WO1998045308A1

WO1998045308A1 - Nonionic gemini surfactants having hydrophilic sugar groups

Info

Publication number: WO1998045308A1
Application number: PCT/US1998/006970
Authority: WO
Inventors: David James Tracy; Ruoxin Li; Jiang Yang
Original assignee: Rhodia Inc.
Priority date: 1997-04-09
Filing date: 1998-04-07
Publication date: 1998-10-15
Also published as: AU7246198A

Abstract

Sugar-derived gemini surfactants contain two disaccharide moieties as the hydrophilic groups that are linked by a bridge. The compounds have general structure (I), wherein R and R1 are the same or different linear, branched, saturated, or unsaturated hydrocarbyl moieties with a carbon chain length of from about C6-C23 and Y and Y1 are the same or different alcohol-containing moieties having at least two and preferably more hydroxyl containing groups such as glucose, fructose, lactose, and the like, and one but not both may be hydrogen, and X is a R2 or -COR2CO- wherein R2 is a C1 to C20 straight or branched chain alkyl, aryl, alkylaryl, dicarboxyaryl, or diaminoalkyl.

Description

NONIONIC GEMINI SURFACTANTS HAVING HYDROPHILIC SUGAR GROUPS

This invention relates to a novel group of nonionic surfactants having at least two hydrophobic moieties and at least two hydrophilic sugar groups per molecule useful as emulsifiers, detergents, dispersants, hydrotropes, wetting

agents, corrosion inhibitors and solubilizing agents.

BACKGROUND OF THE INVENTION

Surfactants are well known materials which can be generally described as having a hydrophobic moiety and a hydrophilic group per molecule. A wide variety of these materials are known and are classified as anionic, cationic,

nonionic and amphote c. They are well known to have numerous uses such as emulsifiers, detergents, dispersants and solubilizing agents in the field of cosmetics, textile treatment, industrial and personal cleaning preparations,

corrosion inhibitors and the like.

In nonionic surfactants, the surface-active portion bears no apparent ionic

charge. Usually polyethoxy chains, glycerides or polyhydroxy functional, e.g.

polyglucosides, constitute the hydrophile. Surfactants generally are compounds having one hydrophilic group and

one hydrophobic moiety. Recently, a group of compounds having two

hydrophobic moieties and two hydrophilic groups have been introduced. These

have become known as "gemini surfactants" in the literature (Chemtech. March

1993, pp 30-33), and J. American Chemical Soc, 115, 10083-10090, (1993) and the references cited therein Since their introduction, cationic and anionic "gemini surfactants" have been disclosed Other surfactant compounds having two hydrophilic groups and two hydrophobic moieties have been disclosed but not referred to as gemini surfactants Sulfate, phosphate, and carboxylate surfactants are currently disclosed in

the literature (See JAOCS 67, 459 (1990), JAOCS 68, 268 (1991 ), JAOCS 68, 539 (1991 ), and JAOCS 69, 626 (1992)

Sugar based gemini surfactants have been previously described in the literature U S Patent No 5,534,197 to Scheibel et al discloses and claims gemini polyhydroxy fatty acid compounds wherein the bridging group consists of a variety of alkyl, aryl, arylalkyl and aminoalkyl compounds having from about 2 to 200

atoms, and the hydrophobic heads are comprised of the same or different alcohol

containing moieties with two or more hydroxyl groups such as glycerol The surfactants are asserted to be useful as active agents in laundry detergents, fabric cleaners, and personal care

U S Patent No 5,403,922 to Garelli-Calvet et al discloses amphiphihc

surfactants containing two sugar or sugar-derived head portions The amphiphihc

head portions are long chain aliphatic or branched aliphatic carbon chains The

chains are interrupted by various functional groups such as amines (-NH) and further comprise reducing glucides comprised of a linear or cyclized carbon chain

The hydrophile is on the ends of the hydrophobe, constituting bola-type

surfactants Bola surfactants are relatively ineffective U. S. Patent No. 5,512,699 to Conner et. al. discloses and claims poly- (polyhydroxy fatty acide amide) compounds that are asserted to be useful in laundry detergents, cleaning compositions, and personal care. Two identical long chain moieties containing hydroxyl groups are joined by a bridge consisting of polyethyleneimines, and polyethyleneamines with molecular weights below about 50,000 and preferably below 10,000. The hydrophobe is connected via carbonyl groups. U. S. Patent No. 4,892,806 to Briggs et. al. discloses nonionic surfactants comprised of two R groups consisting of substituted and unsubstituted alkyls, cycloalkyls, aryls or H joined to two hydrophilic groups represented by the formula -CH₂NHCO(CHOH)_xCH₂OH by a carbon bridge. The compounds are useful in emulsions for photographic light sensitive materials.

EPA 0 688 781 to Adams teaches and claims nonionic surfactants comprised of two polysaccharide sugar moieties that are linked to the central bridge of the molecule by one of their carbonyl groups. The central bridge is comprised of a polyalkyleneamine unit wherein at least one of the amine nitrogen

atoms has a hydrophobic, substituted or unsubstituted hydrocarbon group linked

thereto. The compounds are disclosed as being useful in aqueous hydrophilic

colloid compositions such as light sensitive photographic materials.

PCT Application No. PCT/US95/00767 to Scheibel et. al. discloses and

claims a class of gemini polyether fatty acid amides in which two polyethoxy,

polypropoxy and/or mixed polyethoxypropoxy moieties of the general formula

[(CH₂)_yO]H are joined by branched or linear alkyl or aryl moieties of from 2-200

carbon atoms. The surfactants may be combined with other nonionic and anionic

surfactants and enzymes in soap and laundry detergent formulations. PCT application No PCT/US/00769 to Scheibel et al discloses and claims another class of polyhydroxy diamine compounds in which two "heads" consisting of reducing sugars such as glycerol, glucose, maltose, maltodextπn and the like are joined together by a unsubstituted, linear or branched alkyl, ether alkyl or

ammo alkyl consisting of from two to fifteen carbon atoms

An article by Zhang et al , J Colloid Interface Sci 177 419-426 (1996)

discusses the effect of hydrophobic and hydrophilic chain lengths on the surface active properties of novel polysacchaπde surfactants The nonionic sacchaπde surfactants consist of an amide group that links a hydrophilic sacchaπde segment

such as glucoiactone, maltolactone, and dextrolactone to a hydrophobic alkyl segment such as hexylamine, octylamine and decylamine It was shown that the size of the sacchaπde segment is important in determining the interfacial surface area of the molecule and hence it's surface activity

Eastoe et al , Langmuir .12, 2701 -2705 (1996) discloses nonionic

amphiphile surfactants comprised of two η-alkyl chains and two glucamide head

groups Surfactant purity, surfactant-water phase behavior, air-solution surface

tension and small angle neutron-scattering characteristics are some of the surfactant characteristics disclosed A second Eastoe et al article, Langmuir 10,

4429-4433 (1994) discusses the properties of nonionic surfactants comprised of

two C-₆ hydrophobic chains and two glucamide head groups in the same fashion

An article to Bπggs et al J Chem Soc 46, 379-380 (1995) briefly

discusses the synthesis and properties of nonionic polyol surfactants derived from

carbohydrate lactones The surface properties of these nonionic gemini

surfactants are rare and very few are reported in the literature Due to the need for new and more effective and efficient surfactants, as well as the need for mild surfactants which are biologically compatible in an ecologically sensitive environment, effort has been made to develop a new class of compounds, which demonstrate improved surface-active properties that are further characterized as mild, and environmentally benign

Gemini surfactants contain two hydrophilic heads and two hpophilic chains linked by a small bridge Because gemini surfactants demonstrate very special physical properties such as unusually low critical micelle concentrations (cmc) and pC₂₀ values in aqueous media, they have drawn significant attention It has been reported that ionic gemini surfactants can lower cmc values about 100 times more efficient than single chain analogues and are about 1000 times more efficient at reducing the surface tension (pC₂₀) Beside these outstanding physical properties, nonionic gemini surfactants can be very effective, biodegradable, and to a certain extent, available from renewable resources such as natural fats and sugars Therefore, sugar-containing surfactants have attracted considerable

attention

The new type of sugar gemini surfactant generally contains two aliphatic

long chains as hpophilic groups and two oligosacchaπdes as hydrophilic heads

Because sugar molecules are very water soluble, they are superior as hydrophilic

heads for gemini surfactants

Sugar gemini surfactants use various forms of sugar as hydrophilic groups such as glucose, fructose, maltose, lactose, galactose, mannose, xylose and so

on Another type of gemini surfactant contains a polyhydroxyl group as the

hydrophilic head Their general structure is shown below R H₂-NHCO-(CHOH)_x-CH₂OH

¹ H₂-NHCO-(CHOH)_x-CH₂OH

wherein R and R¹ represent a C₃ to C₂ι straight or branched chain hydrocarbyl moiety. See Eastoe, and Briggs, supra.

Other sugar gemini surfactants have been prepared that contain two glucose hydrophilic groups and two hydrocarbon chains linked by an ethylene group. However, these bis-monosaccharide gemini surfactants were found to be insoluble in water.

DETAILED DESCRIPTION OF THE DRAWINGS

Figure 1 is the graphic results of ¹H-NMR and ¹³C-NMR spectral analysis of N-decyllactosylamine compound produced in example 1.

Figure 2 is the graphic results of ¹H-NMR and ¹³C-NMR spectral analysis

of the N-dodecyllactosylamine compound produced in example 2.

Figure 3 is the graphic results of ¹H-NMR spectral analysis of the N-

hexadecyllactosylamine compound produced in example 3.

Figure 4 is the graphic results of ¹H-NMR and ¹³C-NMR spectral analysis of

the gemini-bis-decylactosylamide produced in example 4.

Figure 5 is the graphic results of ¹H-NMR and ¹³C-NMR spectral analysis of

the gemini-bis-dodecylactosylamide compound produced in example 5. SUMMARY OF THE INVENTION

Sugar-derived gemini surfactants contain two disaccharide moieties as the

hydrophilic groups that are linked by a bridge. The general structure of the compounds is as follows: I. R-N-Y

I x

wherein R and R_T are the same or different linear, branched, saturated, or unsaturated hydrocarbyl moieties with a carbon chain length of from about C₆-C₂₃ and Y and Yi are the same or different alcohol-containing moieties having at least two and preferably more hydroxyl containing groups such as glucose, fructose,

lactose, and the like, and one but not both may be hydrogen, and X is a R₂ or - COR₂CO- wherein R₂ is a Ci to C₂₀ straight or branched chain alkyl, aryl, alkyl aryl, dicarboxyaryl. or diaminoalkyl.

DETAILED DESCRIPTION OF THE INVENTION

The general structure of the sugar-derived gemini surfactants of the

present invention contain two polysaccharides as hydrophilic groups connected by

a bridge. The surfactants are prepared using standard amidation, condensation

and reduction reactions wherein a disaccharide such as lactose, maltose, or

fructose is condensed with a terminal end amine-containing alkyl group to produce

a long chain molecule with the hydroxyl sugar at the hydrophilic end and the long

chain aliphatic group as the hpophilic end. Two of them joined by a carbonyl- containing bridge via amidation/condensation reaction or alkylation using an alpha omega dihalide or reaction with a diisocyanate.

The novel gemini surfactants of the present invention comprise two sugar moieties as the hydrophilic group that, together with the two hydrophobic groups, are linked by a bridge. The general structure of the surfactant composition is as follows:

I. R-N-Y

I x

R^N-Y_T

wherein R and R independently represent the same or different linear or branched, saturated or unsaturated hydrocarbyl moieties with a carbon chain

length of from about C₆ to C₂₃ and wherein Y and Y₁ independently represent the same or different alcohol-containing moieties having at least two and preferably more hydroxyl groups with the further stipulation that one but not both Y groups may be hydrogen and X independently represents R₂ or -COR₂CO- wherein

R₂ is a straight or branched chain alkyl, aryl or alkylaryl, dicarboxyaryl, or diaminoalkyl.

Preferably, the sugar gemini surfactants of the present invention are represented by the general formula:

II. R-N-Y |

C=0

I

R₂

I C=0

I

R_!-N-Y R and Ri independently represent a straight or branched alkyl group of from about six (6) to twelve (20) carbon atoms Preferably the Y moieties are selected from the group comprising monosacchaπdes, disacchaπdes, polysacchandes and the like Suitable monosacchaπdes include glyceraldehyde, erythrose, threose, πbose, arabinose, xylose, lyxose, allose, altrose, glucose, fructose, mannose, gulose, idose, galactose, and talose Disacchaπdes represented by Y and Y^ include, but are not limited to lactose, maltose, cellobiose, sucrose, gentobrose and mixtures thereof Suitable polysacchandes that may be represented by Y and Yi include amylose, amylopectin, trehalose and the like Preferably, the Y groups

represent a disaccharide such as lactose or maltose, and R₂ is aryl

Using lactose (i e R=lactose) as an example, the reaction process can be schematically represented as follows

SYNTHESIS SCHEMATICS

(1 ) [2]R-N-Y Cl R-N-Y

I I I

H + C=0 C=0

I I

R₂ ^► R₂

C=0 C=0

I I

Cl R-N-Y

Alkyl lactosylamine is coupled by reaction with a bisacid chloride such as

terephthaloyl chloride or malomc acid chloride producing the gemini surfactant (2) [2]R-N-Y R-N-Y

I

H Halo-X-Halo x

I

R-N-Y

Alkyl lactosylamine is coupled by reaction with an alpha omega halide such as xylenedihahde or 1 ,4 dichlorobutane producing the gemini surfactant

(3) III

R-N-Y

C=0

CO,H

Alkyl lactosylamine is coupled by reaction with a di-anhydπde such as

1 ,2,4,5 benzene tetracarboxylic anhydride producing the gemini surfactant

(4)

[2]RNHY + OCN-R₂NCO → R-N-Y

I C=0

I

NH

I R₂

I NH

C=0

I

R-N-Y Alkyl lactosylamine is coupled by reaction with a dnsocycanate such as toluene dnsocyanate or methylene bisdiphenyldnsocyanate

Lactose is used as an example in the above descriptions, however, any reducing sugar can be substituted for lactose

Lactose, and dodecylamine are the starting materials in the above reaction

scheme

Compounds of the invention can be prepared by coupling the sugar amine

The sugar amine is prepared by heating the sugar with amine in an alcohol-water mixture or dimethylformamide Usually an excess of amine is used to suppress formation of tertiary amines The main product usually crystallizes from the

reaction mixture Synthesis is described by 0 Lockhoff (Angew Chem Int Ed

Engl 30, 161 1 -1620 (1991 ))

The sugar amines can be coupled via numerous routes the most common being via bisacid chloride, dianhydπde, dnsocyanate and dihahde

It has been reported that the secondary amine in single chain

glycosylamines can react with acid chloride or acid anhydride selectively at low

temperature

Lactosylamine can be easily synthesized in either DMSO or methanol water

solution However, the lactosylamine synthesized in the presence of methanol and water usually retains a small amount of water even though it has been dried

under vacuum The presence of water in this instance could complicate certain

reactions All the compounds were analyzed by thin layer chromatography (TLC) first in a different solvent system The components of any sugar-containing compound were located by spraying the plates with dilute sulfuπc acid (20% in ethanol), followed by heating The sugar portion will react with sulfuπc acid and become a black color after heating The alkyl chain was detected by spraying a phosphomolybohc acid reagent (20% in ethanol) on the plate following the

heating Spots containing the alkyl groups gave a dark blue color The compounds that contain the aromatic ring, the alkyl chains and sugars (Figures 4 and 5) were checked by UV light first and then by diluted sulfuπc acid and phosphomolybdic acid reagents UV active light prove the presence of the

aromatic ring The black color and the dark blue color indicate that the same spot also contains sugar portions and an alkyl chains This TLC method indicated the

compound contains all three portions

Most intermediates and final compounds also were characterized by both H-NMR and ¹³C-NMR spectra (200 MHz and 50 MHz respectively) For the compounds with complicated structures such as II (Figure 4 and 5), special

attention was paid to three chemical shift regions of both ¹H-NMR and ¹³C-NMR

The proton NMR chemical shift in 57 3 - 8 0 indicated an aromatic portion, 53 1 -

4 5 indicated a sugar section and 50 8 - 1 6 indicated an alkyl region The proton

NMR of sugar gemini surfactants all have these three chemical shift regions with

relatively accurate integration These results can at least partially prove their

chemical structure Because these bulk molecules may not stay in the same

plane and can possibly be twisted in three dimensions, the aromatic region may

give multi peaks rather than single peak This kind of structure was further indicated by ¹³C-NMR There are more than two aromatic peaks in the aromatic

region (5120 - 140) The sugar region is in 560 - 104 The peak at 5104 is a very

characteristic chemical shift for the ketyl group in lactose The carbonyl group

was found at around 5174, which indicated the two single lactosylamine chains

are linked together The alkyl chain region is between 515 - 40 Even though

some trace impurities appeared on NMR spectra due to the lack of a chromatographic purification step, overall, the NMR data agrees with the

compounds' structures

Since the surfactants of the invention exhibit an extremely low critical

micelle concentration (cmc) as compared with conventional surface-active agents because of the presence of two hydrophobic moieties and two hydrophilic groups in their molecule, they are able to fully reduce surface tension, are highly soluble in water, and are extremely effective in aqueous solution at low concentrations

The surfactants of the invention can be used in any amount needed for the

particular application and this can be easily determined by a skilled artisan without

undue experimentation

Whereas the surfactants of the invention can be used alone as the

essential hydrotrope component, it has been unexpectedly found that blends of

the compounds of the invention with certain conventional well known anionic,

nonionic, cationic and amphoteric surfactants provide results beyond that

expected and therefore synergistic that can be demonstrated in relation to critical

micelle concentration and surface tension reducing ability

Examples of the nonionic surfactants used herein include fatty acid

glycerine esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglyceπne fatty acid esters, higher alcohol ethylene oxide adducts, single long chain polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene lanolin alcohol, polyoxyethylene fatty acid esters, polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, an alkylpyrrohdone, glucamides, alkylpolyglucosides, mono- and dialkanol amides, a polyoxyethylene alcohol mono- or diamides and alkylamine oxides Examples of the anionic surfactants used herein include fatty acid soaps, ether carboxylic acids and salts thereof,

alkane sulfonate salts, α-olefin sulfonate salts, sulfonate salts of higher fatty acid

esters, higher alcohol sulfate ester salts, fatty alcohol ether sulfates salts, higher alcohol phosphate ester salts, fatty alcohol ether phosphate ester salts, condensates of higher fatty acids and ammo acids, and collagen hydrolysate

derivatives

Examples of the cationic surfactants used herein include

alkyltπmethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyπdinium salts, alkylisoquinohnium

salts, benzethonium chloride, and acylamino acid type cationic surfactants

Examples of the amphoteric surfactants used herein include ammo acid,

betame, sultame, phosphobetames, imidazohne type amphoteric surfactants,

soybean phospholipid, and yolk lecithin

Any of the commonly used auxiliary additives such as inorganic salts such

as Glauber salt and common salt, builders, humectants, solubilizing agents, UV absorbers, softeners, chelatmg agents, and viscosity modifiers may be added to the surfactants of the invention or blends thereof with other surfactants as disclosed herein

The nonionic surfactants of the invention are extremely mild and non- irritating to both eyes and skin They also exhibit enhanced wetting speed, greater surface tension reduction, high foaming and foam stabilization properties,

low toxicity, and excellent compatibility with other anionic, cationic, and nonionic surfactants The products of the invention are stable over a wide pH range and are biodegradable These properties make these surfactants adaptable for use in products ranging from cosmetics to industrial applications and are usable

wherever anionic surfactants have found use These products are particularly useful for non-irritating shampoos, including baby shampoos, body shampoos including bubble baths, bar soaps, bath gels, hair conditioning gels, lotions, skin creams and lotions, make up removal creams and lotions, liquid detergents, dish detergents, and other washing and cosmetic products that contact the skin The

surfactants of the invention can also find use as hard surface cleaners including

cars, dishes, toilets, floors, and the like, laundry detergents and soaps, metal

working aids and the like

Experimental

Example 1

Preparation of N- decyllactosylamine

Lactose (34 5 g) was dissolved in dry dimethyl sulfoxide (70 mL) at 40-

50°C Decylamine (15 g) was added and the reaction was stirred at 50°C for 12

hours A crude product precipitated from the reaction as white solid on the top of the solution The reaction was then stopped by cooling to room temperature and the product was then isolated by filtration The crude product was washed with cold ethanol several times to remove unreacted starting material The product was then dried under vacuum and submitted for ¹H-NMR and ¹³C-NMR spectral

studies NMR data agreed with the expected structure of final product (Figure 1 ) The product, a white solid, weighed 45 g

Example 2

Preparation of N-Dodecyllactosylamine

Lactose (34 g) was dissolved in a small amount of distilled water (60 mL) at

60°C Dodecylamine (22 3 g) dissolved in methanol was added drop-by-drop to

the water solution at 60°C as the reaction mixture was stirred vigorously The

reaction solution became cloudy at the beginning of the reaction and then became

clear again after stirring for about 30 minutes As the reaction continued, a white solid product began to accumulate on the top of the solution The reaction was

continued for three hours and was then stopped White solid crude product was

washed with acetone twice and dried under a vacuum NMR spectra (Figure 2)

agreed with the expected structure of the final compound The yield of the

reaction was about 75%

Example 3

Preparation of Hexadecyllactosylamine

Lactose (26 g) was dissolved in distilled water (60 mL) at 60°C

Hexadecylamine (25 g) dissolved in methanol was added to the water solution

The reaction solution became cloudy at the beginning of the reaction and then became clear again after stirring for 20 minutes The reaction was continued for

another three hours A white solid product that was generated during the reaction accumulated on the top of reaction The reaction was stopped by cooling to room temperature The white solid product was collected by filtration and then washed with methanol and acetone After drying under vacuum, the product was taken for

NMR analysis (See Figure 3) The result from NMR studies verified that this is

the expected product

Example 4

Preparation of Gemini Bis-decyllactosylamide

To decyllactosylamine (5.6 g, 11.23 mmol) prepared in Example 1 dissolved in dry dimethylformamide is added a small amount of dimethylsulfoxide

and triethylamine (0.5 mL) at 0°C. TerephthaloyI chloride (1.14g, 5.6 mmol) in dry

dimethylformamide was added drop-wise to the solution as the solution was stirred

vigorously. The reaction temperature was allowed to slowly warm to room

temperature. After stirring for 17 hours, the reaction was gently heated at 60°C for

a few hours until the thin layer chromatogram showed that all starting material had disappeared. The reaction was stopped by cooling to room temperature. The reaction solution was poured into water and then extracted with mixed solvent systems (chloroform and methanol) twice. After evaporating organic solvent, the solid crude product was dried under vacuum. Thin layer chromatography and NMR (Figure 4) all indicated this material is the expected product.

Example 5

Preparation of Gemini Bis-dodecyllactosylamide

N-dodecyllactosylamine (7 96g, 15 1 mmol) was dissolved in dry dimethylformamide (DMF) in the presence of heat TerephthaloyI chloride (1 5g, 7.39 mmol) dissolved in dimethylformamide and the excess amount of (1 8g)

sodium carbonate were added to the solution at 0°C in an ice/water bath The

stirred reaction was gradually warmed to room temperature and then heated to

60°C for 20 hours After thin layer chromatogram showed that most of the starting

material had disappeared, the reaction was cooled to room temperature The solid inorganic salt was filtered out The organic layer was flushed with ether A light yellow product was collected by filtration The compound was washed twice

with acetone, and then dried under vacuum NMR data (¹H-NMR and ¹³C-NMR

spectra are shown in Figure 5) agreed with the expected structure of the final compound The yield of the final product was 4 6 g

Example 6

Preparation of Xylyl-Bis-dodecyllactosylamide gemini surfactant

N-dodecyllactosylamine (8 0 g, 16 0 mmol) was dissolved in dry

dimethylformamide in the presence of heat Dibromo-p-xylene (1 90 g, 7 2 mmol)

was dissolved in dimethylformamide and the excess amount of sodium carbonate were added to the solution at room temperature The reaction was gently heated

to 64°C and stirred for 15 hours Thin layer chromatography showed that there

was a new UV active sugar-containing product generated The reaction was stopped by cooling to room temperature Sodium carbonate salt was separated

by filtration A large amount of acetone was poured onto the organic layer and a white precipitate formed and was collected by filtration This solid material was washed with cold ethanol twice The final solid material was dried under vacuum The yield of the reaction was about 40% and the NMR result agreed with the

expected structure of the final product

Example 7

Preparation of 1,2,4,5-Benzenetetracarboxylic acid-derived bis-

dodecyllactosylamide gemini surfactant

N-dodecyllactosylamine (10.0 g, 20.0 mmol) was dissolved in dry

dimethylformamide with heat added if necessary. 1 ,2,4,5-benzenetetracarboxylic anhydride (2.18 g, 10 mmol) and a small amount of sodium carbonate were added

to the solution at room temperature. The reaction was stirred at 60°C overnight.

The reaction was then stopped by cooling to room temperature. Thin layer

chromatography indicated a new product was generated. The reaction was then diluted with acetone. Any insoluble inorganic material was separated by filtration and the organic layer was collected. After evaporating the solvent under reduced

pressure, the solid product was washed twice with methanol and then collected.

The material was dried under vacuum. The yield of the reaction was 60%, and the NMR result agreed with the expected structure of the final product.

Example 8

Surface Activity

The surfactants of the invention were measured for critical micelle concentration and surface tension reducing ability The test methods utilized are described as follows

Critical Micelle Concentration (cmc)

Aqueous solutions of the surfactants were prepared at varying

concentrations The surface tension at 20°C was measured by the Wilhelmy plate

method and plotted vs the logarithm of the concentration The critical micelle concentration (cmc) was determined as the value at which the slope of the line of the graph changed abruptly

The surface tension reducing ability was determined from the surface tension at the critical micelle concentration

Surface tension measurements were made for each of the surfactants prepared from examples 1 and 2 using a Kruss K-12 tensiometer (plate method)

The appropriate values were determined as follows

dγ / p = 2 303RT d\ogC_τ ' where

p = surface excess concentration (mol/cm²)

dγ = change in surface or interfacial tension of the solvent

(dyn» cm^"1)

R 8 31x10⁷ erg mol^{"1 ,} K^"1

C = molar concentration of solution T = absolute temperature (°K)

pC-20 at the solution/air interface is defined as the negative logarithm of the surfactant concentration required to lower surface tension by 20 dyne/cm. The results obtained for the surfactants alone are reported in Table 1.

Ross Miles Foam Height

The product was evaluated as a foaming agent using the Ross Miles Foam Height Test as outlined in ASTM method D1173. The foam was evaluated and the results were recorded.

TABLE I

As can be seen from the respective derived values, the surfactants afford

superior foaming characteristics and enhanced surface tension reduction properties.

When the surface properties for the amphoteric gemini surfactant

compounds of the were compared to the corresponding conventional amphoteric surfactants, the novel compounds of the invention showed two unexpected surface active properties, unusually low critical micelle concentration (cmc) and

pC₂₀ values in aqueous media These properties are a measure of the tendency of the surfactant to form micelles and adsorb at the interface, and consequently, to reduce surface tension respectively

This unusually high surface activity for these molecules is a result of their

unique structure, the presence of two optimally spaced hydrophobic chains and

hydrophilic groups

This molecular structure provides energetically favorable decreases in the free energy of adsorption and micelhzation through favorable distortion of water structure, and, at the same time, providing a "close packed" arrangement at the

interface This is reflected by their relatively low area per molecule that is

unexpected from the molecular dimensions for the molecule The area per molecule for the compounds of the invention are comparable to corresponding conventional surfactants The ability of the compounds of the invention to distort

water structure through inhibition of crystalline or liquid crystalline phase formation

in bulk phase and at the same time to pack closely on adsorption at the interface

is contrary to conventional wisdom This again demonstrates the uniqueness of

the molecular design for these compounds which is very critical to providing unexpected exceptional surface and performance properties

Exceptional surface activity and unique structural features for the

compounds of the invention provide two other important performance properties that can have immense practical application in industry, i e , their hydrotropicity,

which is the ability of organic substances to increase the solubility of other insoluble organic substances in water, and solubilization, the dissolving of water insoluble organic compounds into aqueous surfactant solutions above their cmc levels. The compounds of the invention, because of their very low cmc values, are efficient solubilizers. This latter property will not only allow the formulation of homogeneous water insoluble materials, but also will enhance the surface activity

of other surfactants whose low water solubility restrict their use. These novel surfactants of the invention are far better than comparable conventional surfactants in hydrotroping and solubilizing properties.

Because of their unusually high surface activity, coupled with their hydrotropicity and solubilization properties, compounds of this invention will

provide exceptionally high performance properties, at very low concentration, in

practical applications such as detergency emulsification, solubilization, dispersancy, hydrotropicity, foaming and wetting. In addition, due to their extremely low monomer concentration at use levels, because of their extremely low cmc values, use of lower concentration of the compounds of the invention than

conventional surfactants can provide extremely low or no irritancy in personal care

applications.

Claims

What we claim is:

1 ) A gemini surfactant composition comprising the structural formula

R^N-Y

I x

wherein R and Ri independently represent the same or different linear, branched, saturated or unsaturated hydrocarbyl moieties with a carbon

chain length of from about C₆-C₂₃ and wherein Y and Yi independently represent the same or different alcohol-containing moieties having at least two and preferably more hydroxyl groups with the further stipulation that one but not both may be hydrogen and X independently represents R₂ or - COR₂CO- wherein R₂ represents a d to C₂₀ straight or branched chain

alkyl, aryl, caraboxyaryl, alkylaryl, dicarboxyaryl or diammoalkyl

2) The surfactant composition of claim 1 wherein R and R_T independently

represent a straight or branched alkyl group of from about 6 to 12 carbon

atoms

3) The surfactant composition of claim 2 wherein Y and Yi independently represent an alcohol-containing moiety selected from the group consisting

essentially of monosacchaπdes, disacchaπdes, polysacchandes and mixtures

thereof

4) The surfactant composition of claim 3 wherein said monosacchaπdes are

selected from the group consisting essentially of glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, fructose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose and mixtures thereof.

5) The surfactant composition of Claim 3, wherein said dissacharide is selected from the group consisting essentially of lactose, maltose, sucrose, cellobiose,

gentibiose and mixtures thereof.

6) The surfactant composition of Claim 3, wherein said polysaccha de is selected from the group consisting essentially of amylose, amylopectin, trehalose and mixtures thereof.

7) A surfactant composition of Claim 5, wherein X is a straight or branched chain

C₆ to C₁₅ alkyl, aryl, alkylaryl and mixtures thereof.

8) The gemini surfactant of claim 1 comprising the structural formula:

R-N-Y

I C=0

R₂

I c=o

R,-N-Y wherein R₂ represents a straight or branched chain alkyl, aryl or alkyl aryl and

R, Ri and Y have been hereinbefore defined.

9) The gemini surfactant of claim 1 comprising the general formula: R-N-Y

C=0

H0₂C

C=0

R-N-Y

wherein R, R_1t and Y have been hereinbefore defined.

10) A gemini surfactant of claim 1 comprising the general formula:

C=0 I

NH

I R₂

I NH

I c=o wherein R₂ has been hereinbefore defined.

1 1 ) A surfactant composition of Claim 5, further comprising a surfactant selected

from the group consisting of an anionic, nonionic, cationic, and amphoteric

surfactant.

12) The surfactant composition of Claim 1 1 , wherein said nonionic surfactant is

selected from the group consisting of a fatty acid glycerine ester, a sorbitan

fatty acid ester, a sucrose fatty acid ester, a polyglycerine fatty acid ester, a

higher alcohol ethylene oxide adduct, a single long chain polyoxyethylene alkyl

ether, a polyoxyethylene alkyl allyl ether, a polyoxethylene lanolin alcohol, a

polyoxyethylene fatty acid ester, a polyoxyethylene glycerine fatty acid, a polyoxyethylene propylene glycol fatty acid ester, a polyoxyethylene sorbitol fatty acid ester, a polyoxyethylene castor oil or hardened castor oil derivative, a polyoxyethylene lanolin derivative, a polyoxethylene fatty acid amide, a polyoxyethylene alkyl amine, an alkyl pyrrolidone, glucamides, alkylpolyglucosides, a mono- or dialkanol amide, a polyoxyethylene alcohol,

mono- or diamide, an alkylamine oxide, and mixtures thereof.

13) The blend of surfactants of Claim 11 , wherein said anionic surfactant is

selected from the group consisting of a fatty acid soap, an ether carboxylic acid or it's salt thereof, an alkane sulfonate salt, an a-olefin sulfonate salt, a sulfonate salt of a higher fatty acid ester, a higher alcohol sulfate ester salt, fatty alcohol ether sulfate salts, a higher alcohol phosphate ester salt, a fatty alcohol ether phosphate ester salt, a condensate of higher fatty acids and

amino acids, and a collagen hydrolysate derivative.

14) The blend of surfactants of Claim 11 , wherein said cationic surfactant is selected from the group consisting of an alkyltrimethylammonium salt, a dialkyl-

dimethylammonium salt, an alkyldimethylbenzylammonium salt, an

alkylpyridinium salt, an alkylisoquinolinium salt, benzethonium chloride, and an

acylamino acid type cationic surfactant.

15) The blend of surfactants of Claim 11 , wherein said amphoteric surfactant is selected from the group consisting of an amino acids, betaines, sultaines,

phosphobetaines, imidazoline-type amphoteric surfactants, soybean

phospholipid, and yolk lecithin.

16) A cleaning composition comprising an aqueous solution having a cleaningly

effective amount of the composition of Claim 1 dissolved therein. 17) The cleaning composition of claim 16, wherein the solution is selected from the group consisting of hair shampoos, baby shampoos, body shampoos, bubble

baths, bar soaps, bath gels, hair conditioning gels, skin creams and lotions, skin contacting cosmetics, make up removal creams and lotions, liquid detergents, dish detergents, liquid soaps, bleach activators, bleach stabilizers

and the like

18) A method for the preparation of a novel gemini surfactant containing two hydrophilic and two hydrophobic chains connected by a carbonyl containing bridge wherein said hydrophilic chains are comprised of the same or different sugar moieties, said method comprising

a) aminating said sugar moiety with an amine comprising a C₆- C₂₃ straight, branched, substituted or unsubstituted alkyl, aryl or alkylaryl in the presence of DMS0₄ at elevated temperature and b) condensing two of said aminated sugar moieties in the

presence of phthaloyl chloride

19) The method of claim 18 wherein said sugar moiety is selected from the

group consisting essentially of monosacchaπdes, disacchaπdes,

polysacchandes, and mixtures thereof

20) The method of claim 19 wherein said monosacchaπde is selected from the

group consisting essentially of glyceraldehyde, erythrose, threose, πbose,

arabinose, xylose, fructose, lyxose, allose, altrose, glucose, mannose, gulose,

idose, galactose, talose and mixtures thereof 21 ) The method of claim 20 wherein said disaccharide is selected from the group consisting essentially of lactose, maltose, sucrose, cellobiose, gentibiose and mixtures thereof.

22) The method of claim 21 wherein said polysaccharide is selected from the

group consisting essentially of amylose, amylopectin, trehalose and mixtures thereof.