AU771929B2

AU771929B2 - Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants

Info

Publication number: AU771929B2
Application number: AU23995/00A
Authority: AU
Inventors: Hee Cho; Stanley B. Mirviss; Peter J. Spellane; Dale Steichen
Original assignee: Akzo Nobel NV
Current assignee: Akzo Nobel NV
Priority date: 1998-12-31
Filing date: 1999-12-30
Publication date: 2004-04-08
Anticipated expiration: 2019-12-30
Also published as: CN1346395A; EP1147158A1; CA2357756A1; KR20010101352A; JP2003505339A; BR9916711A; HK1043383A1; CN1227321C; ZA200105408B; AU2399500A; WO2000039241A1

Description

1 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.

.eee°.

S. Advantageously, one or more embodiments of the present invention may provide a novel class of cationic multiple functional surfactants that have application in the treatment of textile fibers to provide softeners and static control.

Further advantageously, one or more embodiments of the present invention S:may provide a class of multiple functional surfactants having improved detergency at extremely low concentrations, while at the same time being highly biodegradable.

Even further advantageously, one or more embodiments of the present invention now provide a class of multiple functional surfactants which are useful H:\marieag\Keep\Speci\23995-OO.doc 20/11/03 2 as emulsifiers, phase transfer catalysts, biocides, in ore flotation, in oil well drilling and in other related applications.

Finally, one or more embodiments of the invention may provide a class of multiple functional surfactants which are useful in skin care lotions, hair conditioning compositions and cosmetics compositions at low concentrations.

The above may be 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 multiple 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 multiple 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, the chemical species of the represent invention contain two or more hydrophobic 25 groups and two or more hydrophilic groups in each molecule.

a *eooo H:\marieag\Keep\Speci\23995-00.doc 20/11/03 ACR 6100 R 3 I. Multiple functional quaternary ammonium compounds containing ester or amide spacer group(s) of the general formula:

R

3 R (I) I I R, N R 2 I I Rs R6 2Zwherein R, and R 2 are the same or different and are selected from straight or branched chain, substituted or unsubstituted C1-C22 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 3

R

4 Rs,and R, are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C22 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 20 consisting of: CH -0+CH 2

CH

2 C-O CH2 C-O+CH 2 0 el leO° I l 1 r i1r1r

[CH

2 N-CII CH4Y I--N CH 2

CH

2 2Xc--N+CH ]y O O [CH CH 2

CH

2 N C +CH2-- y +NCH 2

CH

2

CH

2 2z and other ester or amide-functional alkyl groups in the spacer, ACR 6100 R wherein each of x, y and z can independently be an integer of 1-20; and n is an integer of from 1-20; II. Multiple functional quaternary ammonium compounds with ester or amide soacer arouo(s) of the aeneral formula: wherein R 7

R

8 Rio R 1

R

12

,R

3 and R 14 are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C22 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 III. Asymmetric multiple functional quaternary ammonium compounds:

R

15

(CH

2

R

20 wherein R1 5 and R 20 are different and are selected from straight or branched chain, substituted or unsubstituted C8-C22 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 16

R

1 7

R

1 and are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C22 alkyl or alkenyl groups wherein said alkyl or alkenyl groups ACR 6100 R 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,1 R 23

R

24

R

2 N- (CH 2

(CH

2 y N- R 2 R28 R 27 R26 n (IV) wherein R 21

R

2 2

R

23

R

2 4

R

25

R

2 6

R

2 7 and R 2 8 are the same or different and Sare selected from straight or branched chain, substituted, or unsubstituted C,-

A

'C22 alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage or mixtures 20 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 I, II, III and IV, Z' is an anion.

A

i In each of formulae I-III, above, R 2

R

7

R

14

R

15 and R 20 are preferably selected from C3-C,, alkyl groups, optionally containing an ester linkage. It is also preferred that x, y and z are 0-5 and that n is 1-10.

In formula IV above R 21 and R 25 are preferably selected from 2-ethylhexyl, nonyl-alkyl, or a C,3-Ci mixed alkyl group, and R 22

R

23

R

24

R

25

R

2 6

R

27 and R 28 independently selected from methyl, ethyl, or propyl, and n 0,1, or 2.

ACR 6100 R 6 'Concerning the multiple functional quaternary ammonium compounds of formula I, it is preferred that R, and R 2 be selected from 2-ethylhexyl, nonylalkyl, a C13 C15 mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalkyl that R 3

R

4 Rs and R, be independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, or a C,3 Cis mixed alkyl group; and that n be an integer of from 1 to In the multiple functional quaternary ammonium compounds of formula II, it is preferred that each of R 7

R

8

R

9 Ro, R 1

R

12

R

1 3 and R 14 are independently selected from from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C,3 C 1 mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalky; and that n be an integer of from 1 to 15 i Finally, it is preferred that, in the asymmetrical multiple functional quaternary ammonium compounds of formula III, R 5

R

16

R

17

R

18

R,

9 ,and R 20 be selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C,3 Cs mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalkyl, 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 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 compositions and in other uses where the content and volume of waste water effluent streams needs to be controlled.

ACR 6100 R 7 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 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 agents, fragrance, and the like, in the requisite amounts so to provide an effective amount of the compounds of the present invention to the

I

/Itextile 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 ACR 6100 R 8 of formula I which contain ester spacer groups can be prepared by reacting a dialkylalkanol amine of formula

Q,

I

Q

2

Q

3

-OH

wherein each of Q,,Q 2 and Q 3 is independently selected from the group consisting of C,-C22 alkyl groups and a dicarboxviic acid of the formula HOOC (CH 2

COOH

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

The dialkylalkanol amine is preferably prepared by ethoxylating a fatty amine I o compound of the formula 15 Z

H

Y

Wherein Z is a C12-C22 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a substituted or 20 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, hydrogenatedtallowalkyl 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.

ACR 6100 R 9 The multiple functional surfactants of formula I which contain an aminefunctional spacer group can be prepared in the reaction of an N-alkylamino fatty amine compound R-N(H)(CH 2 )n NH 2 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 hexamethylenediamine) with two equivalents of aldehyde, 2-ethylhexanal, or other long chain aldehydes such as nonanal or mixed C13-Cis aldehydes (which are commercially available).

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

H

Sformula

HN-R-N-R-NH

2 S"formula: 2 2 wherein R is a saturated or unsaturated hydrocarbon group, with aldehyde, 2-ethylhexanal, or longer chain aldehyde such as nonanal or mixed C,3-Ci aldehydes (which are commercially available), or an alcohol. For example, trisquaternary ammonium surfactants can be prepared by reaction of bis(hexamethylene) triamine with alkylaldehyde, such as 2-ethylhexanal, 20 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 up to 100 fold. CMC is a measurement employed to determine the effectiveness of a surfactant composition. The lower the CMC values, the ACR 6100 R 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-limiting examples.

Example 1 Preparation of a Multiple Functional Quaternary Ammonium Compound with Ester-functional Spacer Groups

O

CH

3

CH

3 H33C1- N-CisH33 CH3 I 0 UOH 3 10 2Br- 0 CH 3 Preparation of (CH 2

,(CO

2

CH

2

CH

2 NMe 2 from adipic acid and ,dimethlethanolamine in toluene 15 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 2 0 distilled. The product was stripped of solvent on a rotary evaporator at 800 C and 15 mm Hg. The product weighed 270.6 g. Infrared spectroscopy of product indicated only the ester.

Reaction of (CH, 2

)(COH

2 CH, NMe, 2 with hexadecvl bromide Procedure A 1 L Morton flask was charged with 57.6 g of

(CH

2 4

(CO

2

CH

2

CH

2 NMe 2 2 (0.2 mole) and 300 mL of monoglyme. 122.0 g

C

16

H

33 Br (0.4 mole) were added with stirring. The mixture was heated to 850 C with stirring under an N 2 atmosphere and maintained for 73 hours. No solid ACR 6100 R 11 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 Another 30.8 g solid product was reclaimed from the filtrate for an overall yield of 92.6%. NMR analysis of product indicated mole purity of diquaternary compound, 14 mole mono-quaternary and 6 mol 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 15 Compound in Reaction of Aldehyde with Alkyl-diamine: reaction of 1,6hexanediamine with mixed C 1 aldehyde, followed by reduction, methylation, and quaternization o.

.:**Summary:

H

2

N(CH

2 6

NH

2 2 RCHO RCH=N(CH 2 6

N=CHR

sodium borohydride

CH

3

CH

3 I I methylation

RCH

2 N(CH2)6 2R RCH2NH(CH 2 6

H

2 RC (C) 6

NHCH

2

R

CH

3

CI

C H 3C I RCHO C13-Cl5 aldehyde

CH

3

CH

3 1+ RCH2N(CH 2 6

NCH

2

R

H 3 2 cr ACR 6100 R 12 1. Reaction of 1,6-hexanediamine with mixed C,1/C,1 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 1.89 moles) was added in portions to melted 1,6-hexanediamine (107 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 was obtained.

2. Sodium borohydride (32 was added as powder to a solution of the bis-imine compound (404 product in 1 above). The reduction reaction was followed by observing disappearance of the imine carbon's 3C NMR. The reaction mixture was washed thoroughly with water before solvent was removed by evaporation. The product was a pale yellow 15 liquid (400 g.) 3. Methylation of the bis-secondary-amine by Eschweiler-Clarke procedure g.

(see also Leukhart Reaction, Organic Reactions, Volume 5, p. 323). To the bis-sec-amine (360 0.71 mole) 90% formic acid was added 20 slowly, forming a light brown solution as the reaction temperature increased to 750 C and then cooled to 50-600 C. The 37% formaldehyde (66 0.814 mole) was slowly added as CO2 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 650 C on a rotary evaporator. The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 The product was washed with water and dried. A pale yellow liquid (440 was obtained and identified as the bis-tertiary amine.

ACR 6100 R 13 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 800C until all amine had been consumed (in about 10 hours). Filtration and evaporation yielded a brownish yellow thick paste (215 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 15 Akzo Nobel Chemicals Inc., Chicago, IL, using an amine-aldehyde condensation reaction.

H H H H I I I I R-N N-cH 2-ethylhexanal R-N N-ethyhexyl Duomeen 20 where R coco-, tallow-, or oleylalkyl H H I I ,N-ethyhexyl methylation, quaternization -4

CH

3

CH

3 I+ I+ N-ethyhexyl

CH

3

CH

3 2Br- ACR 6100 R 14 Example 4 Preparation of Multiple Functional Quaternary Ammonium Compound in the reaction of bis(hexamethvlene)triamine with mixed C, 3

/C

1 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.

S: 2. Reduction of the bis-imine-mono-sec-amine compound with sodium borohydride. The bis-imine compound (283 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 15 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 1.17 mole). To this solution, formic acid was added slowly, forming a light brown solution as the reaction temperature increased to 750 C and was then cooled to 50-600 C. The 37% formaldehyde (66 0.814 mole) was slowly added as CO 2 gas evolved. The mixture was heated until gas evolution ceased. Ca.

g. of concentrated HCI was added, and the formic acid and any excess formaldehyde were removed at 650 C on a rotary evaporator.

The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 The product was washed with water and dried. A ACR 6100 R pale yellow liquid (247 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 150 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 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: H H 2 R-NN-H dicarboxylic acid to form the bis-amido compound followed by methylation, and then quaternization where R coco-, tallow-, or oleylalkyl ACR 6100 R

OH

3 H 0OH

O

3 0 2X- H OH 3 R coco-, tallow-, or oleylalkyl Example 6 Preparation of Multiple Functional Quaternary Ammonium Surfactant Compounds With Ester-Groups in the Spacer from Ethoxylated Fatt 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.

.00.

Cocoalkyl-N. OH200H2 Ethylene oxide Coco)alkyl-N-/

H

Me

OH

2 Cocoalkyl-N Me H 1I OOC" OOH_ condensation methylation Me 0 Cocoakyl-rN 0 IMe Me O N-Cocoalkyl 0 Me Example 7: Reaction of Ethoxylated Armeen 2HT with Succinic Acid, Followed by Quaternization ACR 6100 R 17 Ethoxylation of dialkylamine, followed by reaction with dicarboxylic acid and methylation, will yield the bis-ester-spaced bis(methyldialklyammmonium) compound.

1. Ethoxylation 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, 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 2 at 50.24 ppm). Additional 11 g of ethylene oxide I was added, and the heating at 800C 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 15 mole%.

i o ACR 6100 R 18 2. Reaction of Ethoxylated Armeen 2HT with Succinic Acid Under an atmosphere of nitrogen, a mixture of ethoxylated Armeen 2HT (172 g, 0.3 mole), succinic acid (17.84 g, 0.15 mole) and 50% aqueous hypophosphorous acid (0.74 g) was heated with stirring at 180-5°C for 5 hours.

An off-white thick paste was obtained. The product consisted of the desired diamine esters 90% and monoamines which accounted for 10% by weight.

3. Quaternization of Bis-(ethoxylated Armeen 2HT) Succinate Diester To a solution of bis-(ethoxylated Armeen 2HT) succinate (89 g, 0.14 equiv) in isopropyl alcohol (20 g) at 75-80 0 C, dimethyl sulfate (about 17 g, 0.135 mole) was slowly added. Free amine should be about 2% indicating substantial completion of quaternization. Evaporation yielded the neat ester diquaternary ammonium compound.

e 15 Example 8 PREPARATION OF BIS(2- ETHYLHEXYLDIMETHYLAMMONIUM)-1.6- HEXANE DI(CHLORIDE) VIA BIS(SCHIFF BASE) INTERMEDIATE Summary ee *°e ACR 6100 R 19 H H2N NH H'C--N N=CsHls NaBH4

H

H C N H17CaN-CaH 7 CH3CI

(III)

2 Cl- 2 0* 1. Reaction of 2-Ethylhexanal with 1,6-Hexanediamine 'To the melt 1,6-hexanediamine (58.1 g, 0.5 mole) at ca. 500 C, 2-ethylhexanal 5 (128.2 g, 1 mole) was slowly added with stirring over three hours. Cooling in an ice-water bath occasionally was necessary because the reaction was exothermic. The reaction was completed as indicated by the disappearance of the aldehyde carbon in the 3C NMR spectrum. The reaction product was washed several times with deionized water. Evaporation yielded a yellow liquid (ca 160 g) in nearly quantitative yield.

2. Reduction of Diimine with Sodium Borohvdride To a solution of the diimine (141.6 g, 0.38 mole) in methanol (150 g) sodium borohydride (ca 20 g)was added in small portions. During the addition, the reaction flask was cooled in an ice water bath from time to time. The reaction was completed as indicated by the disappearance of the imine carbon line at 168 ppm in the 13C NMR spectrum. The reaction mixture was washed with deionized water several times. Evaporation gave a yellowish liquid (ca 138 g).

ACR 6100 R 3. Methylation of N,N'-Di(2-ethylhexyl)-1,6-hexanediamine The addition of 90% formic acid with stirring to the diamine (I)l (126.3 g, 0.37 mole) yielded a light brown solution as the temperature rose to 750 C. Having been cooled to room temperature the mixture was treated with 37.1% formaldehyde solution (65.8 g, 0.814 mole) by adding the formaldehyde in small portions with stirring. The resulting mixture was evaporated on a rotary evaporator at ca 650 C for 2 hours. About 72 g of concentrated HCI was then added. The mixture was heated at 700 C for 3 hours and was then neutralized with 25% aqueous NaOH solution. The product was washed with water several times and evaporated to yield a pale yellow liquid (ca 150 g).

4. Quaternization of the di-tertiary-amine (111) with Methyl Chloride A solution of di(tertiary amine) (147.5 g, 0.4 mole) was quaternized with methyl chloride in the presence of sodium bicarbonate (1.5 at 800 C for about 15 hours. The reaction was completed as indicated by the disappearance of the ,'peak of the methyl carbon on nitrogen at 42.7 ppm in the 3C NMR spectrum.

The reaction mixture was filtered and the filtrate was evaporated to yield the desired diquaternary ammonium salt, a pale yellow paste (189 g).

Example 9 Preparation of bis(2-ethvlhexyldimethylammonium) (dimethylammonium) dihexane trichloride ACR 6100 R Summar

H

H H 0 2

H

Catalytic hyd rogeno-tion

MV

H

CH-N H CH reductive methylation -JD

(VI)

OH

3 quaternization with CH3CI OJ H 3 (VII)

OH

3

OH

3 IH O H 3

OH

3 301 CH 3

OH

3

(VIII)

1. Reaction of di(hexamethvlene)triamine with 2-Ethyihexanal Note that the "triamine" is actually a mixture of triamine and 1 ,6-hexanediamine.

NE (neutralization equivalent) of primary amine 96.46; NE(secondary amine) =341.76: 86% triamine, 14% diamine.

The mixture of "triamine" (101.4 g, 1.05 equivalents primary amine) and 2ethylhexanal (134.7g, 1.05 moles) was heated at 700 C for 4 hours. The crude product was washed with water and evaporated to yield the diimine (220 g).

ACR 6100 R 22 2. Reduction of the Diimine with Sodium Borohydride To a solution of 220 g dimine in methanol (220 g) was added in small portions sodium borohydride powder (20 g) until the reaction was complete as indicated by the disappearance of the imine carbon (168 ppm) in the 13C NMR spectrum. The product was washed with water and evaporated.

3. Methylation of Tris(secondarv amine) compound (VI) To compound VI was added with stirring 90% formic acid (149 g, 2.9 moles).

The temperature was maintained at 50-600 C with cooling. A 37.1% formaldehyde solution (104 g, 1.286 moles) was added in small portions. The resulting mixture was then evaporated on a rotary evaporator to remove the excess formic acid and formaldehyde. After the addition of concentrated HCI (1.4 mole), the mixture was heated at 70° C for 3 hours and was then neutralized with 25% aqueous NaOH solution. The product was separated, washed with water and evaporated. A pale yellow liquid (208 g) was obtained.

4. Quaternization of the Tris(tertiarv amine) Compound (VII) .:Compound VII (140 g, 0.3 mole) dissolved in methanol (140 with added NaHCO 3 was quaternized with methyl chloride at 800 C for 10 hours. The reaction was completed as indicated by disappearance of the methyl carbon

(CH

3 peak in the 13C NMR spectrum. Filtration and evaporation of solvent yielded a pale yellow solid (VIII) (ca. 185 g).

Example 10 Preparation of Multiple Functional Amidoamine Quaternary Ammonium Compounds: Reaction of Duomeen CD with dimethylsuccinate to form bis-Duomeen CD succinate fa bis(secondarv amido-secondarv amine) compound] 0 0 II II

RNHCH

2

CH

2

CH

2

NH

2

CH

3

OCCH

2

CH

2

COCH

3 a ACR 6100 R 23 0 0

RNH(CH

2 3

NHC(CH

2 2

CNH(CH

2 3 NHR, (XXI) 0 0 II I

RN(CH

2 3

NHC(CH

2 2

CNH(CH

2 3

NHR

I

C(CH

2

),CNH(CH

2 3

NHR,

RNH(CH2) 3 NH2, R Coco A mixture of Duomeen® CD (490.8 g, 2 equivalents of primary amine) and dimethyl succinate (136.08 g, 0.93 mole) was heated at 125-130°C under nitrogen for 5 hours. Additional dimethyl succinate (6.8 g, 0.046 mole) was added and the heating was continued for another 5 hours. The bis-Duomeen succinate (XXI), an off-white solid, was obtained. The product consisted of the bis-sec-amines (95% by weight) and unreacted Duomeen S 10 Methylation and quaternization of this bis-sec amine product can be performed in processes like those which have been described elsewhere in this application, to yield the bis(amido-amine) quaternary ammonium compound.

oo* ACR 6100 R 24 Example 11 Alternative Route to Multiple Functional "Internal ester" Quaternary Ammonium Compounds Step 1: Reaction of a primary fatty amine compound with formaldehyde will form the hexahydrotriazine intermediate;

RNH

2 3 HCHO hexahydrotriazine Step 2: hexahydrotriazine is reduced to form secondary amine; Hexahydrotriazine RNH(Me) Step 3: secondary amine is ethoyxlated to form alcohol amine compound; 10 RNH(Me) ethylene oxide RN(Me)CH 2

CH

2

OH

Step 4: two equivalents of ethoxylated amine react with dicarboxylic acid to form Gemini tertiary amine; 2 RN(Me)CH 2 CH20H HOOC(CH) 2 COOH RN(Me)CH 2

CH

2 0OC(CH 2 2 COOCHCH2N(Me)R Step 5: Gemini tertiary amine quaternized in reaction with methylating agent (methyl chloride or methylsulfate).

RN(Me)CH 2

CH

2 0OC(CH 2 2 COOCH2CHN(Me)R methylating agent Gemini "internal ester" quaternary ammonium compound Example 12 Preparation of Ester functional tris-quaternary ammonium Compound step 1 preparation of diesteramine

CH

3 N (CH 2 CHO2H) 2 excess HOOC (CH 2 4 COOH 0 CH3 0 HOOC--CH2C -O-CHCH- 2CH20- C-CH2 COOH

(I)

step 2 Ethoxylation of long chain amino compound (see Example 7, step 1)

OH

cocoalkyl--NcCHI cocoalkyl- NH CH 20

CH

2 3 II 25 step 3 Reaction of ethoxylated amine compound II with dicarboxylic acid I, (see Example 7, step 2) 1 2 II followed by reductive methylation

CH

3 0 0 CH 3 0 O CH 3 N+CH O-C+CH CH H -CHiHp- CI-14-^l 2 N cocoalkyl cocoalkyl step 4 quaternization of III (see Example 7, step 3) In the claims of this application and in the description of the invention, except where the context requires otherwise due to express language or necessary implication, the words "comprise" or variations such as "comprises" or "comprising" are used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention *i H: \rarieag\Keep\Speci\23995-OO.doc 25/11/03

Claims

1. A compound of general formula 1, 11, 111 or IV: R 3 R 4 R, A R Re R 7 N 4 (A)n Rq Rjo I" I N+ Wn N4 R14 J I R12 R13 R16 R 1 7 R 15 (CH 2 N -R 20 Rio R 19 (111) 2Z- (IV) R 2 (2+n)Z- R 21 R22 R 2 3 (CH 2 WN (C H 2 )y ER 2 8 R 27 n wherein each of R, through ER 2 8 are independently selected from straight or branched chain, substituted or unsubstituted C 1 -C 22 alkyl or alkenyl H-\marieag\Keep\Speci\239aO .doc 19/12/03 27 groups, wherein said alkyl 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: 0 0 0 [cH2 C-0 CH2y CH2+ 0 CH2-]c--O CH 0 0 [CH2-CH2O C +CH 2 O-CH -CH2 z 0 0 0 0 0 CH 2 CH 2 CH 2 N xC-H +CH2C-NCH 2 CH 2 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 n is an integer of from 1 to 20, and wherein in each of formulae I, II, III and IV, Z is an anion, with the proviso that R 15 and R 20 are different and are selected from straight or branched chain, substituted or unsubstituted C8-C22 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.

2. The compound of claim 1 wherein R1, R 2 R 7 R 14 R 15 and R 20 are each independently selected from the group consisting of C12-C18 alkyl groups, C12-C18 alkyl groups containing an ester linkage and C12-C18 alkyl groups containing an amide linking group.

3. The compound of claim 1 wherein each of R 21 and R 25 are selected S. 35 from the group consisting of 2-ethylhexyl, nonyl-alkyl, C13-C15 mixed alkyl group and mixtures thereof; R 22 R 23 R 24 R 25 R 26 R 27 and R 28 are independently selected from methyl, ethyl or propyl; and n 0, 1 or 2. H:\marieag\Keep\Speci\23995-00.doc 20/11/03 28

4. The compound of claim 1 wherein each of R 1 R 2 R 3 R 4 R 5 and R 6 are selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C13-C15 mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenated tallowalkyl and mixtures thereof; and n is an integer of from 1 to The compound of claim 1 wherein each of R 7 R 8 R 9 Rio, R 11 R 12 R 13 and R 14 are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13-C15 mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and mixtures thereof; and that n is an integer of from 1 to

6. The compound of claim 1 wherein each of R 15 R 16 R 1 7 R 18 R 1 9 and R 20 is independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13-C15 mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenated tallowalkyl and mixtures thereof with the proviso that R 15 is not the same as R 20 and n is an integer of from 1-20.

7. The compound of claim 1 wherein R 15 and R 20 are each independently selected from the group consisting of C12-C18 alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonylalkyl, and C13-C15 mixed alkyl group, 25 dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenated tallowalkyl and C12-C18 alkyl groups containing an ester or amide function; and n is an integer of from 2 to 3.

8. The compound of claim 1 wherein R 16 R 1 7 R 18 R 19 are independently 30 selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-Ci mixed alkyl group; and n is an integer of from 2 to 3.

9. The compound of claim 1 wherein R 15 and R 2 0 are each independently 35 selected from the group consisting of C1 2 -Cl8 alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-Cis mixed alkyl group and H:\marieag\Keep\Speci\23995-OO.doc 20/11/03 29 C12-C18 alkyl groups containing an ester or amide function; and n is an integer of from 2 to 20, preferably from 5 to 8. The compound of claim 1 wherein R 16 R1 7 R 18 R 19 are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-C18 mixed alkyl group; and n is an integer of from to 8.

11. An ore flotation aid comprising the compound of claim

12. The ore flotation aid of claim 11 wherein said compound R 1 5 and R 2 0 are each independently selected from the group consisting of C12-C18 alkyl groups, and C12-C18 alkenyl groups, and C12-C18 alkyl groups containing an ester or amide function; R 16 R 17 R 18 R 19 are methyl groups; and n is an integer of from 2 to 12.

13. A calcium ore flotation aid comprising the compound of claim 12.

14. A surfactant composition which comprises at least one of the compounds of claim 1. The surfactant composition of claim 14, which comprises at least one of the compounds of claim 1 in combination with at least one conventional surfactant.

16. The surfactant composition of claim 15, wherein said conventional surfactant is a mono-quaternary ammonium compound.

17. A viscosity modifying agent comprising the compound of claim 7 or the 30 compound of claim 8.

18. A process for preparing the multiple functional quaternary ammonium S* compounds of general Formula I which comprises reacting a dialkylalkanol amine of formula H:\marieag\Keep\Speci\23995-00.doc 20/11/03 30 Q, Q 2 -N Q 3 -OH wherein each of Q 1 Q 2 and Q 3 is independently selected from the group consisting of 01-C22 alkyl groups and a dicarboxylic acid of the formula HOOC (CH 2 )n COOH wherein n is an integer of from 1-10, to form a reaction mixture and thereafter quaternizing the reaction mixture.

19. The process of claim 18 wherein said dialkylalkanol amine is prepared by ethoxylating a fatty amine compound of the formula Z\ N-H Y wherein Z is a 012-022 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a 1-C22 S substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group. t The process of claim 19 wherein said fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenatedtallowalkyl amine, dicocoalkylamine, 30 ditallowalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine and mixtures thereof, and the quaternizing agent is a methylating agent.

21. The process of any one of claims 18 to 20 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, H:\marieag\Keep\Speci\23995-00.doc 25/11/03 31 adipic, maleic, fumaric and mixtures thereof, and the quaternizing agent is a long chain alkylhalide reagent.

22. The process of claim 21 wherein the dialkylalkanolamine is dimethylethanolamine and the dicarboxylic acid is adipic acid.

23. A process for preparing multiple functional hydrophilic/hydrophobic compounds which comprises reacting a diamine of the formula: Z- NH (CH 2 )n NH 2 or a triamine or tetramine of the formula: Z NH -(CH 2 CH 2 CH 2 NH)m CH 2 CH 2 CH 2 NH 2 where Z is a C, C22 saturated or unsaturated alkyl group and m is 1 or 2, with a dicarboxylic acid of the formula: HOOC (CH 2 )n COOH wherein n is an integer of from 1

24. The process of claim 23 wherein Z is selected from cocoalkyl, tallowalkyl, or oleylalkyl, and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof. The process of claim 24 wherein the amine is selected from the group consisting of N-coco 1,3 diaminopropane, N-tallow -1,3 diaminopropane, trimethyl-N-tallow-1,3 diaminopropane, N- 25 oleyl-1,3 diaminopropane, 3-tallowalkyl-1,3-hexahydropyrimidine, N- tallowalkyl dipropylene triamine, N-tallowalkyl 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.

26. A process for the preparation of compounds of general formula IV H:\marieag\Keep\Speci\23995-00.doc 20/11/03 32 R22 1 R23 R24 R 21 (CH2) (CH 2 y N R 2 I I I R28 R27 R26 S n (IV) wherein R 2 1 R 2 2 R 23 R 2 4 R 2 5 R 2 6 R 2 7 and R 28 are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C1-022 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 and y are each independently an integer of from 1-20, n is 1-20 and Z is an anion, said process comprising the reaction of a polyaminoalkyl compound with multiple equivalents of alkyl or alkenyl aldehyde or alcohol compounds.

27. The process of claim 26 wherein the diaminoalkyl compound is a compound of the formula: H 2 N-(CH 2 )n-NH 2 and the aldehyde or alcohol compound is selected from the group Sconsisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C12-C18 mixed alkyl groups and mixtures thereof and n is an integer of from 1 to 0 S

28. The process of claim 26 wherein the diaminoalkyl compound is hexamethylenediamine. Dated this 25 day of November 2003 S AKZO NOBEL N.V. By their Patent Attorneys %fe: GRIFFITH HACK Fellows Institute of Patent and 35 Trade Mark Attorneys of Australia S e \\melb-files\home$\mrieag\Keep\Speci\23995-OO dc 25/11/03