WO2000039241A1

WO2000039241A1 - Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants

Info

Publication number: WO2000039241A1
Application number: PCT/US1999/031246
Authority: WO
Inventors: Stanley B. Mirviss; Dale Steichen; Peter J. Spellane; Hee Cho
Original assignee: Akzo Nobel N.V.
Priority date: 1998-12-31
Filing date: 1999-12-30
Publication date: 2000-07-06
Also published as: ZA200105408B; HK1043383A1; CN1227321C; AU2399500A; AU771929B2; JP2003505339A; CN1346395A; CA2357756A1; EP1147158A1; BR9916711A; KR20010101352A

Abstract

A compound of general formula (I), (II), or (III): wherein each of R1 through R20 are independently 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; A is a space group of formula (1) or (2), (3) or an amide group; and X1 and X2 are the same or different and are selected from C1-C22 substituted or unsubstituted alkyl, C1-C22 substituted, or unsubstituted alkenyl wherein said alkyl or alkenyl group optionally contain at least one ester linkage; and wherein in each of formula (I), (II) and (III), Z is an anion, with the proviso that R15 and R20 are not the same. The invention also relates to a compound of formula (IV) wherein R21, R22, R23, R24, R25, R26, R27, and R28 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, and where x and y are each independently an integer of from 1-20, n is greater than 1 and Z is an anion, and to processes for preparing these compounds.

Description

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. Dime c 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 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 l-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 I. Multiple functional quaternary ammonium compounds containing ester or amide spacer group(s) of the general formula:

R₃ R₄ (I)

I I

R₁ - N - (A)_n- N⁺-R₂

I I 2Z^"

wherein R₁ and R₂ are the same or different and are selected from straight or branched chain, substituted or unsubstituted C_rC₂₂ 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; R₃, R₄, R₅,and R₆ are the same or different and are selected from straight or branched chain, substituted or unsubstituted C_rC₂₂ 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 :

O O O

II II II (CH₂)_X — C - O - (CH₂)_y , (CH₂)_X - O -C - (CH₂)_y - C-0-(CH₂)_z ,

O O

II II

(CH₂ CH₂O)_x-C - (CH₂)_y - C -( OCH₂CH₂)_z , O O O

II II II

(CH₂)_X N - C -(CH₂)_y - C-N-(CH₂)_Z , (CH₂)_X - C- N (CH₂)_y

O O || ||

(CH₂CH₂CH₂N)_x- C-(CH₂)_y-C(NCH₂CH₂CH₂)_z

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;

II. Multiple functional quaternary ammonium compounds with ester or amide spacer σroup(s) of the general formula:

R₈ R₉ R₁₀ (II)

I I I R₇ — N^θ — (A)_n— N^θ — (A)_n— N^Θ — R₁₄

I I I

R R₁₂ R₁₃ 3Z^"

wherein R₇, R₈ ,R₉, R₁₀ R_{11 ?} R₁₂ ,R₁₃, and R₁₄ 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

Asymmetric multiple functional quaternary ammonium compounds:

R₁₅- N⁺- (CH₂)_n- N⁺- R 20 R₁₈ R 19

2Z^"

wherein R,₅ and R₂₀ 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; R₁₆, R₁₇, R₁₈ and R₁₉ are the same or different and are selected from straight or branched chain, substituted or unsubstituted C_rC₂₂ 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 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

wherein R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, and R₂₈ 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 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

In each of formulae l-lll, above, R_{1 :} R₂, R₇, R₁₄, R₁₅ and R₂₀ are preferably selected from C₈-C₁₈ 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 R₂₁ and R₂₅ are preferably selected from 2- ethylhexyl nonyl-alkyl, or a C₁₃-C₁₅ mixed alkyl group, and R₂₂, R₂₃, R₂₄, R₂₅ R₂₆, R₂-, and R₂₈ independently selected from methyl, ethyl or propyl, and n = 0 1 , or 2 Concerning the multiple functional quaternary ammonium compounds of formula I, it is preferred that R, and R₂ be selected from 2- ethylhexyl, nonyl-alkyl, a C₁₃ - C₁₅ mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalkyl , that R₃, R₄, R₅ and R₆ be independently selected from methyl, ethyl, propyl, 2- ethylhexyl, nonyl-alkyl, or a C₁₃ - C₁₅ 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 R₇, R₈, R_9l R₁₀, R„ R₁₂, R₁₃ and R₁₄ are independently selected from from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C₁₃ - C₁₅ 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 5.

Finally, it is preferred that, in the asymmetrical multiple functional quaternary ammonium compounds of formula III, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉

,and R₂₀ be selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C₁₃ - C₁₅ 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 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 compositions and in other uses where the content and volume of waste water effluent streams needs to be controlled

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 textιle(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 bπghteners, 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 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 bπghteners 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 I which contain ester spacer groups can be prepared by reacting a diaikylaikanol amine of formula

Q,

I Q₂ - N - Q₃-OH wherein each of Q^Q;, and Q₃ ιs independently selected from the group consisting of C_rC₂₂ alkyl groups and a dicarboxylic acid of the formula

HOOC - (CH₂)_n - 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 diaikylaikanol amine is preferably prepared by ethoxylating a fatty amine compound of the formula

Z

\ N- H Y

Wherein Z is a C₁₂-C₂₂ 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, hydrogenatedtallowalkyl amine, dicocoalkylamine, ditallowalkylamine, dihydrogenated tallowalkylamine dιoctadecylamιne,and mixtures thereof The dicarboxylic acid employed is preferably selected from the group consisting of oxalic, malonic, succinic, glutanc, adipic, maleic, fumanc 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 I which contain an amine-functional spacer group can be prepared in the reaction of an N- alkylamino fatty amine compound

R-N(H)(CH₂)_n NH₂ with a dicarboxylic acid or mixtures of dicarboxylic acιds(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 C₁₃-C₁₅ 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 tπamines of formula. μ

I

H₂N - R - N - R - NH₂, wherein R is a saturated or unsaturated hydrocarbon group, with aldehyde, e g., 2-ethylhexanal, or longer chain aldehyde such as nonanal or mixed C₁₃-C₁₅ aldehydes (which are commercially available), or an alcohol For example, tπs-quaternary ammonium surfactants can be prepared by reaction of bis(hexamethylene) tπmine 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- limitiπg examples

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

Preparation of (CH. CO H CHπNMeA from adipic acid and dimethylethanolamine in toluene

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 H₂O 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 (CH₂)-,(CO H₂CH,NMe )₂ with hexadecyl bromide Procedure - A 1 L Morton flask was charged with 57 6 g of (CH₂)₄(C0₂CH₂CH₂NMe₂)₂ (0 2 mole) and 300 mL of monoglyme 122.0 g C₁₆H₃₃Br (0 4 mole) were added with stirring The mixture was heated to 85° C with stirring under an N₂ atmosphere and maintained for 73 hours 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 mol % mono-quatemary- 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

H₂N(C H₂)₆N H₂ + 2 RC HO »► RC H=N(CH₂)₆N =C HR

RCH₂

H₂R

CH₃C l

RC HO = C 13 C l 5 aldehvdc

C H₃ CH f |+

RCH->N (C H->)₆NCH,R W^2cr 1. Reaction of 1 ,6-hexanediamine with mixed C₁₃/C₁₅ 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 ¹³C NMR. The reaction mixture was washed thoroughly 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 also Leukhart Reaction, Organic Reactions. Volume 5, p. 323). To the bis-sec-amine (360 g., 0.71 mole) 90% 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 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 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. 4. Quatemization 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 oligome c surfactant compounds are prepared from Duomeen®, Triameen®, and Tetrameen® compounds available from Akzo Nobel Chemicals Inc., Chicago, IL, using an amine- aldehyde condensation reaction.

H H H H I I R— N. ,N— H R— . ,N — ethyhexyl

2-ethylhexanal - -> Duomeen where R = coco-, tallow-, or oleylalkyl

H H I R— . , — ethyhexyl

+ methylation, quatemization ->

Example 4 - Preparation of Multiple Functional Quaternary Ammonium Compound in the reaction of bis(hexamethylene)triamine with mixed C₁₃/C₁₅ aldehyde, followed by reduction, methylation. and quatemization 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 ¹³C 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 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 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 Quatemization of the tris-tertiary amine compound The tπs-tert- amine prepared in 3 above was quatemized 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 g )

Example 5 - Preparation of Amido-Bridged Multiple Functional Quaternary Ammonium Surfactant Compounds

Dimenc - or higher multiple functional surfactant compounds with amide groups in the spacer groups are prepared from Duomeen®, Tπameen®, and Tetrameen® compounds from Akzo Nobel Chemicals, Inc in the following manner

H H

R— . ^\ M— H 2 ^""^{^} ^^ + dicarboxylic acid to form the bis-amido compound - followed by methylation, and then quatemization where R = coco-, tallow- or oleylalkyl

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

H

I

Cocoalkyl — N CH20CH2 Cocoalkyl — N- Ethylene oxide

Me Me

+ HOOCv

2 Cocoalkyl — N- OOH condensation methylation Me

Example 7 Reaction of Ethoxylated Armeen 2HT with Succinic Acid. Followed by Quatemization

Ethoxylation of dialkylamine, followed by reaction with dicarboxylic acid and methylation, will yield the bis-ester-spaced bιs(methyldιalklyammmonιum) 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, 0 5 mole) was introduced The mixture was heated at 80°C for two hours The ¹³C NMR indicated that the reaction was good except that some starting amine remained unreacted (HN-CH₂- at 50 24 ppm) Additional 1 1 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 % 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

Quatemization of Bιs-(ethoxylated Armeen 2HT Succinate Diester

To a solution of bιs-(ethoxylated Armeen 2HT) succinate (89 g, 0 14 equiv) in isopropyl alcohol (20 g) at 75-80°C dimethyl sulfate (about 17 g, 0 135 mole) was slowly added Free amine should be about 2% indicating substantial completion of quatemization Evaporation yielded the neat ester diquaternary ammonium compound

Example 8 PREPARATION OF BIS(2- ETHYLHEXYLDIMETHYLAMMONIUM)- 1.6-HEXANE DI(CHLORIDE) VIA BISfSCHIFF BASE) INTERMEDIATE

Summary

1 Reaction of 2-Ethylhexanal with 1 ,6-Hexanedιamιne

To the melt 1 ,6-hexanedιamιne (58 1 g, 0 5 mole) at ca 50° C, 2- ethylhexaπal (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 ¹³C NMR spectrum The reaction product was washed several times with deionized water Evaporation yielded a yellow liquid (ca 160 g) in nearly quantitative yield

Reduction of Dnmine with Sodium Borohydride

To a solution of the dumine (I) (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 ³C NMR spectrum The reaction mixture was washed with deionized water several times Evaporation gave a yellowish liquid (ca 138 g)

Methylation of N,N'-Dι(2-ethylhexyl)-1.6-hexanedιamιne

The addition of 90% formic acid with stirring to the diamine (II) (126 3 g, 0 37 mole) yielded a light brown solution as the temperature rose to 75° 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 65° C for 2 hours About 72 g of concentrated HCI was then added The mixture was heated at 70° 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) Quatemization of the di-tertiary-amine fill) with Methyl Chloride

A solution of dι(tertιary amine) (147 5 g, 0 4 mole) was quaternized with methyl chloride in the presence of sodium bicarbonate (1 5 g), at 80° C for about 10 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 ¹³C 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 bιs(2-ethylhexyldιmethylammonιum)

(dimethylammonium) dihexane trichloride

Summary

(VIII) 1 Reaction of dι(hexamethylene)trιamιne with 2-Ethylhexanal

Note that the "tπamine" 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 2-ethylhexanal (134 7g, 1 05 moles) was heated at 70° C for 4 hours The crude product was washed with water and evaporated to yield the dnmine (V) (220 g)

2 Reduction of the Dnmine (V) with Sodium Borohydride

To a solution of 220 g dimine (V) 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 Trιs(secondary amine) compound (VI)

To compound VI was added with stirring 90% formic acid (149 g, 2 9 moles) The temperature was maintained at 50-60° 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 Quatemization of the Tπsftertiarv amine) Compound (VII)

Compound VII (140 g, 0 3 mole) dissolved in methanol (140 g), with added NaHC0₃, was quaternized with methyl chloride at 80° C for 10 hours. The reaction was completed as indicated by disappearance of the methyl carbon (CH₃-N) 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 [a bisfsecondary amido-secondary amine) compound]

O O

I I II RNHCH->CH₂CH->NH-> + CH₃OCCH,CH,COCH₃ »-

O O

RNH(CH₂)₃NHC(CH₂)₂CNH(CH₂)₃NHR, (XXI)

O O

II II

RN(CH )₃NHC(CHACNH(CHANHR I C(CH₂)₂CNH(CH₂)₃NHR,

O O

RNH(CH₂)₃NH₂,

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 (4%).

Methylation and quatemization 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. 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;

RNH₂ + 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; RNH(Me) + ethylene oxide ^ RN(Me)CH₂CH₂OH

Step 4: two equivalents of ethoxylated amine react with dicarboxylic acid to form Gemini tertiary amine;

2 RN(Me)CH₂CH₂OH + HOOC(CH₂)₂COOH -»

RN(Me)CH₂CH₂OOC(CH₂)₂COOCH₂CH₂N(Me)R

Step 5: Gemini tertiary amine quaternized in reaction with methylating agent (methyl chloride or methylsulfate).

RN(Me)CH₂CH₂OOC(CH₂)₂COOCH₂CH₂N(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

CH₃N (CH₂CH₂OH)₂ + excess HOOC (CH₂)₄ COOH →

O CH₃ O ii I II

HOOC — (CH₂)₄ — C -0- CH₂ CH₂ N — CH₂CH₂ O C — (CH₂)₄ COOH (I)

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

OH cocoalkyl - N + CH₂O CH₂ -» cocoalkyl -N^~

I I

H CH, step 3 Reaction of ethoxylated amine compound II with dicarboxylic acid I, (see Example 7, step 2)

I + 2 11 -> followed by reductive methylation

CH₃ O 0 CH₃ O O CH₃

I II II I II II I cocoalkyl - N -(CH₂)₂ O C (CH₂)₄ C O CH₂ CH₂ - N - CH₂CH₂ O C (CH₂)₄CO (CH₂)₂ N cocoalkyl step 4 quatemization of I II (see Example 7, step 3)

Claims

WE CLAIM:

1 . A compound of general formula I, II or

wherein each of R, through R₂₀ are independently 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; A is a spacer group of the formula:

O O O

II II II

(CH₂)_X — C - O - (CH₂)_y , (CH₂)_X - O -C - (CH₂)_y - C-0-(CH₂)_z , o o

II II

(CH₂ CH₂0)_x -C - (CH₂)_y - C -( OCH₂CH₂)₂

0 0 O

II II II

(CH₂)_X N - C -(CH₂)_y - C-N-(CH₂)_Z , (CH₂)_x-C-N-(CH₂)_y O O

II II (CH₂CH₂CH₂N)_xC-(CH₂)_yC-(NCH₂CH₂CH₂)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 wherein in each of formulae I, II and III, Z^" is an anion, with the proviso that R₁₅and R₂₀ are not the same.

2. The compound of claim 1 wherein that R₁ , R₂ ,R₇ , R₁₄ R₁₅ , and R₂₀ 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, , R₂ ,R₃ , R₄,R₅, and R₆are selected from the group consisting of methyl, ethyl, propyl, 2- ethylhexyl, nonyl-alkyl, C₁₃ - C₁₅ mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and mixtures thereof; and n is an integer of from 1 to 5.

4. The compound of claim 1 wherein each of R₇ , R₈ ,R₉, R₁₀, R„ ,R₁₂, R₁₃ and R₁₄ 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 5.

5. The compound of claim 1 wherein each of R₁₅ ,R₁₆, R₁₇, R₁₈ ,R₁₉ and R₂₀ 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 R₁₅ is not the same as R₂₀ ; and n is an integer of from 1-20.

6. 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 I which comprises reacting a diaikylaikanol amine of formula

wherein each of Q_{1 (} Q₂and Q₃ is independently selected from the group consisting of C₁-C₂₂ alkyl groups and a dicarboxylic acid of the formula

HOOC - (CH₂)_n - COOH wherein n is an integer of from 1-10, to form a reaction mixture and thereafter quatemizing the reaction mixture.

8. The process of claim 7 wherein said diaikylaikanol amine is prepared by ethoxylating a fatty amine compound of the formula

^z \

N- H Y ' wherein Z is a C₁₂-C₂₂ 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.

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 agent is a methylating agent.

10. The process of claim 7 wherein the diaikylaikanol 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 - (CH₂)_n - NH₂ or a triamine or tetramine of the formula: Z - NH - (CH₂CH₂CH₂NH)_m CH₂CH₂CH₂NH₂ 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 - (CH₂)_n - 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, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof.

14. The process of claim 13 wherein the amine is selected from the group consisting of N-coco 1 ,3 - diaminopropane, N-tallow -1 ,3 diaminopropane, N,N,N' - thmethyl-N-tallow-1 ,3 diaminopropane, N-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.

15. The compound of claim 1 wherein R₁₅ and R₂₀ 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, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and C₁₂-C₁₈ alkyl groups containing an ester or amide function ; and n is an integer of from 2 to 3.

16. The compound of claim 1 wherein R₁₆, R₁₇, R₁₈, R₁₉ 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 2 to 3.

17. A viscosity modifying agent comprising the compound of claim 15.

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

19. The compound of claim 1 wherein R₁₅ and R₂₀ are each independently selected from the group consisting of C₁₂-C₁₈ alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C₁₂-C₁₈ mixed alkyl group and C₁₂-C₁₈ alkyl groups containing an ester or amide function; and n is an integer of from 5 to 8.

20. The compound of claim 1 wherein R₁₆, R₁₇, R₁₈, R₁₉ 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 5 to 8.

21. The compound of claim 1 wherein R₁₅ and R₂₀ are each independently selected from the group consisting of C₁₂-C₁₈ alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C₁₂-C₁₈ mixed alkyl group and C₁₂-C₁₈ 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 R₁₅ and R₂₀ 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; R₁₆, R₁₇, R₁₈, R₁₉ 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

wherein R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, and R₂₈ are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C_rC₂₂ 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, n is1-20 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.

26. The process of claim 25 wherein the diaminoalkyl compound is a compound of the formula:

H₂N-(CH₂)_n-NH₂ and the aldehyde or alcohol compound is selected from the group consisting 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 5.

27. The process of claim 25 wherein the diaminoalkyl compound is hexamethylenediamine.

28. A compound of formula IV

wherein R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, and R₂₈ 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 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.