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Publication numberUS3507937 A
Publication typeGrant
Publication dateApr 21, 1970
Filing dateOct 4, 1966
Priority dateOct 4, 1966
Also published asUS3560393
Publication numberUS 3507937 A, US 3507937A, US-A-3507937, US3507937 A, US3507937A
InventorsRoger E Zimmerer
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Reversed zwitterionic phosphorus compounds
US 3507937 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

25 2 9 5 caoss REFERENCE 5 mruggg United States Patent 3,507,937 Patented Apr. 21, 1970 "ice 3 507 937 The novel reversed zwitterionic compounds f hi i vention clean as well as tetrapropylenebenzene sulfonate. REVERSED PHOSPHORUS They remain in active form during conditions ordinarily Roger E. Zimmerer, Springfield Township, Hamilton encountered during washing. In addition, they remain in County, Ohio, assignor to The Procter & Gamble Com- 5 actiYe l mixed with. builders i i anionic pany, Cincinnati, Ohio, a corporation of Ohio nonionic, cationic, a mpholytlc, and zwitterronic deter- N Drawing Filed 4, 19 534,099 gents. Moreover, anionic brighteners remain in active Int. Cl; C07f 9/02, 9/28; C11d 1/34 form when mixed with the present reversed zwitterionic U.S. Cl. 260-924 7 Claims detergent compounds.

The reversed zwitterionic compounds of this invention have the formula R-ZR X wherein R is an aliphatic ABSTRACT OF THE DISC RE radical, e.g., alkyl or alkenyl, containing from about 10 Reversed zwitterionic compounds having a fi fi l to about 20 carbon atoms; Z is a negatively charged radicharged center adjacent a hydrophobic chain and a posical selected from the group consisting of phosphate, phostively charged center removed by a 2 to about 4 carbon 15 Phohate, p p inate radicals; R is an alkylene radiatoms from the negatively charged center are disclosed. cal cohtammg from 2 tQabOl-It 4 carbon atoms; and X is These compounds have the formula 1 wherea positively charged radical selected from the group conin R is an aliphatic radical, alkyl or alkenyl, Col-aim sisting of ammonium and tertiary sulfonium radicals; said ing from about 10 to about carbon atoms; Z is a negaammomum radical having the formula tively charged radical selected from the group consisting 20 9 of phosphate, phosphonate, and phosphinate radicals; NRaRaW R is an alkylene radical containing from 2 to about 4 wherein and R4 are Selected from th gr up concarbon atoms; and X is a positively charged radical sesisting of hydrogen, methyl, and ethyl; said tertiary sullected from the group consisting of ammonium and terfOnium radical having the formula tiary sulfonium radicals; said ammonium radical having e the formula wherein R and R are selected from the group consisting NR R R of methyl and ethyl. The phosphate radical herein has wherein R R and R are selected from the group conthe formula sisting of hydrogen, methyl, and ethyl; said tertiary 5111- 0 fonium radical having the formula {l %Rs o wherein R and R are selected from the group consisting of methyl and ethyl. The reversed zwitterionic compounds The Phosphohate ladlcal herelh has the formula are useful as detergent compounds per se or can be used 0 as zwitterionic detergent components in detergent com- {l O positions.

This invention relates to novel zwitterionic detergent compounds and to detergent compositions containing The Phosphmate Yadlcal herelh has the formula these compounds. These compounds have a negatively 0 charged center adjacent a hydrophobic chain, and a posill tively charged center removed by 2 to about 4 carbon (iatoms from this negatively charged center. These corn- 9 pounds are characterized herein as being reversed zwitterionic compounds to distinguish them from more conven- R R and R can be the same or different within the tional zwitterionic compounds in which a positively same molecule. R and R can be the same or different charged center is adjacent the hydrophobic chain, and a within the same molecule, negatively charged center is removed by two or more For purposes of organization and convenience the carbon atoms from this positively charged center. above compounds wherein R R or R are hydrogen are There are several properties that are regarded as being termed zwitterionics herein. These compounds might essential for a compound to be suitable for use as a determore appropriately be classified as ampholytics since they gent. Foremost, is the cleaning ability of the comopund, deprotonate to the extent of one hydrogen over a wide i.e., its ability to remove soil, e.g., from soiled clothes. In pH range, including the alkaline pH range, forming the addition, the detergent should remain in active form uncorresponding compounds containing an amino moeity. der conditions of usage, e.g., at high temperatures such as Thus, in detergent compositions containing water or moisl40 F. and in aqueous solutions. Although there are a ture or under conditions of usage, these compounds are number of organic detergents which have these properties, detergent compounds such as those of the present invention which have additional desirable properties find wider scope of application.

present in ampholytic form. They, however, may be isolated in zwitterionic form and are ordinarily in this form at the instant of preparation of the detergent composition containing them.

3 Reversed zwitterionic detergent compounds, none of which are known to be described in the prior art, and exemplary of those within the scope of the present invention are set forth in Table I below wherein R, Z, R Z, R R R R and R are applied in the formulas set forth above.

ROl -OR NR R NaOH noi ow innmi NaCl In these equations R and R are each methyl or ethyl,

TABLE I R Z R X B R R R R (l) deeyl phosphate ethylene ammonium methyl methyl methyl dodecyl phosphate ethylene ammonium methyl methyl methyl tetradecyl phosphate trimethylene ammonium methyl methyl methyl octadecyl phosphate tetramethylene ammonium hydrogen methyl methyl octadecyl phosphate ethylene tertiary sulonium ethyl ethyl deeyl phosphonate tetramethylene tertiary sultonium methyl ethyl dodecyl phosphonate ethylene ammonium methyl methyl methyl (8 dodecyl phosphonate trimethylene ammonium ethyl ethyl ethyl (9) dodecyl phosphonate thylene ammonium hydrogen methyl methyl idecyl phosphonate ethylene ammonium hydrogen methyl ethyl hexadecyl phosphonate tetramethylene tertiary sull'onium methyl methyl oleyl phosphonate ethylene ammonium methyl ethyl ethyl eicosyl phosphonate ethylene ammonium hydrogen hydrogen hydrogen deeyl phosphinate tetramethylene ammonium hydrogen hydrogen methyl dodecyl phosphinate ethylene ammonium methyl methyl methyl dodecyl phosphinate ethylene tertiary sullonium methyl methyl hexadecyl phosphinate trimethylene ammonium methyl methyl methyl octadeeyl phosphinate ethylene ammonium hydrogen ethyl ethyl octadecyl phosphinate ethylene ammonium hydrogen methyl ethyl eicosyl phosphinate ethylene ammonium hydrogen hydrogen ethyl (2l) dodecyl phosphate ethylene ammonium hydrogen methyl methyl Preferred reversed zwitterionics of this invention are those compounds wherein R defined generally above contains from 12 to 16 carbon atoms, and X defined generally above is a quaternary ammonium radical or an ammonium radical containing only one hydrogen. The most preferred compounds are compounds (7) and (9) in Table I above, i.e., 2-(trimethylammonio)ethyl dodecylphosphonate and 2-(dimethylammonio)ethyl dodecylphosphonate, respectively.

The compounds of the present invention can be prepared according to the following reaction equations wherein R, Z, R X, R R R R and R are defined as hereinbefore except as specified otherwise hereinafter.

Compounds wherein Z is phosphate and X is ammonium wherein R and R are hydrogen and R is hydrogen, methyl, or ethyl:

hydrogen, methyl, or ethyl. These reactions can be carried out under the following conditions:

Temperature, C.

Reaction Solvent Time 2 hours, 4 hours.

Compounds wherein Z is phosphate and X is ammonium, wherein R is hydrogen and R and R are methyl or ethyl:

and neither of them is hydrogen. The alkyl dichlorophosphate in Reaction V can be made by the process of Reaction I hereinbefore. Reactions V and VI can be carried out under the following conditions:

Tempera- Reaetion Solvent ature, C. Time V Ethylene diehloride VI Methanol 25-40 2 hours, 4 hours. 25-30 15 minutes, 45 minutes.

Compounds wherein Z is phosphate and X is quaternary ammonium:

ll 69 ROZ-OR NRHUR NaI H20 In this equation R R and R are each methyl or ethyl, and none of them is hydrogen. The dialkylammonioalkyl alkylphosphate reactant in this equation can be made by the process of Reaction VI. Reaction VII can be carried out under the following conditions:

I Reaction VII Solvent-dioxane Temperature--refiux (about C. for dioxane) Time-15 mins.45 mins.

Compounds wherein Z is phosphate and X is tertiary sulfonium:

So1ventethylene dichloride Temperature-5O C.--l 00 C. Time-15 mins.-2 hours Compounds wherein Z is phosphonate and X is ammonium wherein R and R are hyd;ogen and R is hydrogen, methyl, or ethyl:

OH XIV.

i u RPOR CI NR2R3R4 RIIJORINRZRKRI IICl ea H 0 These reactions can be carried out under the following conditions:

Compounds wherein Z is phosphonate and X is quaternary ammonium:

XVII.

In this equation R R and R are each methyl or ethyl, and none of them is hydrogen. The dialkylsirrimonioalkyl alkylphosphonate reactant in this equation can be made by the process of Reaction XVI. Reaction XVII can be carried out under the following conditions:

Reaction-XVII Solventethyl alcohol Temperature- C.-80 C. Tirrie-3-6 hours Compounds wherein Z is phosphonate and X is tertiary sulfonium:

x VIII.

H g 63 RIF-ON-Cl msm n on -snuz HCI The phosphonate reactant in the equation of Reaction XVIII can be made by the process of Reaction XIII hereinbefore. Reaction XVIII can be carried out under the following conditions:

Tempera- Solvent ture, C.

Time

Reaction:

IX Excess trialkylphosphrte. 140-150 4 hours, 8 hours. 15 minutes, 1 hour. 1 hour, 2 hours.

2 hours, 4 hours.

30 minutes, 1 hour. 1 hour, 3 hours.

Compounds wherein Z is phosphonate and X is ammonium wherein R is hydrogen and R and R are methyl or ethyl:

l 63 RiOR NHR R NaCl HzCO;

In these equations R and R are each methyl or ethyl, and neither of them is hydrogen. The phosphonic dihalide reactant in Reaction XV can be made by the process of Radiation XI. Reactions XV and XVI can be carried out under the following conditions:

Tempera- Reaction Solvent ture, C. Time XV Ethylene dichloride... 20-60 15 minutes, 2 hours. XVI Acetone 30-50 30 minutes, 1 hour.

Reaction XVIII Solventethylene dichloride Temperature-50-100 C. Time-15 rnins.-2 hours Compounds wherein Z is phosphinate and X is ammonium wherein R and R are hydrogen and R is hydrogen, methyl, or ethyl:

XIX. 0

ll di-terL-butyl perotide R CH=CHz HP-OHs RP-ONa 2atmospheres RIlONa HCl RIF-0H NaCl H H XXI.

XXV. copending application of Roy, Ser. No. 218,863 filed Aug.

23, 1962 and now abandoned.

196 grams (0.78 mole) dodecylphosphonic acid was e placed in a 1-liter flask. This flask was then placed on a steam bath. To this flask on the steam bath was added In equation XIX, R is an aliphatic radical containing two over a 15-minute period 360 grams (1.7 moles) PCl less carbon atoms than the desired R. In equation XXV, This addition was carried out under dry nitrogen. The R and R are each hydrogen, and R is hydrogen, methyl formed mixture was maintained on the steam bath for or ethyl. Reactions XIX-XXV can be carried out under one hour after the PCl addition was completed. During the following conditions: the PCl addition and thereafter the temperature of the Reaction Solvent Temperatures, C. Time XIX Methanol ncmao -20 hours. XX Water/diethy1ether -35..." 5 minutes.

Diethyl ether- 0-10 10-30 minutes.

Toluene 3-5 hours XXV Acetone Reflux (about 56 C. for acetone). 5-10 hours.

Compounds whereZis phosphinate andXis ammonium mixture was maintained at 90-100 C. by the steam wherein R is hydrogen and R and R are methyl Or bath. The flask was then removed from the steam ethyl: bath. The excess PCl in the reaction mixture was then XXVL converted to POCl by rapidly passing S0 into the re- 0 O action mixture for 90 minutes. The POCl and SoCl in g q; the mixture were then removed from the mixture under 3 R I vacuum, and the residue was distilled to yield 210 grams R Br 0 (0.73 mole) of substantially pure dodecylphosphonic dichloride, having a boiling point ranging from 117 C. to 119 C. at 0.1 mm. Hg. 1

400 ml. of triethylamine having been dried over CaSO was then introduced into a 1-liter, 3-necked, roundbottom flask, equipped with a thermometer, a condenser protected with a drying tube, an addition funnel, and a mechanical stirrer. Then, 143.5 grams (0.5 mole) of f Y dodecylphosphonic dichloride was added to the flask with RP-OH 2NR R R RP-IUNRIUR HBr-NWRR stirring over a 45-minute period. Next, 44.5 grams (0.5

mm 6 mole) of Z-dimethylaminoethanol was added to the flask dropwise with stirring over a -minute period. During In this equation, the reactant can be made by the process 40 of Reaction XXIV and R2 R3, and R are each methyl the 2 dimethylammoethanol addition period, the reaction or ethyl, and none of them is hydrogen. This reaction can mixture m the flask was malmamed at 40 50 by he carried outunder the same conditions as reaction was completed the reaction mixture in the flask was XXV.

stirred for one additional hour at C. The reaction Compounds wherem Z 15 phosphmate and x temary mixture was then allowed to cool to room temperature.

In this equation, the phosphinic acid reactant can be made 30 by the process of Reaction XXIV; R is hydrogen and R and R are each methyl or ethyl. This reaction can be carried out under the same conditions as Reaction XXV.

Compounds ,wherein Z is phosphinate and X is quaternary ammonium: 35

sulfomum: 40 To this reaction mixture at room temperature was XXVIII- added dropwise, with stirring, over a 30-minute period, 20

ml. (1.1 mole) of water. During the water addition, the

Q mask temperature of the reaction mixture rose rapidly, and

- 1 b was maintained at about 60 C. by means of a cold water R SR bath. After the 30-minute water addition period, 180 ml.

XXIX- 3 i of water was poured into the reaction mixture to eflect Ri'oNa R 1 RP-R SIUR NaI complete solution of the reaction mixture.

318R 9 To this solution was added 1 liter of water containing grams (1.5 moles) of sodium hydroxide. This addition was carried out by pouring the sodium hydroxide solution mafje by the pr cess of Reaction XXV heiehnbefore fi into the reaction solution. The temperature of the formed muons XV i X can be came out er solution was about 35 C. during and after sodium hythe following commons droxide addition. The formed solution was evaporated 60 on a steam bath under a current of nitrogen. The residue resulting from this evaporation was digested in 1 liter of 583313--. D m u 3 ifig fi g boiling chloroform, and the insoluble materials were then removed by filtration. The chloroform was then evap- The following examples illustrate the preparation of the mated on a sfeam bath under a currept of mtrogen' The compounds of this invention: 160-gram residue was an extremely viscous, amber paste that was hygroscopic. Thls material was equtlibrated with EXAMPLEI the atmosphere over a saturated solution of KSCN at Diisopropyl dodecylphosphonate was prepared b room temperature yielding 172 grams of clear amber gel.

lysis of the gel showed it to be a mixture containing actlng dodecyl bromlde and trnsopropyl phosphtte ac Ana cording to the technique described in Ford-Moore and by we'ght 2(d'methy]ammm)ethy] dodecyl Phos' The phosphinic reactant in Reaction XXVII can be Reaction. Solvent Temperature, C. Time Williams, Journal of the Chemical Society 1947, p. 1465. Phonaie, 9- compound in Ta I hereinbefore and This reaction was carried out at a temperature of 145 10% y welght Water- C. and for a time period of 5 hours. The formed diiso- Into a 3- d, r nd-bottom flask, equipped propyl dodecylphosphonate is converted to dodecylphoswith a heating mantle, a reflux condenser, and a mechanphonic acid using the pyrolytic method described in the 75 ical stirrer, was charged grams of the above gel [0.34

'cooling. After addition of the 2-dimethylaminoethanolmole 2- (dimethylammonio)ethyl dodecylphosphonate] dissolved in 500 ml. of denatured ethyl alcohol. To this solution was added 52.5 grams (0.37 mole) of methyl iodide. This addition was carried out over a 10-minute period. During this addition, the formed mixture was maintained at a temperature of 60-70 C. After this addition, the mixture was borught to reflux temperature, i.e., about 78 C., and was stirred at reflux temperature for four hours. At this point, the reflux condenser was replaced with a distillation head and condenser, and 350 ml. of alcohol was removed by distillation. To the resulting mixture was added with stirring 340 ml. of l N NaOH (0.34 mole NaOI-I). This addition was carried out all at once. During this addition the temperature of the mixture was maintained at 70-80 C. The solvent in the mixture was then evaporated on a steam bath. To the residue was added 1000 ml. water to form a reaction solution. This solution was mixed with about 0.5 equivalent of cation exchange resin in the hydrogen form and with about 0.5 equivalent of anion exchange resin in the hydroxide form. After about 30 minutes during which the mixture was periodically shaken, the resin was removed by filtration. The water in the filtrate was evaporated on a steam bath to provide an amber solid which was equilibrated over saturated KSCN solution at room temperature to yield 101 grams of clear, amber gel. Analysis of this gel showed it to be a mixture of 84% by weight Z-(trimethylammonio)-ethyl dodecylphosphonate, i.e., compound (7) in Table I hereinbefore, 1l% by weight Water, and by weight sodium iodide.

2 (dimethylethylammonio)ethyl dodecylphosphonate can be prepared as above except that an equivalent amount of ethyl iodide is substituted for the methyl iodide above.

EXAMPLE II Into a 2-liter, stainless-steel autoclave were added 84 grams (0.5 mole) l-dodecene, 106 grams (1.0 mole) sodium hypophosphite monohydrate, 1 ml. di-tert.-butyl peroxide, and 350 ml. methanol. The autoclave was sealed, maintained at 120 C., and rocked for 17 hours. During this 17-hour period the pressure in the autoclave was 2 atmospheres. After this 17-hour period, the contents of the autoclave were allowed to cool to room temperature, after which the autoclave was opened and the contents removed. The contents were then diluted with 3 liters of distilled water, and then extracted three times, each time with 500 ml. of petroleum ether, and the extracts discarded.

Into the aqueous solution remaining was poured 100 ml. of concentrated hydrochloric acid. During this addition the temperature of the resulting mixture was approximately 35 C. The resulting mixture was extracted three times, each time with 500 ml. of petroleum ether, and the remaining aqueous phase was discarded. These ether extracts were dried over sodium sulfate, and the dried extracts were evaporated on a steam bath under nitrogen to yield 98 grams of crude dodecylphosphinic acid. Recrystallization from 300 ml. of petroleum ether gave 79 grams (0.34 mole) of substantially pure dodecylphosphinic acid.

70 grams (0.3 mole) of this substantially pure dodecylphosphinic acid is then dissolved in 200 ml. diethyl ether at 0 C. To this solution is added a diethyl ether solution of diazomethane prepared by adding 30 grams of N-nitrosomethylurea to a mixture of 75 ml. of 30% aqueous KOH and 250 ml. diethyl ether at 010 C., and decanting the ether layer from the aqueous layer prior to use. The diazomethane and dodecylphosphinic acid are reacted for 30 minutes at 0-10 C. The produced methyl dodecylphosphinate, 74 grams, is isolated by evaporating the diethyl ether and excess diazomethane on a steam bath under nitrogen.

72 grams (0.28 mole) of this methyl dodecylphosphinate is then dissolved in 250 ml. of toluenewhich has been dried over sodium ribbon. This solution is mixed with 6.5 grams (0.28 mole) sodium dispersed in 250 ml. toluene in a 1-liter, 3-necked, round-bottom flask, equipped with addition funnel, thermometer, reflux condenser protected by a drying tube, and mechanical stirrer. The sodio derivative of the phosphinate is formed by stirring the mixture at 25 C.- C. for four hours.

The resulting mixture is brought to reflux, i.e., to about 101 C. To this refluxing mixture is added over a threehour period, grams (0.32 mole) of Z-bromoethanol. After this three-hour period, the reaction mixture is allowed to cool to room temperature, after which the precipitated sodium bromide is removed by filtration, and the toluene solvent is removed by vacuum evaporation to yield 82 grams of crude methyl-2-hydroxyethyldodecylphosphinate.

This methyl-Z-hydroxyethyldodecylphosphinate is dissolved in 200 ml. of dry petroleum ether contained in a 500 ml. 3-necked flask, equipped with a gas dispersion tube, a drying tube, and a magnetic stirrer. Anhydrous HBr is then passed into the solution for five hours at the rate of 200 cc./min. During the HBr addition the temperature of the mixture rises and levels out at -60 C. After HBr addition, the system is swept with nitrogen for one hour to remove methyl bromide and dissolved HBr. The solvent (petroleum ether and formed water) is evaporated under nitrogen on a steam bath to yield 93 grams of crude 2-bromoethyldodecylphosphinic acid.

This crude 2-bromoethyldodecylphosphinic acid is dis solved in 200 ml. acetone. Into this solution is poured grams (1 mole) of trimethylamine. This mixture contained in a 500 ml. boiling flask surmounted with a reflux condenser is refluxed at about 56 C. for 8 hours. The resulting mixture is evaporated on a steam bath. The residue is dissolved in 200 ml. of methanol. This solution is shaken for 30 minutes with a mixture of 0.5 equivalent of cation exchange resin in the hydrogen form and 0.5 equivalent of anion exchange resin in the hydrox ide form. The resins are then removed by filtration. The filtrate is evaporated to yield grams of 2-(trimethylammonio)ethyl dodecylphosphinate, i.e., compound (15) in Table I hereinbefore.

2 (dimethylethylammonio)ethyl dodecylphosphinate and 2-(triethylammonio)ethyl dodecylphosphinate can be prepared as above except that dimethylethylamine and triethylamine, respectively, are substituted for the trimethylamine above.

In another case, grams (0.3 mole) of 2-bromoethyldodecylphosphinic acid prepared as above is dissolved in 500 ml. of dioxane. To this solution is added 45 grams (0.64 mole) sodium methyl mercaptide. This mixture is maintained at 30 C. for 18 hours. A fast stream of nitrogen is passed through the mixture to remove methyl mercaptan. To the resulting mixture is added 50 grams (0.45 mole) methyl iodide. This reaction mixture is re fluxed at about 101 C. for 4 hours. Purification of the refluxed mixture yields 88 grams of 2- (dimethylsulfonio) ethyl dodecylphosphinate, i.e., compound (16) in Table I hereinbefore.

- EXAMPLE III Into a l-liter, 3-necked flask, equipped with a thermometer, gas inlet tube, dropping funnel, and mechanical stirring assembly is placed 106 grams (0.69 mole) of POCl and 500 ml. of dry ethylenedichloride. To this formed solution, with stirring, is added dropwise over a 30-minute period 93 grams (0.5 mole) of l-dodecanol. During this addition, dry nitrogen is passed slowly through the stirred solution. The temperature of the solution starts out at room temperature, i.e., 25 C., and rises about 5 C. during the dodecanol addition. Stirring is continued for 3 hours after addition is completed, during which the temperature of the reaction solution ranges from 25 C. to 30 C. The excess POCl and the ethylenedichloride are then removed by evaporation under 11 water pump vacuum using a 70 C. water bath to speed the evaporation.

The residue from the evaporation, consisting of crude dodecyl dichlorophosphate, is dissolved in 500 ml. of dry ethylenedichloride in apparatus identical with that described in the above paragraph. To this solution is added with stirring over a 45-minute period, 44 grams (0.5 mole) 2-(dimethylamino)ethanol. Stirring is continued for 2 hours after this addition. During the Z-(dimethylamino)ethanol addition period and during the stirring thereafter the temperature of the reaction solution ranges from C. to C. The solvent is then removed by vacuum evaporation.

The residue from this evaporation is dissolved in 500 ml. of methanol containing grams of NaOH and 50 ml. water. This solution is shaken from time to time during a thirty-minute period 'with a mixture of 1.5 equivalents of cation exchange resin in the hydrogen form and 1.5 equivalents of anion exchange resin in the hydroxide form. The resin is then removed by filtration. The solvent is then evaporated to yield 147 grams of 2-(dimethylammonio)ethyl dodecylphosphate, i.e., compound (21) in Table I above.

In another case, 100 grams (0.3 mole) of 2-dimethy1- ammonio)ethyl dodecylphosphate prepared as above is dissolved in 500 ml. dioxane. To this solution is added over a 10-minute period, grams (0.32 mole) of methyl iodide. The mixture is then brought to reflux temperature, i.e., to about 105 C., and is stirred at this temperature for 30 minutes. To the resulting mixture is added with stirring over a 5-minute period 300 ml. of l N NaOH (0.3 mole NaOH). The temperature of the mixture during this addition ranges from 100 C. to 72 C. The resulting mixture is purified by ion exchange to yield 94 grams of Z-(trimethylammonio)-ethyl dodecylphosphate, i.e., compound (2) in Table I hereinbefore.

Z-(dimethylethylammonio)ethyl dodecylphosphate can be prepared in the same manner as'the 2-(trimethylammonio)ethyl dodecyl hosphate above except that an equivalent amount of ethyl iodide is substituted for the methyl iodide above.

Compounds of this invention are useful per se as detergent and surface active agents. Desirably they are used with other materials to form detergent compositions, as for example, liquid, bar, tablet, granular or other compositions. Such detergent compositions can contain the reversed zwitterionics of this invention, and water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts or mixtures thereof in a ratio of reversed zwitterionic to builder salt of about 4:1 to about 1:20. Such detergent compositions ordinarily contain from 5% to of detergent active and from 5% to of builder salt.

Granular detergent compositions preferably contain about 5% to about 50% of the reversed zwitterionics of this invention and liquid formulations preferably contain from about 2% to about 30% of such reversed zwitterionics. Granular detergents preferably contain at least an equal amount of an alkaline builder salt. Liquid formulations preferably contain from about 5% to about 40% of a water-soluble alkaline builder salt, the balance of the composition being a solvent such as water, and/or other liquid vehicles. Liquid formulations can also con tain a hydrotroping electrolyte, e.g., sodium toluene sulfonate. All percentages and parts herein are by weight unless specified otherwise.

Water-soluble inorganic alkaline builder salts which can be used in this invention alone or in admixture are alkali metal carbonates, borates, phosphates, polyphos' phates, bicarbonates and silicates. Ammonium or substituted ammonium, e.g., triethanol ammonium, salts of these materials can also be used. Specific examples of suitable salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium and potassium pyrophosphate, sodium and ammonium bicarbonate, potassium tripolyphosphate, sodium hexaphosphate, sodium sesquicarbonate, sodium orthophosphate, and potassium bicarbonate. The preferred inorganic alkaline builders according to this invention are alkali metal tripolyphosphates for built granular and tablet compositions and alkali metal pyrophosphates for built liquid compositions. Potassium is the preferred alkali metal used in liquid compositions and sodium finds best application for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used in this invention alone or in admixture are alkali metal, ammonium or substituted ammonium, aminocarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(Z-hydroxyethyl)-nitrilodiacetates, sodium and potassium nitrilotriacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as organic alkaline sequestrant builder salts (see U.S. Patent 2,739,942). Also suitable as organic alkaline sequestrant builder salts are the watersoluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl Ser. No. 269,359, filed Apr. 1, 1963 and now U.S. Patent 3,308,067 (e.g., polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene).

Polyphosphonates are also valuable builders in terms of the present invention, includingspecifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium and potassium salts of methylene diphosphonic acid, sodium and potassium salts of ethylene diphosphonic acid, and sodium and potassium salts of ethane-1,1,Z-triphosphonic acid. Other examples include the alkali metal salts of ethane-Z-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,Z-triphosphonic acid, propanel,1,3,3-tetraphosphonic acid, propanel 1 ,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.

Besides the builders being used together with the present reversed zwitterionics, it is also possible according to the present invention to use the reversed zwitterionic compounds of this invention in combination with other cleaning agents such as anionic, nonionic, and other ampholytic and zwitterionic organic detergent compounds. When it is desired to use such reversed zwitterionic compounds in combination with other detergent compounds, they are preferably utilized with anionic detergents because of the sudsing characteristics of the latter. The ratio of the reversed zwitterionic to such other detergent compound is from about 10:1 to 1:5. If it is desired to use such a reversed zwitterionic in admixture with another detergent compound as the active portion of a cleaning composition, the ratio of such a mixture to the builder salt should be within the previously prescribed range of 4:1 to 1:20. A composition prepared along these lines can contain from 5% to 50% of such a mixture and 5% to 85% of a builder salt selected from water-soluble inorganic alkaline builder salts, water-soluble organic sequestrant builder salts, and mixtures thereof, within the prescribed ratio range.

Examples of anionic soap detergents which can be used in admixture with the reversed zwitterionic detergent, if desired, are the sodium, potassium, ammonium and alkylolammonium salts of higher detergent range fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of suitable anionic organic nonsoap detergents in the form of their water-soluble salts are: alkylglycerylethersulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkylpolyethenoxy ether sulfates; acylsarcosinates; acyl esters of isethionates;

N-acyl-N-methyl taurides; alkylbenzenesulfonates wherein the alkyl substituent is straight chain or branched chain; sulfonated alpha-olefins, e.g., such as described in the copending application of Kessler et al., Ser. No. 561,397, filed June 29, 1966 and now US. Patent 3,332,880; alkylphenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 24 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylolammonium salts, for example. Specific examples are: sodium la-uryl sult'ate, sodium tallow alkyl sulfate; sodium salt of sulfonated alpha-tridecene; potassium N-methyl-N- lauroyl tauride; triethanolammonium tetrapropylbenzene sulfonate; sodium (linear) dodecyl benzene sulfonate.

Examples of nonionic organic detergents which can be used in the compositions of this invention, if desired, are: polyethylene oxide condensates of alkylphenols wherein the alkyl group contains from 8 to 15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to 20:1; condensation products of ethylene oxide with the product resulting from the reacti n of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5000 to 11,000; the condensation products of from about to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms, e.g., condensation product of 6 moles of ethylene oxide with one mole of lauryl alcohol; higher alkyl di-lower alkyl amine or phosphi1e oxides, e.g., dodecyldimethylamine oxide or dodeclyd methyl phosphine oxide; alkyl methyl sulfoxides such as dodecyl methyl sulfoxide.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the. aliphatic radical can be straight chain or branched and wherein one of the aliphatic substituents contains from about to about 20 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate, Examples of compounds falling within this definition are sodium 3-dodecylaminopropiqnate, sodium 3-(N-methyl-N-hexadecylamino)-2-hydroxypropane-l-sulfonate and its dodecyl homolog, sodium 3-dodecylaminopropane-l-sulfonate, sodium dodecyl-beta-alanine, sodium N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of United States Letters Patent No. 2,658,072, N-higher alkyl aspartic acids such as those produced according to the teaching of United States Letters Patent No. 2,438,091, and the products sold under the trade name Miranol and described in United States Letters Patent No. 2,528,378.

Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 10 to about 20 carbon atoms and one contains an anionic water solubilization group, e.g., carboxy, sulfonate, sulfate, phosphate, phosphinate, or phosphonate. Examples of compounds falling within this definition are: 3 (N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate and the corresponding dodecyl and tetradecyl homologs and 3 (N,N-dimethyl-N-dodecylammonio)-propane-1-sulfonate and the corresponding hexadecyl and tetradecyl homologs.

It is also possible according to the present invention to use the present reversed zwitterionic detergents in combination with anionic brighteners. A detergent composition employing the combination of ingredients ordinarily can contain from about 0.01% by weight to about 2% by weight optical brightener. Examples of anionic optical brighteners which can be used herein are sodium 2-sulfo- 4-(2-naptho-1,2-triazolyl)stilbene and sodium 4,4-bis(4- anilino-6-morpholino s triazo-Z-ylamino)-2,2'-stilbene disulfonate.

The detergent compositions of this invention can also contain any of the usual adjuvants, diluents, and additives, for example, perfumes, anti-tarnishing agents, bacteriostatic agents, dyes, suds builders, suds depressors, and the like, without detracting from the advantageous properties of the composition.

The following examples illustrate detergent compositions containing the reversed zwitterionic compounds of this invention which can be used under .conditions of ordinary usage to clean, for example, soiled clothing or dishes. All percentages herein are by weight unless otherwise specified.

EXAMPLE IV Solidgranules Percent 2-(trimethylammonio)ethyl dodecylphosphonate 17.5 Sodium tripolyphosphate 50.0 Sodium silicate (Na O:SiO =1:2.5) 10.0 Sodium sulfate 17.5

Moisture 5.0

EXAMPLE v Compressed granulestablet Percent 2-(trimethylammonio)ethyl dodecylphosphate 31.0 Tetrasodium pyrophosphate 52.0 Trisodium phosphate 10.0 Moisture 7.0

EXAMPLE VI Solid-granules Percent 2-(trimethylammonio)ethyl dodecylphosphinate 32.0 Pentasodium ethane-l-hydroxy-l,1,2-triphosphonate 64.0

Moisture 4.0

EXAMPLE VII Solid-granules Percent 3 (N,N-dimethyl-N-hexadecylammonio 2 hydroxypropane 1 sulfonate 20.0 2-dimethylsulfonio)ethyl dodecylphosphinate 25.0 Sodium tripolyphosphate 35.0 Sodium carbonate 10.0 Sodium silicate (Na O:SiO =1:2.5) 5.0 Moisture 5.0

EXAMPLE VIII Solidgranules Percent 3-(trimethylammonio)propyl octadecylphosphonate 20.0 Sodium tallow alcohol sulfate 10.0 Trisodium ethane 1 hydroxy-l,l-diphosphonate 20.0 Sodium tripolyphosphate 10.0 Sodium nitrolotriacetate 10.0 Sodium sulfate 8.0 Sodium silicate (Na O:SiO =1:2.5) 11.0 Moisture 11.0

EXAMPLE IX Liquid Percent 2-(dimethylsulfonio)ethyl decylphosphonate 5.0 Sodium salt of S0 sulfonated 1:1 weight mixture of alpha-dodecene and alpha-tetradecene 10.0 Tetrapotassium pyrophosphate 19.0 Sodium silicate (NflzOZSiOg=1I1-6) 3.8 Potassium toluene sulfonate 8.5 Carboxymethyl hydroxyethyl cellulose .3 Water Balance 15 EXAMPLE X Liquid Percent 2-(dicthylsulfonio)ethyl decylphosphate 6.0 Sodium (linear) dodecyl benzene sulfonate 6.0

Tetrapotassium propane-1,l,3,3-tetraphosphonate 20.0

Sodium silicate (Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5 Carboxymethyl hydroxymethyl cellulose .3 Water Balance EXAMPLE XI Solidgranules Percent 2-(dimethylammonio)ethyl dodecylphosphonate 5.0 Condensation product of moles of ethylene oxide and one mole of tallow fatty alcohol 5.0

Sodium (linear) tridecyl benzene sulfonate 10.0

It will be appreciated that the reversed zwitterionic compounds used in the present invention can be incorporated into many other liquid or granular detergent compositions with suitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquid or granule detergent compositions can be added to the compositions of this invention without adversely afiecting or modifying basic cleaning characteristics. For example, a tarnish inhibitor such as benzotriazole or ethylene thiourea may be added in amounts up to about 1%. Fluorescers, perfume, gleachingageu color, antiredeposition agents, antibacterial agents, thic ening agents,

opacifiers, and blending or viscosity control agen'sywhi le not essential in the compositions of this invention, mi}! also be added.

The compositions of the present invention can be used in conjunction with cool water washing situations as well as with warm and hot water.

What is claimed herein is:

1. A reversed zwitterionic detergent compound havin the formula R--Z-R --X wherein R is seected from alkyl and alkenyl of from about 10 to about 20 carbon atoms; Z is a negatively charged radical selected from the group consisting of phosphate, phosphonate, and phosphinate radicals; R is an alkylene radical containing from 2 to about 4 carbon atoms; and X is a positively charged radical selected from the group consisting of ammoniuin and tertiary sulfonium radicals; said ammonium radical having the formula wherein R R and R are each selected from the group consisting of hydrogen, methyl, and ethyl; said tertiary sulfonium radical having the formula as s RSRO wherein R and R are each selected from the group consisting of methyl and ethyl.

2. A reversed zwitterionic compound of claim 1 Wherein R has from about 12 to about 16 carbon atoms.

3. A reversed zwitterionic compound of claim 2 wherein R is an ethylene radical.

4. A reversed zwitterionic compound of claim 3 wherein Z is a phosphonate radical.

5. A reversed zwitterionic compound of claim 4 wherein X is a quaternary ammonium radical.

6. A reversed zwitterionic compound of claim 5 wherein R R and R are each methyl and R is dodecyl.

7. A reversed zwitterionic compound of claim 4 wherein R is dodecyl and X is ammonium wherein R is hydrogen and R and R are each methyl.

CHARLES B. PARKER, Primary Examiner A. H. SUTTO, Assistant Examiner U.S. Cl. X.R.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3711493 *Jan 25, 1971Jan 16, 1973Ici LtdPlant growth regulating composition
US3867482 *Jul 24, 1972Feb 18, 1975Basf Ag2-Chloroethanephosphonic acid derivatives
US3870619 *Jan 29, 1973Mar 11, 1975TechnicProcess for producing bright electrodeposits of gold and its alloys
US3925453 *Jan 25, 1974Dec 9, 1975Monsanto CoQuaternary aminoalkylene phosphonic acids and method of preparation
US3928509 *Apr 10, 1974Dec 23, 1975Hoechst AgHybrid ionic phosphorus compounds
US4181634 *May 5, 1978Jan 1, 1980Johnson & JohnsonMild cleansing compositions comprising an alkyleneoxylated bisquaternary ammonium compound and an anionic or amphoteric detergent such as a phosphobetaine
US4263431 *May 17, 1979Apr 21, 1981Ciba-Geigy CorporationCationic fluorescent whitening agents
US4384121 *Oct 27, 1980May 17, 1983Ciba-Geigy CorporationCationic fluorescent whitening agents
US4432886 *Sep 22, 1982Feb 21, 1984Ciba-Geigy CorporationCationic fluorescent whitening agents
US4542023 *Jan 31, 1984Sep 17, 1985Rhone-Poulenc AgrochimieFungicidal salts of organophosphorus derivatives
DE3506973A1 *Feb 27, 1985Sep 5, 1985Kao CorpPhosphorsaeureester und verfahren zu ihrer herstellung
EP0108565A2 *Oct 27, 1983May 16, 1984Takeda Chemical Industries, Ltd.Phospholipids, their production and use thereof
Classifications
U.S. Classification558/166, 510/302, 510/469, 510/340, 510/237, 510/352, 987/224, 987/159, 510/351, 510/467, 510/446, 510/445, 987/186, 510/303
International ClassificationC07F9/30, C07F9/141, C11D3/00, C07F9/08, C07F9/38, C07F9/09, C07F9/40, C11D1/88
Cooperative ClassificationC11D1/886, C07F9/38, C07F9/091, C07F9/4075, C07F9/301, C07F9/1411, C07F9/08
European ClassificationC07F9/141A1, C07F9/30A1, C07F9/40C1, C07F9/09A1, C07F9/38, C07F9/08, C11D1/88C