (en) * 1972-07-10 1976-05-25 Bristol-Myers Company Hair dressing compositions containing a hair substantive quaternary resin
US4169279A (en) * 1978-09-25 1979-09-25 Lester Laboratories, Inc. Method for neutralizing static electricity with mixed atmospheres
DE3046352A1 (en) * 1979-12-10 1981-09-10 Berol Kemi AB, 44401 Stenungsund Boundary-active quaternary ammonium compounds and their use for the treatment of textile and cellulose materials
US4313895A (en) * 1980-06-24 1982-02-02 Akzona Incorporated Alkoxylated diquaternary ammonium compounds
US4314308A (en) * 1980-10-06 1982-02-02 Lester Laboratories, Inc. Increasing the rate of neutralization of static electricity
US5464807A (en) * 1990-02-05 1995-11-07 Monsanto Company Methods of using glyphosate compositions comprising alkoxylated quaternary ammonium surfactants
US5430005A (en) * 1991-08-02 1995-07-04 Monsanto Company Herbicidal compositions
US5525261A (en) * 1994-10-18 1996-06-11 Henkel Corporation Anti-static composition and method of making the same
US10035880B2 (en) 1997-11-06 2018-07-31 Nektar Therapeutics Heterobifunctional poly(ethylene glycol) derivatives and methods for their preparation
US8940801B2 (en) 1997-11-06 2015-01-27 Nektar Therapeutics Heterobifunctional poly(ethylene glycol) derivatives and methods for their preparation
US7642323B2 (en) * 1997-11-06 2010-01-05 Nektar Therapeutics Heterobifunctional poly(ethylene glycol) derivatives and methods for their preparation
US20050176896A1 (en) * 1997-11-06 2005-08-11 Bentley Michael D. Heterobifunctional poly (ethylene glycol) derivatives and methods for their preparation
US7482315B2 (en) 1999-04-20 2009-01-27 Ecolab Inc. Composition and method for road-film removal
US7223722B2 (en) 1999-04-20 2007-05-29 Ecolab Inc. Polish compositions for gloss enhancement, and method
US6339054B1 (en) 1999-04-20 2002-01-15 Ecolab, Inc. Composition and method for road-film removal
US6350725B1 (en) 1999-04-20 2002-02-26 Ecolab, Inc. Composition and method for road-film removal
US7951245B2 (en) 1999-04-20 2011-05-31 Ecolab Usa Inc. Composition and method for road-film removal
US6551974B1 (en) 1999-04-20 2003-04-22 Ecolab Inc. Polish compositions for gloss enhancement, and method
US6864220B2 (en) 1999-04-20 2005-03-08 Ecolab Inc. Composition and method for road-film removal
US6602350B2 (en) 1999-04-20 2003-08-05 Ecolab Inc. Composition and method for road-film removal
US20050199272A1 (en) * 1999-04-20 2005-09-15 Ecolab Inc. Composition and method for road-film removal
US20090188533A1 (en) * 1999-04-20 2009-07-30 Ecolab Inc. Composition and method for road-film removal
EP1320285A1 (en) * 2001-12-11 2003-06-18 Girolamo Barbieri Method and apparatus for neutralizing electrostatic charges from an electrostatically charged element
US6686325B2 (en) 2002-03-15 2004-02-03 Ecolab Inc. Alkaline sensitive metal cleaning composition, method for cleaning an alkaline sensitive metal surface, and washing facility
US8110537B2 (en) 2003-01-14 2012-02-07 Ecolab Usa Inc. Liquid detergent composition and methods for using
US20040138084A1 (en) * 2003-01-14 2004-07-15 Gohl David W. Liquid detergent composition and methods for using
US20040264295A1 (en) * 2003-06-26 2004-12-30 William Lewis Mixing apparatus
US20040266658A1 (en) * 2003-06-26 2004-12-30 Lenhart John G. Cleaning formulations and methods for manufacturing the same
US7140405B2 (en) 2003-06-26 2006-11-28 Relevant Engineering Development Mixing apparatus
US8210215B2 (en) 2003-06-26 2012-07-03 R. Lewis Technologies, Inc. Mixing apparatus and methods of using the same
US8905088B2 (en) 2003-06-26 2014-12-09 R. Lewis Technologies, Inc. Mixing apparatus and methods of using the same
US20040261887A1 (en) * 2003-06-26 2004-12-30 William Lewis Mixing apparatus and methods using the same
US7530373B2 (en) 2003-06-26 2009-05-12 R. Lewis Technologies, Inc. Mixing apparatus and methods using the same
US20060223736A1 (en) * 2005-03-30 2006-10-05 R. Lewis Technologies, Inc. Dye and scent pouches and methods of making the same
US10005983B2 (en) 2015-02-12 2018-06-26 Reuben H Chow Cleaning formulations and methods of use thereof

Similar Documents

Publication Publication Date Title
US3123640A (en) Cation-active surface active aryldi-
US3123641A (en) Cation-active surface active trilower-
US3141905A (en) Cation-active surface active quaternary ammonium compounds
US3155591A (en) Hair rinse compostions of polyoxypropylene quaternary ammonium compounds
US2280792A (en) Cyanoalkyl ethers of ether alcohols
US3231619A (en) Basic primary amino polyether compositions
US2160058A (en) Process for preparing hexadecyl amines
US2087132A (en) Quaternary ammonium compounds
GB1430608A (en) Polyquaternary ammonium compounds and their use as petroleum demulsifiers
US2230753A (en) Unsaturated ethylamine derivatives
US2355337A (en) Preparation of ether amines
US3084187A (en) Substituted aminoalkanesulfonic acids
US4480126A (en) Process for the preparation of quaternary ammonium compounds
CA1191868A (en) Quaternized epichlorohydrin adducts of perfluoro substituted ethanols
US4982000A (en) Process for preparing quaternary ammonium compounds
US3274257A (en) Synthesis of (alkylthio) phenols
US3493617A (en) Production of allylic-substituted secondary and tertiary amines
US2287464A (en) Preparation of aminomethyl ethers
US2520275A (en) Aromatic diquaternary ammonium compounds
US2312743A (en) Alkoxy meta-dioxanes
US2996504A (en) New morpholine compounds
US2806060A (en) Polyvalent metal ion chelating agent
US3465026A (en) Borate n - oxides derived from borate esters of amino secondary alkanols
US2547965A (en) Reaction of alkylphenol, tertiary amine, and epihalohydrin
US2287465A (en) Aminomethyl ethers of ether alcohols