ZA200105408B

ZA200105408B - Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants.

Info

Publication number: ZA200105408B
Application number: ZA200105408A
Authority: ZA
Inventors: Stanley B Mirviss; Peter J Spellane; Dale Steichen; Hee Cho
Original assignee: Akzo Nobel Nv
Priority date: 1998-12-31
Filing date: 2001-06-29
Publication date: 2002-09-30
Also published as: CN1346395A; EP1147158A1; CA2357756A1; KR20010101352A; JP2003505339A; BR9916711A; HK1043383A1; CN1227321C; AU2399500A; AU771929B2; WO2000039241A1

Description

. FE

Cationic Gemini and Related Multiple Hydrophilic/Hydrophobic Functional

Compounds and Their Use As Surfactants

Field of invention

The present invention generally relates to improved multiple hydrophilic/hydrophobic functional quaternary ammonium compounds "multiple functional” surfactants, useful in detergents and personal care, mining, industrial, and catalyst products, in biocidal compositions at higher concentrations, and as emulsifiers.

Background of The Invention

Conventional surfactants have one hydrophilic group and one hydrophobic group. Dimeric surfactants which are commonly called “Gemini” surfactants are those which comprise two hydrophilic functional groups and two hydrophobic functional groups. Gemini surfactants have unique physical properties resulting from constraint of two hydrophilic groups in close proximity and the consequent micellar properties, which has led to an intensive study of Gemini surfactants as detergents, softeners, emulsifiers, phase transfer catalysts, biocides, and as components in skin care lotions, hair conditioning compositions and cosmetics compositions. Their use is also being investigated in ore flotation, oil well drilling and in other industrial applications.

It is therefore an object of the present invention to provide a novel class of cationic multiple functional surfactants that have application in the treatment of textile fibers to provide softeners and static control.

It is also an object to provide a class of multiple functional surfactants having improved detergency at extremely low concentrations, while at the same time being highly biodegradable.

It is also an object of the present invention to provide a class of multiple functional surfactants which are useful as emulsifiers, phase transfer catalysts, biocides, in ore flotation, in oil well drilling and in other related applications.

Finally, it is an object of the invention to provide a class of multiple functional surfactants which are useful in skin care lotions, hair conditioning compositions and cosmetics compositions at low concentrations.

These and other objectives are realized by the compositions and methods of the present invention.

Summary of the Invention

The present invention generally relates to several new classes of ] cationic muitiple functional surfactants and to compositions containing same. The invention also relates to various processes for preparing the multiple functional surfactants of the present invention.

Detailed Description of The Present Invention ~The present invention generally relates to muttiple functional surfactants of the formulae I-IV, below, to compositions containing same and to methods for their preparation. The beneficial features of the multiple functional surfactants of the present invention derive from their multiple functional character, i.e., the chemical species of the present invention contain two or more hydrophobic groups and two or more hydrophilic groups in each molecule.

W000/39241 PCT/US99/31246 t

I Multiple functional quaternary ammonium compounds containin r or amide spacer aro of the general formula:

S R, R, (

R, —N— (A),— N'—R,

Rs Rs 2Z wherein R, and R, are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C,, alkyl or alkenyl groups wherein said alky! or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof;

Ry, R.. Rs,and Rq are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C,, alkyl or alkenyl ' groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof; and A is a ’ spacer selected from the group consisting of : oO 0 O ll | ll (CH;),—C —0 —(CH,),, (CH,),-0-C —(CH,),- C-O-(CH,), , 0 0 ll ll (CH, CH,0),-C —- (CH,), - C -( OCH,CH,), , 0) oO 0) ll ll I (CH;), N = C -(CH,), - C-N-(CH,), , (CH,),—C- N (CH,), 0 0]

Il ll (CH,CH,CH,N),- C-(CH,),-C(NCH,CH,CH,), or other ester - or amide-functional alkyl groups in the spacer,

wherein each of x, y and z can independently be an integer of 1-20: and n is an integer of from 1-20; il Multiple functional quaternary ammonium compounds with ester or amide spacer group(s) of the general formula:

Rs R, Rio (th

R; — N° — (A), — N® — (A), — N® — Rie !

Ris Ri. Ris 3Z wherein R.. R; \R;, R,, R,,. R,, .R,,, and R,, are the same or different and are selected from straight or branched chain, substituted or unsubstituted

C,-C.; alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof, and A is a spacer group as defined above. and wherein x y and z are each independently an integer of 1-20; and n is an integer of from 1-20: or

II. Asymmetric multiple functional quaternary ammonium compounds:

Ris Rs (1)

Ris— N'— (CH,), — N'— Ry,

Rus Rug 2Z wherein R,, and R,, are different and are selected from straight or branched chain, substituted or unsubstituted C,-C,, alkyl! or alkenyl groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof; R,q, R,,, R,s

© yo 0039241 PCT/US99/31246 and R,, are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C,, alkyl or alkeny! groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof: and n is an integer of from 1-20.

IV. Symmetric “gemini” quaternary ammonium compounds prepared in the reaction of alkyl multiple amine compounds with long chain aldehyde or alcohols of the general formula IV

R, Rs R,. -

R,— | (CH,), — i (CH,), — 0 — Rs

Ros R,, Ry n (2+n)Z- Iv wherein R,,, R,,, Ry, Rui Rus, Rye, R,7, and R,, are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C,-C,, alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage or mixtures thereof, and where x an y are each independently an integer of from 1-20 and n is an integer from 0-20; wherein in each of |, Il, lll and IV, Z is an anion.

In each of formulae I-1ll, above, R,, R,, R,, R,,, R,; and R,, are preferably selected from C,-C,, alkyl groups, optionally containing an ester linkage. tis also preferred that x, y and z are 0-5 and that n is 1- 10.

In formula IV above R,, and R,; are preferably selected from 2- ethylhexyl. nonyl-alkyl, or a C,,-C,; mixed alky! group, and R,,, R,,, Ry.

Ras Ry Ror. @and Ry independently selected from methyl, ethyl. or propyl, and n=20.1, or 2.

Concerning the multiple functional quaternary ammonium compounds of formula I, it is preferred that R, and R, be selected from 2- ethylhexyl, nonyl-alkyl, a C,, — C. mixed alkyl group, or from the group 5S consisting of dodecylalkyl, hexadecylalkyl, octadecylalky!, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated taliowalky! ; that R,, R,,

Rs and R, be independently selected from methyl, ethyl, propyl, 2- ethylhexyl, nonyl-alkyl, or a C,, - C,, mixed alkyl group; and that n be an integer of from 1 to 5.

In the multiple functional quaternary ammonium compounds of formula II, it is preferred that each of R; Rg Rg, Ry, Ry), Ry, Ry, and R.. are independently selected from from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C,; — C,; mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalky!, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl!, or hydrogenated tallowalky; and that n be an . integer of from 1 to 5.

Finally, it 1s preferred that, in the asymmetrical muitiple functional quaternary ammonium compounds of formula MM, Ri; Ry Ry, Ry Ry .and R;, be selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a

Cys = C,; mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalky!, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalky or other long chain fragment with the proviso that the group of substituents on one N* be not identical to the group of substituents which surround the other N* center and that n is an integer of from 1 to 20.

The ester or amide containing multiple functional compounds of the present invention exhibit enhanced biodegradability which is extremely desirable for obvious environmental reasons. For example, enhanced biodegradability is a desired attribute in fabric softening

When used in a fabric softening composition, the compounds of the present invention are preferably delivered to the textile to be softened in amounts effective to impart the desired softness and/or anti-static properties to said textile(s). Said effective amount typically ranges in an amount of from about 0.5 to 3 grams of softening compound(s) per average load of laundry.

Delivery of the compounds of the present invention to the textile to be treated can be conducted by various means. For example, the. compounds of the present invention can be formulated into liquid softening compositions, solid formulations and/or solid articles. In a liquid formulation, the compounds of the present invention are dissolved and/or } suspended in water, wherein said formulation optionally also contains other conventional softeners as well as other ingredients and diluents } such as detergents, optical brighteners, viscosity aids, soil release i agents, fragrance, and the like, in the requisite amounts so to provide an effective amount of the compounds of the present invention to the textile to be treated.

With solid formulations, the multiple functional surfactants of the present invention are formed into small flowable particles or beads on a water-soluble carrier such as a solid detergent, which is optionally compounded with builders, brighteners, fragrance and the like.

Finally, the multiple functional surfactants of the present invention can be combined with a distribution agent and applied, or coated on a solid carrier such as a woven, or non-woven fabric or bonded polyester sheet. Alternatively, the composition can be inserted into a container designed for insertion into a clothes dryer.

The present invention also relates to various methods for the preparation of multiple functional surfactants. For example, the multiple functional surfactants of formula | which contain ester spacer groups can be prepared by reacting a dialkylaikanol amine of formula

Q,

Q, -N -Q,-OH wherein each of Q,,Q, and Q, is independently selected from the group consisting of C,-C,, alkyl groups and a dicarboxylic acid of the formuia

HOOC - (CH,), - COOH wherein n is an integer of from 1-12. to form a reaction mixture, or a diester of same, and thereafter quaternizing the reaction mixture.

The dialkylalkanol amine is preferably prepared by ethoxylating a fatty amine compound of the formula 7

Zz “

J N- H

Y

Wherein Z is a C,,-C,, substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a C,-C,, substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group.

Preferably, the fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenatedtallowalky! amine, dicocoalkylamine, ditallowalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine,and mixtures thereof.

The dicarboxylic acid employed is preferably selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof. The most preferred dicarboxylic acid is adipic acid. or mixed short chain di-acids which are commercially available from, for example, DuPont.

The multiple functional surfactants of formula | which contain an amine-functional spacer group can be prepared in the reaction of an N- alkylamino fatty amine compound

R-N(H)(CH,), NH, with a dicarboxylic acid or mixtures of dicarboxylic acids(or diesters of same).

The multiple functional quaternary ammonium compounds of

Formula IV can be prepared by reacting a bis-primary amine alkane (e.g., hexamethylenediamine) with two equivalents of aldehyde, e g., 2- * ethylhexanal, or other long chain aldehydes such as nonanal or mixed

C,;-C,; aldehydes (which are commercially available).

Other multiple functional quaternary ammonium surfactants of general Formuia IV of the present invention can be prepared by reaction of aliphatic triamines of formula:

H

HN-R- HR NH, wherein R is a saturated or unsaturated hydrocarbon group, with aldehyde, e.g., 2-ethylhexanal, or longer chain aldehyde such as nonanal or mixed C,,-C,; aldehydes (which are commercially available), or an alcohol. For example, tris-quaternary ammonium surfactants can be prepared by reaction of bis(hexamethylene) trimine with alkylaldehyde, such as 2-ethylhexanal, followed by methylation and quaternization.

The cationic gemini and related multiple functional hydrophilic/hydrophobic functional compounds of the present invention can be employed alone, or in combination with typical surfactants,

including mono-quaternary ammonium compounds. When employed in combination with mono-quaternary ammonium compounds, it has been found that as little as 5-10% of the compounds of the present invention can reduce the Critical Micelle Concentration (CMC) from 10 up to 100 fold. CMC is a measurement employed to determine the effectiveness of a surfactant composition. The lower the CMC values, the better the surfactant. Thus, by using small amounts of the surfactants of the present invention in combination with conventional surfactants, the addition rates of the conventional surfactants can be greatly reduced.

The present invention shall now be illustrated by the following non- miting examples.

Exampie 1 - Preparation of a Multiple Functional Quaternary Ammonium

Compound with Ester-functional Spacer Groups

CH, o

TOE J NR PN

EE (gi Er ) 28r- 0 CHy

Preparation of (CH. 1(CO,CH,CH NMe,}, from adipic acid and dimethylethanolamine in toluene «0 Procedure - A 1 L round bottom flask was charge with 14.6 g of adipic acid (1.00 mole), 196.0 g of dimethylethanolamine (2.20 mole - 10% excess), 300 mL toluene and 1.5 g of p-toluenesulfonic acid. The reaction mixture was heated to reflux with stirring. A Dean-Stark trap was attached to one neck of the 4-neck flask and to a water condenser. The reaction was heated at reflux for a total of 22 hours as 54.5 mL H,0 distilled. The product was stripped of solvent on a rotary evaporator at 80° C and 15 mm Hg. The product weighed 270.6 g. Infrared spectroscopy of product indicated only the ester.

Reaction of (CH,),(CO,CH,CH,NMe,), with hexadecy! bromide

Procedure - A 1 L Morton flask was charged with 57.6 g of (CH,),(CO,CH,CH,NMe,), (0.2 mole) and 300 mL of monoglyme. 122.0 g

C,¢H;;Br (0.4 mole) were added with stirring. The mixture was heated to 85° C with stirring under an N, atmosphere and maintained for 73 hours. 9 No solid was evident at the conclusion of heating but did form on standing over several days. The total product was suction filtered and the beige solid was sucked dry. It was then washed twice with diethylether and again sucked dry, then let stand in a crystallization dish overnight. The solid product weighed 135.5 g (theoretical yield: 179.6 g). Another 30.8 g solid product was reclaimed from the filtrate for an overall yield of 92.6%.

NMR analysis of product indicated 80 mole % purity of diquaternary compound, 14 mole % mono-quaternary and 6 mo! % mono-quaternary- monoacid product.

A composition was prepared comprising 90% Arquad® 12 (available from Akzo Nobel Chemicals Inc., Chicago, IL) and 10% of the ) compound of example 1. This composition exhibited a 50 fold reduction of CMC values compared to a composition comprising 100% Arquad® 12.

Example 2 — Preparation of Multiple Functional Quaternary Ammonium

Compound in Reaction of Aldehyde with Alkyl-diamine: reaction of 1.6- hexanediamine with mixed C,,/C,, aldehyde. followed by reduction methylation, and quaternization

Summary:

HoN(CH;)¢NH,; + 2 RCHO ——» RCH=N(CH,){N=CHR sodium borohydride oh

RCHN(CH,)¢NCH1R Methylation RCH;NH(CH,)NHCH,R

CH;Cl

RCHO = CI13-Cl15 aldehyde

CH; CH,

H +

RCH;N(CH,),NCH,R én, dy, 207

1. Reaction of 1,6-hexanediamine with mixed C,./C,, aldehyde. The mixed aldehyde was used as obtained from Celanese Ltd.

Chemicals Division (Dallas, TX); the average molecular weight was estimated to be 211. The aldehyde mixture (400 g., 1.89 moles) was added in portions to melted 1,6-hexanediamine (107 g., 0.92 mole). The reaction was exothermic and was therefore cooled occasionally. The product was washed with water; after solvent was removed by evaporation, a oily yellow liquid (428 g.) was obtained. 2. Sodium borohydride (32 g.) was added as powder to a solution of the bis-imine compound (404 g., product in 1 above). The reduction reaction was followed by observing disappearance of the imine carbon's *C NMR. The reaction mixture was washed thoroughiy with water before solvent was removed by evaporation.

The product was a pale yellow liquid (400 g.) : 3. Methylation of the bis-secondary-amine by Eschweiler-Clarke procedure (see aiso Leukhart Reaction, Organic Reactions,

Volume 5, p. 323). To the bis-sec-amine (360 g., 0.71 mole) 80% formic acid was added slowly, forming a light brown solution as the reaction temperature increased to 75° C and then cooled to 50-60°

C. The 37% formaldehyde (66 g., 0.814 mole) was slowly added as CO, gas evolved. The mixture was heated until gas evolution ceased. Ca. 80 g. of concentrated HCI was added, and the formic acid and any excess formaldehyde were removed at 65° C on a rotary evaporator. The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 g.). The product was washed with water and dried. A pale yellow liquid (440 g.) was obtained and identified as the bis-tertiary amine.

© WO 00/39241 PCT/US99/31246 4. Quaternization of the bis-tertiary amine compound prepared in 3 above. In a 1-liter titanium autoclave, a solution of bis-tertiary- amine in methanol (150 g) with sodium bicarbonate was purged with nitrogen and heated with methyl chloride at about 80°C until all amine had been consumed (in about 10 hours). Filtration and evaporation yielded a brownish yellow thick paste (215 g.) that was identified as the bis-quaternary ammonium compound.

Example 3 - Preparation of Asymmetric Multiple Functional Quaternary

Ammonium Surfactant Compounds

Asymmetric dimeric- or higher oligomeric surfactant compounds are prepared from Duomeen®, Triameen®, and Tetrameen® compounds available from Akzo Nobel Chemicals Inc., Chicago, IL, using an amine- aldehyde condensation reaction.

Cy no

R—N N—H R—N N—ethyhexyl ~~ + 2-ethylhexanal > => ~

Duomeen where R = coco-, tallow-, or oleylalkyl vo

R—N N—ethyhexyl

NN + methylation, quaternization >

CH, CH,

R—N N'—ethyhexy

ITN

CH, CH, 2Br-

Example 4 — Preparation of Multiple Functional Quaternary Ammonium

Compound in the reaction of bis(hexamethylene)triamine with mixed

C.JC,s aldehyde, followed by reduction. methylation, and quaternization

1 The mixed aldehydes were added in portions to melted bis(hexamethylene)triamine; and the exothermic reaction was cooled.

The reaction mixture was washed with water, then solvent removed by evaporation to yield the bis-imine mono -secondary amine compound, a pale yellow liquid.

2. Reduction of the bis-imine-mono-sec-amine compound with sodium borohydride.

The bis-imine compound (283 g.) prepared in 1 above was dissolved in 150 g. methanol To this 25 g. sodium borohydride was added in small portions until the reduction was complete.

The reduction reaction was followed by observing disappearance of the imine carbon’s °C NMR.

The reaction mixture was washed thoroughly with water before solvent was removed by evaporation.

The product was a pale yellow liquid

(247 g.)

3 Methylation of the tris-secondary amine compound prepared in 2 above.

The tris sec amine compound (245.6 g., 1.17 mole). To this solution, formic acid was added slowly, forming a light brown solution as the reaction temperature increased to 75° C and was then cooled to 50-60° C.

The 37% formaldehyde (66 g., 0.814

- mole) was slowly added as CO, gas evolved.

The mixture was heated until gas evolution ceased.

Ca. 80 g. of concentrated HCI was added, and the formic acid and any excess formaldehyde were removed at 65° C on a rotary evaporator.

The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 g.). The product was washed with water and dried.

A pale yellow liquid (247 g.) was obtained and identified as the tris-tertiary amine.

4 Quaternization of the tris-tertiary amine compound. The tris-tert- amine prepared in 3 above was quaternized in a procedure like those described elsewhere in this application. In a 1-liter titanium autoclave, a solution of tris-tertiary-amine in methanol (155 g. compound in 1560 g. methanol) with sodium bicarbonate was purged with nitrogen and heated with methyl chloride at about 80°C until all amine had been consumed (in about 10 hours).

Filtration and evaporation yielded a brownish yellow thick paste (210 g.).

Example 5 - Preparation of Amido-Bridged Multiple Functional Quaternary

Ammonium Surfactant Compounds

Dimeric - or higher multiple functional surfactant compounds with amide groups in the spacer groups are prepared from Duomeen®, Triameen®, and Tetrameen® compounds from Akzo Nobel Chemicals, inc. in the } following manner: no

R—N N—H 2 NTN + dicarboxylic acid to form the bis-amido compound => followed by methylation, and then quaternization where R = coco-, tallow-, or oleylalkyl

CHs H 0

R—N* N i

CH

0 2X- H CHy

R = coco-, tallow-, or oleylalkyl

Example 6 -- Preparation of Multiple Functional Quaternary Ammonium

Surfactant Compounds With Ester-Groups in the Spacer from Ethoxylated

Fatty Amine Compounds

Various mono- and di-alkyl fatty amine compounds are available from

Akzo Nobel Chemicals, Inc. and are useful as starting materials. The following route to a di-ester linked multiple functional quaternary ammonium compound can usefully be employed.

Cocoalkyl—N + CH20CH2 _— Cocoalkyl—N

Me Ethylene oxide Me

OH

2 cocosbyi—N— COOH condensation methylation

Me

Me 0

C tkyl IN Hono i 0COa - ~. i" NE Cocoalky!

Me i 0] Me

Example 7 Reaction of Ethoxylated Armeen 2HT with Succinic Acid

Followed by Quaternization

Ethoxylation of dialkylamine, followed by reaction with dicarboxylic acid and methylation, will vieid the bis-ester-spaced bis{methyldialklyammmonium) compound. 1. Ethoxyiation of Armeen 2HT

In a 1-liter autoclave, Armeen 2HT (234.7 g, 0.5 mole) was dissolved in isopropyl alcohol (80 g) by heating. After nitrogen purging, ethylene oxide (22g, 0.5 mole) was introduced. The mixture was heated at 80°C for two hours. The *C NMR indicated that the reaction was good except that some starting amine remained unreacted (HN-CH,- at 50.24 ppm).

Additional 11 g of ethylene oxide was added, and the heating at 80°C continued for two more hours. After evaporation, a white solid paste (250 g) was obtained. The product, ethoxylated Armeen 2HT, consisted of monoethoxylated amine, 71.3 mole %; polyethoxylated amine, 26.0 mole % with n= 2.7; and unreacted amine, 2.7 mole %.

Claims

WE CLAIM:

i 1. A compound of general formula I, Il or II: R, R, (h R,—N—(A),—N"—R, Rs Re 2Z Re R, Rio (i) R, —N® — (A),—N°®— (A),— N®* — R, Ry, Ry, Ri, 3z Ris Ris (tn) ) + + Ris — N— (CH,)— N —Ry wherein each of R, through R,, are independently selected from straight or branched chain, substituted or unsubstituted C,-C,, alkyl or alkenyl groups, wherein said alky! or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof: A is a spacer group of the formula: Oo O Oo ll Il ll (CHy),—C — 0 —(CH,),, (CH,,-0-C- (CH,), = C-O-(CH,), , 40

0) O ll Il (CH, CH,0), -C = (CH,), - C -( OCH,CH,), Oo 0) Oo ll ll i (CH), N — C -(CH,), = C-N-(CH,),, (CH,),-C-N-(CH,), Oo 0) Il ll (CH,CH,CH,N),C-(CH,),C-(NCH,CH,CH,), or other ester- or amide-functional alkyl group, where x, y and z are each independently selected from an integer of from 1 to 20 and wherein in each of formulae |, Il and Ill, Z is an anion, with the proviso that R,sand Rare not the same.

2. The compound of claim 1 wherein that R,, R, ,R,, R,, R,,, and R,, are each independently selected from the group consisting of C,,-C,; alkyl groups, C,, — C,s alkyl groups containing an ester linkage and C,, — Cis alkyl groups containing an amide linking group.

3. The compound of claim 1 wherein each of R, , R, ,R,, R..Rs, and Rsare selected from the group consisting of methyl, ethyl, propyl, 2- ethylhexyl, nonyl-alkyl, C,, — C,; mixed alkyl group, dodecylaikyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalky!, hydrogenatedtallowalkyl and mixtures thereof; and n is an integer of from 1to 5. 4 The compound of claim 1 wherein each of R, , Ry R,, R,,, R,, Ri, R,;and R,, are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethythexyl, nonyl-alkyl, a C,, — C,; mixed alky! group, dodecylalkyl, octadecylalkyl, oleylalky!, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and mixtures thereof ; and that n is an integer of from 1 to 5.

5. The compound of claim 1 wherein each of R,; ,R,s, Ry7, Rip ,Rg and R,, is independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C,, — C,5; mixed alkyl group, dodecylalkyl, octadecylalky!, oleylalkyl, cocoalky!, soyaalkyl, tallowalkyl, hydrogenated tallowalkyl and mixtures thereof with the proviso that R,; is not the same as Ry; and nis an integer of from 1-20.

8. A surfactant composition which comprises at least one of the compounds of claim 1.

7. A process for preparing the multiple functional quaternary ammonium compounds of general Formula | which comprises reacting a dialkylalkanol amine of formula Q [ Q, -N -Q;-OH : wherein each of Q;, Q, and Q; is independently selected from the group consisting of C,-C,, aikyi groups and a dicarboxyiic acid of the formuia HOOC — (CH), —- COOH wherein nis an integer of from 1-10, to form a reaction mixture and thereafter quaternizing the reaction mixture.

8. The process of claim 7 wherein said dialkylalkanol amine is prepared by ethoxylating a fatty amine compound of the formula “\ N-H y 7 wherein Z is a C,,-C,, substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a C,-C,, substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group. : 26 SUBSTITUTE SHEET (RULE 26)

9. The process of claim 8 wherein said fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenatedtallowalkyl amine, dicocoalkylamine, ditallowalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine,and mixtures thereof, and the quaternizing agentis a methylating agent.

10. The process of claim 7 wherein the dialkylalkanol amine is selected from the group consisting of dimethylethanolamine, diethylethanol amine, and mixtures thereof: and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof, and the quaternizing agent is a long chain alkylhalide reagent.

11. The process of claim 10 wherein the dialkylalkanolamine is dimethylethanolamine and the dicarboxylic acid is adipic acid.

12. A process for preparing multiple functional hydrophilic/hydrophobic compounds which comprises reacting a diamine of the formula: Z~NH-(CH,),-NH, or a triamine or tetramine of the formula: Z - NH — (CH,CH,CH,NH),, CH,CH,CH,NH, where Z is a C, — C,, saturated or unsaturated alkyl group and mis 1 or 2, with a dicarboxylic acid of the formula: HOOC - (CH,), — COOH wherein n is an integer of from 1-10.

13. The process of claim 12 wherein Z is selected from cocoalkyl, tallow alkyl, or oleylalkyl, and the dicarboxylic acid is selected from the group consisting of oxalic. malonie, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof.

14. The process of claim 13 wherein the amine is selected from the S group consisting of N-coco 1,3 — diaminopropane, N-tallow —1,3 diaminopropane, N,N,N’ — trimethyl-N-tallow-1,3 diaminopropane, N-oleyl- 1,3 diaminopropane, 3 —tallowalkyl-1,3-hexahydropyrimidine, N- tallowalky! dipropylene triamine, N-tallowalky! tripropylene tetramine and mixtures thereof, and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof.

15. The compound of claim 1 wherein R,s and R,, are each independently selected from the group consisting of C,,-C,, alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonylalkyl, and C.5-C,s mixed aikyl group, dodecylalkyl, octadecylalkyl, oleylalkyi, cocoalkyl, soyaalky!, : tallowalky!, hydrogenatedtallowalkyl and C,,-C,s alky! groups containing an ester or amide function ; and n is an integer of from 2 to 3. :

16. The compound of claim 1 wherein Rie, Riz, Rig, Ry are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyi-alky!l, and a C,,-C,, mixed alkyl group: and n is an integer of from 2 to 3.

17. Aviscosity modifying agent comprising the compound of claim 15.

18. A viscosity modifying agent comprising the compound of claim 16.

18. The compound of claim 1 wherein R,, and R,, are each independently selected from the group consisting of C,,-C,, alkyl groups, methyl, ethyl, propyl, 2-ethylhexy!, nonyl-alkyl, and a C,,-C,, mixed alky!

group and C,,-C,, alkyl groups containing an ester or amide function: and nis an integer of from 5 to 8.

20. The compound of claim 1 wherein R,,, R,,. R,s, R;, are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C,,-C,; mixed alkyl group; and n is an integer of from 5 to 8.

21. The compound of claim 1 wherein R,; and R,, are each independently selected from the group consisting of C,,-C,, alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C,,-C,, mixed alkyl group and C,,-C,, alkyl groups containing an ester or amide function, and n is an integer of from 2 to 20.

22. An ore flotation aid comprising the compound of claim 21.

23. The ore flotation aid of claim 22 wherein in said compound R,s and R,, are each independently selected from the group consisting of C,,-Cye alkyl groups, and C,,-C,, alkenyl groups, and C,,-C,, alkyl groups containing an ester or amide function; Rs, R,;, R,s, R,, are methyl groups; and n is an integer of from 2 to 12.

24. A calcium ore flotation aid comprising the compound of claim 23.

25. A process for the preparation of compounds of general formula IV i fa Fa + * Ry—N— (CH,),— N= (CH,), — NR, R, Ra Rae n (2+n)Z- (IV)

wherein R;.. Ry. Ry. Ry. Ry, Ry, R,;, and R,, are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C,-C,, alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at ieast one ester linkage, at least one amide S linkage or mixtures thereof and where x an y are each independently an integer of from 1-20, n is1-20 and Z is an anion, said process comprising the reaction of a polyaminoalky! compound with multiple equivalents of alkyl or alkenyl aldehyde or alcohol compounds.

26. The process of claim 25 wherein the diaminoalkyl compound is a compound of the formula: H,N-(CH,),-NH, and the aldehyde or alcohol compound is selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyi, nonyl-alkyl, C,,-C,, mixed alkyl groups and mixtures thereof and n is an integer of from 1 to 5.

27. The process of claim 25 wherein the diaminoalky! compound is hexamethylenediamine. :

28. A compound of formula IV R, Ras Ras K 4 * Ry—N—(CH,), —N'—+ (CH,), —N—R,, (2+n)Z- Rag Ry; Rus n Iv wherein R,,, R,,, R,5, Ry, Rus, Ry, Ryy, and Ry, are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C,-C,, alkyl or alkenyl! groups, wherein said alkyl or alkenyl

PCT/US99/31246 groups optionally contain at least one ester linkage, at least one amide linkage or mixtures thereof, and where x an y are each independently an integer of from 1-20, n is greater than 1 and Z is an anion.

29. A surfactant composition which comprises at least one compound of claim 1 in combination with at least one conventional surfactant.

30. The composition of claim 29 wherein said conventional surfactant is a mono- quaternary ammonium compound.

31. A surfactant composition which comprises at least one compound of claim 28 in combination with at least one conventional surfactant.

32. The composition of claim 31 wherein said conventional surfactant is a mono- quaternary ammonium compound.

33. A compound according to claim 1 or claim 28, substantially as herein described and illustrated.

34. A composition according to claim 6 or claim 29 or claim 31, substantially as herein described and illustrated.

35. A process according to claim 7 or claim 12 or claim 25, substantially as herein described and illustrated.

36. An agent according to claim 17 or claim 18, substantially as herein described and illustrated. 31 AMENDED SHEET

' [J PCT/US99/31246

37. A flotation aid according to claim 22 or claim 24, substantially as herein described and illustrated.

38. A new compound, a new composition, a new process for preparing compounds, a new agent, or a new aid, substantially as herein described. 32 AMENDED SHEET