CN1346395A

CN1346395A - Cationic gamini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants

Info

Publication number: CN1346395A
Application number: CN99815940A
Authority: CN
Inventors: S·B·默维斯; D·斯泰肯; P·J·斯佩兰; H·周
Original assignee: Akzo Nobel NV
Current assignee: Akzo Nobel NV
Priority date: 1998-12-31
Filing date: 1999-12-30
Publication date: 2002-04-24
Anticipated expiration: 2019-12-30
Also published as: EP1147158A1; CA2357756A1; KR20010101352A; JP2003505339A; BR9916711A; HK1043383A1; CN1227321C; ZA200105408B; AU2399500A; AU771929B2; WO2000039241A1

Abstract

A compound of general formula I,II, or III: wherein each of R1 to 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 double structures and related compounds with multiple hydrophilic/hydrophobic functions and their use as surfactants

Technical Field

The present invention relates generally to improved "multi-functional" surfactants of multi-hydrophilic/hydrophobic functional quaternary ammonium compounds that are useful in detergent and personal care, mining, industrial, and catalyst products, in higher concentrations for biocide compositions, and as emulsifiers.

Background

Conventional surfactants have one hydrophilic group and one hydrophobic group. Dimeric surfactants, often referred to as "double structures", contain two hydrophilic groups and two hydrophobic groups. The unique physical properties and hence micellar properties of gemini surfactants due to the restriction of the proximity of two hydrophilic groups have led to intensive research into gemini surfactants as detergents, softeners, emulsifiers, phase transfer catalysts, biocides, and as components of skin care lotions, hair conditioning compositions, and cosmetic compositions. It has also been investigated for use in ore flotation, oil well drilling and other industrial applications.

It is therefore an object of the present invention to provide a new class of cationic multifunctional surfactants useful in treating textile fibers to provide softeners and static control.

It is another object of the present invention to provide a class of multifunctional surfactants having improved detergency at very low concentrations while being highly biodegradable.

It is yet another object of the present invention to provide a class of multifunctional surfactants that can be used as emulsifiers, phase transfer catalysts, biocides, in ore flotation, oil well drilling and other related applications.

Finally, it is a further object of the present invention to provide a class of multifunctional surfactants that can be used at low concentrations in skin care lotions, hair conditioning compositions and cosmetic compositions.

These and other objects are achieved by the compositions and methods of the present invention.

Summary of the invention

The present invention relates generally to several novel classes of cationic, multifunctional surfactants and compositions containing them. The present invention also relates to various methods of making the multifunctional surfactants of the present invention.

Detailed description of the invention

The present invention relates generally to multifunctional surfactants having the following structural formulae I-IV, compositions containing them, and methods for their preparation. The excellent features of the multifunctional surfactants of the present invention are derived from their multifunctional character, i.e., the inventive chemical species comprise two or more hydrophobic groups and two or more hydrophilic groups per molecule.

I. A multifunctional quaternary ammonium compound comprising an ester or amide spacer group of the general formula (I):

wherein R is₁And R₂Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least oneAn ester linkage, at least one amide linkage, or mixtures thereof; r₃、R₄、R₅And R₆Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; and a is a spacer selected from:or other ester-or amide-functional alkyl groups in the spacer, wherein x, y, and z can independently be integers from 1 to 20; and n is an integer from 1 to 20; a multifunctional quaternary ammonium compound comprising an ester or amide spacer group of the general formula (II):

wherein R is₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃And R₁₄Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains 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 integers from 1 to 20; and n is an integer of 1-20; or

Asymmetric multifunctional quaternary ammonium compounds:

wherein R is₁₅And R₂₀Different and selected from linear or branched, substituted or unsubstituted C₈-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; r₁₆、R₁₇、R₁₈And R₁₉Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; and n is an integer from 1 to 20.

Preparation of a catalyst havingA symmetric "dual structure" quaternary ammonium compound of formula IV:

wherein R is₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇And R₂₈Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; and wherein x and y are each independently integers 1 to 20 and n is an integer 0 to 20;

wherein in each of formulae I, II, III and IV, Z-is an anion.

In the above formulas I to III, R₁、R₂、R₇、R₁₄、R₁₅And R₂₀Preferably selected from C optionally containing ester linkages₈-C₁₈An alkyl group. It is also preferred that x, y and z are 0-5 and n is 1-10.

In the above formula IV, R₂₁And R₂₅Preferably selected from 2-ethylhexyl, nonyl alkyl, or C₁₃-C₁₅Mixed alkyl radicals, and R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇And R₂₈Independently selected from methyl, ethyl or propyl, and n ═ 0, 1 or 2.

With respect to the polyfunctional quaternary ammonium compounds of formula I, preferably, R₁And R₂Selected from 2-ethylhexyl, nonyl alkyl, C₁₃-C₁₅Mixed alkyl groups, or selected from dodecyl, hexadecyl, octadecyl, oleyl, coco, soy bean, tallow, or hydrogenated tallow alkyl; r₃、R₄、R₅And R₆Independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl alkyl, or C₁₃-C₁₅Mixed alkyl groups and n is an integer from 1 to 5.

In the polyfunctional quaternary ammonium compounds of the formula II, it is preferred that R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃And R₁₄Each independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl alkyl, C₁₃-C₁₅Mixed alkyl groups, or selected from dodecyl, hexadecyl, octadecyl, oleyl, coco, soy bean, tallow, or hydrogenated tallow alkyl; and n is an integer from 1 to 5.

Finally, preferably in the asymmetric polyfunctional quaternary ammonium compounds of the formula III, R₁₅、R₁₆、R₁₇、R₁₈、R₁₉And R₂₀Selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl alkyl, C₁₃-C₁₅Mixed alkyl groups, or selected from dodecyl, hexadecyl, octadecyl, oleyl, coco, soya, tallow, or hydrogenated tallow alkyl or other long chain segments, provided that one N is present⁺With the substituent group on surrounding another N⁺The substituents at the center are different, and n is an integer of 1 to 20.

The polyfunctional ester-or amide-containing compounds of the present invention have enhanced biodegradability, which is clearly particularly desirable for environmental reasons. For example, enhanced biodegradability is a desirable characteristic in fabric softening compositions and in other applications where control of the content and volume of wastewater effluent is desired.

If used in fabric softening compositions, the compositions of the present invention are preferably delivered to the fabric to be softened in an amount effective to impart the desired softness and/or antistatic properties to the fabric. The effective amount is typically about 0.5 to 3 grams of softening compound per average laundry load.

The compounds of the present invention may be delivered to the fabric to be treated by various means. For example, the compounds of the present invention may be formulated into liquid soft compositions, solid dosage forms and/or solid articles. In liquid dosage forms, the compounds of the present invention are dissolved and/or suspended in water, wherein the formulation optionally further comprises other conventional softening agents in the required amounts, as well as other ingredients and diluents such as detergents, optical brighteners, viscosity builders, soil release agents, perfumes and the like, such that an effective amount of the compounds of the present invention is provided to the fabric to be treated.

For solid dosage forms, the multifunctional surfactants of the present invention are carried on a water-soluble carrier, such as a solid detergent, optionally compounded with builders, brighteners, fragrances, and the like, and formed into flowable granules or beads.

Finally, the multifunctional surfactants of the present invention can be combined with a partitioning agent and applied or coated onto a solid support such as a woven or non-woven fabric or a bonded polyester sheet. Alternatively, the composition may be placed in a container designed for insertion into a fabric dryer.

The present invention also relates to various methods of making the multifunctional surfactants. For example, a multi-functional surfactant of formula I containing an ester spacer group can be prepared by reacting a dialkylalkanolamine having the following formula:

wherein Q₁、Q₂And Q₃Each independently selected from C₁-C₂₂An alkyl group and a dicarboxylic acid having the following structural formula:

HOOC-(CH₂)_n-COOH

wherein n is an integer from 1 to 12, to form a reaction mixture or a diester thereof, and then quaternizing the reaction mixture.

The dialkylalkanolamine is preferably prepared by ethoxylating a fatty amine compound having the formulaAnd the preparation:

wherein Z is C₁₂-C₂₂Substituted or unsubstituted, saturated or unsaturated, straight-chain or branched alkyl, and Y is C₁-C₂₂Substituted or unsubstituted, saturated or unsaturated, straight or branched alkyl.

Preferably, the fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soya oleylamine, tallowalkylamine, hydrogenated tallowalkylamine, dicocoalkylamine, ditalloalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine, and mixtures thereof. The dicarboxylic acid used is preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and mixtures thereof. The most preferred dicarboxylic acid is adipic acid, or a mixed short chain diacid such as available from DuPont.

The multifunctional surfactant of structural formula I containing an amine functional spacer group can be prepared in the presence of an N-alkyl amino fatty amine compound:

R-N(H)(CH₂)_nNH₂

with a dicarboxylic acid or a mixture of dicarboxylic acids (or diesters thereof).

The multifunctional quaternary ammonium compound of formula IV can be prepared by reacting a diprimary amine alkane (e.g., hexamethylenediamine) with 2 equivalents of an aldehyde, such as 2-ethylhexanal, or other long chain aldehydes such as nonanal or mixed C₁₃-C₁₅Aldehydes (commercially available).

Other multifunctional quaternary ammonium surfactants of the present invention having structural formula IV can be prepared by reacting an aliphatic triamine having the following structural formula;

wherein R is a saturated or unsaturated hydrocarbon radical, with an aldehyde, such as 2-ethylhexanal, or a long-chain aldehyde, such as nonanal, or mixed C₁₃-C₁₅Aldehydes (commercially available), or alcohols. For example, trisquatemary ammonium surfactants can be prepared by reacting bis (hexamethylene) triamine with an alkyl aldehyde such as 2-ethylhexanal, followed by methylation and quaternization.

The cationic double structures and related multifunctional hydrophilic/hydrophobic functional compounds of the present invention may be used alone or in combination with conventional surfactants, including mono-quaternary ammonium compounds. It has been found that as low as 5-10% of the compounds of the invention can reduce the Critical Micelle Concentration (CMC) by a factor of 10-100 if used in combination with a mono-quaternary ammonium compound. CMC is one measure used to determine the effectiveness of a surfactant composition. The lower the CMC value, the better the surfactant. That is, by using a small amount of the surfactant of the present invention in combination with a conventional surfactant, the amount of the conventional surfactant to be added can be greatly reduced.

The invention will now be illustrated by the following non-limiting examples.

Example 1 preparation of a multifunctional Quaternary ammonium Compound having an ester functional spacer group

Preparation of (CH) from adipic acid and dimethylethanolamine in toluene₂)₄(CO₂CH₂CH₂NMe₂)₂

Step-a 1-liter round bottom flask was charged with 14.6 grams adipic acid (1.00 mole), 196.0 grams dimethylethanolamine (2.20 mole-10% excess), 300 milliliters toluene, and 1.5 grams p-toluenesulfonic acid. The reaction mixture was heated to reflux with stirring. A dean-stark trap was attached to one neck of a 4-neck flask and a water condenser. The reaction was heated under reflux for a total of 22 hours to distill off 54.5 ml of H₂And O. The product was stripped of solvent on a rotary evaporator at 80 ℃ and 15 mm Hg. The product weighed 270.6 grams. The infrared spectrum of the product showed only an ester.

(CH₂)₄(CO₂CH₂CH₂NMe₂)₂Reaction with cetyl Bromide

step-A1 liter Morton flask was charged with 57.6 grams (CH)₂)₄(CO₂CH₂CH₂NMe₂)₂(0.2 mol) and 300 ml of monoglyme. Add 122.0 g of C with stirring₁₆H₃₃Br (0.4 mol). The reaction mixture is stirred under N₂The mixture was heated to 85 ℃ with stirring under an atmosphere and held for 73 hours. No solid material was visible at the end of the heating, but formed after a few days of standing. All product was suction filtered and the beige solid was suction dried. It was then washed 2 times with ether and sucked dry again and then left overnight in the crystallization dish. The solid product weighed 135.5 g (theoretical yield: 179.6 g). An additional 30.8 grams of solid product was recovered from the filtrate in an overall yield of 92.6%. NMR analysis of the product showed 80 mole percent purity of the diquaternary ammonium compound, 14 mole percent monoquaternary ammonium, and 6 mole percent monoquaternary ammonium monoacid product。

Compositions were prepared comprising 90% Arquad 12 (available from Akzo Nobel chemical Inc., Chicago, IL) and 10% of the compound of example 1. The CMC value of this composition was reduced by a factor of 50 compared to the composition comprising 100% Arquad 12.

Example 2-preparation of a multifunctional quaternary ammonium compound in the reaction of an aldehyde with an alkyldiamine: 1, 6-hexanediamine with blend C₁₃/C₁₅Aldehyde reaction followed by reductive methylation and quaternization

To summarize:

1, 6-hexanediamine with blend C₁₃/C₁₅Reaction of aldehyde. Mixed aldehydes from Celanese ltd. chemicals Division (Dalls, TX) were used; the average molecular weight was estimated to be 211. The aldehyde mixture (400 g, 1.89 mol) was added portionwise to molten 1, 6-hexanediamine (107 g, 0.92 mol). The reaction is exothermic and therefore cooled off without time. The product was washed with water and, after removal of the solvent by evaporation, an oily yellow liquid (428 g) was obtained.

2. Sodium borohydride (32 g) powder was added to a solution of the bisimine compound (404 g, product in 1 above). After the reduction reaction, the imine carbon is observed¹³C NMR disappeared. The reaction mixture was washed well with water and then the solvent was removed by evaporation. The product was a pale yellow liquid (400 g).

3. Methylation of bis-secondary amines was carried out by the Eschweiler-Clarke method (see also the Leukhart reaction, organic reactions, Vol.5, p.323). To the secondary diamine (360 g, 0.71 mol) was added slowly 90% formic acid to form a light brown solution as the reaction temperature rose to 75 ℃ and then cooled to 50-60 ℃. 37% formaldehyde (66 g, 0.814 mol) was slowly added with CO evolution₂A gas. The reaction mixture was heated until the evolution of gas ceased. Approximately 80 g of concentrated HCl were added and the formic acid and any excess formaldehyde were then removed on a rotary evaporator at 65 ℃. The residue was dissolved in water and neutralized with 25% aqueous NaOH solution (about 65 g). Washing the product with waterWashed and dried. Obtaining a light yellow liquid(440 g) and identified as a di-tertiary amine.

4. Quaternization of the bis-tertiary amines prepared in 3 above. In a 1 liter titanium autoclave, a solution of bis-tertiary amine in methanol (150 grams) and sodium bicarbonate were purged with nitrogen and then heated at about 80 ℃ with methyl chloride until all of the amine was consumed (about 10 hours). Filtration and evaporation gave a brown yellow viscous paste (215 g) which was identified as the bis-quaternary ammonium compound.

EXAMPLE 3 preparation of asymmetric multifunctional Quaternary ammonium surfactant Compounds

Asymmetric dimer-or higher oligomer surfactant compounds are prepared by Duomeen condensation using amine-aldehyde condensation^®、Triameen^®And tetramethyleen^®Compounds (available from Akzo nobel chemicals inc., Chicago, IL) were prepared.

Example 4 by bis (hexamethylene) triamine with blend C₁₃/C₁₅Preparation of multifunctional quaternary ammonium compounds by reaction of aldehydes, followed by reduction, methylation, and quaternization

1. Adding the mixed aldehyde in portions to the molten bis (hexamethylene) triamine; the exothermic reaction system was then cooled. The reaction mixture was washed with water, and then the solvent was removed by evaporation to give the bis-imine mono-secondary ammonium compound as a pale yellow liquid.

2. Reduction of a diimine mono-secondary amine compound with sodium borohydride. The bisimine compound (283 g) prepared in 1 above was dissolved in 150 g of methanol. To which sodium borohydride was added in small portionsUntil the reduction is completed. After the reduction reaction, the imine carbon is observed¹³The CMR disappears. The reaction mixture was washed well with water and then the solvent was removed by evaporation. The product was a pale yellow liquid (247 g).

3. Methylation of the tertiary amine compound prepared in 2 above. Tertiary amine compound (245.6 g, 1.17 mol). Formic acid was slowly added to the solution, forming a light brown solution as the reaction temperature rose to 75 ℃ and then cooled to 50-60 ℃. 37% formaldehyde (66 g, 0.814 mol) was slowly added with CO evolution₂Gas (es). The mixture was heated until the gas evolution ceased. About 80 g of concentrated HCl was added and the formic acid and any excess formaldehyde were then removed in a rotary evaporator at 65 ℃. The residue was dissolved in water and neutralized with 25% aqueous NaOH solution (about 65 g). The product was washed with water and dried. A pale yellow liquid (247 g) was obtained and identified as the tri-tertiary amine.

4. Quaternization of the tri-tertiary amine compound. The tertiary amines prepared in 3 above were quaternized in a manner similar to that described elsewhere in this application. In a 1 liter titanium autoclave, a solution of tri-tertiary amine in methanol (150 grams of compound in 150 grams of methanol) and sodium bicarbonate were purged with nitrogen and then heated at about 80 ℃ with methyl chloride until all of the amine was consumed (about 10 hours). Filtration and evaporation gave a tan viscous paste (210 g).

EXAMPLE 5 preparation of amido-bridged multifunctional Quaternary ammonium surfactant Compounds

Dimer-or higher-polymer polyfunctional surface-active compounds having an amide group in the spacer group are prepared from Duomeen by^®、Triameen^®And tetramethyleen^®Compound (available from Akzo Nobel Chemicals Inc.).Example 6 preparation of a PolyPolyEthyl Ether having an ester group in the spacer group from an ethoxylated fatty amine CompoundFunctional quaternary ammonium surfactant compounds

Various mono-and di-alkyl fatty amine compounds are available from Akzo Nobel Chemicals inc. The following route can be advantageously used to obtain diester-bonded multifunctional quaternary ammonium compounds.

Example 7: reaction of ethoxylated Armeen 2HT with succinic acid followed by quaternization

Ethoxylation of the dialkylamine followed by reaction with a dicarboxylic acid and methylation affords the diester interrupted bis (methyldialkylammonium) compound.

Ethoxylation of Armeen 2HT

In a 1 liter autoclave, Armeen 2HT (234.7g, 0.5mole) was dissolved in isopropanol (80 g) with heating. After nitrogen purge, ethylene oxide (22 g, 0.5 mol) was added. The mixture was heated at 80 ℃ for 2 hours.¹³C NMR showed good reaction, except that some of the starting amine remained unreacted (HN-CH)₂-, 50.24 ppm). An additional 11 g of ethylene oxide were added and heating was continued at 80 ℃ for 2 hours. After evaporation, a white solid paste (250 g) was obtained. The product (ethoxylated Armeen 2HT) had the following composition: monoethoxylated amine, 71.3 mole percent; polyethoxylated amine, 26.0 mol%, n 2.7; and unreacted amine, 2.7 mol%.

2. Reaction of ethoxylated Armeen 2HT with succinic acid

A mixture of ethoxylated Armeen 2HT (172 g, 0.3 mole), succinic acid (17.84 g, 0.15 mole) and 50% aqueous hypophosphorous acid solution (0.74 g) was heated under nitrogen atmosphere with stirring at 180-5 ℃ for 5 hours. An off-white viscous paste was obtained. The product consists of 90% of the desired diamine and 10% by weight of monoamine.

3. Quaternisation of bis- (ethoxylated Armeen 2HT) succinate diesters

To a solution of bis- (ethoxylated Armeen 2HT) succinate (89 g, 0.14 eq) in isopropanol (20 g) was slowly added dimethyl sulfate (about 17 g, 0.135 mol) at 75-80 ℃. The free amine should be about 2%, meaning that quaternization is substantially complete. Evaporation gave the pure ester diquaternary ammonium compound.

Example 8 preparation of bis (2-ethylhexyldimethylammonium) -1, 6-hexanedi (chloride) Using bis (Schiff base) intermediate overview

Reaction of 1, 6-hexanediamine with 2-ethylhexanal

To molten 1, 6-hexanediamine (58.1 g, 0.5 mol) at about 50 deg.C was slowly added 2-ethylhexanal (128.2 g, 1 mol) with stirring over 3 hours. Cooling in an ice-water bath is required from time to time as the reaction is exothermic. At the completion of the reaction, it appears as aldehyde carbon¹³Disappearance in C NMR spectrum. The reaction product was washed several times with deionized water. Evaporation gave a yellow liquid (about 160 g), almost quantitative yield.

2. Reduction of diimines with sodium borohydride

To a solution of this diimine (1) (141.6 g, 0.38 mole) in methanol (150 g) was added sodium borohydride (about 20 g) in small portions. During the addition, the reaction flask was cooled in an ice-water bath from time to time. At the completion of the reaction, the imine carbon line at 168ppm is shown¹³Disappearance in C NMR spectrum. The reaction mixture was washed several times with deionized water. Evaporation gave a pale yellow liquid (about 138 g).

Methylation of N, N' -bis (2-ethylhexyl) -1, 6-hexanediamine

To the diamine (II) (126.3 g, 0.37 mol) was added 90% formic acid with stirring, which gave a light brown solution as the temperature rose to 75 ℃. After cooling to room temperature, the mixture was treated by adding 37.1% formaldehyde solution (65.8 g, 0.814 mol) in small portions with stirring. The resulting mixture was evaporated at about 65 ℃ for 2 hours on a rotary evaporator. About 72 grams of concentrated HCl was then added. The mixture was heated at 70 ℃ for 3 hours and then neutralized with 25% aqueous NaOH. The product was washed several times with water and evaporated to give a pale yellow liquid (about 150 g).

4. Quaternisation of the di-tertiary amines (III) with methyl chloride

A solution of the di-tertiary amine (147.5 g, 0.4 mol) was quaternized with methyl chloride in the presence of sodium bicarbonate (1.5 g) at 80 ℃ for about 10 hours. The methyl carbon peak at 42.7ppm on nitrogen at the completion of the reaction¹³Disappearance in C NMR spectrum. The reaction mixture was filtered and the filtrate was evaporated to give the desired diquaternary ammonium salt as a pale yellow paste (189 g).

EXAMPLE 9 preparation of bis (2-ethylhexyldimethylammonium) (dimethylammonium) dihexyltrichloro compound

SUMMARY

1. Reaction of bis (hexamethylene) triamine with 2-ethylhexanal

Note that "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% of triamine and 14% of diamine.

A mixture of "triamine" (101.4 g, 1.05 eq primary amine) and 2-ethylhexanal (134.7 g, 1.05 mol) was heated at 70 ℃ for 4 hours. The crude product was washed with water and evaporated to give diimine (V) (220 g).

2. Reduction of diimine (V) with sodium borohydride

To a solution of 220 g diimine (V) in methanol (220 g) was added sodium borohydride powder (20 g) in small portions until the reaction was complete, as indicated by the imine carbon (168ppm) in¹³Disappearance in C NMR spectrum. The product was washed with water and evaporated.

3. Methylation of the Tri (Secondary) amine Compound (VI)

To compound VI was added 90% formic acid (149 g, 2.9 mol) with stirring. The temperature was maintained at 50-60 ℃ with cooling. A 37.1% formaldehyde solution (104 g, 1.286 mol) in formaldehyde was added in small portions. The resulting mixture was then evaporated in a rotary evaporator to remove excess formic acid and formaldehyde. After addition of concentrated HCl (1.4 mol), the mixture was heated at 70 ℃ for 3 hours and then neutralized with 25% aqueous NaOH. The product was isolated, washed with water and evaporated. This gave a pale yellow liquid (208 g).

4. Quaternisation of the Tri (Tertiary amine) Compounds (VII)

Compound VII (140 g, 0.3 mol) dissolved in methanol (140 g) and added with sodium bicarbonate was quaternized with methyl chloride for 10 hours at 80 ℃. Present as methyl Carbon (CH) at the completion of the reaction₃-N) peak at¹³Disappearance in C NMR spectrum. Filtration and evaporation of the solvent gave (VIII) as a pale yellow solid (about 185 g).

Example 10-preparation of a multifunctional amidoamine quaternary ammonium compound: reaction of Duomeen CD with dimethyl succinate to form bis-Duomeen CD succinate [ bis (secondary amido-secondary amine) Compound]

A mixture of Duomeen CD (490.8 g, 2 equivalents of primary amine) and dimethyl succinate (136.08 g, 0.93 moles) was heated at 125 ℃ and 130 ℃ under nitrogen for 5 hours. Additional dimethyl succinate (6.8 g, 0.046 mol) was added and heating was continued for an additional 5 hours. bis-Duomeen succinate (XXI) was obtained as an off-white solid. The product consisted of bis-secondary amine (95% by weight) and unreacted Duomeen (4%).

Methylation and quaternization of the bis-secondary amine product can be carried out in analogy to the methods described elsewhere in this application to give the bis (amido-amine) quaternary ammonium compound.

Example 11-other route to multifunctional "lactone" Quaternary ammonium Compounds

Step 1: reacting a primary aliphatic amine compound with formaldehyde to form a hexahydrotriazine intermediate;

step 2: hexahydrotriazine is reduced to form a secondary amine;

and step 3: the secondary amine is ethoxylated to form an alcohol amine compound;

and 4, step 4: reacting 2 equivalents of an ethoxylated amine with a dicarboxylic acid to form a di-structural tertiary amine;

and 5: the di-structural tertiary amines are quaternized in the reaction with a methylating agent (methyl chloride or methyl sulfate).

EXAMPLE 12 preparation of ester-functional Quaternary ammonium Compounds

Step 1: preparation of diester amines

Step 2: ethoxylation of Long chain amino Compounds (see example 7, step 1)

And step 3: reaction of ethoxylated amine Compound II with dicarboxylic acid I (see example 7, step 2)

And 4, step 4: quaternization of III (see example 7, step 3)

Claims

1.A compound of formula I, II or III:

wherein R is₁-R₂₀Each independently selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; a is a spacer of the formula:

or other ester-or amide-functional alkyl groups, wherein x, y, and z are each independently selected from the integers 1 to 20; and wherein in each of formulas I, II and III, Z-is an anion, with the proviso that R₁₅And R₂₀Are not identical.

2. A compound according to claim 1, wherein R₁、R₂、R₇、R₁₀、R₁₅And R₂₀Each independently selected from C₁₂-C₁₈Alkyl, C containing ester bond₁₂-C₁₈Alkyl and C containing amide bonding groups₁₂-C₁₈An alkyl group.

3. A compound according to claim 1, wherein R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C₁₃-C₁₅Mixed alkyl, dodecyl, octadecyl, oleyl, cocoalkyl, and stearylSoya alkyl, tallow alkyl, hydrogenated tallow alkyl and mixtures thereof; and n is an integer from 1 to 5.

4. A compound according to claim 1, wherein R₇、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃And R₁₄Independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C₁₃-C₁₅Mixed alkyl, dodecyl, octadecyl, oleyl, coco, soy bean, tallow, hydrogenated tallow, and mixtures thereof; and n is an integer from 1 to 5.

5. A compound according to claim 1, wherein R₁₅、R₁₆、R₁₇、R₁₈、R₁₉And 20 are each independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C₁₃-C₁₅Mixed alkyl, dodecyl, octadecyl, oleyl, coco, soy bean, tallow, hydrogenated tallow, and mixtures thereof, provided that R is₁₅And R₂₀Different; and n is an integer from 1 to 20.

6. A surface-active composition comprising at least one compound according to claim 1.

7. A process for the preparation of a multifunctional quaternary ammonium compound of formula I, which process comprises reacting a dialkylalkanolamine of the formula:

wherein Q₁、Q₂And Q₃Each independently selected from C₁-C₂₂Alkyl, with a dicarboxylic acid of the formula:

HOOC-(CH₂)_n-COOH

wherein n is an integer from 1 to 10, to form a reaction mixture, and then quaternizing the reaction mixture.

8. The process according to claim 7, wherein the dialkylalkanolamine is prepared by ethoxylating a fatty amine compound of the formula:

9. The method according to claim 8, wherein the fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soya alkylamine, tallowalkylamine, hydrogenated tallowalkylamine, dicocoalkylamine, ditalloalkylamine, dihydrotallowalkylamine, dioctadecylamine, and mixtures thereof, and the quaternizing agent is a methylating agent.

10. The process according to claim 7, wherein the dialkylalkanolamine is selected from the group consisting of dimethylethanolamine, diethylethanolamine, and mixtures thereof; and said dicarboxylic acid is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and mixtures thereof; and the quaternizing agent is a long chain alkyl halide agent.

11. The method according to claim 10, wherein the dialkylalkanolamine is dimethylethanolamine and the dicarboxylic acid is adipic acid.

12. A process for preparing a multifunctional hydrophilic/hydrophobic compound comprising reacting a compound of formula Z-NH- (CH)₂)_n-NH₂Of a diamine or

Formula Z-NH- (CH)₂CH₂CH₂NH)_m-CH₂CH₂CH₂NH₂With Z being C₁-C₂₂Saturated or unsaturated alkyl and m is 1 or2，

And formula HOOC- (CH)₂)_n-a dicarboxylic acid of-COOH,

wherein n is an integer of 1 to 10.

13. The method according to claim 12, wherein Z is selected from cocoalkyl, tallowalkyl, or oleylalkyl, and the dicarboxylic acid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and mixtures thereof.

14. The method according to claim 13, wherein the amine is selected from the group consisting of N-coco-1, 3-diaminopropane, N-tallow-1, 3-diaminopropane, N' -trimethyl-N-tallow-1, 3-diaminopropane, N-oleyl-1, 3-diaminopropane, 3-tallowalkyl-1, 3-hexahydropyrimidine, N-tallowalkyldipropylenetriamine, N-tallowalkyltripropylenetetramine, and mixtures thereof, and the dicarboxylic acid is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and mixtures thereof.

15. A compound according to claim 1, wherein R₁₅And R₂₀Each independently selected from C₁₂-C₁₈Alkyl, methyl, ethyl, propyl, 2-ethylhexyl, nonyl alkyl, and C₁₃-C₁₅Mixed alkyl, dodecyl, octadecyl, oleyl, coco, soya, tallow, hydrogenated tallow and C containing ester or amide functions₁₂-C₁₈An alkyl group; and n is an integer from 2 to 3.

16. A compound according to claim 1, wherein R₁₆、R₁₇、R₁₈、R₁₉Independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and C₁₂-C₁₈A mixed alkyl group; and n is an integer from 2 to 3.

17. A viscosity modifier comprising a compound according to claim 15.

18. A viscosity modifier comprising a compound according to claim 16.

19. A compound according to claim 1, wherein R₁₅And R₂₀Each independently selected from C₁₂-C₁₈Alkyl, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and C₁₂-C₁₈Mixed alkyl and C containing ester or amide functions₁₂-C₁₈An alkyl group; and n is an integer from 5 to 8.

20. A compound according to claim 1, wherein R₁₆、R₁₇、R₁₈、R₁₉Independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and C₁₂-C₁₈A mixed alkyl group; and n is an integer from 5 to 8.

21. A compound according to claim 1, wherein R₁₅And R₂₀Each independently selected from C₁₂-C₁₈Alkyl, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and C₁₂-C₁₈Mixed alkyl and C containing ester or amide functions₁₂-C₁₈An alkyl group; and n is an integer from 2 to 20.

22. An ore flotation aid comprising a compound according to claim 21.

23. An ore flotation aid according to claim 22, wherein in the compound, R₁₅And R₂₀Each independently selected from C₁₂-C₁₈Alkyl, and C₁₂-C₁₈Alkenyl and C containing an ester or amide function₁₂-C₁₈An alkyl group; r₁₆、R₁₇、R₁₈、R₁₉Is methyl; and n is an integer from 2 to 12.

24. A calcium ore flotation aid comprising a compound according to claim 23.

25. A process for preparing a compound of formula IV:

wherein R is₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇And R₂₈Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least one amide linkage, or mixtures thereof; and wherein x and y are each independently an integer from 1 to 20, n is from 1 to 20 and Z-is an anion, comprising the reaction of a polyaminoalkyl compound with a plurality of equivalents of an alkyl or alkenyl aldehyde or alcohol compound.

26. The method according to 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 methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C₁₂-C₁₈Mixed alkyl groups or mixed forms thereof and n is an integer from 1 to 5.

27. The method according to claim 25, wherein the diaminoalkyl compound is hexamethylenediamine.

28. A compound of formula IV:

wherein R is₂₁、R₂₂、R₂₃、R₂₄、R₂₅、R₂₆、R₂₇And R₂₈Identical or different and selected from linear or branched, substituted or unsubstituted C₁-C₂₂An alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester linkage, at least oneAn amide linkage or a mixture thereof; and wherein x and y are each independently integers of 1 to 20, n is greater than 1 and Z-is an anion.

29. A surfactant composition comprising at least one compound according to claim 1 and at least one conventional surfactant.

30. The composition according to claim 29, wherein the conventional surfactant is a mono-quaternary ammonium compound.

31. A surfactant composition comprising at least one compound according to claim 28 and at least one conventional surfactant.

32. The composition according to claim 31, wherein the conventional surfactant is a mono-quaternary ammonium compound.