CA1083170A - Ethoxylated sulfonium switterionic compounds and detergent compositions containing them - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Compounds of the formula wherein R1 and R2 are each straight chain, branched chain or cyclic alkyl, alkenyl, aryl, aralkyl or alkaryl moieties having from 1-30 carbon atoms, R3 is a C2-C8 alkylene, alkenylene, arylene or alkarylene moiety; R4 is a C1-C8 alkylene.
alkenylene, arylene or alkarylene moiety: A is water-solubilizing anionic moiety: and n is from 1 to about 100 are useful as surfactants. Compounds wherein groups R1, R2 and R3 and integer n are selectively chosen provide good clay soil detergency performance even in the absence of boulders.
The compounds are usefully combined With other organic surfactants to provide detergent compositions having good clay and oily soil removal performance.

Description

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Bl\CKGROUl\lD OF T~IE INVENTION
Th;is invention relates to etho~ylatcd sulfonium æwitterionic compounds ~hich e~hibit une.Ypectedly high clay soil removal even in very low built or unbuilt detergent systems and which are surprisingly stable under alkaline conditions. The invention further relates to detergent compositions containing the novel sulfonium compounds in combination wi-th co-surEactants andior builders. :
While a variety of surfactant classes are known, e.g., nonionic, anionic, cationic and zwitterionic, none .", :~;:~
f the conventional types of detersive surfactants are Xnown to provide the advantageous performance of the instant compounds. The shortcomings of the commonly-used surfactants are well-known, and such materials must be built and/or otherwise precisely formulated to provide good soil removal ? `, -~under a variety of conditions.
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3~70 Eforts have been made to prepare specific types of surfactants for particular purposes and, in particular, zwittexionic compounds have been thoroughly explored and attemp-ts have been made to tailor these compouns in a particular way which would provide especially useful detersive surfactants.
Such known zwitterionic surfactants have generally been based on a nitrogen cation and surfactant classes such as the ammonio-sulfates, ammonio-sulfonates and ammonio- ~ -carboxylates have been proposed. The analogous materials based upon a phosphorus cation have also been suggested, although very much less frequently.
While certain of the above mentioned classes of compounds have been found to provide useful detergent properties, they have not, for several reasons, enjoyed any substantial commercial success. One reason for this may be that questions have been raised regarding the environmental effect of materials containlng nitrogen or ~-phosphorus.

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~, , Also, such surfactants have been expensive to prepare commercially.
It is an object of the present invention to provide zwittexionic detergent compounds which are effective in removing particulate soil from fabrics, and which do not contain nitrogen or phosphorus.
It is another object herein to provide detergent compositions which can be used to cleanse both fabrics and hard surfaces without the need for builders or additives.

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DESCRI PTI O~ OF THE PR OR ART ;;
Various zwitterionic compounds are well known, and~ `

it is also known to include oxygen-containing moieties in . - . ~
the charge-separating part of the molecule. In particular, U.S. Patent 3,684,427, issued August 15, 1972 to Walz and Ouaedvlizg relates to certain ethoxylated zwitterionic - ~ ~
compounds having long ethoxylate chains, the compounds being .. ; ~, . .
useful as dyeing assistants. Also, German Offenlegungschrift 2,009,802, published November 5, 1970 and assigned to CIBA ~-~

Ltd. refers generally to ethoxylated am~onio-sulphates as ~ -dyeing assistants. 'Belgian Patent 813,052, issued to GAF
: , :
Corporation, concerns amphoteric surfactants having an ~
..... _ - : N,M-bis-(ethoxylate sulfate) structure. U.S. Patents :

3,452,066, lssued ~une 24, 1969, and 2,781,390, issued February 12, 1957, both to Mannheimer, broadly relate to ;
various zwitterionic surfactants optionally containing a seemingly limitless varlèty of oxygen-containing, presumably ~:
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3~70 hydrophilic, moieties, includi~g alkylene oxides. U.S.
Patent 3,769,311, issued October 30, 1~73, to Armstrong and Dawald, discloses ethoxylated ammonio propionate zwitter-ionics, and describes compounds having limited ranges of ethyleneoxy and hydrophobic groups attached to the positive charge center.
U.S. Patent No. 3,925,262, issued December 9, 1975 and 3,929,678, issued December 30, 1975, both assigned to The Procter & Gamble Company, relate to particlar ethoxylated zwitterionic compounds based on a nitrogen cationic center.
, In contrast to the numerous patents relating to nitroyen-based ~iitterionics, there is relatively little prior art relating to sulfonium z~itterionic compounds.
U.S. Patent 2,813,898, assigned to Monsanto, discloses compounds of the general formula R - I - (CEI2)n SO3 wherein R and R' are hydrocarbon radicals containing from 1 to 18 carbon atoms and n is 1-4. The compounds having a long chain alkyl group are stated to pOSSC!SS surFacc activ~
properties.

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lOB3~70 The German Specifieation No. 943,830, assigned to Bohme Fettchemie, discloses compounds of the yeneral formula R - S - CH

in which R i5 alkyl. The compounds are stated to have disinfectant and textile treating properties.
The U.K. Patent Specification ~o. 988,512, assigned to Tootal Broadhurst Lee Company, relates to sulfonium ;~
sulfates which are used as intermediates in the formation of certain polymers. -~

SUMMARY OF T~E INVENTION `
I ~ This invention encompasses zwitterionlc surfactant compounds of the formula l ~ _ R30 (CH2CE~20)n ~ R4A

, ; wherein Rl, R2, R3, R4, A and n are as defined below. ~ ~
., `~ 115~ ~ DETAILED DESCRIPTION OF THE INVENTION

In its hroadest aspect, the present invention relates to æwitterionic compounds comprising molecules ,.. . .
made up of our distinct parts. Ref rring to the foregoing formula, the compounds herein comprise a hydrocarbon portion composed of groups Rl and R2; a cationic charge center which is a sulfonium ion; an anionic charge center, ;` A; and a charge-separating moiety interposed between said l;
cationic and anionic charge centers.

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The hydrocarbon (hydroph~bic) portion of the present compounds comprises straight chain, branched chain or cyclic alkyl, alkenyl, aryl, aralkyl or alkaryl moieties having from 1 to 30 carbon atoms. It will be understo~d by those skilled S in the detergency arts that the hydrocarbon groups Rl and R2 can contain other substituents, such as halogen, hydroxyl, alkoxyl, and the like.
In preferred compounds according to the invention, R
and R2 together contain at least 12 carbon ~oms, although in certain circums~ances useful compounds may be obtained when R1 and R2 together contain fewer than 12 carbon atoms; for example, when there is a substantial degree of hydrophobic character ;
in the charge separating group, correspondingly less hydrophobic character is necessary on the groups Rl and R2 in order to obtain a compound having the requisite detersive properties.

In particularly preferred compounds, group Rl is a straight chain or branched chain C10-C30 alkyl moiety, or an alkaryl moiety h~aving a C6-C26 alkyl group, and R2 is a Cl-C4 alkyl ~ moiety or is an alkaryl or aralkyl moiety having 1 to 4 carbon ; 20 atoms in the alkyl moiety, especially benzyl moiety. More pre-.
ferably, Rl is a Cl2-C22 alkyl moiety and R2 is a Cl-C3 alkyl moiety, especially methyl.
Other detersive surfactants are th~se wherein Rl and ~ R2 are each independently selected from C6-C22 alkyl moieties ;;~ 25 and alkaryl moieties having C6-C18 alkyl group (preferably Rl and R2 are each independently selected from C8-C18 alkyl !'.' moieties, most preferably C10-C14 alkyl moieties). -The anionic charge center, A, is any water-solubilizing ~

anionic moiety, and can be, for example, sulfonate, sul~ate, i, .

carboxylate and the like negatively charged moieties well j~

- recognized in the detergency art as use~ul for imparting water-solubility to detersive surfactants. Compounds of the present -,. 1-:~

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type wherein A is sulfate or sulfonate, especially the former, are preferred from the standpoint of ease of manufacture and detergency performance.
The charge-separating moiety of the compounds of the S present invention includes as an essential feature a poly-ethylene oxide chain made up of at least two ethylene oxide !` units. This part of the charge separating moiety is essential for the instant compounds to exhibit the good detergent pro-perties, especially good particulate soil removal. In pre-ferred compounds, the charge separating moiety consists in its ~ ;
entiret~ of ethylene oxide units, in which case both of the `~
R3 and R4 are ethylene.
However, in its broadest aspect, the invention encom-passes compounds wherein R3 is a C2-C8 aIkylene, alkenylene, -~ 15 arylene or alkarylene moiety and R4 is a Cl-C8 alkylene, alkenylene~
arylene or alkarylene moiety. Where the anionic center, A, is a carboxylate anion, it is preferred that R4 is methylene or C3-C8 alkylene, as a propionate moiety at the anionic center is relatively unstable. It will be understood that R3 and R4 may f~ 20 contain other substituents, e.g., hydroxyl, halogen, alkoxyl, ~ ;
' and the like.
.~ ~ . . i Also, in certain cases it may be desirable that R3 has ~` more than two carbon atoms. This is because the presence of a relatively labile ether oxygen atom in close proximi~y to the :. .
~ 25 sulfur atom tends to make the compound somewhat unstable during ;` preparation. The preparation of the compounds of the present f invention can therefore be simplified i R3 is, for example, a C3 or C4 alkylene or an arylene moiety. ~ ;

In the above general formula, the number of ethylene oxide units, n, in the charge separating moiety may range ~;` from l to 100. The lower limit is a function of solubility, ., ::i . :. . -:
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and it has been found that some compounds where n is 1 or 2 are insufficiently soluble to perform adequately as the sole surfactant in an aqueous solution. However, in combination with other surfactants, notably nonionic surfactants, the compounds of the present invention where n = 1 or 2 are useful. For good clay soil removal performance, it is also important that the chain length of the charge 6eparating moiety is not more than about 100 ethylene oxide units. To secure truly superior clay soil removal from fabrics, ~he degree of ethoxylation, n, is preferably from

4 to about 50, most preferably about 4 to about 20.
It will be understood that the numbers recited herein ~ -for ethylene oxide content may refer either to single com~
pounds having, for example, 3 units of ethylene oxide per molecule, or to compound mixtures in which the average l;
~egree of ethoxylation is equal to, for example, 9 units of ethylene oxide per molecule. Commercial processes for preparing polyethylene oxide c~ains normally result in mixtures of compounds having a distribution of polyethylene oxide chain lengths.
- As can be seen from the foregoing, the random selection of groups Rl and R2 for substitution at the sulphur atom and the charge separating moiety does not suffice to define detersive surfactants, rather~the totaL hydrophobic .~ .
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effect resulting from the interrelation of groups Rl and ~ `
R2 on the one hand and of R3 and the ethylene oxide moiety -on the other hand must be considered. In general, it can be stated that when there is a higher degree of hydrophobic character within the charge separating ~oiety, for example, when R3 has ~rom 4 to 8 carbon atoms, useful compounds can be obtained with Rl and R2 gxoups having less hydrophobic character.
The range of selection of group R4 is somewhat less critical than the other R groups, and is usually dictated merely on the basis of the scheme used to prepare the compounds of choice. Of course, if R4 is too long, water solubility of the compounds can be adversely affected. Conveniently, R4 can be a Cl-C4 alkylene, a C3-C4 hydroxy-substituted alkylene or a phenylene group.
Most preferably, R4 is ethylene except that, as noted ~; above, when the group A is COO , R4 is most preferably -' methylene.
The compounds of the type described hereinabove are water-soluble,(i.e., solubility of about 60 to 75 ppm, -or much greater, in' 105F. water). Surprisingly, the compounds are so superior in detergency perfor~ance that onlylminimal solubi1ity is required. Indeed, a solution -concentration of only about 75 ppm of the pr~sent zwitter-ionics is sufficient to launder fabrics, although higher r .
concentrations can be utilized to speed the cleansing process.
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The synthesis of these compounds can be carried out according to the following scheme.
A polyethylene glycol having up to 100 ethylene oxide units is reacted in pyridine with an equimolar amount of p-toluenesulfonyl (tosyl) chloride to gi.ve the mono-tosylate compound CH3 ~ ~ _ S02 - 0 - ~CH2CH2O)nH ~I) together with some of the corresponding ditosylate.
The mono-tosylate (I) is purified by chromatography and added slowly to a heated mixture of an alkyl mercaptan : , , R ~ SH (II) and sodium hydride in 1,2-dimethoxyethane. Refluxing of the reaction mixture for about 16 hours followed by filtering and evaporating solvent yields the thioether .~ ~
R - S ' (CH2CH2)n H (III) ~ ;
' The thioether (III) can also be prepared by the more attractive commercial route in which the mercaptan (II) is eth- , -oxylated di~ectly with ethylene oxide in an autoclave at 140- l~
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` 160C, 540 lb. pressure and, preferably, in the presence of a base.

The thioether ~III) is then sulfated using chloro-, ~ . ~
- suLfonic acid or sulfur txioxide, followed by neutralization l to give the anionic compound I -~ , .
~ R - S - (CH2CH20)n S03 Na (IV) - . .

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Finally, the compound IV is alkylated using an alkylating agent such as methyl iodide or dimethyl sulfate to give the sulfonium sulate ' .

R - S - ~CH2CH2O)n SO3~ (V) CH3 ~;~

It will ~e understood that deriva~ives other than the methylated compound can be obtained by using other -~
alkylating agents. For example, the co~pound (IV) can be reacted with benzyl chloride to give the analogous benzyl compound or with ethyl chloroacetate to give the carbo-` 10 ethoxymethyl compound.
As will be discussed hereinafter, the compounds of the present invention, especially those having ethoxylate `~ ~ chain lengths of at least 4, and preferably 6-12 ethylene .
~ oxide units, provide useful clay SQil removal performance ; ~ I5 on their own, without the need for builders or surfactants.
However, it is frequently desirable to employ the;~
; compounds of the present invention in compositions which ~.
include co-surfactants, or builders or ~oth~ In particular, comp~unds of the present invention having short (n < 4) ethylene oxide chains are preferably combined with ~a co~
surfactant or builder which helps to solubilize the zwitterionic~
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~ sulfonium compound.

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,; The present invention therefore also provides ~;
.
detergent compositions comprising from l~ to 99~ by weight . 25 of the sulfonium zwitterionic compound and from 99% to l~
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'~ of an organic detergent. The ratio of sulfonium compound ,,' :, . '' ; ~ ' . . .

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the co-surfactant can be varied depending on the end use o the composition and its desired physical ~orm. The ratio of zwitterionic compound:co-surfactant is preferably fro~ 10:1 to 1:10, most preferably from 4:1 to 1:10 by weight. Preferred S compositions comprise from 10~ to 80~ of zwitterionic compound and from 90% to 20~ of co-surfactant.
A wide range of organic detexgen~s can be mixed, i.e~ can be considered compatible with the ethoxylated zwitterionic compounds to form compositions useful in the present invention. In the context of this invention "compatible"
is defined as causing no appreciable decrease in the ability of the ethoxylated zwitterionic compound to remove and suspend particulate soil.
Classes of compa~tible detergents that are especially useful co-surfactants include the nonionic, zwitterionic, and ampholytic surfactants and fatty acid salts which can be used - in a broad range of proportions to the ethoxylated zwitterionic !: compound.~ These co-surfactants tend to increase the clay ! removal performance of the sulfonium compounds, especially those with short ethoxylate chains. In contrast, most synthetic anionic detergents do not enhance the particulate soil removal performance of the ethoxylated zwitterionic compounds to the same extent, especially on synthetic fibers, although anionic sur~actants can usefully be employed in combination with the 25 sulfonium compounds for other reasons, e.g~ to obtain particularly desirable sudsing characteristics. Amongst the cationic surfactants, only those having a polyoxyalkylene function are compatible with the ethoxylated zwitterionic compounds ~ ` useful in the present invention. ~
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~3~0 Nonionic Synthetic Deter~_nts Most commonly, nonionic sur~actants are compounds produced by the condensation of an alkylene oxide (hydrophilic in nature) with an orgarlic hydrophobic compound which is usually aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene moiety which is ; condensed with any particular hydrophobic compound can be rcadily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Another variety of nonionic surfactant is the semi-polar nonionic typified by the amine oxide, phosphine oxides, and sulfo~ides.
Examples of suitable nonionic surfactants are disclosed in Nirschl et al U. S. Patent 3,862,058, Column 9, 15 line 38 through Column 11, line 51 inclusive.
~.

Preferred nonionic surfactants are the conclensation : _ . . r, products of primary and secondary aliphatic alcohols with ethylene oxide, including but not being limited to the Tergito ~ secondary alcohol ethoxylates manufactured by 20 Union Carbide Corporation and the Neodol~ primary alcohol j~ O
cthoxylates marketed by Shell Chemical Company. ~ highly preferred nonionic surfactant is Neodol 45-7, a predominantly ~` C14-C15 primary OXO alcohol condensed with seven moles of ;~ ethylene oxide.
. 2S ~mpholytic Synthetic Deter~ents ,,, ~i; :
~` Ampholytic synthetic detergents can be broadly ~ described as derivatives of aliphatic or aliphatic '~` derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least -~

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one conta~ns an anionic water-solubili~lng c~roup, e.c3., carboxy, sulfonate, sulfato. Examples oE compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulEate, sodium 2-(dimethyl-amino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)-propane-l-sulfonate, disodium octadecyl-iminodiacetate, sodium l-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.
Sodium 3-(dodecylamino)propane-1-sulfonate is preferred.

Zwitterionic_Synthetic Detergents Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of lS quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The cationic atom in the quaternary compound can be part of a heterocyclic ring. In all of these .
compounds there is at least one aliphatic group, straight chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent containing an anionic water-solubilizing ~roup, e.g. carboxy, sulfonate, sulfate, , . . .
phosphate, or phosphonate. Examples of various classes of zwitterionic surfactants operable herein are disclosed in Nirschl et al U. S. Patent 3,862,058 at Column 12, line 5 through Column 14, line 60 inclusive .
,: .-Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N-dimethyl-N-alkylammonio)-propane-l-sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein ;~

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in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylclmmonio)-propane-l-sulfonate; 3(N,N-dimethyl-N-hexad~cylammonio)-2~hydroxypropane-1-sulfonatc; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-l-sulfonate; 3-(N-dodecyibenzyl-N,N,dimethylammonio)-2-hydroxypropane-1-sulfonate; N-dodecylbenzyl-N,N-d.imethylammonio acetate; 3-(N-dodecyl-benzyl-N,N-dimethylalT~onio)propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and N,N-dimethyl-N-hexa-decylammonio acetate.

Anionic Detergents ~he anionic component of the instant detergent compositions can be an organic sulfuric reaction product having in its molecular structure an alkyl group containing . .
from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group, or mixtures thereof.
(Included in the term "alkyl" is -the alkyl portion of ;
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acyl groups.) Examples of this group of synthetic detersive surfactants which can be used in the presen~ invention are the alkyl sulfates, especially those obtained by ~ `
` sulfating the higher alcohols (C8-C18 carbon atoms) produced from the glycerides of tallow or coconut oil; ~-~
` and alkyl benzene sulfonates, in which the alkyl group -~
. . .
contains from about 9 to about 14 carbon atoms, in - (~
! . .
!,` 25 straight chain or branched chain conEiguration, e.g., those of the type described in U. S. Patents 2,220,099 ~` and 2,477,383. Linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 13 carbon atoms, abbreviated as C13L.~S, as well as mi~ed Cll 2 and Cll 8 (avg.) L~S are typically used. Cll-C14 branched chain alkyl ~'` .
~ 15 s . . ~. , , .; - . . -, 33~0 benzene sulfonates (ABS), which are excellent sudsers, can also be used.
Examples of commercially available alkyl benzene sulfonates (free acid form) useful in the instant invention include Conoca SA 515, SA 597, and SA 697, all marketed by the Continental Oil Company, and Calsoft LAS 99, marketed by the Pilot Chemical Company.
Other anionic surfactant compounds herein include the alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; coconut oil fatty acid monoglyceride sulfonates and sulfates; and alkyl phenol ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups ;
contain about 8 to about 12 carbon atoms.
Other useful anionic surfactants herein include the esters of ~-sulfonated fatty acids containing from about

6 to 20 carbon atoms in the ester group; 2-acyloxy- -alkane l-sulfonic acids containing from ahout 2 to 9 `~
carbon atoms in th~ acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyi group and from abou-t 1 to 30 moles of ethylene oxide;
olefin sulfonates containing from about 12 to 24 carbon atoms; and ~-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Anionic surfactants based on the higher fatty acids, i.e., "soaps" are useful anionic surfactants herein.
Alkali metal salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 .

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, to about 20 carbon atoms are useul anionlc surfactants in the present compositions. Particularly useful are the soaps derivable from the mixtures of fatty acids made from coconut oil and tallow.
Preferred water-soluble anionic organlc surfactants herein ~nclude linear alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group;
branched alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; the tallow range alkyl sulfates, the coconut range alkyl glyceryl sulfonates; alkyl ether (ethoxylated) sulfates wherein the alkyl moiety contains from about 12 to 18 carbon atoms and wherein the average degree of ethoxyla-tion varies between l and 12, especially 3 to 9; the sulfated condensation products of tallow alcohol with ;1 15 from about 3 to 12, especially 6 to 9, moles of ethylene oxide; olefin sulfonates containing from about 14 to 16 'i i ~ carbon atoms; and soaps, as hereinabove defined. -`~ Specific preferred anionics for use herein ;
~~ include: the linear C10-Cl4 alkyl benzene sulfonates (LAS);
the branched C10 to C14 alkyl benzene sulfonates (ABS);
the tallow alkyl sulfates; the coconut alkyl glyceryl ether sulfonates; the sulfated condensation products o ~; -~ mixed C10-Cl8 tallow alcohols with from about 1 to about `~ 14 moles of ethylene oxide; and tallow soap.

; 25 It is to be recognized that any o the foregoing ,~ .
j~ anionic surfactants can be used separately herein or as ~ixtures. Moreover, commercial grades of the surfactants can contain non-interfering components which are pro-cessing by-products. For example, commercial C10-C14 ~ 30 alkaryl sulfonates can comprise alkyl benzene sulfonates, .~ .
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1~3~70 alkyl toluene sulfonates, alkyl naphthalene sulfonates and alkyl poly-benzenoid sulfonates. Such materials and mixtures thereof are fully contemplated for use herein.

Cationic Deter~ent S Only those cationic detergents having a hydro-philic grouping with the molecule have been ~ound to be compati~lejin solution with the ethoxylated 7witterionic compounds useul in the present invention.
Thus compounds of the class 12 '~
Rl - N63 - (CH2CH2O)pH X

can be employed where Rl is a C12-Cla linear or branched alkyl or alkenyl group R~ and R3 are Cl- ~ alkyl or hydroxy alk~l groups, p has a value in the range 3-50, and X is a compatible anion. Analogous bis-ethoxylated quaternary ammonium salts can also be used. ~

Detergent Builders ~ ;
The novel compounds of the present invention are also especially useful when combined with builders, and the invention therefore also provides detergent composi-tions comprising from 1% to 99~ by weight of the sulfonium zwitterionic compound and from 99% to 1~ of a detergent builder. The actual level of builder depends on the end ;~
use of ~he composition and its desired physical form;
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preEerably, the cornpositions contain 10~ to 75~, most preferably 25~, to 60~ of builder.
Suitable inorganic builders include the alkali metal polyphosphates (including the pyrophosphates and glassy high polymeric phosphates) phosphonates, carbonates, sesqui-carbonates, bicarbonates, bo.rates, silicates, sulphates, and aluminosilicates.
Aluminosilicate builder. salts found to be useful in the present invention have the general formula:

Naz[(AlO2)z (si2)y] x H2O ,r, ' ~ ;
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264. Such alumino-silicates also should have a particle size diameter in the range 0.1 to 100 microns, a calcium ion exchange capacity of at : :
least about 200 milligram CaCO3 equi.valent/c3ram and a calcium ion exchange rate of at least about 2 grains/U. S. gallon/ .
minute/gram. Detergent compositions incorporating alumino-silicate builder salts of this type are disclosed in the commonly assigned Belgian Patent No. 814,874 issued November 12, 1974.
Suitable water soluble detergent builders are dis-closed in Nirschl U. S. Patent No. 3,862,058 at column 15, line 8 to column 16, line 18.
Examples of organic builders .; are set forth in Diehl U. S. Patent No. 3,308,067 and mix-~ tures of certain preferred organic and inorganic builders :~ are disclosed in Canadian Patent No. 755,038.

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The above-discussed builders can also usefully be incorporated into the detcrgent compositions colnprising a mixture of the sulfonium/~witterionic compound and a co-surfactant.

S Optional In~redicnts ~ -In addition to the above-mentioned components, det~rgent compositions according to the invention may also contain other ingredients conventionally employed in such produc-ts. -One such optional ingredient that may be incor-porated is an enzyme for removal of protein-based or carbo-hydrate-based stains. Enzymes for removing protein-based stains are proteolytic in nature such as those sold under ; the trade names "Alcalase" and "Es-terase" by Novo Industries . ~ . . . .
A/S Denmark or under the trade names "Maxatase" and "A2 Protease" by Gist~Brocades N.V. The Netherlands. These materials are normally incorporated at levels of up to 1 by weight~ preferably 0.25~ to 0.75% by weight, and are preferably coated or prilled with inert additives to minimize ~ 20 dust formation and improve storage stability. A wide range '` of enzyme materials and means for their incorporatlon into !-' ' synthetic detergent granules is disclosed in U.S.P. 3,553,139 ~
issued on January 5, 1971, to ~IcCarty, Roald, DeOude, Blomeyer, ~;
and Cracco .

A further ingredient that may be incorporated to improve product performance is a bleaching agent of the halogen or oxy~en-containing type. Examples of the hypohalite ~` bleach type include trichloro isocyanuric acid and the sodium ;
and potassium dichloroisocyanurates and N-cllloro and N-bromo alkane sulphonamides. Such materials are normally added ~i at 0.5%-10~ by weight of the finished product, preferably ;i~
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1~-53 by ~eicJht.
Examples of oxyyen-containing bl~aches include sodium perborate, sodium p~rcarbonate, and potassium non-opersulphate that are incorporated at levels of 5-30~, preferably 10-25Q by weight of the final product. The inclusion of or~anic bleach activators such as phthalic anhydridc, tetra acetyl ethylene cliamine, tetra acetyl ~ethyl~lle diamine or tetra acetyl glycouril lead to the in situ production during the washing process of the corres-pondi.ng organic peroxy acids which have enhanced lowtemperature bleaching performance. Activators of this type are normally used with sodium perborate, at usage levels o 5-15~ by weight of the final product.
Materials to boost or modify the sudsing pattern of the compositions of the present invention may also be included. Examples of suds boosters include coconut and tallow mono- and di-alkanolamides, particularly ethanolamides and C12 15 alkyl di-lower alkyl amine oxides. Typical suds depressors include long chain fatty acids such as those disclosed in U. S. Patent 2,954,347 issued September 27, 1960, to l~ayne St. John and combinations of certain nonionics ~ ;
therewith as disclosed in U. S. Patent 2,954,348 issued September 27, 1960, to Eugene Schwoeppe.
`
Other optional ingredients in granular products include hydrotropes and antica~ing additives such as salts of lower al~yaryl sulphonic acids, salts of ~-sulphobenzoic acid, and urea, normally utilized at levels of 0.5~6 to 5 by weight of the final product, preferably at levels of 1~-3~ by weight. C12-C18 alkyl acid phosphates and their ~ , ~
- 21 - ~

'P, ' ' ' . ' ' ' ' ' ' ' ~ ' .. .. : ' ' '. ~ ' ' ' . . ' ' 1'. :. ' ' . ' - 1~3831~

condensation products with ethylene oxid~ ay also be i~
incorporated at similar levels for contro: of crutcher mix viscosity. Antiredeposition agents suc~ as glassy polymeric phosphates,magnesium silicates, co loidal silicas, carboxymethyl cellulose, hydroxyethyl cellulose, and their derivatives may also be incorpolated. Preferred anti-redeposition agents are glassy phosphates containing more than ten phosphorus atoms per molecule and colloidal silicas.

Anti-tarnish and anti-corrosion agents, perfume and color may also be included, the last ingredient being conveniently added either as a general color or in the form of a speckle applied to a separate granule fraction of the entire formulation or to a granulate of one or more of the ingredients.
Anionic optical brightening agents or fluorescers i;
such as the bis(triazinylamino)stil~ene disulphonates can be included in the formulations of the present invention but their efficiency is not as high as in conventional formula~
tions unless they are incorporated together with an anionic surfactant.
.
The pH of detergent formulations in accordance with the present invention can lie anywhere within the range 4-ll but is preferably chosen to fall within the 25 range 6-10. However, the use of specific optional com- i ponents such as enzymes may require the selection of a product pH that will permit optimum f1~nctioning of the `~ component concerned.

,, .` 1 - 22 - i~ ~
: ' , ' ,' - '' .. , .. , ''': ~...... ;', , . ' 1(~8~

Granular formulations embodying the compositions of the present invention may be formed by simple admixture of the components, by adsorption of the surfactant onto a carrier granule, by an atomizing and spray-drying process, 5 or by pan or drum granulation of the components Liquid or pasty formulations embodying the compositions of the present invention may contain builders or may be unbuilt, If the compositions are unbuilt, they contain from 10%-90%
of total surfactant in aqueous or alcoholic solution.
Optionally, such liquid compositions can include from 1%~10%
of an organic base such as mono, di, or tri-alkanolamine.
Such compositions will normally be homogeneous single phase liquids of low viscosity (approximately 100-150 centipoises at 75F).
Built liquid detergent compositions may also be ~ single phase liquids provided that the bu lder can be solu-t bilized in the mixture at its level of use. Such liquids may contain 5/~30% total surfactant, 10%-20% builder which may be organic or inorganic, 5/~10% of a hydrotrope system and 40%~80% pf water. Liquids of this type also have low viscosity (100-150 c.p.s. at 75F). Built liquid detergents incorporating components that form heterogeneous ~;
mixtures or levels of builder that cannot be completely dissolved can also embody the compositions of the present invention. Such liquids conventionally employ viscosity modifiers to produce systems having plastic shear character-istics to maintain stable dispersions and to prevent phase separation or solid settlement.

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-" ~0~3~70 Performance ~ata In this specification the assessment of particulate soil removal performance both of detergent formulations of the invention and of comparative formulations is carried out using the following procedure.
Soil removal testing is carried out in a washing machine simulator and involves a 10-minute wash cycle at 105F in 7 grains pex U.S. gallon hard water (calculated as CaCO3) using a 3:1 ratio of Ca:Mg salts. The fabrics are washed, rinsed and tumble-dried prior to being graded on a Gardner whiteness meter. The fabric load for particulate ~-soil removal testing comprises a mixture of white cotton, polycotton (65% DACRO ~/35~ cotton), and polyester (KODEL~
swatches which are stained with a standardized clay-type :~
soil.
The results (expressed as relative clay removal ~:
index~ for each formulation represent a percentage ~ -of the whiteness value achieved by a commercial synthetic detergent standard tested at the same time under identical ~ ;
20 conditions. This standard formulation has the following :-composition by weight: ::

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Sodium C12 alkylbenzene sulphonate 7.55 Sodium tallow alkyl sulphate 9.25 Coconut alcohol + 6 mole E0 0.60 Diethanolamide 1.60 5Sodium tripolyphosphate S0.00 Sodium silicate solids 5.90 Sodium sulphate 14.20 Moisture 10.00 Miscellaneous 0.30 100. 00 Performance data was obtained using three representative compounds of the present invention. These ~ ~
three compounds had the general formula ;

18H37 1 - (CH2CH20) S0 '`: . ~ ' ~ ` ' where n is, respectively, 3, 9 and average 17. These three compounds are below designated E3, Eg and E17 respectively.
Table 1 shows the clay soil removal performance , .
~ ~ - o the zwitterionic compounds-themselves in water. I~

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The table shows that the clay removal performance of E3 on its own is poor; this is attributable to the incomplete solubility of this compound. The completely -soluble Eg and E17 compounds have a performance equal to that of the control composition, even in the absence of co-surfactants or builders.
As can be seen from the data obtained for Eg at pH 10~5, there was no substantial decrease in performance indicating that the zwitterionic compound is stable at thls pH.
Table 2 shows the clay removal performance of compositions including a builder. ~ ~
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It can be seen that builders significantly improve the performance of the poorly~soluble E3 compound and also offer some advantage in combination with the Eg compound.
Table 3 shows the effect of combining various co-surfactants with the sulfonium compounds.

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As can be seen from the above table, various co-surfactants can be combined with the sulfonium compounds to give useful compositions. The performance of the poorly soluble E3 compound is markedly improved by the addition of a nonionic surfactant lNeodol 45-7), the nonionic surfactant serving to solubilize the zwitterionic as well as providing a synergistic effect.
Table 4 shows performance data for aompositions formulated both with co-surfactant and builder.

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The above compositions offer good clay soil remov~l performance at a builder level which is very low when compared with many conventional, heavy-duty detergent products.
In order to obtain a measure of the stability of the zwitterionic compounds of the present invention, compositions g 18H371S (cH2cH2o)3so3 ~ and C18H37S ~(CH2CH O) S

were allowed to stand for abotlt 2 1/2 weeks in a carbonate/silicate slurry at about pH 10.5 and room tem-perature. No decrease in clay soil removal performance of the compositions was observed at the end of this time.
Additional examples of formulations which show satisfactory performance even after prolonged storage are as follows:
: ' :' ' is Liquid Product ~ C18H37S1 63 (cH2cN2o)l7so3 25.0%

Triethanol amine 10.0%
HCl 1.2%
Water 63.8% ~ ;
~ 20 Powder Admix ,~ C18H371 (CH2CH20)17 3 38.4%
. ~
~ H3 `~ Sodium carbonate 30.8~ ~ ~
. :
Sodium silicate (SiO2:Na20=3.2) 30.8~ ~

' ~:
The following examples serve to illustrate the invention.
. . . ' ' ' ' ' ' .

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8~1~70 ', EXAMPLE I ~ ~
. . .
Preparation of 8-methyloctadecylsulfonio-3,6-dioxaoct~rl sulfate (A) PreParation of 8-iodo-3,6-dioxaoctanol -~ ! ' One hundred grams (0.59 mole) of 2--[2-~2-chloroethoxy)-ethoxy]-ethanol ~Aldrich 16,297-3) was added to a solution ., ~ .
of 450 g. (3 mol) of sodîum iodide in 2.5 1 acetone and stirred, in the dark, for 5 hours at reflux and then at room temperature for 16 hours. The precipitate was filtered and the acetone evaporated off at 30C. The residue was dissolved in chloroform, extracted with saturated sodium chloride solution, and then with saturated sodium bisulfate solution. The chloroform extract was dried (MgSO4) and ~ evaporated at room temperature to yield 137 g.(53%) of the r: title compound.

~ ~ 15 (B) Preparation of 3,6-dioxa-9-thiahePtacosanol -r; ~
~ ~ To a solution of 31.5 g. (0.11 moles1 of n~octadecanethiol p ~ ~ in 200 ml. of 1,2-dimethoxyethane which had been heated to ; -~
40C, under argon, was added slowly 0.11 moles of sodium hydride (5.3 g. 50%) which had been rinsed with hexane to `~ ~ 20 remove the mineral oil and then slurried in 1,2-dimethoxy-t .
ethane. The reaction mixture was then heated at reflux , ~-(85C) with stirring or 2 hours. A solution of 39 g. '-0.11 mole~ of the monoiodide in 200 ml of 1,2-dimethoxy~
ethane was added dropwise and the reaction mixture was 2~ allowed to reflux with stirrin~ for 16 hours. The mixture was cooled, the insoluble salts filtered, and the solvent evaporated. The residue, a mixture of the title compound ;~

i , . ' . .

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:

and sodium iodide, was dissolved in chloroEorm and washed with water. The chl~roform extract was dried, evaporated, and the residue crystallized from hexane to yield 11.5 g.
(0.027 26% yield) of the title compound.

(C) Preparation of sodium 3,6-dioxa-9-thlaheptacosyl sul~ate - 3,6-Dioxa-9-thiaheptacosanol,(11,5 g, 0.027 mole) -was sulfated with chlorosulfonic acid (0.14 mole) by the general sulfation procedure described below to afford the title compound, (D) Preparation of 8-methyloctadecylsulfonio-3,6-dioxa_ctLl sulfate - The sodium 2,6-dioxa-9-thiaheptacosyl sulfate was dissolved in methanol and 92 ~ (0.65 mole) of methyl iodide was added. The reaction mixture was refluxed with stirring for 6 ho~rs. Insoluble salts were filtered and the methanol and excess methyl iodide were evaporated The residue was purified hy the mixed-bed ion-exchange meihod described below and crystallized from ether to yield 4.0 g. (`008 mole) of a white powder which was identlfied as the compound '~ '.

C18H37 ~ I ~ ~CH2C~2 )3 3 j. . :
' .

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EXAMPLE II ,.: ~`
Preparation of 26-methyloctadecylsulfonio-3,6,9,12,15,18 21,24-octaoxahexacosyl sulfate (A~ Preearation of Nonaethy_eneqlyco - Under nitrogen, 46 grams (2 moles) of sodium pellets were added cautiously to 2,664 ml (20 moles) of previously dried and distilled triethyleneglycol. The tempexature was kept below 100C.
A~ter all the sodium had reacted, the temperature was adjusted ;
~o 100C and 187 grams (1 mole) of 1,2-bis-(2-chloroethoxy) ethane was added in a slow stream. The mixture was heated overnight at 100C (still under nitrogen) and then filtered hot to remove most of the sodium chloride. Excess triethylene-gIycol was stripped under vacuum and the mixture was again filtered while hot. me material was purified by molecular -~
distillation and has a b.p. of 170-175C at O.OOl mm.

(B) Preparation of 26-hydroxy-3,6,9,12,15,18,~1,24 octaoxahexacosyl p-toluenesulfonate - One hundred grams (0.24 moles) of nonaoxyethylene glycol was dissolved in '~ ~
300 ml dry pyridine and cooled to 0C. An equal molar amount ¦ ~ -`; 20 of tosyl chloride was added in small portions with stirring.
The reaction mixture was then stirred at 0-5C for 5 hours, ~ poured into an equal volume of cold water, and acidified to ~
5. ~-. pH 3 with 6N h~drochloric acid. The solution was extracted ~ -3 times with chloroform, dried (MgS04), and evaporated. ~ I

25 The residue, 124 g., was a pale yellow liquid, slightly viscous. TLC (silica gel GF, I2, 95% butanone-5% H20) indicated J
a mixture of unreacted glycol (Rf 0.1), the monotosylate t ~ ~Rf 0.5) and the ditosylate (Rf 0.9). One hundred grams ,; of the reaction mixture was dissolved in a minimal amount ... . . . ..
~ 30 of 2-butanone and passed through 1000 g. of silica gel ~''~; ' ' ' ' ~ .

. . ~ . . ~ .

1~8~

100-200 mesh MCB SX144-06 grade 923. The column was eluted with 2-butanone; 41 g. of pure monotosylate was isolated. The product was a colorless oil which was characterized by I.~. ~two sharp bands at 1180 and 1190 cm 1) and proton NMR.

(C) Preparation of 3,6,9!12,1S,18,21,24-octaoxa-27-thiapentatetracontanol - To a heated (40C) solution of 20.1 g (0.97 mole) of n-octadecanethiol in 200 ml of dried 1.2-dimethoxyethane was slowly added under argon 0.07 mole (3.4 g., 50%) of sodium hydride (rinsed with hexane to remove the mineral oil) slurried in 1,2-dimethoxyethane. The reaction mixture was then heated at reflux (85C) with stirring ;, for 2 hrs. A solution of 40 g. (0.07 mole) of the nonaethylene glycol monotosylate in 200 ml. 1,2-dimethoxyethane was added dropwise and the reaction mixture allowed to reflux with stirring for 16 hours. The mixture was cooled, ¦~
insoIu~le salts were filtered, and the solvent was evaporated to yield a near quantitative yield (0.07 mole) of the thioether. .

(D) Pr~aration of sodium 3,6,9,12!15,18 21_24-octaoxa-27-thiapentatetraconty~ sulfate - 3,6,9,12,15,18, 21,-24-Octaoxa-27-thiapentatetracontanol (49 g., 0.07 mole) ~.
was sulfated according to the general procedure described below using 88 g. (0.76 mole) of chlorosulfonic acid to 25 yield the ti~le compound. ¦~ -s" 1 ~ .

s,`~ I. ,~' . . . .

~' ' ' ~ ' s ~, .
.
, . ?

S31~(3 (E) Preparation of 26-Methyloctadecylsulfon10-3,6,9,12,15,18,21,24-octaoxahexacosyl sulfate Sodium 3,6,9,12,15,18,21,24-octaoxa-27-thiapentatetracontyl sulfate was dissolved in 300 ml MeOH and 75 ml (1.2 moles) of methyl iodide was added. The mixture was heated at reflux 21 hours.
q'he MeOH and excess methyl iodide were evaporated, the residue was purified by two mixed-bed ion-exchange treatments, and crystallized from ether which gave 4 g. (0.005 moles) of a white crystalline solid, identified as the compound ..
:
C18H37 - I - (CH2CH20)9 3 :. . -~ .,.

:'` ' , - ' ~ :
. ~ ' ~ ~:

~ .

. . .
....

~83~0 EXAMPLE I I I
. . .
Preparation of a polyoxyethylene taverage monomer units = 17) separated methyloctadecylsulfoniosulfate (A) Preparation of polyoxyethyl (n = -17) octadecyl sulfide ~ Octadecanethiol, 250 g. (O.B7 mole), was . . .
di6solved in 250 ml of bis-(2-me~hoxyethyl) ether. Three grams (0.13 mole) of cut sodium spheres were added and the reaction mixture was transferred to a rocking autoclave and ~ 462 g. of ethylene oxide was bled into the autoclave over a period of 3 hours at 140-160~C. The maximum pressure observed was 540 lbs. After all the ethylene oxide had been added, rockiny was continued for an additional hour. ~ -The mixture was cooled, the bis-(2-methoxyethyl) ether was evaporated under reduced pressure, and the residue crystallized from hexane to give a white solid in 65% yield based on ~ - the octadecane thiol.
1 :
(B) Preparation of _dium polyoxyethylene (n - ~ 17) separated octadecylthiasulfate - A solution of 556 g. (0.54 mole) of the ethoxylated mercaptan dissolved in 2 liters dry pyridine was cooled to -5 to 0C under argon, Chlorosulfonic acid, 115 ml (117 mole?, was added dropwise very slowly over a period of 7 hours, during which time the t~mperature was kept below 10C by continued cooling. The mixture was then stirred at room temperature overnight and made basic by adding 600 ml cold 25% sodium hydroxide. An additional liter of distilled water was added, the solution extracted twice with chloroform, dried tMgSU4), and concentrated to give ~: 551 g (0.49 mole) of the crude sulfate which was then crys~allized rom 2 liters of acetone to give 358 g of ~, 30 the title compound.

7`. . . :
:~. . ' ' , ' ~f 39 . - :

~ ~, '' ' .

~i831~0 (C) Preparation of polyoxyethylene ~ - ~ 17) _ separated methvloctadecylsulfoniosulfate - To a solution of 16S g (0~15 mole) o~ sodium polyoxyethylene n = - 171 separated octadecylthiasulfate dissolved in 2 liters of hexane was added 57 g. (0.45 mole) of freshly distilled dimethylsulfate. The mixture was stirred at reflux for 2 hours. The product was insoluble in hexane and separated from the hexane as an oil. The hexane was decanted and the residue was rinsed with hexane. The residue was purified by two mixed-bed ion exchange treatments: 1) 800 g. mixed bed resin for 16 hours, and 2) 800 g. mixed bed resin for 4 1/2 hours. Crystallization from ether gave 76 g. of the title compound as a white powder ~45D~o yield).

- , ~:, _ General Sulfation Procedure lS The alcohol was dissolved in dry pyridine (4 x weight basis) and cooled to 0C, under argon. A 3 molar excess of -~ chlorosulfonic acid was added dropwise very slowly over a , period of 3 to 7 hours, during which time.the temperature -~ was kept below 20C by continued cooling. The reaction mixture was then allowed to warm to room temperature and ` stirring was continued for an additional 2-16 hours. The mixture was then made basic by slowly pouring with stirring ~1 into a two molar excess of cold 25% NaOH. The solution was . .................................................................... ~ . .
extracted 3 times with chloroform, dried (MgS04), and l -evaporated.

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.

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1~831~

Gencral Purifica-tion Procedurc of %~/itterionics bv lon ~xchanqe .. . _ , . _ _ .. ..
The crude zwitterionic was dissolved in methanol and stirxed 6-24 hours with a 10 molar equivalent excess of mixed becl r~sin, which had been soaked and rinsed with met~ nol.
The mixed bed resin used was Rohm and EIau~ Amberlite ~nobed InN-lS0, G-0425 tecilnical grade, or Fisher R-207, Rexyn 300 ~I-OII. The average total exchange capacity of the wet volume resin was about 1 meq/g. ~fter stirring, the resin was filtered by use of a Buchner funnel and vacuum aspirator and rinsed several times with methanol. The methanol was evapora-ted or additional distilled water was added and the solution extracted three times with chloroform. The chloroform was dried (MgSO4) and evaporated to give the pure zwitterionic.

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Claims (22)

WHAT IS CLAIMED IS:

1. A detersive compound of the formula wherein R1 and R2 are each straight chain, branched chain or cyclic alkyl, alkenyl, aryl, aralkyl or alkaryl moieties having from 1-30 carbon atoms; R3 is a C2-C8 alkylene, alkenylene, arylene or alkarylene moiety; R4 is a C1-C8 alkylene, alkenylene, arylene or alkarylene moiety; A is a water-solubilizing anionic moiety; and n is from 1 to about 100.

2. A compound according to claim 1 wherein R1 is a straight chain or branched chain C10-C30 alkyl moiety or an alkaryl moiety having a C6-C26 alkyl group and R2 is a C1-C4 alkyl moiety or is an alkaryl or aralkyl moiety having 1 to 4 carbon atoms in the alkyl moiety.

3. A compound according to claim 2 wherein R1 is a C12-C22 alkyl moiety; R2 is a C1-C3 alkyl moiety, or a benzyl moiety; R3 is a C2-C4 alkylene moiety, a C3-C4 hydroxy-substituted alkylene moiety or an arylene moiety;
R4 is ethylene; and n is from 4 to 50

4. A compound according to claim 1 wherein A is sulfonate, sulfate or carboxylate.

5. A compound according to claim 1 wherein R1 is C18 alkyl, R2 is methyl, A is sulfate and n is from 4 to 20.

6. A compound according to claim 1 wherein R1 and R2 are each independently selected from C6-C22 alkyl moieties and alkaryl moieties having C6-C18 alkyl groups.

7. A compound according to claim 6 wherein R1 and R2 are each C8-C18 alkyl moieties.

8. A compound according to claim 6 wherein R3 is a C2-C4 alkylene moiety or an arylene moiety, R4 is ethylene and n is from 4 to 50.

9. A compound according to claim 6 wherein A is sulfate, sulfonate or carboxylate.

10. A detergent composition comprising (a) from 1% to 99% by weight of a compound having the general formula wherein R1 and R2 are each straight chain, branched chain or cyclic alkyl, alkenyl, aryl, aralkyl or alkaryl moieties having from 1-30 carbon atoms; R3 is a C2-C8 alkylene, alkenylene, arylene or alkarylene moiety; R4 is a C1-C8 alkylene, alkenylene, arylene or alkarylene moiety;
A is a water-solubilizing anionic moiety; and n is from 1 to about 100; and (b) from 99% to 1% by weight of the composition of a detergent builder.

11. A detergent composition according to claim 10 wherein the detergent builder is an inorganic detergent builder selected from the group consisting of alkali metal, ammonium and alkanolammonium polyphosphates, carbonates, bicarbonates, silicates, aluminosilicates, borates and sulfates.

12. A detergent composition according to claim 10 wherein the compound has the formula wherein R1 is a C12-C22 alkyl moiety; R2 is a C1-C3 alkyl moiety or a benzyl moiety; R3 is a C2-C4 alkylene moiety, a C3-C4 hydroxy-alkylene moiety or an arylene moiety; R4 is ethylene; A is sulfate or sulfonate; and n is from 4 to 50.

13. A detergent composition according to claim 12 wherein the detergent builder is an inorganic detergent builder selected from the group consisting of alkali metal, ammonium and alkanolammonium polyphosphates, carbonates, bicarbonates, silicates, aluminosilicates, borates and sulfates.

14. A detergent composition according to Claim 10 comprising from 40% to 75% of the detergent compound and from 60% to 25% of the detergent builder.

15. A detergent composition comprising (a) from 1% to 99% of a compound having the general formula wherein R1 and R2 are each straight chain, branched chain or cyclic alkyl, alkenyl, aryl, aralkyl or alkaryl moieties having from 1-30 carbon atoms;
R3 is a C2-C8 alkylene, alkenylene, arylene or alkarylene moiety; R4 is a C1-C8 alkylene, alkenylene, arylene or alkarylene moiety;
A is a water-solubilizing anionic moiety; and n is from 1 to about 100; and (b) from 99% to 1% of another organic detergent.

16. A detergent composition according to Claim 15 wherein the detergent is selected from the group consisting of nonionic, ampholytic and zwitterionic surfactants, fatty acid salts, and mixtures thereof.

17. A detergent composition according to Claim 15 wherein the compound has the general formula wherein R1 is a C12-C22 alkyl moiety; R2 is a C1-C3 alkyl moiety or a benzyl moiety; R3 is a C2-C6 alkylene moiety, a C3-C4 hydroxy-alkylene moiety or an arylene moiety; R4 is ethylene; A is sulfate or sulfonate;
and n is from 4 to 50.

18. A detergent composition according to Claim 17 wherein the detergent is selected from the group consisting of nonionic, ampholytic and zwitterionic surfactants, fatty acid salts, and mixtures thereof.

19. A detergent composition according to Claim 17 comprising from 15% to 80% of the sulfonium zwitterionic compound and from 90% to 20% of the co-surfactant.

20. A detergent composition according to Claim 19 wherein the co-surfactant is selected from polyethylene oxide condensates of aliphatic alcohols, linear alkyl benzene sulfonates, alkyl ether ethoxylate sulfates, alkyl sulfates and water-soluble salts of fatty acids.

21. A detergent composition according to Claim 15, additionally comprising from about 25% to about 60% of a detergent builder.

22. A detergent composition according to Claim 21, wherein the detergent builder is an inorganic detergent builder selected from the group consisting of alkali metal, ammonium and alkanolammonium polyphosphates, carbonates, bicarbonates, silicates, aluminosilicates, borates and sulfates.