CA1038766A

CA1038766A - Amphoteric surface active agents

Info

Publication number: CA1038766A
Application number: CA193,997A
Authority: CA
Inventors: Robert J. Verdicchio; Louis J. Nehmsmann (Iii)
Original assignee: GAF Corp
Current assignee: GAF Corp
Priority date: 1973-04-09
Filing date: 1974-03-04
Publication date: 1978-09-19
Also published as: FR2224445A1; NL7404799A; JPS5051984A; CH601473A5; GB1470712A; AU6643874A; DE2416018A1; IT1010925B; BE813502A; BR7402654D0; DE2416018B2; AU484180B2; FR2224445B1

Abstract

Abstract of the Disclosure There is disclosed compounds having the formula:

Description

~13~766 This invention relates to new types of amphoter.ic surfactants, and quaternary phosphates or sulfates, more particularly to ethoxylated amines which are quaternized and thereaEter phospha-ted or partially sulfated, and -me-thod of use therefor. There is disclosed novel deriv- ~
atives of certain amphoteric, water-soluble compounds :
characterized by the following formula:

,`:

R COCH2 ( CH2 ) X~Y ~Z ~SHV

\ + / M A ~: -~10 Rl [OCH2(CH2)X~y tz ]tHu wherein R and Rl represent similar or dissimilar alkyl chains containing from 1 to 22 carbon atoms, Z is a P0 or~S03, x is an integer from 1-3, y is an integer of from 1-50; t and s each individu~lly are integers of from 0.05 15 to 1, u and v each individually are integers from 0 to . .
0.9S, the sum of (s+v) and (t+u) each mus-t equal 1. The .~ '~
sum of s, v, t, and u must equal 2. M is hydrogen, a cation such as any metal or amine and A represents an anion from the group consisting of halogen, sulfate or alkyl sulfate.
The prior art describes many and varied types of .
amine phosphonates or sulfonates, phosphates or sulfates and related compounds. However, none of these compounds have achieved significant commercial acceptance and in none are found all of the desirable properties of the instant invention.

" .
, ~
:i, .

-~ 3766 ~-:
Considerable research has been carried out with re-spect to -the phospha-tes during the past few years directed towards improving the lubrica-ting and rust and corrosive inhibiting proper-ties of the new synthetic surfactant compositions. Most of -these surfactant compositions have as the active surfactant ingredient, anionic ions. Re-search has also been carried Ollt with respect to the sulfates during the pas-t few years directed towards ~-improving the detersive and foaming properties o-E the new -synthetic detergent compositions. Most of these snythetic detergent compositions have as the active detersive in-gredient, anionic ions. As representative of the various additivies which have beem employed for improving the -~
detersive surfactant and foaming properties of such anionic which may be detergent compositions, there may be mentioned alkali metal phosphates, borates, carbonates, ~
; sulfates, chlorides, silicates, higher aliphatic alcohols - ~ -:
such as, lauryl alcohol and higher fatty acid amides and ~
alkylol amides such as, lauroyl amide, lauroyl mono and `

dialkyl amides, lauroyl ethanolamide, and lauroyl di-ethanolamide. The use o-f the aforementioned alkali metal salts, particularly the phosphates and borates, generally ;
resulted in what is known as built or heavy duty type detergents. While such compositions are partially suit- -able for use in cleaning machines of various types, they find limited use in applications wherein any degree o~
metal lubrication and cleaning is involved. They also find limited use in applications wherein any substantial amount of contact with the skin is involved in view of their alkaline reaction and chernical nature. For the latter type of use, unbuil-t or light duty type detergent

-2~

:1~3~76~
of a subs-tantially neutral pH are preferred.
When used for shampooing the SOQpS commonly used sometimes form insoluble sal-ts which deposit on the hair thereby imparting a dull appearance thereto and generally require rinses oE' acidic nature f'or -their removal; are eye stinging, tend to precipita-te at pH o~ 7 or below, and foam poorly at pH of 6~7. ;
While the amides of said amino acids do exhibit better '~
resistance to'hard water when compared with common soaps, -~
they exhibit poor foarn and poor f'oam stability in hard water; they dull hair as do the common soaps but to a less'er extent when used as shampoos and they precipitate ;: ' : . ' out in aqueous media at pH 4.5.
It hàs been found that the compositions accordgng to the instant invention comprise very valuable surface~
active agents which may be used either alone or admixed with other cationic, anionic or non-ionic surface~active ~n agents in~the different fields as above re~erred,to.
The'instant compositions comprise a very valuable group of surface-active ~gents, known as amphoteric com-pounds, i.e., chemical agents containing both cationic and anionic groups in a single molecule, and therefor exhibit a high degree of stability and remarkable utili-ty in ' concentrated electrolytic solutions. These compounds also ' 25 show unusual chemical stabglity under prolonged con-tact i with allsallne ~ystems. Products made from the instant '~ compounds have the following advantages: -they possess good surface-active properties so that they can be used as detergents. They can also be used as hair shampoos over or under pH range for example from 3 -to 10. They have the advantage of preventing the accumulation of electrostatic ,~ .

~L~3876~ii charges, are well tolerated by the skin and eyes, there-for, do not cause any appreciable irritation thereto.
This proper-ty of said compounds is useful when incorpora-t-ed into liquid bubble bath, bar of soap, -fabric softeneer mix, lubricants, rust inhibitors, corrosion inhibi-tors, hard surface cleaners, alkali soluble cleaners, agriculkure emulsifiers, hydraulic fluids, or in emulsion polymeriza-tion.
These amphoterics employ the phosphate or sulfate ester as the~anionic moiety, thereby in addi-tion -to providing dual cationic/anionic functionality offer novel properties such as metal lubrication, and cleaning, en-hanced corrosion inhibition, alkali solubility or in the -sulfate form in hair shampoos and soaps.
The phosphate~esters of this invention have the ~-following unexp~cted combination of properties: they are ;~
better foamers in average or hard water; they have good foam stability; they tolerate the presence of chlorine bleaches; they may be used in shampoos and other cosme-tics at pH of 4.~5-8.5 and under these conditions are better foaming agen~s; they are better detergents with average or hard water; do not precipitate; at pH as low as 4.5 they are non-irritating to the eyes and skin and they are re-latively non~toxic.
The instant amphoteric compounds are useful as de-tergent~, foaming, wetting, ernulsrating and emulsifying agents and also possess a unique combination of properties which will provide new and improved produc-ts ~or lubri-cants, pesticide emulsifiers, hard surface cleaners, etc.
They are also useful as surface active agents in treating ~3i!3766 natural and synthetic ibers in the textile ancl related fields where they may be employed as synthetic detergents, dye assiskants and softeners.
The sulfate esters of this invention have the following unexpected combination of properties: they are substantially non-eye stinging in those concentrations in ~hich appreciable eye-stinging is evidenced with some other detergents; they are better foamers in average or hard water; they have good foam stability; they tolerate the presence of chlorine bleaches, they do not dull hair when used for shampooing and consequently no special after rinse is required; they impart softness and manageability to hair which has been sham-pooed therewith in ordinary as well as hard water; they may be used in shampoos and other cosmetics at pH of 4.5-8.5 and under these conditions are better ~ ~
foaming agents; they are better detergents with average or hard water; do not ~ ~-precipitate; at pH as low as 4.5 they are non-irritating to the eyes and skin and they are relatively non-toxic.
The instant amphoteric compounds are useful as detergen~s, foaming, wetting, emulgating and emulsifying agents and also find application in the fields of shampoos and cosmetics. They are also useful as surface active agents in treating natural and synthetic fibers in the textile and related fields ~ -where they may be employed as synthetic detergents, dye assistants and soft-eners.
The oxyalkylated amines or their quaternized derivatives from which the compounds of the present invention may be derived are themselves useful as surface active agents, having good foaming characteristics and find use as general purpose detergents, textile treating agents, emulsifying agents, and also as components in .~

,' :

~87~6 cosmetics, toiletries and shampoos, The present invention represents in part ~h0 unexpected and surprising discovery that in ~he class of compounds involved, by first quaterni~ing an alkoxylated amine and thereafter phosphatlng or sulfating same, there is produced compounds containing the amine, hydroxyl, quaternary ammonium and phosphate or sulphate functionalities.
These amphoteric surfactants also show an advantage over the prior the prior art and seemingly do not exhibit a pronounced ioselectric point where general surface-active and physical properties such as solubility, foaming, etc., are at a minimum. ;
The present învention provides amphoteric chemical compositions that may be used in aqueous solutions ~t acid, neutral or alkaline pH. In the former, thPy serve as cationic surface-active agents; in the latter3 as ; ~ ~ -anionic surface-active agents. ~-The present invention provides for new articles of manufacture, such as surface-active compositions, rust and corrosion inhibitors, hard surface cleaners~ agricultural emulsifiers, pesticide emulsifiers, wetting ~-agents, lubricants, shampoos, soaps, bubble baths, textile treating, wetting agents or fabric softeners.
The present invention provides a method comprising washing human hair and skin with an aqueous composition containing an effective washing amount of an amphoteric surface active agent of the formula:
R / ~R2 0 )y i Zl \ + / A
/ N

Rl ~R2-0 )Y2~ Z2 wherein R i~ C6 22 alky or alkenyl Rlis lower alkyl or benzyl R2Ø is -CH2CH20-, an H atom of which may be substituted by -C~13 or C21[5 - 6 _ " ~ ' ,, .

~3~3766 i` .~
~1 and Y2 are each integers of 1-50 :~ :
~ is with the bonded 0 atom, a sulfate or phosphate ester group in acidic or salt form ^ :
Z2 is }I or Zl ;~
A is an anion / -The present invention also provides aqueous shampoo, bubble bath . - :~
and solid detergent bar compositions containing an effective washing amount of an agent as defin~d above in combination with conventional ingredients of .~
,~ ., "
such compositions including a dermatologically acceptable carrier.
lOBroadly speaking, the instant invention comprises the provision .
j! . ~ .
of an amphoteric compound characterized by the following generic ormula~

, . ~ ~ ,, :' .:
; ?

'.~;

'' ":~

;~' ' '' :

:, ' , ' ' ' , `

3~7~6 ~ [OC~12 (C~12) x] y o [ Z I sHV

N / M A

R / [0C~l2(cH2)x]y o[z ]tHU

wherein R and Rl represent similar or dissimilar alkyl chains containing from 1 - 22 carbon atoms, Z is a P03 or S03, x is an integer from 1 - 3, y is an integer of from 1 - 50, t and s each individually are integers of from 0.05 to lg u and v are integers from 0 to 0.95, the sum of (s~v) and (t~u) each must equal 1. The sum of s, v, t and u must equaI 2. M is hydrogen, a cation such as any metal or amine and A represents an anion from the group consisting of halogen, sulfate or alkyl sulfate.
Preferably R and Rl will be 1 to 18 carbon atoms, -optimally 2 - 12, x is preferably 1 and y is preferably 2 - 20, and optimally 3 - 10, together. M, when a metal, may be Na, K, Mg, Ca, Al, though preferably Na or K. M, when an amine, may be an alkanol amine or alkylamine; though preferably mono-ethanolamine, diethanolamine, or triethanol-amine. A, when a halogen, may be chlorine, fluorine, bromine or iodiné and preferably chlorine. When a sulfate, A may be an alkyl sul~ate, preferably ethyl sulfateO R and Rl, can be dissimilar, one being a long alkyl chain, the other being a shorter alkyl chain. Also disclosed are methods of making same and uses therefor.
~ The novel compounds of ~he instant invention may be ¦ prepared ~rom a precursor material by first condensing an ~ alkyl amine containing 6 - 22 carbon atoms in its alkyl J

:

,, , ~ . .

` :

~3~76~ :
chain with an alkylene oxide in the presence of base. To produce the quaternized component, a quaternizing agent ^~
is added thereto and the ethoxylated amine is thereafter quaternized. The quaternized ethoxylated amine is there-after phosphated or sulfated so as to produce a quaternary phosphate or sulfate. The phosphated or sulfated amphoteric is generally a mixture containing varying amounts of mono-phosphate or monosulfate, diphosphate or disulfate, non-phosphated or non-sulphate into non-ionic (ethoxylate)O
The alkyl portion of the amine can be saturated or unsaturated, substituted or free from substitution. A
pure source of alkyl amine to be employed may vary in carbon length from 6 - 22 carbon atoms; examples of pure saturated acids which could be used as precursors for such an amine are caproic, caprylic, capric, lauric, myristic palmitic~ stearic, arachidic and behenicO Unsaturated pure fatty acid precursors include those such as oleic, lauroleic and palmitoleicO An example o a substituted fatty acid useful in this invention is ricinoleic. Mixtures of the above fatty acids commonly found in vegetable oils, ~ ~-animal fats and oils and the marine fats, oils may also ~-~
be used successfully as precursors. Examples o vegetable sources of useful pr0cursor fatty acids containing mixtures in various proportions are coconut oil, linseed oil, olive oil, palm oil, peanut oil, tung oil and rape seed oil. Animal and marine sources ofatty acids contain-ing saturated and unsaturated atty acids substituents are lard, tallow and sardine oil. Any fatty acid or mix-tures of fatty acids whether pure or from impure sources -may be cmployed as an amine precursor without departing - ;
~31~6 from the spirit of the invention as long as they con-tain from 6-22 carbon a-tom~ in -their chain length.
Preferred f'atty acids are those contained in coconut vegetable oi~. A typical coconut vegetable oil may contain fatty acids varying in length from 8-18 carbon atoms.
These fatty acids from coconut oil may be sa-tura-ted or un-saturated.
The alkyl amines used in this invention may also be derived from the esters of the fatty acids without depart-ing from the scope of the invention. The methyl or ethyl esters o~ the fatty acids may be easily condensed with the polyamines of substituted polyamines with ready removal of methanol or ethanol occurring.
The fatty acid amine precursor is prepared in accord- ~-ance with procedure~s well known in the art and, according-ly, that reaction and reaction product per se, form no part of the instant invention.
The thus produced alkyl amine is then subjected to an ethoxylation reaction in accordance with procedures ,' well known in'the art, such as for example by reacting the amine with the required number of moles of ethylene oxide to produce the ethoxylated amine employed in the instant invention. This oxyethylation reaction is well Icnown in the art and fully describe'd in U.~. Patent 25 No. 1,970,578 and in many other patents. The reaction , '~
is preferably carried out at elevated temperatures and pressures and may be catalyzed by quaternary hydroxides, amines, acids and/or coordinating type compounds although strong allcaline catalysts such KOH or NaO~I and -the like because are pref'erred of the fewer by-products formed and the more easily controllable reaction conditions. Since the ~3~76~
reaction is substantially quantitative, the molecular proportions of ethylene oxidc and amine employed determine the average oxyethylene chain length of the resulting ethoxylated amineJ although it will be understood that the product is a mixture of ethoxylated amines of varying oxyethylene chain length. As stated above, sufficient ethylene oxide is employed to produce an ethoxylated amine containing by weight about 25 - 90 percent of combined ethylene oxide. ~he optimum oxyethylene chain length will in any particular instance be determined mainly by the particular amine being oxyethylated, the particular de-tergent with which it is to be admixed, the hardness of the water in which the detergent is to be employed, the ``~
; desired efficacy of the finished product for the par-ticular application and the like.
Throughout the specification, the invention is des-cribed wi~h reerence to both the phosphated quaternized alkoxylated amine and the sulfated quaternized alkoxylated amine.
2Q The product of the invention is then conveniently ~ ~
prepared by reacting appropriate proportions of alkoxy- ; -lated amine in the presence of said hypophosphorus acid and a quaternizing agent, such as diethylsulfate, the latter being present in the amounts of 50 - lOO mole %, preferably 90 - 100 mole %.
The alkoxylated amine starting materials prepared by alkoxylating primary amines, have the structure R-N-[~CH2-CH20)nH~2: wherein R is an alkyl group as above described and n is a positive integer of from 1 - SO, co~
pounds with n = 2 to 15 being preferred.

:^, ~. ,.
,.,, ,, :

~ r~-.", ~lD3876~;

After com~letion o~ the reactlon, the alkoxylated amine 19 thereafter submitted to treatment conduclve to quaternlzatlon o~ the tertiary am~no ~rou~ utiliæinF a conventlonal quaternizlng agent. Thus, notlng the above structural ~ormula, sultable quaternizln~ agents include, dlalkyl sul~ate~, e.g. dlmethyl sulrate~ dlethy~ sulfate, etc.; alkyl sulronic acid~, e.g. meth~l sulfonic acld, ethyl sulfonic acid, etc.; benzyl halide~, e.g. benzyl chlorlde~ benzyl bromide, benzyl lodlde, etc.; alkyl halides, e.g. methyl chloride, etc. Accordln~l~, any conventional quaternizing a~ent can be ad~antageously employed in the production o~ the quaternary alkox~lated ;~
amines used hereln.
The above quaternized composition ls then preferably but not nece~sarily strlp~ed of any unreacted quaternizin~
agent and thereafter reacted wlth a ~hos~hating or sul-fatlng agent so as to effect the quaternlzed alkoxylated ~mlne ko become a quaternized phosphate or sulrate. Suit~
able phos~hatlng agepts include phosphorous pentoxlde, Pol~lp~0sphor~Dk ~c dL~ ~7~ and ~hosphorous ox~chlorlde, mlxtures, and the like. Sultable sul~ating agents include chloro-3ulronlc acld, ~ulrur trioxlde, sulfamlc acid, and sul~uric acld oleum.
In accordance with the procedure of the pre~ent lnventlon, the alkoxylated ratty amlne and hy~o~hos~horic acld are mixed to~ether and heated to about 90-100C under ~ -vacuum, The product thereof 1~ therearter cooled to 20 ~90C, prererably to 30C and thereto there 18 added 50 -lO0 mole %~ pre~erably 90-lO0 mole % o~ a quaternlzln~
agent and the mlxture 18 thereafter heated ~o as to e~ect ,, .
,.

~3~7~6 ~
quaternization of the alkoxylated atty acid amine.
~ny unreacted quaternizing agent may be stripped away at elevated temperature and under vacuumO The remaining product is thereafter cooled and there is slowly added thereto the phosphating or sulfating agent in amounts of 10 - 200 mole %, preferably 90 - 110 mole % at tempera- ~
tures of 20 - 110C; preerably 40 - 50C. If phosphorous ?
oxychloride is used as the phosphating agent, the reaction mixtur0 is bubbled with nitrogen at such tempera-ture until a desired low degree of chloride ion is reached, preferably 0.01 - 100% by weight. The phosphorous oxy-chloride is then drowned in~o water and base and there is thereafter obtained the surfactant solution containing the instant product.
If chloro-sulfonic acid is used as the sulfating agent, the reaction mixture is bubbled with nitrogen at such temperature until a desired degree of chloride ion is ~;~
reached, preferably 0.01 - 1.0 % by weight. The sulfate acid is then drowned into water and base and there is there-after obtained the surfactant solution containing the instant product.
The nature of the invention will be best under-stood by setting forth the detailed procedure for prepar-ing a typical member of the phosphated and sulfated quaterniz- ;
ed ethoxylated amphoterics; all parts, proportions and percentages in the following examples, as well as in the appended clairns, are by weight unless indicated otherwise.

"~ , ~3~37~6 EXAMPLE I
Charge into a l-liter flask equipped with an agitator, thermometer and gas inlet, 320 parts (0.5 mole) of cocoamine ~ 10~0 and 2 parts of 50% hypophosphorous acid. Dry the mixture und~r vacuum ~10 - 15 mm.) at 80 -100C. Cool under dry nitrog0n to 40 - 50C and add 80 parts ~0.52 mole) of diethyl sulfate at 40 - 50C over tws hours Strip any unreacted diethyl sulfate at 90 - 100C
under good vacuum. Cool to 30 - 40C and under a nitrogen blanket add 35.5 parts of phosphorous pentoxide and stir at 100C for 5 hours. Cool to 80 - 85C, add 5 parts water, and stir for 2 hours. There is obtained 433 parts of active surfactant. This represents a 99% yield.
EXAMPLE II
Operating as in Example I, 460 parts ~0.4 mole) of tallowamine + 20EO and 2 parts of 50% hypophosphorous acid are charged to a l-liter flask. The mixture is dried at 90 - 100C under a good vacuum, cooled to 30 - 40C and 60 parts of diethyl sulfate added over 2 hoursO The ~ , mixture of quaternized amine ethoxylate is phosphated in the following manner. Hypophosphorous acid ~50%) 1 part, ;~
is added at 40 - 50C followed by 29 parts of phosphorous pentoxide at 50 60C. The mixture is heated to 100C ~-For 5 hours under a nitrogen blanket, cooled to 80 - 85C
and 5 parts water are added~ The system is stirred for 2 hours at 80 - 85C. There is obtained 553 parts of 100%
active surfactant ", . .

~3~766 ~:
EXAMPLE III ~ -According to Example I, 460 parts of tallowamine 20E0, 2 par-ts o r 50% hypophosphorous acid and 60 parts of diethyl sulfate are reacted to form 520 par-ts of quaternized tallowamine + 20E0. To this mi~ture 1 part of 50% hypophosphorous acid ls added ~-t 40-60 C followed by 170 parts of 115% polyphosphoric acid at 40-60C under a nitrogen blanket. The phosphating mixture is heated at 100C for 5 hours and then cooled to 80-85C and 5 parts of water are added. After -two hours at 80-85C, 1 part of 35% hydrogen peroxide is added to yield 697 par-ts --of 100% active surfactant.
EXAMPLE IV
-- , ~, ..
As in ~xample I, 586 parts of oleylamine + 7E0 and -2 parts of 50% hypophosphorous acid are dried and reacted with 286 parts of~oleyl chloride at 60-70 C for 10 hours.
The quaternized amine ethoxylate mixture is mixed with -~
1 part 50% hypophosphorous acid and 28 parts water.
Phosphorous pentoxide, 142 parts, is added slowly under ~-~
a nitrogen blanket at 40-50 C over 2 hours. The reaction mixture is heated for 3 hours at 90 C, and then 5 parts of water are added. The resulting surfactant is heated an additional 2 hours at 80-90C, cooled to 60C and then ~
1 part 35% hydrogen peroxide is added. There is obtained ; ~.
1,042 parts of surfactant.
EXAMPLE V
, As in Example I, 708 parts of stearyl amine ~
lOE0, 2 parts of 50% hypophosphorous acid and 126 parts ', : :

~38~if~
o~ bfenzyl chlorlde are reacted at 70-aOC to ~orm the quaternlzed amine ethoxylate. Thls materlal is then reacted with 75 parts o~ phosphorous oxychloride at 40-50C over 4 hoursO The hydrogen chlorlde is removed by nltro~en bubbling to a con~tant chloride lon content. ;~
The phosphated acid mixture was drowned lnto 120 parts B ~ 50% caustlc soda5 to obtain 980 part~ of surfactant ~;
.~
solutlon. ~ ~ s EXA~fTPLR VI

The P20~ ester o~ tallowamine + 20R0 diethyl sul~ate 1~ tested ~or soak tank metal cleaning using .1% `~
sur~actant ln 5% mixed alkall at 80C. A 5 minute wash is employed. The present detergency compared to a commercial control is 3hown below. `~
.: - , , Table 1 Product % Soi] Removal (Detergency) Phosphate e3ter amphoteric 40 . O .;
Commer¢ial Control 53.
, .~-, . . ;
EXAMPLE ~II

f~ As in ~xample VI above, the monophosphate ester 1 evaluated ror metal cleaning. The experimental amphoterlc showed 33~ ~oll remo~al compared to 53% ~or the commercial 'f control. ~-, EXAMPLE VIII

,, The 301ubility and stabillty ln cau~tic o~ a 1~
~ 25 surractant solutiofn whlch shows clarlty from 0-100C
,~, -15_ , i/

ls shown below. 1~38766 Table ? :
.. , -;
Percent Caustlc : -Phosphate e~ter amphoterlc ~ 5.3 :
Phosphate e~ter amphoteric - 17.3 :.

., .. . ~
EXAr/lr?LR IX

An emulsiflable pesticide concentrate is prepared ~ ~ :
a~ ~ollow~, uslng a single surractant a~ a result of~ ~
both catlonlc and anlonlc groups on the molecule. .~-U~e Ingredlent: % By Weight Pho~phate ester amphoteric - 5 - 10 Alkanolamine 2 ~ L~ 5 Pestlclde 20 -40 : Inert Sol~ent . to 100 The rOllOw~ng; ~ur~actant compositlons are prepared .
:15 ~or the uses as lndicated~
: . . -~rab le 3 All Part~ by Wt.

:~ Liquld Drain Steam Hard Cleaner Degreaser Sur~ace ~ : ~ Cleaner ~-Phosphate ester -` :
amphoteric 1.0 1.0 1.0 ::~
NaOH 9.0 17.0 2.0 :~
TKPP ~ 10.0 Water 90.0 - ~2.0 8?.o 20'rotals 100.0 100.0 100.0 ,~
Rust Metal Inhibitor Lubrlcant Phosphate e~ter am~hoterlc 10.0 10~0 Trle~hanolamine 20.0 20,0 Sodlum Nltrlte - -- 4.0 Wat~r 70.0 66.0 T~al3 100.0 100,0 ~16-,..... .
, .... . .

~ ``

~3~76~i :
EXAMP~E X ~_XV :

~ hese compounds are also applicable as alkaline hard surface cleaners, exhlbitin~ excellent caustlc stabillty depending upon the de~ree o~ ethoxylation, anionlc ~unctionality, and h~drophobe. Alkali solublllty is shown on Table 4: ~
Table 4 ~`-~:- . --Caustic Solubillty - 1~ Sur~actant Soluble ;
From 0 to 100C in (x)_% NaOH
Sample No. Compound % NaOH ~;
~ , ....
10Sodium Phosphate o~ Cocoamine +
5E0 dlethyl sul~ate 9.4 -~ ~
llSodium Phosphate of Cocoamlne + ~ ~ -10E0 diethyl sul~ate o.6 -.
12Sodium Phos~hate of Cocoamine + . .
15E0 diethyl sulfate 4.9 :.
13Sodium Phos~hate o~ Cocoamine + .
20E0 diethyl sulfate 4.25 - ..
14Sodlum Phosphate of Cocoamine + -. . ~
: 30E0 diethyl sul~ate 3.2 .
~: 15Sodlum Phosphate of Cocoamine ~
50E0 diethyl sulfate 2.4 ., ~.. . .
15 ~XAMPLE_~YVI

Fabrlc softener~ and detergent/so~tener~ and .' sanitizers may be prepared for use on textiles as rOllOws: :

~able 5 All parts by wt. %
l 2 3 Amphoteric Sur~actant ~-7 10-30 10-30 nl~tearyl dlmethyl ammonlum halide -~- 3-7 3-7 ~:
n-al~yl dimethyl benzyl ammonium halide --- -- 5-10 .Sodium acetate 1-2 ~tlater to 100~ to 100~ to 100 ~ 8766 ~:
EXAMPLE XVII
"., Charge into a l-llter flask equi~ped with an ~ -agitator~ thermometer and ~as inlet, 320 parts (0.5 mole) of cocoamine ~ 10~,0 and 2 parts of 50Z hy~ophos~horous ; ~ ;
acld. Dry the mixture under vacuum (10-15 mm.) at 90 100C, Cool under dry nitrogen to 40-50C and add ~0 parts (0.52 mole) o~ diethyl sul~ate at 40-50C over two hours.
Strl~ any unreacted diethyl sul~ate at 85-90C under `~
vacuum. Cool to 30-40C and add slowly over 2 hours, wlth -a nitrogen ~et disperslng the drop~ets, 60 parts (0.52 mole) Or chloro-sul~onlc acld at 30-40C~ Continue nitrogen J,-~
bubbling ~or six hours at 30-40~C,~until the Cl ~s 0.5%.
The sul~ate acid~la then drowned lrl 150 ~arts Or water ~ ~ ;
15~ and 51~parts of~50% caustic to ~a pH~ Or 7~3. There is obtained 615 g. o~ surfactant solution containin~ 440 parts acti~e material. Thls répre~ent~ a 98~ yleld, EXAMPLE XVIII

Operatlng as in Example XVII, charge 430 parts Or cocoamine + 15EO (O.5 molé), 2 parts o~ hypophosDhorous acId and dry under vacuum. At 40-50C add 80 parts o~
dlethyl ~ul~ate (0.52 mole) and hold 2 hours at 40-50C.
Dlstlll unreacted volatiles at 85-90C under 2 mm. vacuum and then add at 40C, 60 parts chloro-~ulronic acid (0.52 mole) wlth a nltrogen Jet to disparge the acld. Contlnue nltrogen purglng ~or slx hours and then drown in 150 ~arts water and 50 parts of 50% cau~tic. The pH ls 7.~. There ls obtained 713 g. o~ amPhoterlc surractant solutlon corltalnlng 540 ~. actlve material representing a ~8%
yleld~

.. . . .

~L~3i~i6 E AMPLE XIX ~ ~

~roceedin~ as described ln Exam~le XVII, mlx 400 parts ~ ;
1~ Or ~1~4w~*~ 15E0 (0.5 mole) with 1 part hy~o~
phosphorous acld (50%) and dry under vacuum. Add 63 parts benzyl chlQride (0.5 mole) and stlr at 100C for 60 hours, Cool to 30-40C and pass through a llquld rilm ; -sulfur trloxide (Sulfan) unit at such a rate that 40 parts (0.5 mole) sulfur trloxlde is absorbed. The acid is .
drowned in 150 parts water and 60 parts 50% potassium h~droxlde to a pH of 7.6. There is obtained 710 parts of surfactant solutlon containing 520 parts of actiYe .
material.

EXAMPLE XX
~, -~ As in Example XVII, charge 600 parts (0.25 mole) `~
~ cocoamlne + 50E0 and 2 parts o~ 50% hypophosDhoruos acld. A~ter drying under vacuum, 40 parts (0.26 mole) of dlethyl sulfate are added at 40-50C over two hours.
A~ter an additional two hours at temperature, the re~
actlon mlxture ls stripped at 85-goc under ~acuum and :
30 parts (0.26 mole) of chlorosulfonlc acld is added with nltrogen dlsper~ion at 40C. Six hours of nltrogen .
bubbllng reduced the Cl to 0.07%. The crude acid is drowned in 150 parts water and 28.5 parts 50% caustic to yleld 810 parts Or 80.5% active ~urfactant solution of pH 7.5.
, EXA!~1PLE XXI ~
-~:
~peratin~ accordlng to Example XVII, 315 parts of .
cocoamine + 5E0 (Armark's Ethomeen C-l ~ and 2 parts Or ,e ~a~k ~l~3~76~; ~
50~ hypophos~horous acld are dried and reacted with 125 ..
.:?.~: :
parts Or diethyl ~ulrate. The r~sultlng quaternary ls reacted wlth 88 part~ of chloro-sulfonic acid and purged wlth inert ga~ to reduce the Cl content to 0.2~. The quaternized sulrate acld is drowned in 150 ~ar~s water and 70 parts 50~ caustic to yleld 653 parts o~ 70,8% ; ~ :
actlve surractant ~olutlon at a pH of 706. ~ :
.: , EXAMPLE XXII

. .
A shampoo ~ormulatlon was prepared in accordance .~;
10wlth the ~ollowing~
.. . ~, .
Shampoo Formulatlon Ingredients % By Weight Sodlum sulfate of cocoamine + ..
lOEO
diethyl sulfate 20.0 (sollds) Mvristyl 5.0 amlne oxide (30~ solids) Water 1OO.O . ~

The product prepared above was evaluated for Ross ~ :
Mlles foaming ln soft and hard water, ~tabllity (overnl~ht) ;-.at 0C, surrace tension and pH.

Table 20Result~ of Experimental Amphoteric Shampoo ~OAM HT. - mm .25~ at 30C in dlstilled water -- ~
160 (lnitial) 140 (after 5 min.) :
POAM HT - mm .25% at 30~C ln ppm CaCo~ :
(hard water) -- 175 (inlt~al) 150 (after 5 min.) Cla~ty - 12 hrs. at 0C -- clear and stable dyne~ cm. ,25% solutlon at 25C -- 31.6 pH (a~ ls) -- 8.o As ~hown above, ~hamPoo formulations can be ~repared which: roam well in both hard and so~t water; do not ~ 387~
freeze upon overnlght storage at 0C (i.e. Krarft point ~ '~
is less than C'). The ~ s (surface tension) of a .25%
solution is 31.6 dyne~cm. at 25C, well wlthin the , acceptable level for a high quallty shampoo which should ~ , lower the ~ s to le~ than 40 dynes/cm. at .1 to .25% in ' water, The same propertles are exhibited uslng compounds ~ -contalnlng 5-15 and 20 moles of ethylene oxide.

EXAMPLE XXIII ,,~ ~ , ~,.'~' . : .
The lime Roap dis~erslon index ~Journal American Oil '~
Chem. Soc., Vol. XXVII-88, 1950) of several Or the above '~
amphoterlcs is determined and compared to a commercial am~hoteric control (Miranol C2~) normally used in shampoo - '' and cosmetic Products. The results appear in Table 7.
The lower the number the better the lime soap dispersant ' properties.
Table Lime Soap Dispersion Index ,~
./, -~ ~ .:
Llme Soa~
Product ~lspers'ion'~ndex ., Sodium sulfate of cocoamine ~ 5E0 ~
diethyl sulfate 2.5-5.0 20Sodium sulfate o~ cocoamine ~ 15E0 ~;y;
diethyl sulfate 2.5-5.0 '~
Sodium sulrate o~ cocoamine + 10E0 benzyl chloride 2.5-5.0 ' Sodium ~ulrate of` tallowamine + 15E0 dlethyl sulrate 2,5-5. n ~;
Mlranol C2M - conc. - (ImidazoIine ;~
type the ~'~iranol Corp.) P,0 EXA~IPLE ~ XVI'~ , The rollowin~ concentrate~ (8-11) were ~renflred u~inp, the experlmental am~hoterlc~ o~ Exam~le XX, with varyinr~ der~rees Or ethox!~latlon and were evaluated as ll~uid concentrate~ rOr bubble bath, ~ k _21-, . . .

~3~3766 : ~
Table 8 Li~uid Bubble Ba~h Concentrates Ingredient A _ y Welght %
XXIV XXV XXVI XXVII
8-Sodium sulfate of cocoamine +5EO
diethyl sulfate ~solids) 20 0 9-Same as (8) with lOE0 (solids) - 20.0 10-Same as (8) with 15~0 " - - 20.0 ll-Same as (8) with 20~0 " - - - 20.0 Coconut diethanolamide - 5.0 5.0 5.0 5.0 Water - 75.0 75.0 _ ~ ;
To~als 100.0 100.0 100.0 100.0 All of these formulations foamed well in both hard and soft water and in the presence of soap and hard wa~er. The latter is a major criteria for a high quality bubble bath. The results ar~ shown in TABLe 9.

Table 9 Ross Miles Porm Tests on Bubbie Bath Conc. 1-4 of ~xamples XXIV - XXVII

Foam HT in MM (Initial/
~ after 5 min.) PercentPPMCaCO3 Pormulation Number ~ -Concen-Water Temp. %
trationHardness C Soap XXIV XXV XXVIXXVII

(1) 25 0 30 0 170/145175/155 180/155 185/165 (2) .25200 30 0 185/160185/160 190/165 190/170 (3) .0~5 200 37 .5 200/170 205/180 215/175 210/175

(4) .125 200 37 .5 ~00/175 195/165 185/160 205/180 All of the above concentrates were stable to overnight refrigeration and also to one cycle of freeze/thaw.
~XAMPLE XXVIII-XXXIII

These compounds are also applicable as alkaline hard surface .. .. .
cleaners, exhibiting excellent caustic stability dependlng upon the degree of ethoxylation, anionic functionality, and hydrophobe. Alkali solubility is shown on TABLE 10:

"C
~"~

~ ,;
.,' ' , .

76~i ;
Table 10 ' .
Caustic Solubility - 1% Suractant Soluble From O to 100C in ~x) % NaOH ~ `

Example Compound % NaOH - ~.
XXVIIISodium Sulfate of Cocoamine ~ i -5EO diethyl sulfa~e 9.4 .
XXIXSodium Sulfate of Cocoamine ~
lOEO diethyl sulfate 6.6 XXXSodium Sulfate of Cocoamine +
15EO diethyl sulfate 4.9 XXXISodium Sulfate of Cocoamine 20EO diethyl sulfate 4.25 XXXIISodium Sulfate of Cocoam.ine ~
30EO diethyl sulfate 3.2 XXXIIISodium Sulfate of Cocoamine ~
50EO diethyl sulfate 2.4 ., .~, EXAMPLE XXXIV
Toilet bars of the soap syndet and syndet types with lime soap dispersan~J emollient and antibacterial properties may be prepared as ~., ~, , .
shown on TABLE 11. `; : ~ :

Table 11 All parts.by wt. % ~ ~:

Paraf~in Wax -- 5-15 5-15 ..
20 Amphoteric Sur.factant 5-15 20-50 20-50 ~ ; :
Tallow Coconut Oil Soap 60-80 Stearic Acid 0-lO 0-20 0-20 .. `:.
Alkyl dimethyl benzyl ammonium halide -- .5-1.0 -- :~ :
Talc -- 20-60 20-60 Water to 100% to 100~to 100%

Various fillers or diluents may be advantageously used in the above:toilet bars to lower costs. Clay, hydrogenated tallow, powdered : :polyvinyl chloride rcsin, paraffin wax, starch and stearic acid are examples o~ such materlals. ~hese~ o~ course, are preferably used in limited amounts to avoid a~ecting substantially the properties of the bar, such as . ~ .
lat~rmg power and , ,~.
, ~ , " , ~ ` ~

~13~76~i surface slipperiness. Limitcd amounts (e.g. below 10%) of certain fillers or diluents such as starch and stearic acid ac-~ually enhance the surface slipperi-ness of the bar. Some fillers, such as glycerine, polyglycerine ~e.g. of --degree of polymerizatlon of about 6), sugar, pec~in, gelatin, finely divided silica, in limited amounts ~e.g. less than 15%~ inhibit the cracking of the bars which may occur when the bars dry out after use.
, Additional features of the above-ou~lined invention include: foam formation without water pressure, foam regeneration, foam compatibility with soap and soap foam, sequestration properties, solution compatibility with very high quantities of electrolytes and/or alkalies, compatibility with quaternary germicides, germicidal, germistatic, fungicidal, and fungistatic properties, " ~ , deoderizing properties, and "non-drying" properties on the skin.
The products of the instant invention may also be further compounded with other ingredients to provide for the following uses:
Liquid steam cleaning compounds, floor maintenance products, wax removers, automobile care products, waterless hand claaners, oil tank degreaser, aluminum ~ -cleaner, hand washing compound, sanitizing hand dishwashing or light duty cleaning compound, pet shampoos, rug and upholstery shampoos, mothproofing, rug shampoo, and the like.

~ r

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method comprising washing human hair and skin with an aqueous composition containing an effective washing amount of an amphoteric surface active agent of the formula:
A-wherein R is C6-22 alky or alkenyl R1 is lower alkyl or benzyl R2Ø is -CH2CH2O-, an H atom of which may be substituted by -CH3 or C2H5 y1 and y2 are each integers of 1-50 Z1 is with the bonded 0 atom, a sulfate of phosphate ester group in acidic or salt form Z2 is H or Z1 A is an anion

2. A method as defined in claim 1 in which R2Ø is -CH2CH2O-.

3. A method as defined in claim 1 in which Z1 is in the form of the Na or K salt.

4. A method as defined in any of claims 1-3 wherein Z1 is a sulfate ester group.

5. A method as defined in any of claims 1-3 wherein Z1 is a phosphate ester group.

6. A method as defined in any of claims 1-3 wherein A is a halide or lower alkyl sulfate.

7. A method as defined in any of claims 1-3 wherein the sum of y1 and y2 is 5-20.

8. A method as defined in any of claims 1-3 wherein R is derived from cocoamine.

9. A method as defined in any of claims 1-3 wherein R is derived from tallowamine.

10. A method as defined in any of claims 1-3 wherein said com-position is an aqueous solution of an aqueous shampoo formulation contain-ing 20% of said agent and 1.5% of long chain amine oxide.

11. A method as defined in any of claims 1-3 wherein said composition is an aqueous solution of an aqueous bubble bath concentrate containing 20% of said agent and 5% of coconut diethanolamide.

12. A method as defined in any of claims 1-3 wherein said composition is a solid bar containing 5-15% of said agent, 60-80% of tallow coconut oil soap and 0-10% of stearic acid.

13. A method as defined in any of claims 1-3 wherein said composition is a solid bar containing 20-50% of said agent, 5-15% of paraffin wax, 0-20% of stearic acid, 0.5-1.0% of alkyl dimethyl benzyl ammonium cloride, and 20-60% of talc.

14. A method as defined in any of claims 1-3 wherein said composition is a solid bar containing 20-50% of said agent, 5-15% of paraffin wax, 0-20% of stearic acid, and 20-60% of talc.

15. Aqueous shampoo, bubble bath and solid detergent bar compositions containing an effective washing amount of an agent as defined in claim 1 in combination with conventional ingredients of such compositions including a dermatologically acceptable carrier.