US2669546A - Detergents containing imidazoline lactates - Google Patents

Description

Patented Feb. 16, 1954 DETERGENTS CONTAINING IMIDAZOLINE LACTATES Hyman W. Zussman an Providence, R. I., assig Company, Cranston,

Rhode Island 41 Robert L. Bernstein, nors to Alrose Chemical R. L, a corporation of No Drawing. Application December 23, 1949, Serial No. 134,863

12 Claims. (01. 252-153) This invention relates to surface active agents of the cation-active type, and more particularly to the lactate salts of certain substituted imidazolines. It also relates to surface active compositions for use in organic liq'uids. The primary use of the lactate salt of the substituted imidazcline of the present invention is in the preparation of cleaning fluids, particularly for dry cleaning of garments and other textile fabrics. Although this is the primary commercial use, they can be employed with successful results in the cleaning of metals and other solid surfaces where an organic solvent is employed, to free them of films, coatings or deposits including grease, oil and attached extraneous solid matter, etc.

1 .The cation-active type surface active agents of the present invention have. detergent and sludge dispersing properties and; because .of which, when used in fuel oil and lubricants are effective in dispersing sludge and varnish deposits in engines.

In the dry cleaning of textiles, e. g. finished materials composed of cotton, wool, natural silk,

cellulose esters, regenerated cellulose, nylon or other synthetic fibers or filaments, and mixtures of these recited fibers or filaments, it has been a common practice to employ a volatile organic solvent such as Stoddard solvent, a poly-chlor hydrocarbon, benzene or white spirit in which is dissolved a soap, for instance potassium or triethanol ammonium oleate, and if desired Water. And dry cleaning fluids which contain a quaternary ammonium salt, polyethylene glycol esters of fattyacids, polyethyleneoxide ethers of higher alcohols or phenols and ammonium salts of alkyl aryl sulfonates and other surface active agents have been utilized in dry cleaning and related branches ofliquid detergency. .Many of these aforesaid mentioned surface active agents are not, however, very effective in improving the removal of solid soil. Many of them do little more than permitthe inclusion of water in the solvent, which is recognized as possessing two advantages: reducing the build-up of static electricity and increasing the removal of water-soluble stains in the cleaning processes.

1 Stoddard solvent is described in a U. S. Bureau of Standards publication Stoddard Solvent CS3-40." designated as petroleum distillate with a flash point not lower than 100 F. when tested in the Tag closed heater. The distillation range when a sample is distilled in a certain specified apparatus is that not more than 50% shall be recovered in the receiver when the thermometer reads 3 B1, and the end point perature shall not be higher than 410 F.

of maximum distillation tein- We have discovered that the lactate salts of substituted imidazolines of the type described below are surface active agents which when incorporated in organic solvents produce unusually effective liquid detergents. They surpassed such cationic-active types of surface active agents as fatty acid amides, aliphatic primary-, secondary-, and tertiary amines, quaternary ammonium compounds, oxazolines and other imidazolines when formed into corresponding dry cleaning detergents.

The lactate salt of imidazolines substituted in the 2-position by a saturated aliphatic hydrocarbon of seventeen carbon atoms, particularly by the alkyl group we have found possess very pronounced surface active properties. Where this substituent has less than seventeen (17) carbon atoms the eifective'ness is less as a detergent in organicli-quids. Salts other than the lactate, which wereiinvestigated; including the caprate, oleate, acetate, hydr'oxyacetate, gluconate and tartrate were far less'efiectivethan the lactate.

The lactate salts of Z-heptadecyl imidazolines in-" corporated in very small quantities in the conventional solvents of the dry cleaning industry are unusually eifective liquid detergents.

. Its formula is:

N-CH2 v cums-c .CHaCH(OH)COOH NIH-CH2 It can be-d'efinitely asserted'that the 2 -position substituted imidazolines in the form of a lactate salt, the substituent of which ispreferably an alkyl radical of seventeen carbon atoms, when incorporated .in such volatile, solvents as.

Stoddard solvent, perchloroethylene,trichloro ethylene or carbon tetrachloride, produced-a cleaning fluid superior to either these respective solvents alone or to such solvents containing such other cationic agents as'mentioned supra. It has also been found that this type of imidazoline salt substituted also in the l-position by such' groups as hydroxylethyl, aminoethyl, benzyl and ethyl'benzene was also effective when incorporated in the above mentioned conventionahvolatile organic solvents. Of these substances, the lactate salt of l-hydroxylethyl 2- heptadecyl imidazoline is preferred. Its formula is:

N-om

Cl'I IMiO ..CH3CH(OH)COOH v N-CH:

HO-CzHa The compounds of the present invention mentioned supra may be used as additives in any of the dry cleaning solvents commonly in use such as those mentioned by Brown in the Journal of the Society oLDyersand Colourists- 1933, page 42. Since-very small; quantities of; any of these substances is all that is usually necessary, the cleaning processes employing the same are com nomical. This does not preclude the use of larger quantities. The amount for optimumresultscanl be determined for any one compound, solvent and textile goods by a few trialsa The preferred BmDOdimCHtOfithiSiIIVfiIltiOMfislates to detergent compositionsiwliichaeontain the lactate salt of l-hydroxylethyl Z-heptadecyl imidazoline. In the dry cleaning. pmcessesthe. fluids would ordinarily be those conventionally employed and in the metal cleaning processes those customarily employed in that branch of detergency.

The;effectiveness=,ofi this oationimsuriacez active agent. as; relates to; dintzremovalifrcm fabrics; will: heaproven. The;- testr'employedwamthe measurement of reflectance ofaswatches: of. the sciledrcels lulose; acetate. fabric: and: the same soiled fabric; cleaned! by various dry; cleaning; fiuidsz: amhotnevolt-reflectometen'moderfilOawas-usedl Thi'semat chine sendsabeannoficonstantl intensity ofilight' against-the swatch;v The:principle ofioperationsiss that a. centaimpercentage: or. this; light: is: re-

flected back and picked up by azphotoelectriczceil; With; a perfect-reflecting;- sur;face;. the reflectance will? be 100%; or: 100,; leaving. off the; percentage. 5:. periectlyrblacle. body: will: have: a reflectance of: ZCIIDJDEIQCBBI'I, 12.6.0).

The: swatches of: soiled: fabric were: cleaned, identical: conditions. The. solvent: in: each cleaning: operatiom im the: table: was? pen-- chlomethylenez-ami there werafiveatestsinzwhicin 012.5%; of thez various' surface? active materialslisted this; table: was present in:v the: solventr. 'llhmreflectanceivaluesfm' each appear: imthe-tahlei,

Nature of Fhbrid'I i-eatment Reflectance Check, i. e. Soiled Fabric (no treatment). 6 Solvent alone l9 Solvent Naccolenc 30 Solvent steary1amine.. 32 Solvent Hydroxyethyl 01eamide 33 Solvent Span 3 33 'Naccoleuc" is a trademark prodiictunderstoodito. beamam: moniunrselt of an alkyl-aryl sulionatm From this: table: it; iss quite; apparent; that", the reflectance ot. thisv imidazolinee derivative solvent treated; swatch; is, iarxinr. excess of;- any others; meaning. that there-sis: lesszresidual dint il iIlZthBFffibfi-C; Comparable:resultsaliasrealsotbeen ohtainedemploying "Stoddardssolventi"insteadlci the.-perchloroethylene;above: whereimsuchzvariect fabrics as rayon; wooliand cottonzhave been: suhejectedlto. thisreflectanceatest, ,each: demonstrating: the: table the: superiors-soil removing; cat Danity: of;thislimidazolinezderivative;

Tlherpowerfulldispersingr andlsuspending: action: of this imidazoline derivative in dry cleaning sol-- vents has in a qualitative, yet effective way been demonstrated asvfollows:

Two pieces of white cotton fabric were well marked with lipstick; oneapiece was put into a jar of pure solvent and the other intathe same or (ill orange and hairdressing stains from garments,

as well as loosen glue and other spots even when usedzwithoutr'moisturee With moisture such solutipnsi areemore: eflfcient in removing the more water-soluble stains, including perspiration.

However; watersolutions alone are never employed. A; solution: of the lactate salt of 2- heptadecyl imidazoline in Stoddard solvent, perchloroethylene or other common organic volatile solvents; when used without moisture will not cause shrinkage or wrinkling. Such solutions wilhclsarrknittedzhlcosely woven and softi wool'ens without? changeein dimensions. They are excel'-= lent: detergents for:- textile materials: which t'end to faderinr. cleaning such as draperies; and seat covers. As little asatwo orthree ouncesof this: salt; per hundred: pounds: of garments employed at concentrations=.:irr organic scivents'-of-; & to V4?" 0t L%. or thereaboutswill step up' di'rt removal capacity'of petroleum solvent at least- 25 and cffStoddardsolVent! approximately-40%;

2'-hepta'decyl' imidazolin'e lactate and such 1 position substitutedxlerivativesas=the l -liydroxyw ethyl hav limited: solubility 11mm; of the or genie-solvents.- Theysare; therefore; impractlc e: somewhat difficult: to incorporate in the'oonve'n tional dry cleaning solvents: It has been:- found advantageous 'to" liquety 'thESBFlECtHtESEIfS, which are'in; their" pure form waxy 'solid's; by* the addi r tion ofvariousoil-soluhilizing poiyalcohol esters of; higher fatty acids; petroleumsulfonates' and other: oili-sclubilizing surfaceactive agents; at the same time these lactate salts are by this: made miscible with: the organic" solvent. Many ofithesesolubilimng agents also improve thewater' emulsifying action of the detergent; The More-- said. polyhydric; esters= can be those of glycerol, ethylene glycol, di'propylene' glycol; propylene glycol, polyethylene'glycoh etc;

While:.it has? been= noted that some of these oil'esoluhilizingagents; suchas" polyethylene gly'- coir 2005* monolaureat'e polyethyleneglycor 300 monolaurate or polyethylene glycol 400 -mono; (nearehave: a: detrimental effect on the deter gency or" the. lactate saltoff l-hydrcxyethyl 2- heptadecyl: imidazoline; several other oil-sol'u bilizing; agents; while themselves rather'p'oor dry cleaning detergents; exhibit; a marked synergistic; effects. when: mixedtwith: this i'midazoline salt: Thus; while; 012.5%. of: dinropyleneglyccl m'ono ol'eatezincreasesxthe i'efiect'ance of standard?rayon fabric commie-221m perchloroethylene, and a 0.25%; solutioinoithenlactat'e of-ll-hydroxyethyl' zj-heptade'cyh imidazoline alone. increases the reflectancatov 4e; a1.0.25;%':solution of l z'li 1:2 and Zilz mixture: of the. fornrer'with the latter' eachproduce; reflectance of? as to: 4-37 employing thesame: solvent: in; each: comparative test;-

It may also be desirabletovadct'small quanti ties of isopropanol, ethyleneglycol, carbitols i: e:. diethyleneglycoiemonoethyl? ether; or=liexyleneglycols etc. as. coupling agents to= improve; the, physical stability: or the 2 hept'adecyll. imid'irst; numbers; 20121 3002 and. 400:. mean; that, the; polyethylenezglycolffrom'which Vtheseirespectiveaestermweree aside hadthe moicculan-vreight;correspomiingtolthatmu n azoline lactate concentrates as articles of commerce. By coupling agents is meant a chemical substance which possesses the property of solubilizing or dispersing a compound that is normally only partially soluble in a solvent, which may be either an aqueous or a non-aqueous type. In the absence of the second additive this first substance would settle out of solution due to its limited solubility. The term "coupling agent is broader than oil-solubilizing agent which is restricted to promoting solubility of the compound in the Water-immiscible organic solvents.

The following examples are given to illustrate the invention but do not limit the invention. The parts are by weight.

Example 1 Parts Lactate salt of l-hydroxyethyl 2-heptadecyl imidazoline 40 Dipropylene glycol mono-oleate Glycerol mono-oleate Ethylene glycol monobutyl ether 5 One quart per hundred pounds of garments of a dry stock solution prepared by thoroughly dispersing one part of the above material into ten parts of petroleum solvent will be found to increase the coil removal efficiency of petroleum solvent at least while enabling complete or at least partial removal in the dry cleaning machine of such stains as lipstick, paint, and ink and at the same time will prevent soil redeposition.

Two quarts per hundred pounds of garments of a wet stock emulsion prepared by emulsifying one part of water with one part of the above dry stock solution will be found to increase the soil removal efficiency of petroleum solvent while removing such stains as coffee, fruit juices, gravy, etc. in the dry cleaning wheel in addition to removing the stains by the dry stock solution alone, as mentioned supra. As in the case of dry stock solution, soil redeposition is prevented.

Both the dry stock solution and the wet stock emulsion will increase the number of silk pass ups at least and at the same time decrease the number of re-runs which are necessary. In ad dition, the wet stock emulsion will increasereversible pass ups 80% or better while keeping the amount of Wet cleanin down to a maximum of 10%.

Example 2 Parts Lactate salt of l-hydroxyethyl 2-heptadecyl imidazoline 30 Nonisol 200 25 Glycerol mono-cleats 40 Ethylene glycol monobutyl ether 5 Four fifths of a pint per 30 pounds of garments of a dry stock solution prepared by thoroughly dispersing one part of the above material into ten parts of synthetic solvent (trichlorethylene) it will be found to be at least double the soil removal eiiiciency of this solvent while enabling the complete or at least partial removal in the dry cleaning machine of such stains as lipstick, paint, and ink. At the same time the use of this dry stock solution will prevent soil redeposltion.

One pint per 30 pounds of garments of a wet stock emulsion prepared by emulsifying four parts of water with eleven parts of this dry stock solution using chlorinated solvent will do all that the dry stock solution will do and, in addition, will remove such stains as cofiee, paint, and ink plus the usual soft and sweet stains.

Both the dry stock and the wet stock emulsion will be found to increase the number of silk pass ups while decreasing the number of reruns necessary. In addition, the wet stock emulsion will increase reversible pass ups or better and will keep the amount of wet cleaning needed to a maximum of 10%.

Nonisol 200 is a trade-mark product of the non-ionic type of the Alrose Chemical Company, Cranston, Rhode Island.

Example 3 Parts Lactate salt of 2 heptadecyl imidazoline 20 Petroleum solvent 80 One quart of the above mixture per pounds of garments will be found to increase the soil removal efiiciency of petroleum solvent, prevent soil re-deposition, remove many stains not affected by the solvent alone and when used in conjunction with water will remove common water soluble stains.

One gallon of such formulations supra as exemplified (based upon the non-inclusion of the solvent) will ordinarily clean 4000 to 6000 lbs. of clothes. It can be added directly to the wheel. When employed in a dry condition, only one or two ounces per fifty pounds of clothes is sufficient. A stock solution may be prepared from 1 quart of the formulation from Examples 1, 2 or 3 and 20 quarts (5 gallons) of solvent. As a moisturized detergent one quart of one of the formulations, 7 quarts of solvent and one quart of water is suggested. A ratio of 1.5 pints of this moisturized stock detergent solution per fifty pounds of garments (light or dark woolens, silks, whites) is usually ample-to secure excellent cleaning results. More moisture may be used as desired.

For prespotting, a higher ratio of the formula tion to solvent is employed, such as one part of the formulation to 3-4 parts of solvent, with or without moisture emulsified in it; this makes a powerful prespotting preparation. Heavily moisturized prespotting preparations with such salts as these imidazoline derivatives therein may be used in cleaning plants employing carbon tetrachloride to derive the benefits of moisturized cleaning but without putting moisture into the dry cleaning machines.

Some of the advantages in employing lactate salts of imidazoline substituted in the 2-position by an alkyl group of seventeen carbon atoms will now be summarized. The flash point of the lactate salt of both the 2-heptadecyl imidazoline and the l-hydroxyethyl Z-heptadecyl imidazoline is 235 C. It may be used with or without moisture as desired in organic solvent detergency, depending upon whether the presence or absence of moisture is the most efficient or whether water will cause shrinkage. It prevents soil re-deposition in dry cleaning. It secures an improvement in dry cleaning quality, reducing spotting and wet cleaning costs and giving better cleaned garments. Silk pass-ups 7 in plants using it have doubled, and pass-ups on reversibles have been 80% and higher. In dry cleaning its use produces garments with a soft. fresh feel and the garments are easy to press and finish. More- 'A pass-up is a garment which does not have to be put upon the spotters board for further cleaning because of spots or stalns. A reversible pass-up is understood as any garment usually made of cotton which is worn as a raincoat or light overcoat.

over it; leaves-.110: odorruponzthe garments; Used with organic solvents. itzbuilds? up no filtenprese SHIBWIRDTOlOIIEEdJlSE. It maybe-usedawith any dry cle'aningi equipment. and with any filter aid. And' in the recoveryof; solvent it. does not foam hr the! still; It? is noncorrosive: to metals-.- and actuallyreduces the danger ofcorrosion when carbon tetrachloride: iszem'ployed;

In cleaningi solid. surfaces higherboiling; sol!- vents= may be used. instead. of these customarily employedfin the: dry. cleaning industry; But the cationic-active surface: active. agents of the present invention may. be employed with such organic liquids with similar effectiveness. In fact it finds service in organic.liquiddetergency in its many diverse industrialfields'.

Moreover because of its surface active'propertiesfi the" lactate salts' of the? seventeen. carbon atoms saturated aliphatic hydrocarbom, substituted" imidazolin'esand the 1-position substituted derivatives of the type indicated hereinalso car he used to disperse sludge in"- fuel. oil and l'ubricantsz While the invention has been describediwith reference to particular embodiments-2 and: specific examples; it'- isnot intended: that: our: invention shall be limited to such, except ashereinaft'er described inthe'appended' claims. lttwill be reali'zed by those skilled in' the: arts" that various changes may be made in the: composition andformulation of the detergents: and cleaning agents;

We claimasourinvention:

l.- A surf ace active 3 compound? whichr. 15131181128? tate salt of the iinidazoline substituted; in the' 2-position'-by an alliyl group of seventeenicarbon atoms, but whose 4 an'd 5 positions: are: unsub stit'uted.

2? A surface" active 6-. A' surface aptive=composition=comprising the lactatesa'lt of an imidazolinewhich'is suhstituted' ih"the'2'-position' by an alkyl group ofseventeen' carbon. atoms and" is substituted in the I-p'osition by the'hydroxyethyl group, but whose 4 and 5 positions areunsubstituted, and a polyhydri'c alcohol ester of" a higherfatty acid; this last mentioned"componentbeing present in'an' amount' sufficient to liquify the former and render it miscible with the chosen liquid selected from the group consisting of hydrocarbons and polychlorinated hydrocarbons.

75 A surface active composition comprising: a

compound" whichv is. the v lactatesal't of the-imidazo'lihe substit'uted inzthe lactate-salt. of. an. imidazoline. which. is' substl tuted in=the 2aposition .by analkyLgroun-of sevem teen carbon. atoms. butwhose- 4 and. 5 positions areunsubstituted, admixed with-azdipropylene glycoliester of. a higher fatty'acid, thelast component. being present in. an amount suffie cientto-liquefyrthe. former. and render it miscible with .thechosen liquid solvent selectedfrom the group consisting of hydrocarbons and polychlo. rinated hydrocarbons;

8. A surface. activecomposition comprising. the lactatesaltfof. 2-heptadecyl imidazoline. admixed. with a dipropylene glycol ester of a higher fattyacid, the last. component. being present. in: an amount sufficient to liquefy the former and render it miscible with the chosenliquidsolvent selected from the group consisting of hydrocarbons and polychlorinated hydrocarbons.

9'; A surface active composition comprising the lactate salt of l-hydroxyethyl 2-heptadecyl* imidazolinelactate admixed with a dipropylene glycol'esterof a higher fatty acid, the last com-' ponentbeing present in an amount suficient-to' liquefy the former and render it miscible withthe chosen liquid solvent selected from the'group consisting' of hydrocarbons and polychlorinatedrhydrocarbons.

10. A' liquid detergent comprisingv a volatile organic liquid solvent. selected from the group consisting of hydrocarbons and. polychlorinated hydrocarbons containing therein alactate salt of an. imidazoline which is substituted in the-2.- position by analkyl. group of seventeen. carbon atoms out whose i and 5 positions are unsubstituted, the said lactate-Salton the imidazolinebeing present in the liquid detergent irran amount of not over a few per cent based on the:concen trationdn the. organic liquid solvent.

11. A liquid. detergent. comprising a volatile. organic liquidv solventselectedfrom the. group consisting of hydrocarbons and polychlorinated.

hydrocarbons; containing therein a lactate-salt of. animidazoline which is substituted in. the 2 position by an alkyl group of seventeen carbon atoms but whose 4 and 5. positions-are unsubstituted andis-substituted. in the l-positionby. a member of the group. consisting. of hydroxyl.- ethyl, aminoethyl,. benzyl. and ethyl. hexyl, the said lactate :salt of. theimidazoline. being present in .the liquid. detergent in an amount of. not over. a. few. per cent. based. on. the: concentration. in the organic liquid solvent.

12. A surface active composition comprising the lactate salt of l-hy'di'oxylethyl Z-heptadecyl imidazoline and dipropylene glycol mono-oleate, the ratio oftheformer to'the latter being 221-122;

- HYMAN'W. ZUSSMAN.

ROBERT L. BERNSTEIN.

References. Cited. in; the. file of this patent UNITED.- STATES. PATENTS Number Name Date 2,155, 877' Waldmann et a1. Apr. 25, 1939' 2,194,906 Krzikalla Mar. 26, 1940 2,211,001 Chwala Aug. 3, 1910 2,267,965 Wilson Dec; 30; 1941* 2 ,317,112 Pings Apr; 20, 1943

Claims (2)

1. A SURFACE ACTIVE COMPOUND WHICH IS THE LACTATE SALT OF THE IMIDAZOLINE SUBSTITUTED IN THE 2-POSITION BY AN ALKYL GROUP OF SEVENTEEN CARBON ATOMS, BUT WHOSE 4 AND 5 POSITIONS ARE UNSUBSTITUTED.

6. A SURFACE ACTIVE COMPOSITION COMPRISING THE LACTATE SALT OF AN IMIDAZOLINE WHICH IS SUBSTITUTED IN THE 2-POSITION BY AN ALKYL GROUP OF SEVENTEEN CARBON ATOMS AND IS SUBSTITUTED IN THE 1-POSITION BY THE HYDROXYETHYL GROUP, BUT WHOSE 4 AND 5 POSITIONS ARE UNSUBSTITUTED, AND A POLYHYDRIC ALCOHOL ESTER OF A HIGHER FATTY ACID, THIS LAST MENTIONED COMPONENT BEING PRESENT IN AN AMOUNT SUFFICIENT TO LIQUIFY THE FORMER AND RENDER IT MISCIBLE WITH THE CHOSEN LIQUID SELECTED FROM THE GROUP CONSISTING OF HYDROCARBONS AND POLYCHLORINATED HYDROCARBONS.