US3686282A - Alkyl vicinal hydroxy alkoxy ether maleate compounds - Google Patents

Alkyl vicinal hydroxy alkoxy ether maleate compounds Download PDF

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US3686282A
US3686282A US856206A US3686282DA US3686282A US 3686282 A US3686282 A US 3686282A US 856206 A US856206 A US 856206A US 3686282D A US3686282D A US 3686282DA US 3686282 A US3686282 A US 3686282A
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hydroxy alkoxy
soap
alkoxy ether
compounds
alkyl
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US856206A
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Roger L Kidwell
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Monsanto Co
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids

Definitions

  • x and y are each integers from 1 to 17, the sum of x y being from 12 to 18; R is hydrogen or methyl; and M is sodium or potassium, are useful surfactants and lime soap dispersants, which provide, in admixture with natural soaps, excellent cleansing compositions having reduced tendency to deposit precipitates in hard water.
  • This invention relates to novel compounds and to improved soap compositions containing such compounds. More particularly, the invention relates to alkyl vicinal hydroxy alkoxy ether maleates and to natural soap formulations containing such compounds and exhibiting reduced tendency to deposit precipitates in hard water.
  • soaps derived from animal fats and vegetable oils e.g., lauric, myristic, palmitic, stearic, tallow and coconut oil acid soaps are well-known.
  • hard water i.e., water containing substantial quantities of alkaline earth metal ions-particularly calcium or magnesium
  • Such undesirable effects are exemplified by such phenomena as the ring around the tub" which frequently demarcates the water line of washing vessels utilized in geographical localities having hard water supplies.
  • novel compounds of this invention are alkyl vicinal hydroxy alkoxy ether maleates as hereinafter described.
  • the improved soap compositions of this invention comprise natural soaps in combination with minor amounts of such novel compounds.
  • alkyl vicinal hydroxy alkoxy ether maleates of this invention are represented by the formula:
  • x and y are each integers from l to 17, the sum ofx +y being from 12 to 18; z is an integer from 1 to 3; R is hydrogen or methyl; and M is sodium or potassium.
  • x and y are each integers from l to 17, the sum ofx +y being from 12 to 18; z is an integer from 1 to 3; R is hydrogen or methyl; and M is sodium or potassium.
  • the compounds of this invention can be prepared by various procedures.
  • straight chain internal olefins such as obtained by catalytic dehydrogenation of paraffins can be epoxidized by reaction with peracetic acid, and the epoxide reacted with ap basementte monoor poly-ethylene or propylene glycols in the presence of a Lewis acid catalyst to yield an alkyl vicinal monoor poly-alkoxylate which is reacted with maleic anhydride and neutralized with a sodium or potassium base to yield the compounds of this invent1on.
  • the foregoing compounds are excellent surfactants and, additionally, are found to inhibit precipitate deposition of natural soaps in hard water.
  • the soap compositions of this invention comprise a soap derived from natural products, (hereinafter referred to in the specification and claims as natural soaps) in combination with the alkyl vicinal hydroxy alkoxy ether maleates described above.
  • any of the well-known natural soaps conventionally employed is soap bars and/or powders, can be utilized in the compositions of this invention.
  • Such natural soaps include sodium and potassium salts of acids obtained by saponification of animal fats and vegetable oils, for example, lauric, myristic, palmitic, stearic, tallow and coconut oil acids and mixtures thereof.
  • the selection of natural soap constituents is based on the physical and performance characteristics desired as well as cost and availability of the natural products from which the soaps are derived.
  • compositions of this invention may contain a single hydroxy alkoxy ether maleate; a mixture of position isomers wherein the hydroxy and alkoxy ether maleate substituents are attached at various isomeric positions, e.g., 2,3 or 3,4, or 4,5 etc.; a mixture of hydroxy alkoxy ether maleates of various alkyl chain lengths, i.e., a homolog mix, or; homolog mixes wherein individual homologs comprise a mixture of position isomers.
  • the compositions of this invention must contain at least 12 percent by weight of the hydroxy alkoxy ether maleate (based on the combined weight of the maleate and natural soap) to effectively inhibit precipitate deposition. The use of greater than 25 percent by weight maleate does not provide bar soaps of acceptable physical characteristics. A maleate content of from 15 to 20 percent by weight is particularly preferred.
  • compositions of this invention may contain minor amounts of perfumes, dyes, abrasives, antiperspirants, germicides or other additives conventionally employed in soap compositions.
  • perfumes dyes, abrasives, antiperspirants, germicides or other additives conventionally employed in soap compositions.
  • the invention is further illustrated by the following examples, wherein all percentages are by weight unless otherwise indicated.
  • Vl Alkyl vicinal hydroxy alkoxy ether maleates are prepared by reacting internal olefins as shown in Table 1 below with peracetic acid which is added dropwise to the olefin, the reaction mixture being maintained at a temperature of about 50 C via an ice bath.
  • the epoxide formed is separated as a top layer from the reaction mixture, washed with aqueous Na CO and water until the wash water is neutral and dried by contact with Na SO
  • the epoxide is then reacted with monoor polyethylene or propylene glycols as shown in Table l at about 90 C, and the product reacted with maleic anhydride.
  • the acids produced are neutralized with a percent by weight NaOH solution at C to yield the maleates indicated.
  • Deposition properties are determined by immersing black tile plates in 1 percent solutions of each composition in water containing 200 parts per million by weight calcium; removing, draining and drying the plates at ambient temperatures; and observing the amount of precipitate deposited thereon. Relative precipitate deposition is reported in the Table.
  • Ex. II (20% coconut oil soap tallow sou 25% product 7 of Ex. VI (20% coconut oil soap 80% tallow soap) l5% product of Ex. I (20% coconut oil soap 8O tallow soap) 20% product 80% of Ex. III (20% coconut oil soap 80% tallow soap) weight mix (20% coconut of products oil soup of examples 80% tallow IV & V soap) good negligible XI good negligible XII good negligible XIII good negligible wherein x andy are each integers from 1 to 17, the sum ofx-l-y being from 12 to 18, z is an integer from I to 3, R is selected from the group consisting of hydrogen and methyl and M is selected from the group consisting of sodium and potassium.

Abstract

New compounds represented by the formula:

WHEREIN X AND Y ARE EACH INTEGERS FROM 1 TO 17, THE SUM OF X + Y BEING FROM 12 TO 18; R is hydrogen or methyl; and M is sodium or potassium, are useful surfactants and lime soap dispersants, which provide, in admixture with natural soaps, excellent cleansing compositions having reduced tendency to deposit precipitates in hard water.

Description

United States Patent Kidwell [451 Aug. 22, 1972 [541 ALKYL VICINAL HYDROXY ALKOXY ETHER MALEATE COMPOUNDS [72] Inventor: Roger L. Kidwell, Kirkwood, Mo.
[73] Assignee: Monsanto Company, St. Louis, Mo.
[22] Filed: Sept. 8, 1969 I21 1 Appl. No.: 856,206
[52] U.S. Cl ..260/485 G, 252/108, 252/132 [51 Int. Cl ..C07c 69/60 [58] Field of Search ..260/485 G [56] References Cited UNITED STATES PATENTS 3,242,200 3/1966 Johnson ..260/485 G Primary ExaminerLorraine A. Weinberger Assistant ExaminerE. Jane Skelly Att0rneyHerbert B. Roberts, Roger R. Jones,
Thomas N. Wallin and Neal E. Willis [57] ABSTRACT New compounds represented by the formula:
wherein x and y are each integers from 1 to 17, the sum of x y being from 12 to 18; R is hydrogen or methyl; and M is sodium or potassium, are useful surfactants and lime soap dispersants, which provide, in admixture with natural soaps, excellent cleansing compositions having reduced tendency to deposit precipitates in hard water.
4 Claims, No Drawings ALKYL VICINAL HYDROXY ALKOXY ETHER MALEATE COMPOUNDS BACKGROUND OF THE INVENTION This invention relates to novel compounds and to improved soap compositions containing such compounds. More particularly, the invention relates to alkyl vicinal hydroxy alkoxy ether maleates and to natural soap formulations containing such compounds and exhibiting reduced tendency to deposit precipitates in hard water.
The excellent performance characteristics of soaps derived from animal fats and vegetable oils, e.g., lauric, myristic, palmitic, stearic, tallow and coconut oil acid soaps are well-known. However, when such soaps are employed in hard water, (i.e., water containing substantial quantities of alkaline earth metal ions-particularly calcium or magnesium) they interact with the anionic constituents of such water to form insoluble precipitates which tend to deposit on washing vessels and items being washed. Such undesirable effects are exemplified by such phenomena as the ring around the tub" which frequently demarcates the water line of washing vessels utilized in geographical localities having hard water supplies.
Although deposition of precipitates by such compositions can be inhibited by use of sequestrants to soften the water, such sequestrants are inert compounds which do not contribute to the cleansing power of the compositions in soft water. Further, such additives sometimes impair physical characteristics of bar soap compositions in terms of hardness, gloss, solubility, etc., and therefore, are not desired for use therein.
SUMMARY OF THE lNVENTlON It is an object of this invention to provide novel compounds and improved soap compositions based on such compounds.
The novel compounds of this invention are alkyl vicinal hydroxy alkoxy ether maleates as hereinafter described. Basically, the improved soap compositions of this invention comprise natural soaps in combination with minor amounts of such novel compounds.
The invention will be understood from the following description of the preferred embodiments.
DESCRlPTlON OF THE PREFERRED EMBODlMENTS The alkyl vicinal hydroxy alkoxy ether maleates of this invention are represented by the formula:
wherein x and y are each integers from l to 17, the sum ofx +y being from 12 to 18; z is an integer from 1 to 3; R is hydrogen or methyl; and M is sodium or potassium. These compounds are effective both as surfactants and for use as lime soap dispersants in natural soap compositions of the type hereinafter described. For optimum performance in these applications, compounds wherein the sum ofx +y is from 14 to 16, z is l, and R is hydrogen are preferred.
The compounds of this invention can be prepared by various procedures. For example, straight chain internal olefins such as obtained by catalytic dehydrogenation of paraffins can be epoxidized by reaction with peracetic acid, and the epoxide reacted with ap propriate monoor poly-ethylene or propylene glycols in the presence of a Lewis acid catalyst to yield an alkyl vicinal monoor poly-alkoxylate which is reacted with maleic anhydride and neutralized with a sodium or potassium base to yield the compounds of this invent1on.
The foregoing compounds are excellent surfactants and, additionally, are found to inhibit precipitate deposition of natural soaps in hard water.
The soap compositions of this invention comprise a soap derived from natural products, (hereinafter referred to in the specification and claims as natural soaps) in combination with the alkyl vicinal hydroxy alkoxy ether maleates described above.
Any of the well-known natural soaps conventionally employed is soap bars and/or powders, can be utilized in the compositions of this invention. Such natural soaps include sodium and potassium salts of acids obtained by saponification of animal fats and vegetable oils, for example, lauric, myristic, palmitic, stearic, tallow and coconut oil acids and mixtures thereof. As is known to those skilled in the art, the selection of natural soap constituents is based on the physical and performance characteristics desired as well as cost and availability of the natural products from which the soaps are derived.
The compositions of this invention may contain a single hydroxy alkoxy ether maleate; a mixture of position isomers wherein the hydroxy and alkoxy ether maleate substituents are attached at various isomeric positions, e.g., 2,3 or 3,4, or 4,5 etc.; a mixture of hydroxy alkoxy ether maleates of various alkyl chain lengths, i.e., a homolog mix, or; homolog mixes wherein individual homologs comprise a mixture of position isomers. The compositions of this invention must contain at least 12 percent by weight of the hydroxy alkoxy ether maleate (based on the combined weight of the maleate and natural soap) to effectively inhibit precipitate deposition. The use of greater than 25 percent by weight maleate does not provide bar soaps of acceptable physical characteristics. A maleate content of from 15 to 20 percent by weight is particularly preferred.
In addition to the foregoing essential components, the compositions of this invention may contain minor amounts of perfumes, dyes, abrasives, antiperspirants, germicides or other additives conventionally employed in soap compositions. The invention is further illustrated by the following examples, wherein all percentages are by weight unless otherwise indicated.
EXAMPLE I Vl Alkyl vicinal hydroxy alkoxy ether maleates are prepared by reacting internal olefins as shown in Table 1 below with peracetic acid which is added dropwise to the olefin, the reaction mixture being maintained at a temperature of about 50 C via an ice bath. The epoxide formed is separated as a top layer from the reaction mixture, washed with aqueous Na CO and water until the wash water is neutral and dried by contact with Na SO The epoxide is then reacted with monoor polyethylene or propylene glycols as shown in Table l at about 90 C, and the product reacted with maleic anhydride. The acids produced are neutralized with a percent by weight NaOH solution at C to yield the maleates indicated.
TABLE I Vicinal Internal Vicinal Hydroxy Alkoxy Example Olefin Glycol Ether Maleate l tetraethylene tetradecyl hydroxy monoethoxy decene glycol ether sodium maleate II hexa ethylene hexadecyl hydroxy monoethoxy decene glycol ether sodium maleate III hexa propylene hexadecyl hydroxy monopropoxy decene gl col ether sodium malente IV octaethylene octadecyl hydroxy monocthoxy deccne glycol ether sodium muleute V octadiethyloctadecyl hydroxy diethoxy decene ene glycol ether sodium muleate VI eicosene triethyleicosyl hydroxy triethoxy one glycol ether sodium maleate EXAMPLES vrr x111 Soap bars are prepared by blending the ingredients shown in Table 2 below (percentages are based on dry weight) with about 18 percent by weight water and pressing the blended mass in a 2 A inch diameter die at about ten thousand pounds per square inch. Physical properties are reported in the table. Deposition properties are determined by immersing black tile plates in 1 percent solutions of each composition in water containing 200 parts per million by weight calcium; removing, draining and drying the plates at ambient temperatures; and observing the amount of precipitate deposited thereon. Relative precipitate deposition is reported in the Table.
of Ex. II (20% coconut oil soap tallow sou 25% product 7 of Ex. VI (20% coconut oil soap 80% tallow soap) l5% product of Ex. I (20% coconut oil soap 8O tallow soap) 20% product 80% of Ex. III (20% coconut oil soap 80% tallow soap) weight mix (20% coconut of products oil soup of examples 80% tallow IV & V soap) good negligible XI good negligible XII good negligible XIII good negligible wherein x andy are each integers from 1 to 17, the sum ofx-l-y being from 12 to 18, z is an integer from I to 3, R is selected from the group consisting of hydrogen and methyl and M is selected from the group consisting of sodium and potassium.
2. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 1 wherein R is hydrogen.
3. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 2 wherein z is l.
4. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 3 wherein the sum of .x y is from 14 to 16.

Claims (3)

  1. 2. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 1 wherein R is hydrogen.
  2. 3. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 2 wherein z is 1.
  3. 4. Alkyl vicinal hydroxy alkoxy ether maleates according to claim 3 wherein the sum of x + y is from 14 to 16.
US856206A 1969-09-08 1969-09-08 Alkyl vicinal hydroxy alkoxy ether maleate compounds Expired - Lifetime US3686282A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2338334A1 (en) * 1974-03-29 1977-08-12 American Cyanamid Co PARTIAL ESTERS OF HYDROXY-POLYCARBOXYLIC ACIDS AND THEIR USE AS AN INHIBITOR OF CORROSION AND SCALE IN CIRCULATING WATER NETWORKS

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242200A (en) * 1962-03-07 1966-03-22 Swift & Co Esters of higher fatty acids having hydroxy and ether substituents on adjacent carbon atoms of the acyl moiety

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242200A (en) * 1962-03-07 1966-03-22 Swift & Co Esters of higher fatty acids having hydroxy and ether substituents on adjacent carbon atoms of the acyl moiety

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2338334A1 (en) * 1974-03-29 1977-08-12 American Cyanamid Co PARTIAL ESTERS OF HYDROXY-POLYCARBOXYLIC ACIDS AND THEIR USE AS AN INHIBITOR OF CORROSION AND SCALE IN CIRCULATING WATER NETWORKS

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