US3298956A - Lime soap dispersants - Google Patents

Lime soap dispersants Download PDF

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US3298956A
US3298956A US500170A US50017065A US3298956A US 3298956 A US3298956 A US 3298956A US 500170 A US500170 A US 500170A US 50017065 A US50017065 A US 50017065A US 3298956 A US3298956 A US 3298956A
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soap
lime
lime soap
dispersant
groups
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Riyad R Irani
Moedritzer Kurt
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Monsanto Co
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Monsanto Co
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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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/34—Organic compounds, e.g. vitamins containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen

Definitions

  • This invention relates to lime soap dispersants and more particularly to the use of organo-amino polymethyl phosphonic acids and/ or the salts thereof as lime soap dispersants in soap formulations, to the compositions resulting therefrom, and to the use of such compositions in aqueous systems.
  • lime soap i.e., the water insoluble scum or curd of wash water when soap is used for laundering, personal washing and bathing is, of course, familiar.
  • the lime soap which results from the reaction of soap with so called hardness i-ons such as, calcium, magnesium and iron is particularly objectionable because of its ability to stick to surfaces such as bathtubs, Washing tubs, clothes and the like with which it comes into contact, and its ability to resist removal therefrom.
  • lime soap dispersants In general, the most widely accepted method for reducing and minimizing the objectionable effects of the lime soap involves the use of lime soap dispersants. These agents are believed to disperse the lime soap and keep the lime soap dispersed by a peptizing action in the aqueous system in order to reduce or minimize the build up of lime soap thereby reducing the objectionable tendencies to stick to the surfaces with which they come into contact.
  • the more Widely used lime soap dispersants are synthetic surface active agents although only a very few of these synthetic surface active agents have the necessary qualifications to be useful as lime soap dispersants. As can be appreciated, therefore, there is a constant demand for better and more economical lime soap dispersants.
  • Another object of this invention is to provide a soap composition having incorporated therein a lime soap dispersant.
  • a still further object of this invention is to provide an improved soap composition having incorporated therein a lime soap dispersant, said soap composition exhibiting improved properties in aqueous systems.
  • X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and amine ions
  • Y and Y are members selected from the class con sisting of hydrogen and lower alkyl groups (1-4 carbon atoms);
  • R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms, and
  • R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms,
  • n is an integer from 1 to 30;
  • organoaamino polymethylphosphonic acids or the salts thereof generically described all of the foregoing.
  • the groups may be branched or straight chained and wherein R and R represent aliphatic groups, the groups may be branched or straight chained as Well as being saturated or unsaturated although it is preferred that if the groups are unsaturated they be ethylenically unsaturated.
  • the foregoing mentioned groups may contain substituent groups, such as, hydroXyl, halides, i.e., fluoride, chloride, bromide, and iodide, alkoxy groups, sulfonyl groups, carboxyl groups, amide groups and amino groups.
  • the lime soap dispersant of the instant invention need contain only two phosphonic acid groups, in most cases the more such groupings the compound contains the better lime soap dispersant it appears to be and, therefore, it is preferred that the lime soap dispersant of the instant invention contain at least 3 phosphonic acid groups and especially preferred are those containing 4 or more phosphonic acid groups.
  • the organo-amino polymethylphosphonic acids or the salts thereof may be prepared by various means.
  • the method comprises as a first step the preparation of the corresponding esters by reacting under reactive conditions a primary amine or secondary amine, a compound containing a carbonyl group such as an aldehyde or ketone, and a dialkylphosphite.
  • the free organo-amino polymethylphosphonic acids may be prepared by hydrolysis of the esters.
  • R R Y and Y represent the same groups as in the foregoing general Formula I and R represents an alkyl group.
  • Another method for preparing organo-amino polymethylphosphonic acids or the salts thereof comprises preparing the free acid directly by reacting under reactive conditions a primary or secondary amine, a compound containing a carbonyl group such as an aldehyde or ketone, and orthophosphorous acid. This process is set-forth in co-pending application Serial No. 217,276.
  • R R Y and Y represent the same groups as in the foregoing general Formula I.
  • a still further method for preparing organo-amino polymethylphosphonic acids or the salts thereof comprises preparing the free acid by the substitution reaction between a halomethylphosphonic acid and an alkylene amine (preferably a di or poly alkylene amine).
  • n is an integer between 1 and 30 and X is a halogen (preferably chlorine or bromine).
  • the salts of the organo-amino polymethylphosphonic acids can be prepared by the neutralization of the acids with a stoichiometric amount of a base that contains essentially the desired cation.
  • Bases such as those containing an alkali metal, ammonium and amines are especially suited.
  • a sodium salt one of organo-amino polyrnethylphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
  • any water soluble salt such as the ammonium salt and the amine salts, which exhibit the characteristics of the alkali metal salt may be used to practice the invention.
  • amine salts prepared from low molecular weight amines i.e., having a molecular weight below about 300, and more particularly the alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups, such as, ethyl amine, diethyl amine, propyl amine, propylene diamine, hexyl amine, Z-ethyl hexyl amine, N-butyl ethanolamine, triethanol amine and the like, are the preferred amine salts.
  • soap means an alkali metal, ammonium, or amine salt of a fatty acid or mixtures of 55 fatty acids which are capable of being used as washing and cleansing agents in aqueous mediums, and any of the Water soluble soaps formulated for industrial, household or toilet use may be employed.
  • the character of the soap constituent may vary widely in its composition depending on, inter alia, whether the final soap composition is to be in powder, spray-dried, flake, bar, paste, liquid or other form.
  • Water soluble soaps such as the sodium soaps and other suitable alkali metal, ammonium, or amine soaps derived from such fats and oils as tallow, coconut oil, cottonseed oil, soy bean oil, corn oil, olive oil, palm oil, peanut oil, palm kernal oil, lard, greases, fish oils and the like as well as their hydrogenated derivatives, and mixtures thereof, properly blended to yield the desired soap quality may be used in the soap composition of the present invention.
  • Illustrative examples of such soaps include a soap containing about 15 to 20% of sodium salts of fatty acids derived from coconut oil and 80 to 85% of sodium salts of fatty acids derived from tallow, a soap containing about 100% of sodium salts of fatty acids derived from tallow, a soap containing about 20% of potassium salts of fatty acids derived from coconut oil and about of potassium salts of fatty acids derived from soy bean oil and the like.
  • the amount of the lime soap dispersant necessary to be used with the soap may vary, depending upon, inter alia, the end use, type of soap employed, pH conditions and the like. In general, any amount and especially amounts above about 1 weight percent based on the weight of soap in the compositions exhibit lime soap dispersant properties, however, it is preferred that amounts of lime soap dispersants on a weight ratio to soap of from about 5:95 and 70:30 percent be utilized.
  • organo-amino polymethylphosphonic acids may be used by adjusting the pH, if required, of the soap compositions or the resulting aqueous solution to the desired alkaline pH condition.
  • the pH of the soap composition or the aqueous medium be such as to result in an aqueous washing solution having at least a pH of 7 or above and at least a pH of 9 or above is especially preferred such as a pH of from about 9 to about 11, when the soap composition is used in amounts to give effective cleansing action.
  • the resulting soap composition that is, the soap and the lime soap dispersant composition, of the present invention is generally effective when used in aqueous systems in conventional amounts such as is normally used with soap compositions and which is generally above about .01% concentration.
  • the lime soap dispersant can be used with any form of the soap, i.e., bar soap, soap flakes, soap powder and the like and can be blended with the soap prior to the time the final soap composition is formed or can be added to the aqueous medium in which the soap composition is intended to be used prior to or after the soap composition has been added.
  • the blending operation with soap can be carried out, if desired, in conventional soap equipment such as a crutcher, or in practically any mixing vessel that can be used to formulate soap (i.e., in which molten soap can be handled), such as a conventional amalgamator, a conventional refiner, or even a conventional soap mill.
  • the soap composition After the soap composition is formed it can generally be handled via conventional techniques and equipment in a manner similar to that in which lain or conventional soap is handled: for example, through the usual plodding, sizing, cooling, stamping and packaging operations.
  • the lime soap dispersant is intended to be used with the soap at the time of application as a cleansing agent.
  • the soap compositions in which the lime soap dispersant may be incorporated may contain, if desired, other materials, usually in amounts below about 50% by weight of soap, which are commonly used with soaps, such as, synthetic detergents of the anionic and nonionic class, polyphosphate builders, antiredepositon agents (e.g. carboxy methyl cellulose), brightening agents (e.g. fluorescent dyes), bleaching agents and the like as long as the usual considerations of compatability are applied.
  • synthetic detergents of the anionic and nonionic surface active compound type these may be any of the conventional detergents which are suitable as cleansing agents.
  • Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and hydrophobic .groups in their molecular structure and which ionize in an aqueous medium to give anions containing the hydrophobic group.
  • These compounds are usually the alkali metal salts of oragnic sulfonates or sulfates, particularly the sodium salts, such as alkyl, aryl, sulfonates (e.g. sodium dodecylbenzene sulfonate), sulfates of straight chain primary alcohols (e.g. sodium lauryl sulfate) and the like.
  • Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain, usually polyorryethylene, While the hydrophobic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines.
  • the polyethylene oxide condensates of alkyl phenols e.g., condensation product formed from 1 .mole nonyl phenol and moles ethylene oxide
  • the condensation products of aliphatic alcohols and ethylene oxide e.g., condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide
  • alkyl phenols e.g., condensation product formed from 1 .mole nonyl phenol and moles ethylene oxide
  • condensation products of aliphatic alcohols and ethylene oxide e.g., condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide
  • polyalkylene diamine polymethylphosphonic acids or the water soluble salts thereof are particularly effective as lime soap dispersants and are, therefore, the preferred lime soap dispersants of the organo-amino polymethylphosphonic acids or the salts thereof.
  • These polyalkylene diamine polymethylphosphonic acids or the salts thereof have the following formula:
  • n is an integer from 2 to inclusive;
  • R R R and R are selected from the class consisting of H and with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and amine ions.
  • polyalkylene diamine polymethylphosphonic compounds containing four phosphonic groups that is, a pair of two phosphonic groups separated by a nitrogen-polyalkylene-nitrogen chain containing not more than 14 carbon atoms.
  • Such polyalkylene diamine tetra(rnethylphosphonic) compounds include ethylene diamine tetra(methylphosphonic acid), trimethylene diamine tetra(methylphosphonic acid), hexamethylene diamine tetra(methylphosphonic acid), octamethylene diamine tetra(methylphosphonic acid), decamethylene diamine tetra(methylphosphonic acid), dodecamethylene diamine tetra(methyl-phosphonic acid), and tetradecamethylene diamine tetra-(methylphosphonic acid).
  • Table 1 illustrates some of the benefits that can result from utilizing the preferred polyalkylene diamine polymethylphosphonic acids or the salts thereof as lime soap dispersants.
  • the test which is used herein i.e., the measurement of the relative stickiness of lime soap scum or curds, has been found to correlate remarkably Well with the effectiveness of the lime soap dispersant in actual use. Effective lime soap dispersants decrease or minimize the stickiness of the lime soap curds.
  • the test which is conducted at a temperature between 30 and 35 C., 250 parts per million hard water (calculated as CaCO having a CazMg ratio of 2:1 is utilized. Five mls.
  • soap and lime soap dispersant blend a 1 weight percent soap solution (or soap and lime soap dispersant blend) are shaken vigorously in a 50 ml. test tube. Then the resulting foam is immediately stirred slowly into 500 mls. of hard water in a 600 ml. beaker. After all of the foam is quenched and the solution has stood undisturbed for 2 hours, the amount and particle size of scum, or suspended lime soap curd, are observed and rated in comparison with soap alone and standard soap and lime soap dispersant composition. Soap gives a rating of 10, while the standard soap and lime soap dispersant composition is rated 3 in a test such as that just described.
  • the soap is comprised of about 15% of sodium salts of fatty acids derived from coconut oil (primarily ltttll'ic acid) and 85% of sodium salts of fatty acids derived from tallow (approximritfily 40% stearic acid, 30% oleic acid and 30% palmitic ac
  • the preferred compounds of the instant invention function as lime soap dispersants as well as or better than conventional lime soap dispersants when compared with the standard soap and lime soap dispersant composition and by comparison with the soap control they markedly affect the lime soap formation in aqueous systems.
  • n is an integer from 1 to 30;
  • Z is a member selected from the class consisting of hydrogen and and Z is a member selected from the class consisting of hydrogen,
  • m is an integer from 1 to 30; with at least one of the groups represented by R and R containing at least one group.
  • a process for utilizing an organo-amino polymethylphosphonic compound as a lime soap dispersant comprises adding soap and said lime soap dispersant simultaneously or in any order to water and dissolving said addition mixture in said water, said organoamino polymethylphosphonic compound having the formula R YO N( l Br Y wherein X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and lower molecular weight alkyl, alkylene and alkanol amine ions; Y and Y are members selected from the class consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms; R is a member selected from the class consisting of hydrogen aliphatic groups containing from 1 to 30 carbon atoms, and
  • R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms,
  • n is an integer from 1 to 30;
  • m is an integer from 1 to 30; with at least one of the groups represented by R and R containing at least one group and said lime soap dispersant being added in amounts of at least 1% by Weight based on the weight of said soap.
  • a process of making a soap composition having low scumming characteristics which comprises blending into a molten soap at least 1 weight percent based on the 10 weight of said soap of a compound capable of being represented by the formula wherein X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and lower molecular weight ,alkyl, alkylene and alkanol amine ions; Y and Y are members selected from the class consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms; R is a member selected from the class consisting of hydrogen aliphatic groups containing from 1 to 30 carbon atoms, and
  • R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms wherein n is an integer from 1 to 30;
  • Z is a member selected from the class consisting of hydrogen and and Z is a member selected from the class consisting of hydrogen,
  • m is an integer from 1 to 30; with at least one of the group represented by R and R containing at least one OOX with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and lower molecular weight alkyl, alkylene and alkanol amine ions. 5.
  • a process of making a soap composition having low scumming characteristics which comprises blending into molten soap in amounts of from about 5% to about 70% by weignt based on said soap of a compound capable of being represented by the formula 1 1 wherein n is an integer from 2 to 20 inclusive; R R R and R are selected from the class consisting of H and OOX with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and lower molecular weight alkyl, alkylene and alkanol amine ions. 6.
  • a soap composition consisting essentially of soap and a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said lime soap dispersant being an alkali metal salt of polyalkylene diamine polymethylphosphonic acid, said salt having the formula N H2)n N R, R wherein n is an integer from 2 to 20 inclusive; R R R and R are selected from the class consisting of H and OOX with not more than two of the groups being H and wherein X is an alkali metal cation.
  • a soap composition coonsist essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95 to 35 :70, said lime soap dispersant being a polyalkylenediamine tetra(methylphosphonic) compound having the formula wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion, and lower molecular weight alkyl, alkylene and alkanol amine ions.
  • a soap composition consisting essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said lime soap dispersant being an alkali metal salt of a polyalkylene diamine tetra(methylphosphonic acid) having the formula HO 0 0 OH i 11.0 ol-ni 110 011 no 0 0 on i HzC CHzi wherein n is an integer from 2 to 14 inclusive.
  • a soap composition consisting essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said iime soap dispersant being an alkali metal salt of ethylene diamine tetra(methylphosphonic acid).
  • a soap composition consisting essentially of, in addition of soap, a lime soap dispersant in a weight ratio of said soap to said lime dispersant of from about :5 to 30:70, said lime soap dispersant being an alkali metal salt of hex-amethylene diamine tetra(met-hylphosphonic acid).
  • a process for utilizing a polyalkylene diamine tetra(methylphosphonic) compound as a lime soap dispersant comprises adding soap and said lime soap dispersant simultaneously or in any order to water and dissolving said addition mixture in said water, said polyalkylene diamine tetra(methylphosphonic) compound having the formula X0 0 0 OX ii H2O CHZIIL/ X0 ⁇ OX X0 0 0 0X ii' HzC CH2ii X0 OX wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion, and lower molecular weight alkyl, alkyene and alkanol amine ions, said lime soap dispersant being added in amounts
  • said lime soap dispersant is a sodium salt of said polylalkylene diamine tetra(methylphosphonic acid).
  • a process of making a soap composition having low scurnming characteristics which comprises blending into molten soap in amounts of from about 5 to 70% by weight based on said soap of a polyalkylene diamine tetra(methylphosphonic) compound capable of being represented by the formula wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ions, and lower molecular weight alkyl, alkylene and alkanol amine ions.
  • said lime soap dispersant is a sodium salt of said polyalkylene diamine tetra- (methylphosphonic acid).

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Description

United States Patent 3,298,956 LIME SOAP DISPERSANTS Riyad R. Irani, St. Louis, and Kurt Moedritzer, Webster Groves, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Oct. 21, 1965, Ser. No. 500,170 20 Claims. (Cl. 252-117) This is a continuation-in-part of application Serial No. 272,830, filed April 15, 1963, now abandoned.
This invention relates to lime soap dispersants and more particularly to the use of organo-amino polymethyl phosphonic acids and/ or the salts thereof as lime soap dispersants in soap formulations, to the compositions resulting therefrom, and to the use of such compositions in aqueous systems.
The formation of lime soap, i.e., the water insoluble scum or curd of wash water when soap is used for laundering, personal washing and bathing is, of course, familiar. The lime soap which results from the reaction of soap with so called hardness i-ons such as, calcium, magnesium and iron is particularly objectionable because of its ability to stick to surfaces such as bathtubs, Washing tubs, clothes and the like with which it comes into contact, and its ability to resist removal therefrom.
In general, the most widely accepted method for reducing and minimizing the objectionable effects of the lime soap involves the use of lime soap dispersants. These agents are believed to disperse the lime soap and keep the lime soap dispersed by a peptizing action in the aqueous system in order to reduce or minimize the build up of lime soap thereby reducing the objectionable tendencies to stick to the surfaces with which they come into contact. The more Widely used lime soap dispersants are synthetic surface active agents although only a very few of these synthetic surface active agents have the necessary qualifications to be useful as lime soap dispersants. As can be appreciated, therefore, there is a constant demand for better and more economical lime soap dispersants.
Therefore, it is an object of this invention to provide a lime soap dispersant for soap formulation.
Another object of this invention is to provide a soap composition having incorporated therein a lime soap dispersant.
A still further object of this invention is to provide an improved soap composition having incorporated therein a lime soap dispersant, said soap composition exhibiting improved properties in aqueous systems.
Other objects will become apparent from the following detailed description and the claims appended hereto.
It has now been discovered that organo-amino polymethylphosphonic acids or the water soluble salts thereof are effective lime soap dispersants in aqueous mediums containing soap as will be more fully discussed hereinafter, said organo-amino polymethylphosphonic acids or the salts thereof being of the following formula 1 I CP=(OX)2 l R; Y
wherein X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and amine ions; Y and Y are members selected from the class con sisting of hydrogen and lower alkyl groups (1-4 carbon atoms); R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms, and
and R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms,
and
a D Z wherein n is an integer from 1 to 30; Z is a member selected from the class consisting of hydrogen and Y =(OX)g and Z' is a member selected from the class consisting of hydrogen and Y O i =(OX)2 "I z m a wherein m is an integer from 1 to 30, with either R or R containing at least one X i d -P= 0X group. As used hereinafter the term organoaamino polymethylphosphonic acids or the salts thereof generically described all of the foregoing.
In the foregoing general formula wherein Y and Y represent lower alkyl groups, the groups may be branched or straight chained and wherein R and R represent aliphatic groups, the groups may be branched or straight chained as Well as being saturated or unsaturated although it is preferred that if the groups are unsaturated they be ethylenically unsaturated. In addition, the foregoing mentioned groups may contain substituent groups, such as, hydroXyl, halides, i.e., fluoride, chloride, bromide, and iodide, alkoxy groups, sulfonyl groups, carboxyl groups, amide groups and amino groups.
Although, in general, the lime soap dispersant of the instant invention need contain only two phosphonic acid groups, in most cases the more such groupings the compound contains the better lime soap dispersant it appears to be and, therefore, it is preferred that the lime soap dispersant of the instant invention contain at least 3 phosphonic acid groups and especially preferred are those containing 4 or more phosphonic acid groups.
The organo-amino polymethylphosphonic acids or the salts thereof may be prepared by various means. One
method comprises as a first step the preparation of the corresponding esters by reacting under reactive conditions a primary amine or secondary amine, a compound containing a carbonyl group such as an aldehyde or ketone, and a dialkylphosphite. The free organo-amino polymethylphosphonic acids may be prepared by hydrolysis of the esters.
The following general reaction equation is illustrative of the preparation of the esters as outlined above.
wherein R R Y and Y represent the same groups as in the foregoing general Formula I and R represents an alkyl group.
Another method for preparing organo-amino polymethylphosphonic acids or the salts thereof comprises preparing the free acid directly by reacting under reactive conditions a primary or secondary amine, a compound containing a carbonyl group such as an aldehyde or ketone, and orthophosphorous acid. This process is set-forth in co-pending application Serial No. 217,276.
The following reaction equation is illustrative of the preparation of the free acids as outlined above.
wherein R R Y and Y represent the same groups as in the foregoing general Formula I.
A still further method for preparing organo-amino polymethylphosphonic acids or the salts thereof comprises preparing the free acid by the substitution reaction between a halomethylphosphonic acid and an alkylene amine (preferably a di or poly alkylene amine).
The following general reaction equation is illustrative of the preparation of the free acids as outlined above.
wherein n is an integer between 1 and 30 and X is a halogen (preferably chlorine or bromine).
The salts of the organo-amino polymethylphosphonic acids can be prepared by the neutralization of the acids with a stoichiometric amount of a base that contains essentially the desired cation. Bases such as those containing an alkali metal, ammonium and amines are especially suited. For example, to prepare a sodium salt, one of organo-amino polyrnethylphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
The following compounds which can be prepared by methods such as those previously mentioned are illustrative of lime soap dispersants of the instant invention and include:
( 1 ethylene diamine tetra (methylphosphonic acid) 2 zl2 z) 2 2 )2]2 (2) trimethylene diamine tetra(methylphosphonic acid) 2 )2] 2 2) 3 [CH2PO(OH)2] 2 (3) hexamethylene diamine tetra(methylphosphonic acid) z )2]2 2)s 2 212 (4) lugptamethylene diamine tetra (methylphosphonic (5 octamethylene diamine tetra (methylphosphonic acid) 2 2] 2 2) BN[CHZPO(OH)2] 2 (6) nonamethylene diamine tetra(methylphosphonic acid) 2 )2]2 2) 9 [CHZPO(OH) 2] 2 (7) decamethylene diamine tetra (methylphosphonic acid) (8) dodecamethylene diamine tetra (methylphosphonic acid) 2 2] 2 2) 12N 2 2]2 (9) te1t)radecamethylene diamine tetra(methylphosphonic 2 2] 2 2) n l z 2] z (10) oleyl methylene diamine tetra(methylphosphonic acid) 2 )2] 2NCIBHMN[CHZPO 212 (11) ethylene diamine tri(methylphosphonic acid) [CH PO (OH) N (CH NH[CH PO(OH) (12) ethylene diamine di(methylphosphonic acid) [CH PO (OH) HN(CH NH[CH PO (OH) 13) hexamethylene diamine tri (methylphosphonic acid) 2 2] 2) e l z 2] 2 14) hexamethylene diamine di(methylphosphonic acid) [CH PO(OH) ]HN(CH NH[CH PO(OH) 15) n-oleyl amine di(methylphosphonic acid) 1s 35 2 2] 2 16) n-hexyl amine di(methylphosphonic acid) s 1a 2 )z]2 (17) diethylene triamine penta (methylphosphonic acid) (18) ethylene triamine penta(methylphosphonic acid) (19) ethanol amine di(methylphosphonic acid) OHCH CH N[CH PO(0H) (20) amino tri(methylphosphonic acid) 2 )2]a (21) amino di(methylphosphonic acid) (22) n-hexyl amino(isopropylidene phosphonic acid) (methyl phosphonic acid) (23) ethylene diamine(isopropylidene phosphonic acid) (methyl phosphonic acid) (24) amino di(methylphosphonic acid) (butylidene phosphonic acid) (25) tris hydroxy methyl, methyl amino di(methylphosphonic acid) (26) carbethoxy amino di(methylphosphonic acid) C H O CN[CH PO(OH) (27) sulfonyl ethylene amino di(methylphosphonic acid) HO SOCH CH N[CH PO(OH) 5 (28) acetonyl amino di(methylphosphonic acid) CH OCH N[CH PO(OH) (29) carboxy methyl amino di(methylphosphonic acid) HO CCH N[CH PO(OH) (30) propenyl amino di(methylphosphonic acid) CH =CHCH N [CH PO (OH) 2 (31) chloroacetamino di(methylphosphonic acid) ClCH CON [CH PO OH) 2 (3 2) bromoethylene amino di(methylphosphonic acid) BI'CH2CH2N 2] 3 (33 propylene diamine tetra(methylphosphonic acid) CH C [N [CH PO (OH CH N [CH PO (OH) 2 (34) triethylene tetra amine hexa(methylphosphonic acid) (35) monoethanol, diethylene triamine tri(rnethylphosphonic acid) In addition, the alkali metal salts and particularly the sodium and potassium salts as well as the ammonium salts and amine salts of the foregoing compounds illustrative of the lime soap dispersants of the instant invention can also be utilized.
It is to be understood that although the sodium salts of organo-amino polymethylphosphonic acids are preferred, other alkali metal salts, such as, potassium, lithium, and the like, as well as mixtures of the alkali metal salts, may be substituted therefor. In addition, any water soluble salt, such as the ammonium salt and the amine salts, which exhibit the characteristics of the alkali metal salt may be used to practice the invention. In particular, amine salts prepared from low molecular weight amines, i.e., having a molecular weight below about 300, and more particularly the alkyl amines, alkylene amines and alkanol amines containing not more than 2 amine groups, such as, ethyl amine, diethyl amine, propyl amine, propylene diamine, hexyl amine, Z-ethyl hexyl amine, N-butyl ethanolamine, triethanol amine and the like, are the preferred amine salts.
As used herein, the term soap means an alkali metal, ammonium, or amine salt of a fatty acid or mixtures of 55 fatty acids which are capable of being used as washing and cleansing agents in aqueous mediums, and any of the Water soluble soaps formulated for industrial, household or toilet use may be employed. In addition, the character of the soap constituent may vary widely in its composition depending on, inter alia, whether the final soap composition is to be in powder, spray-dried, flake, bar, paste, liquid or other form. Water soluble soaps such as the sodium soaps and other suitable alkali metal, ammonium, or amine soaps derived from such fats and oils as tallow, coconut oil, cottonseed oil, soy bean oil, corn oil, olive oil, palm oil, peanut oil, palm kernal oil, lard, greases, fish oils and the like as well as their hydrogenated derivatives, and mixtures thereof, properly blended to yield the desired soap quality may be used in the soap composition of the present invention. Illustrative examples of such soaps include a soap containing about 15 to 20% of sodium salts of fatty acids derived from coconut oil and 80 to 85% of sodium salts of fatty acids derived from tallow, a soap containing about 100% of sodium salts of fatty acids derived from tallow, a soap containing about 20% of potassium salts of fatty acids derived from coconut oil and about of potassium salts of fatty acids derived from soy bean oil and the like.
The amount of the lime soap dispersant necessary to be used with the soap may vary, depending upon, inter alia, the end use, type of soap employed, pH conditions and the like. In general, any amount and especially amounts above about 1 weight percent based on the weight of soap in the compositions exhibit lime soap dispersant properties, however, it is preferred that amounts of lime soap dispersants on a weight ratio to soap of from about 5:95 and 70:30 percent be utilized.
Since most of the soap compositions are used in alkaline aqueous systems, organo-amino polymethylphosphonic acids may be used by adjusting the pH, if required, of the soap compositions or the resulting aqueous solution to the desired alkaline pH condition. In view of the foregoing, it is preferred that the pH of the soap composition or the aqueous medium be such as to result in an aqueous washing solution having at least a pH of 7 or above and at least a pH of 9 or above is especially preferred such as a pH of from about 9 to about 11, when the soap composition is used in amounts to give effective cleansing action.
The resulting soap composition, that is, the soap and the lime soap dispersant composition, of the present invention is generally effective when used in aqueous systems in conventional amounts such as is normally used with soap compositions and which is generally above about .01% concentration.
In general, the lime soap dispersant can be used with any form of the soap, i.e., bar soap, soap flakes, soap powder and the like and can be blended with the soap prior to the time the final soap composition is formed or can be added to the aqueous medium in which the soap composition is intended to be used prior to or after the soap composition has been added. The blending operation with soap can be carried out, if desired, in conventional soap equipment such as a crutcher, or in practically any mixing vessel that can be used to formulate soap (i.e., in which molten soap can be handled), such as a conventional amalgamator, a conventional refiner, or even a conventional soap mill. After the soap composition is formed it can generally be handled via conventional techniques and equipment in a manner similar to that in which lain or conventional soap is handled: for example, through the usual plodding, sizing, cooling, stamping and packaging operations. In any event, the lime soap dispersant is intended to be used with the soap at the time of application as a cleansing agent.
Also, the soap compositions in which the lime soap dispersant may be incorporated may contain, if desired, other materials, usually in amounts below about 50% by weight of soap, which are commonly used with soaps, such as, synthetic detergents of the anionic and nonionic class, polyphosphate builders, antiredepositon agents (e.g. carboxy methyl cellulose), brightening agents (e.g. fluorescent dyes), bleaching agents and the like as long as the usual considerations of compatability are applied. With respect to the foregoing mentioned synthetic detergents of the anionic and nonionic surface active compound type, these may be any of the conventional detergents which are suitable as cleansing agents. Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and hydrophobic .groups in their molecular structure and which ionize in an aqueous medium to give anions containing the hydrophobic group. These compounds are usually the alkali metal salts of oragnic sulfonates or sulfates, particularly the sodium salts, such as alkyl, aryl, sulfonates (e.g. sodium dodecylbenzene sulfonate), sulfates of straight chain primary alcohols (e.g. sodium lauryl sulfate) and the like. Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain, usually polyorryethylene, While the hydrophobic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. For example purposes only, the polyethylene oxide condensates of alkyl phenols (e.g., condensation product formed from 1 .mole nonyl phenol and moles ethylene oxide), the condensation products of aliphatic alcohols and ethylene oxide (e.g., condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide) are suitable nonionic surface active compounds in practicing the invention.
It has been found that polyalkylene diamine polymethylphosphonic acids or the water soluble salts thereof are particularly effective as lime soap dispersants and are, therefore, the preferred lime soap dispersants of the organo-amino polymethylphosphonic acids or the salts thereof. These polyalkylene diamine polymethylphosphonic acids or the salts thereof have the following formula:
wherein n is an integer from 2 to inclusive; R R R and R are selected from the class consisting of H and with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and amine ions.
Especially preferred are the polyalkylene diamine polymethylphosphonic compounds containing four phosphonic groups, that is, a pair of two phosphonic groups separated by a nitrogen-polyalkylene-nitrogen chain containing not more than 14 carbon atoms. Such polyalkylene diamine tetra(rnethylphosphonic) compounds include ethylene diamine tetra(methylphosphonic acid), trimethylene diamine tetra(methylphosphonic acid), hexamethylene diamine tetra(methylphosphonic acid), octamethylene diamine tetra(methylphosphonic acid), decamethylene diamine tetra(methylphosphonic acid), dodecamethylene diamine tetra(methyl-phosphonic acid), and tetradecamethylene diamine tetra-(methylphosphonic acid).
The following Table 1 illustrates some of the benefits that can result from utilizing the preferred polyalkylene diamine polymethylphosphonic acids or the salts thereof as lime soap dispersants. Although there are a number of lime soap dispersant tests which can be used, the test which is used herein, i.e., the measurement of the relative stickiness of lime soap scum or curds, has been found to correlate remarkably Well with the effectiveness of the lime soap dispersant in actual use. Effective lime soap dispersants decrease or minimize the stickiness of the lime soap curds. In the test, which is conducted at a temperature between 30 and 35 C., 250 parts per million hard water (calculated as CaCO having a CazMg ratio of 2:1 is utilized. Five mls. of a 1 weight percent soap solution (or soap and lime soap dispersant blend) are shaken vigorously in a 50 ml. test tube. Then the resulting foam is immediately stirred slowly into 500 mls. of hard water in a 600 ml. beaker. After all of the foam is quenched and the solution has stood undisturbed for 2 hours, the amount and particle size of scum, or suspended lime soap curd, are observed and rated in comparison with soap alone and standard soap and lime soap dispersant composition. Soap gives a rating of 10, while the standard soap and lime soap dispersant composition is rated 3 in a test such as that just described.
8 TABLE 1 Lime soap dispersancy test data Sample tested? Rating (1) Soap control 10 (2) Hexasodium ethylene diamine tetra(methy1- phosphonate) 3 (3) Hexasodium tetra methylene diamine tetra (methylphosphonate) 2 (4) Hexasodium penta methylene diamine tetra (methylphosphonate) 2 (5) Hexasodium hexamethylene diamine tetra (methylphosphonate) 2 (6) Hexasodinm hepta methylene diamine tetra (methylphosphonate) 3 (7) Hexasodiurn octa methylene diamnie tetra (methylphosphonate) 2 (8) Hexasodium nona methylene diamine tetra (methylphosphonate) 2 *Lime soap dispersants tested as a 15 weight percent blend of the dispersant with weight percent of soap. The soap is comprised of about 15% of sodium salts of fatty acids derived from coconut oil (primarily ltttll'ic acid) and 85% of sodium salts of fatty acids derived from tallow (approximritfily 40% stearic acid, 30% oleic acid and 30% palmitic ac As can be observed from the above table, the preferred compounds of the instant invention function as lime soap dispersants as well as or better than conventional lime soap dispersants when compared with the standard soap and lime soap dispersant composition and by comparison with the soap control they markedly affect the lime soap formation in aqueous systems.
Although the lime soap dispersants, the soap formulations containing said lirne soap dispersants and the uses of such compositions have been described with a degree of particularity, the invention herein is intended to be limited only by the claims set forth hereinafter.
What is claimed is:
l. A soap composition consisting essentially of soap and at least one weight percent based on the weight of said soap of an organo-amino polymethylphosphonic compound of the formula Y ll JP=(OX)z and R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms,
wherein n is an integer from 1 to 30; Z is a member selected from the class consisting of hydrogen and and Z is a member selected from the class consisting of hydrogen,
wherein m is an integer from 1 to 30; with at least one of the groups represented by R and R containing at least one group.
2. A process for utilizing an organo-amino polymethylphosphonic compound as a lime soap dispersant, which process comprises adding soap and said lime soap dispersant simultaneously or in any order to water and dissolving said addition mixture in said water, said organoamino polymethylphosphonic compound having the formula R YO N( l Br Y wherein X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and lower molecular weight alkyl, alkylene and alkanol amine ions; Y and Y are members selected from the class consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms; R is a member selected from the class consisting of hydrogen aliphatic groups containing from 1 to 30 carbon atoms, and
and R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms,
Y i l -+P(OX)2 and -NZ Y Y n 2' wherein n is an integer from 1 to 30; Z is a member selected from the class consisting of hydrogen and Y i P=(OX)2 and Z is a member selected from the class consisting of hydrogen,
wherein m is an integer from 1 to 30; with at least one of the groups represented by R and R containing at least one group and said lime soap dispersant being added in amounts of at least 1% by Weight based on the weight of said soap.
3 A process of making a soap composition having low scumming characteristics which comprises blending into a molten soap at least 1 weight percent based on the 10 weight of said soap of a compound capable of being represented by the formula wherein X is a cation selected from the class consisting of hydrogen, alkali metal ion, ammonium ion, and lower molecular weight ,alkyl, alkylene and alkanol amine ions; Y and Y are members selected from the class consisting of hydrogen and lower alkyl groups containing from 1 to 4 carbon atoms; R is a member selected from the class consisting of hydrogen aliphatic groups containing from 1 to 30 carbon atoms, and
and R is a member selected from the class consisting of hydrogen, aliphatic groups containing from 1 to 30 carbon atoms wherein n is an integer from 1 to 30; Z is a member selected from the class consisting of hydrogen and and Z is a member selected from the class consisting of hydrogen,
wherein m is an integer from 1 to 30; with at least one of the group represented by R and R containing at least one OOX with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and lower molecular weight alkyl, alkylene and alkanol amine ions. 5. A process of making a soap composition having low scumming characteristics which comprises blending into molten soap in amounts of from about 5% to about 70% by weignt based on said soap of a compound capable of being represented by the formula 1 1 wherein n is an integer from 2 to 20 inclusive; R R R and R are selected from the class consisting of H and OOX with not more than two of the groups being H and wherein X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion and lower molecular weight alkyl, alkylene and alkanol amine ions. 6. A soap composition consisting essentially of soap and a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said lime soap dispersant being an alkali metal salt of polyalkylene diamine polymethylphosphonic acid, said salt having the formula N H2)n N R, R wherein n is an integer from 2 to 20 inclusive; R R R and R are selected from the class consisting of H and OOX with not more than two of the groups being H and wherein X is an alkali metal cation.
7. The soap composition of claim 6 wherein said alkali metal salt is a sodium salt.
8. A soap composition coonsisting essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95 to 35 :70, said lime soap dispersant being a polyalkylenediamine tetra(methylphosphonic) compound having the formula wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion, and lower molecular weight alkyl, alkylene and alkanol amine ions.
9. A soap composition consisting essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said lime soap dispersant being an alkali metal salt of a polyalkylene diamine tetra(methylphosphonic acid) having the formula HO 0 0 OH i 11.0 ol-ni 110 011 no 0 0 on i HzC CHzi wherein n is an integer from 2 to 14 inclusive.
10. The soap composition of claim 11 wherein said alkali metal salt is a sodium salt.
11. A soap composition consisting essentially of, in addition to soap, a lime soap dispersant in a weight ratio of said soap to said lime soap dispersant of from about 95:5 to 30:70, said iime soap dispersant being an alkali metal salt of ethylene diamine tetra(methylphosphonic acid).
12. The soap composition of claim 11, wherein said alkali metal salt is sodium.
13. The soap composition of claim 12, wherein said lime soap dispersant is hexasodium ethylene diamine tetra (methylphosphonate) 14. A soap composition consisting essentially of, in addition of soap, a lime soap dispersant in a weight ratio of said soap to said lime dispersant of from about :5 to 30:70, said lime soap dispersant being an alkali metal salt of hex-amethylene diamine tetra(met-hylphosphonic acid).
15. The soap composition of claim 14, wherein said alkali metal is sodium.
16. The soap composition of claim 14 wherein said lime soap dispersant is hexasodium hexa-methylene diamine tetra(methylphosphonate 17. A process for utilizing a polyalkylene diamine tetra(methylphosphonic) compound as a lime soap dispersant, which process comprises adding soap and said lime soap dispersant simultaneously or in any order to water and dissolving said addition mixture in said water, said polyalkylene diamine tetra(methylphosphonic) compound having the formula X0 0 0 OX ii H2O CHZIIL/ X0 \OX X0 0 0 0X ii' HzC CH2ii X0 OX wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ion, and lower molecular weight alkyl, alkyene and alkanol amine ions, said lime soap dispersant being added in amounts of from about 5 to 70% by weight based on the weight of said soap.
18. The process of claim 17, wherein said lime soap dispersant is a sodium salt of said polylalkylene diamine tetra(methylphosphonic acid).
19. A process of making a soap composition having low scurnming characteristics which comprises blending into molten soap in amounts of from about 5 to 70% by weight based on said soap of a polyalkylene diamine tetra(methylphosphonic) compound capable of being represented by the formula wherein n is an integer from 2 to 14 inclusive and X is a cation selected from the class consisting of hydrogen, alkali metal ions, ammonium ions, and lower molecular weight alkyl, alkylene and alkanol amine ions.
20. The process of claim 19 wherein said lime soap dispersant is a sodium salt of said polyalkylene diamine tetra- (methylphosphonic acid).
References Cited by the Examiner UNITED STATES PATENTS 2,240,957 5/1941 Munz 252-117 OTHER REFERENCES Fields: I. Am. Chem. Soc., vol. 74, 1952 (pp. 1528- 1531 relied on).
Frank: Chem. Review, vol. 61, August 1961 (-pp. 392- 394 relied on).
Petrov et a1.: Chem. Abst., vol. 54, col. 260, 1960.
SAMUEL H. BLECH, Primary Examiner.
LEON D. ROSDOL, Examiner.
I. T. FEDIGAN, Assistant Examiner.
Edward M. Fletcher, Jr.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 298 ,956 January 17 1967 Riyad R. Irani et a1.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 11, line 35, for "35:70" read 30:70 38 to 45, for, the left-hand portion of the formula reading lines 0 X0 X0 L P read column 12, line 32 for "alkyene" read alkylene Signed and sealed this 30th day of January 1968 (SEAL) Attest:
EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A SOAP COMPOSITION CONSISTING ESSENTIALLY OF SOAP AND AT LEAST ONE WEIGHT PERCENT BASED ON THE WEIGHT OF SAID SOAP OF AN ORGANO-AMINO POLYMETHYLPHOSPHONIC COMPOUND OF THE FORMULA
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US3475293A (en) * 1964-09-22 1969-10-28 Monsanto Co Electrodeposition of metals
US3483178A (en) * 1968-04-18 1969-12-09 Monsanto Co Esters,salts,and acids of organo-phosphono-amine oxides
US3678164A (en) * 1969-02-12 1972-07-18 Procter & Gamble Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue
US4080375A (en) * 1971-02-05 1978-03-21 Petrolite Corporation Methylene phosphonates of amino-terminated oxyalkylates and uses therefor
US3714067A (en) * 1971-07-07 1973-01-30 Monsanto Co Methods of inhibiting corrosion with condensed polyalkylenepolyamine phosphonates
US3974209A (en) * 1971-08-04 1976-08-10 Monsanto Company Substituted tertiary amines and processes for preparing the same
US3976589A (en) * 1971-08-04 1976-08-24 Monsanto Company Methods of scale inhibition
US4084950A (en) * 1972-03-24 1978-04-18 Petrolite Corporation Use of polyquaternary ammonium methylene phosphonates as microbiocides
US3723347A (en) * 1972-05-17 1973-03-27 Monsanto Co Corrosion inhibition compositions containing substituted diamine phosphonates and processes for using the same
USB336566I5 (en) * 1973-02-28 1975-01-28
US4065491A (en) * 1974-06-27 1977-12-27 Chinoin Gyogyszer Es Vegyeszeti Termekek Gyara Rt. Process for the preparation of N-phosphonomethyl-glycine
US4187245A (en) * 1975-06-02 1980-02-05 Petrolite Corporation Hydroxypropylene-amino-phosphonic-sulfonic acids
US4143128A (en) * 1976-02-25 1979-03-06 Colgate Palmolive Company Oral compositions for calculus retardation
US4033896A (en) * 1976-06-18 1977-07-05 Monsanto Company Method of corrosion inhibition and compositions therefor
US4184912A (en) * 1976-08-09 1980-01-22 Nalco Chemical Company Pitch control method
US4144324A (en) * 1976-10-08 1979-03-13 Colgate Palmolive Company Oral compositions for calculus retardation
US4177258A (en) * 1978-10-13 1979-12-04 Colgate Palmolive Company Dentifrice for dental remineralization
US4183915A (en) * 1978-10-13 1980-01-15 Colgate-Palmolive Company Stable solution for dental remineralization
US4229294A (en) * 1979-05-24 1980-10-21 Petrolite Corporation Hydroxypropylene-amino-phosphonic-sulfonic acids for inhibiting scale formation
US4297299A (en) * 1980-01-10 1981-10-27 National Starch And Chemical Corporation Novel N-(alkyl)-N-(2-haloethyl)-aminomethylphosphonic acids, a method for the preparation thereof and their use in the preparation of starch ether derivatives
US4450116A (en) * 1981-07-21 1984-05-22 Hoechst Aktiengesellschaft 3-Oxypropyleneimino-bis-(methylene phosphonic acids) and their salts, process for their manufacture and their use
US4548757A (en) * 1984-03-02 1985-10-22 The Procter & Gamble Company Aqueous aminomethylenephosphonic acid solutions containing organic carboxylate stabilizing agent
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