JP2003505339A - Cationic gemini and related hydrophilic / hydrophobic polyfunctional compounds and their use as surfactants - Google Patents

Abstract

  (57) [Summary] A compound of general formula (I), (II) or (III);₁~ R₂₀Each independently is a linear or branched, substituted or unsubstituted C₁~ C_{twenty two}Selected from an alkyl or alkenyl group, wherein the alkyl or alkenyl group optionally contains at least one ester bond, at least one amide bond or a mixture thereof; A has the formula (1), (2) or X is a spacer group or an amide group of (3);₁And X_TwoAre the same or different and C₁~ C_{twenty two}Substituted or unsubstituted alkyl, C₁~ C_{twenty two}A substituted or unsubstituted alkenyl, said alkyl or alkenyl group optionally containing at least one ester bond; in each of formulas (I), (II) or (III), Z^-Is an anion, provided that R_FifteenAnd R₂₀Are not the same. The present invention also relates to compounds of formula (IV) and methods of making these compounds, wherein R_{twenty one}, R_{twenty two}, R_{twenty three}, R _{twenty four}, R_{twenty five}, R₂₆, R₂₇And R₂₈Are the same or different, straight-chain or branched, substituted or unsubstituted C₁~ C_{twenty two}Selected from alkyl or alkenyl groups, wherein the alkyl or alkenyl group optionally contains at least one ester bond, at least one amide bond or a mixture thereof, and x and y are each independently 1-20 Where n is greater than 1 and Z is an anion.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention generally relates to improved polyhydrophilic / hydrophobic functionalized quaternary ammonium compounds in detergent and personal care, mining, industrial and catalytic products, in biocide compositions at higher concentrations, and It relates to "multifunctional" surfactants useful as emulsifiers.

[0002]

[Prior art]

Conventional surfactants have one hydrophilic group and one hydrophobic group. Normal"
Dimeric surfactants, referred to as "Gemini" surfactants, are those that contain two hydrophilic and two hydrophobic functional groups. Gemini surfactants have unique physical properties resulting from the binding of two hydrophilic groups in close proximity and the resulting micellar properties, which make them useful as detergents, softeners, emulsifiers, phase transfer catalysts, biocides. , And a thorough study of Gemini surfactants as ingredients in skin care lotions, hair conditioning compositions and cosmetic compositions. Their use has also been investigated in flotation of ores, in oil well mining, and in other industrial applications.

[0003]

[Problems to be Solved by the Invention]

Accordingly, it is an object of the present invention to provide a new class of cationic multifunctional surfactants having application in the treatment of fabric fibers to provide softeners and static control. The object of the present invention is also to provide a class of multifunctional surfactants which have improved detergency at significantly lower concentrations, but which are also very biodegradable. It is also an object of the present invention to provide a class of multifunctional surfactants useful as emulsifiers, phase transfer catalysts, biocides, in ore flotation, oil well mining, and other related applications. Is. Finally, it is an object of the present invention to provide a class of multifunctional surfactants useful at low concentrations in skin care lotions, hair conditioning compositions and cosmetic compositions.

[0004]

[Means for Solving the Problems]

These and other objects are met by the compositions and methods of the present invention. The present invention generally relates to several new classes of cationic polyfunctional surfactants and compositions containing them. The present invention also relates to various methods of making the multifunctional surfactants of the present invention. The present invention relates generally to the following multifunctional surfactants of Formulas I-IV, compositions containing the same and methods of making the same. The beneficial characteristics of the multifunctional surfactants of the present invention derive from their multifunctional properties. That is, the chemical species of the present invention has 2 molecules in each molecule.
It comprises one or more hydrophobic groups and two or more hydrophilic groups.

[0005] I. General formula:

[Chemical 12] (Wherein R ₁ and R ₂ are the same or different and are selected from linear or branched, substituted or unsubstituted C _{1 to} C ₂₂ alkyl or alkenyl groups, wherein the alkyl or alkenyl groups are optionally Containing at least one ester bond, at least one amide bond or mixtures thereof; R ₃ , R ₄ , R ₅ and R ₆ are the same or different and are linear or branched, substituted or unsubstituted C ₁ is selected from -C ₂₂ alkyl or alkenyl group, the said alkyl or alkenyl groups optionally at least one ester bond, include at least one amide bond, or mixtures thereof; a is the following:

[Chemical 13] A spacer selected from the group consisting of or another ester or amide functional alkyl group in the spacer, each of x, y and z independently,
A polyfunctional quaternary ammonium compound containing an ester or amide spacer group, which may be an integer of 1 to 20 and n is an integer of 1 to 20);

[0006] II. General formula:

[Chemical 14] (Where R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are the same or different,
It is selected from linear or branched, substituted or unsubstituted C _{1 to} C ₂₂ alkyl or alkenyl groups, which alkyl or alkenyl groups optionally contain at least one ester bond, at least one amide bond or A is a spacer group as defined above, x, y and z are each independently an integer from 1 to 20 and n is an integer from 1 to 20) A polyfunctional quaternary ammonium compound having a spacer group; or

[0007] III. Asymmetric polyfunctional quaternary ammonium compounds:

[Chemical 15] (Wherein R ₁₅ and R ₂₀ are different and are selected from linear or branched, substituted or unsubstituted C _{8 to} C ₂₂ alkyl or alkenyl groups, wherein the alkyl or alkenyl group is optionally at least one. An ester bond, at least one amide bond or a mixture thereof; R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are the same or different and are linear or branched, substituted or unsubstituted C ₁ -C. ₂₂ alkyl or alkenyl groups, said alkyl or alkenyl groups optionally comprising at least one ester bond, at least one amide bond or mixtures thereof; n is an integer from 1 to 20).

[0008] IV. Alkyl polyamine compounds and the general formula IV:

[Chemical 16] _{(Wherein, R 21, R 22, R} 23, R 24, R 25, R 26, R 27 and R ₂₈ are the same or different, linear or branched, C ₁ substituted or unsubstituted -C ₂₂ Selected from alkyl or alkenyl groups, said alkyl or alkenyl groups optionally comprising at least one ester bond, at least one amide bond or mixtures thereof; x and y are each independently 1-20 Is a whole number, and n is an integer from 0 to 20), and is a symmetrical "Gemini" produced by reaction with a long-chain aldehyde or alcohol
Quaternary ammonium compound.

Here, in each of I, II, III and IV, Z ⁻ is an anion.

In each of the above formulas I-III, R ₁ , R ₂ , R ₇ , R ₁₄ , R ₁₅ and R ₂₀ are preferably selected from C _{8 to} C ₁₈ alkyl groups optionally containing ester bonds. . It is also preferred that x, y and z are 0-5 and n is 1-10.

In the above formula IV, R ₂₁ and R ₂₅ are preferably 2-ethylhexyl, nonyl-
Alkyl, or selected from C _{13 to} C ₁₅ mixed alkyl groups, R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ ,
R ₂₆ , R ₂₇ and R ₂₈ are independently selected from methyl, ethyl or propyl, n
= 0, 1 or 2.

With respect to the polyfunctional quaternary ammonium compound of formula I, R ₁ and R ₂ are selected from 2-ethylhexyl, nonyl-alkyl or C ₁₃ -C ₁₅ mixed alkyl groups or dodecylalkyl, hexadecylalkyl , Octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl or hydrogenated tallowalkyl; R ₃ , R ₄
, R ₅ and R ₆ are independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl or C ₁₃ -C ₁₅ mixed alkyl groups; and n is preferably an integer from 1 to 5 .

In the polyfunctional quaternary ammonium compound of formula II, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ are each independently selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl or C ₁₃ -C ₁₅ mixed alkyl groups, or dodecylalkyl, hexadecylalkyl, octadecyl Selected from the group consisting of alkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl or hydrogenated tallowalkyl; and n
Is preferably an integer from 1 to 5.

Finally, in the asymmetric polyfunctional quaternary ammonium compound of formula III, R ₁₅ ,
R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl or C ₁₃ -C ₁₅ mixed alkyl groups, or dodecylalkyl, hexadecylalkyl. , Octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl (t
allowalkyl) or hydrogenated tallowalkyl or other long chain fragment, provided that the substituents on one N ⁺ are not the same as the substituents surrounding the other N ⁺ center; and n Is preferably an integer from 1 to 20.

The ester- or amide-containing polyfunctional compounds of the present invention exhibit enhanced biodegradability, which is clearly highly desirable for environmental reasons. For example, enhanced biodegradability is a desirable property in fabric softener compositions and other applications where the content and volume of waste effluent streams need to be controlled.

When used in a fabric softener composition, the compounds of the invention are preferably in an amount effective to impart to the fabric to be softened the desired softness and / or electrostatic resistance. Given in. The effective amount typically ranges from about 0.5 to 3 grams of softener compound per average laundry amount.

The application of the compounds of the invention to the fabric to be treated can be done by various means. For example, the compounds of the present invention may be used in liquid softener compositions, solid formulations and / or
Or it can be formulated into a solid product. In liquid formulations, the compounds according to the invention are dissolved and / or suspended in water, the formulation optionally also comprising other conventional softeners and other ingredients and diluents, such as detergents, optical brighteners, Viscosity aid
aids, soil release agents, fragrances and the like in amounts necessary to provide effective amounts of the compounds of the invention to the fabric to be treated.

With solid formulations, the multifunctional 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 builder, enriched. Compounded with whitening agents, fragrances, etc.

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

The present invention also relates to various methods of making multifunctional surfactants. For example, a multifunctional surfactant of Formula I containing an ester spacer group has the formula:

[Chemical 17] (Wherein each of Q ₁ , Q ₂ and Q ₃ are independently selected from the group consisting of C ₁ -C ₂₂ alkyl groups) and a formula:

[Chemical 18] It can be prepared by reacting a dicarboxylic acid (where n is an integer of 1 to 12) to form a reaction mixture or a diester thereof and then quaternizing the reaction mixture. The dialkylalkanolamine preferably has the formula:

[Chemical 19] (Here, Z is a C _{12 to} C ₂₂ substituted or unsubstituted saturated or unsaturated linear or branched alkyl group, and Y is a C _{1 to} C ₂₂ substituted or unsubstituted saturated or unsaturated. (Which is a linear or branched alkyl group of 1) is ethoxylated.

Preferably, the aliphatic amine compound is dodecylamine, hexadecylamine,
From octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenated tallowalkylamine, dicocoalkylamine, ditallowalkylamine, di (hydrogenated tallowalkylamine), dioctadecylamine and mixtures thereof. Is selected from the group consisting of The dicarboxylic acid used is preferably selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and mixtures thereof. The most preferred dicarboxylic acids are adipic acid or mixed short chain diacids commercially available, for example from DuPont.

Polyfunctional surfactants of formula I containing amine-functional spacer groups are N-alkylaminoaliphatic amine compounds

[Chemical 20] And a dicarboxylic acid or a mixture of dicarboxylic acids (or diesters thereof).

The polyfunctional quaternary ammonium compound of formula IV comprises a bis-primary amine alkane (eg hexamethylene diamine) and 2 equivalents of an aldehyde such as 2-ethylhexanal or other long chain aldehydes such as nonanal or mixed C ₁₃ ~ C ₁₅ aldehyde (
It can be produced by reacting with (commercially available and available).

[0024]   Other multifunctional quaternary ammonium surfactants of general formula IV of the present invention have the formula:

[Chemical 21] (Wherein R is a saturated or unsaturated hydrocarbon group) with an aliphatic triamine and an aldehyde such as 2-ethylhexanal or a long chain aldehyde such as nonanal or a mixed C ₁₃ -C ₁₅ aldehyde (commercially available Available) or by reaction with alcohol. For example, a tris quaternary ammonium surfactant can be produced by reacting bis (hexamethylene) triamine with an alkyl aldehyde such as 2-ethylhexanal, followed by methylation and quaternization.

The cationic gemini and related multifunctional hydrophilic / hydrophobic functional compounds of the present invention can be used alone or can include typical surfactants (including mono-quaternary ammonium compounds). ) Can be used in combination. It has been found that when used in combination with mono-quaternary ammonium compounds, as little as 5-10% of the compounds of the invention can reduce the limiting micelle concentration (CMC) by a factor of 10-100. CMC is a measurement used to determine the effectiveness of a surfactant composition. The lower the CMC value, the better the surfactant. Thus, by using a small amount of the surfactant of the present invention in combination with a conventional surfactant, the addition ratio of the conventional surfactant can be greatly reduced.

[0026]   The present invention will now be described by the following non-limiting examples.

Preparation of the polyfunctional quaternary ammonium compounds having the EXAMPLE 1 ester functional spacer group

[Chemical formula 22]

Procedure for producing (CH ₂ ) ₄ (CO ₂ CH ₂ CH ₂ NMe ₂ ) ₂ from adipic acid and dimethylethanolamine in toluene- 14.6 g adipic acid (1.00 mol) in a 1 liter round bottom flask , 196.0g
Dimethyl ethanolamine (2.20 mol-10% excess), 300 mL toluene and 1.
5 g of p-toluenesulfonic acid was charged. The reaction mixture was heated to reflux with stirring. A Dean-Stark trap was attached to one neck of a 4-neck flask and fitted with a water condenser. The reaction was heated at reflux for a total of 22 hours while distilling out 54.5 mL H ₂ O. The product was solvent removed on a rotary evaporator at 80 ° C. and 15 mm Hg. The product weighed 270.6 g. The infrared spectrum of the product showed only the ester.

[0028]Reaction of (CH ₂ ) ₄ (CO ₂ CH ₂ CH ₂ NMe ₂ ) ₂ with hexadecyl bromide Procedure-In a 1 liter Morton flask, add 57.6 g (CH₂)_Four(CO₂CH₂CH₂NM
e₂)₂(0.2 mol) and 300 mL of monoglyme were charged. 122.0 g C ₁₈ H₃₃Br (0.4 mol) was added with stirring. N while stirring the mixture₂Under the atmosphere
It was heated to 85 ° C. and held for 73 hours. Solid was not apparent at the end of heating,
It formed when left for several days. All product is suction filtered and beige solid is suction dried
did. Then it was washed twice with diethyl ether, sucked dry again and crystallized.
It was left in a chewing dish overnight. The solid product weighed 135.5 g (theoretical yield: 179.
6g). Another 30.8 g of solid product was recovered from the filtrate and the overall yield was 92.6%.
It was NMR analysis of the product shows that 80 mol% pure diquaternary compound, 14 mol% mono-quaternization
Compound and 6 mol% mono-quaternary-monohydric acid product.   90% Arquad ™ 12 (Akzo Nobel Chemic
als), Chicago, Illinois) and 10% of the compound of Example 1.
A composition was prepared. This composition comprises a composition containing 100% Arquad ™ 12
It showed a 50-fold decrease in CMC value.

Example 2-Reaction of aldehyde with alkyldiamine: mixed with 1,6-hexanediamine
Preparation of multifunctional quaternary ammonium compounds by reduction, methylation and quaternization after reaction with combined C ₁₃ / C ₁₅ aldehydes Summary:

[Chemical formula 23]

1. Reaction of 1,6-hexanediamine with mixed C ₁₃ / C ₁₅ aldehydes. Celanese (C
Elanese Ltd.), a mixed aldehyde obtained from the Chemicals Department (Dallas, Tex.) was used and the average molecular weight was estimated to be 211. Aldehyde mixture (400g, 1.89
Mol) in small portions and added to molten 1,6-hexanediamine (107 g, 0.92 mol). The reaction was exothermic and was therefore cooled occasionally. Wash the product with water,
After removing the solvent by evaporation, an oily yellow liquid (428 g) was obtained.

2. Sodium borohydride (32 g) as a powder, bis-imine compound (404 g,
The product of (1) above was added to the solution. After the reduction reaction, the disappearance of ¹³ C NMR of the imine carbon was observed. After washing the reaction mixture thoroughly with water, the solvent was removed by evaporation. The product was a pale yellow liquid (400g).

3. The Eschweiler-Clarke method (also Leuchhard
(Leukhart) Reaction, Organic Reactions (Organic Reactions, Vol. 5, p. 323)) methylation of bis-secondary amine. Bis-secondary amine (360g, 0
.71 mol), 90% formic acid is slowly added, and after the reaction temperature rises to 75 ℃, 50 ~ 6
As it cooled to 0 ° C., a light brown solution formed. While CO ₂ gas is generated,
37% formaldehyde (66 g, 0.814 mol) was added slowly. The mixture was heated until gas evolution ceased. About 80 g of concentrated HCl was added and the formic acid and excess formaldehyde were removed on a rotary evaporator at 65 ° C. The residue was dissolved in water and neutralized with 25% aqueous NaOH (about 65g). The product was washed with water and dried. A pale yellow liquid (440g) was obtained and identified as a bis-tertiary amine.

4. Quaternization of the bis-tertiary amine compound prepared in 3 above. In a 1 liter titanium autoclave, purge the solution of bis-tertiary amine in methanol (150 g) with sodium bicarbonate with nitrogen until all amine is consumed (about 10 hours).
, Heated to about 80 ° C. with methyl chloride. Filtration and evaporation gave a brownish-yellow viscous paste (215 g) which was identified as a bis-quaternary ammonium compound.

EXAMPLE 3-Preparation of Asymmetric Polyfunctional Quaternary Ammonium Surfactant Compounds Asymmetric dimeric or higher oligomeric surfactant compounds are commercially available from Akzo Nobel Chemicals, Chicago, Illinois. Available from Du
From omeen ™, Triameen ™ and Tetrameen ™ compounds, amines
-Manufactured using an aldehyde condensation reaction.

[Chemical formula 24] (Where R = cocoalkyl, tallowalkyl or oleylalkyl)

[Chemical 25]

Example 4-Reaction of bis (hexamethylene) triamine with mixed C ₁₃ / C ₁₅ aldehydes
Preparation of polyfunctional quaternary ammonium compound by subsequent reduction, methylation and quaternization

1. The mixed aldehyde was added in small portions to the molten bis (hexamethylene) triamine and the exothermic reaction was cooled. After washing the reaction mixture with water, the solvent was removed by evaporation to obtain a pale yellow liquid bis-imine-mono-secondary amine compound.

2. Reduction of the bis-imine-mono-secondary amine compound with sodium borohydride.
The bis-imine compound (283 g) produced in the above 1 was dissolved in 150 g of methanol.
To this, 25 g of sodium borohydride was added in small portions until the reduction was complete. After the reduction reaction, the disappearance of ¹³ C NMR of the imine carbon was observed. After washing the reaction mixture thoroughly with water, the solvent was removed by evaporation. The product was a pale yellow liquid (24
7g).

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

4. Quaternization of tris-tertiary amine compound. The tris-tertiary amine prepared in 3 above was quaternized by a procedure similar to that described elsewhere herein. In a 1 liter titanium autoclave, a solution of tris-tertiary amine in methanol containing sodium bicarbonate (155 g compound in 150 g methanol) was purged with nitrogen until all amine was consumed (about 10 H) and heated at about 80 ° C. with methyl chloride. Filtration and evaporation gave a brownish-yellow viscous paste (210 g).

Example 5-Preparation of Amido-Crosslinked Polyfunctional Quaternary Ammonium Surfactant Compounds Dimeric or higher polyfunctional surfactant compounds having an amide group in the spacer group were commercially available from Akzo Nobel Chemicals ( Duomee from Akzo Nobel Chemicals)
Prepared from n (TM), Triameen (TM) and Tetrameen (TM) compounds in the following manner:

[Chemical formula 26] (Where R = cocoalkyl, tallowalkyl or oleylalkyl)

[Chemical 27] R = cocoalkyl, tallowalkyl or oleylalkyl

Example 6-Ethoxylated Aliphatic Amine Compound Having Ester Group on Spacer
Of multifunctional quaternary ammonium surfactant compound

Various mono- and di-alkyl aliphatic amine compounds are available from Akzo Nobel Chemicals and are useful as starting materials. The following routes to diester-bonded multifunctional quaternary ammonium compounds are described below.
It can be usefully used.

[Chemical 28]

Example 7-Ethoxylation of quaternized dialkylamines followed by reaction of ethoxylated Armeen 2HT with succinic acid , followed by reaction with dicarboxylic acid and methylation were separated by a bis-ester. This produces a bis (methyldialkylammonium) compound.

[0044] 1.Ethoxylation of Armeen 2HT   In a 1 liter autoclave, by heating, Armeen 2HT (234.7 g, 0.5
Mol) was dissolved in isopropyl alcohol (80 g). After purging with nitrogen,
Tylene oxide (22 g, 0.5 mol) was introduced. The mixture was heated at 80 ° C. for 2 hours. ¹³ C NMR left some starting amine unreacted (HN-CH₂-50.24ppm) or less
The outside showed that the reaction was good. Add another 11g of ethylene oxide
Heating at 80 ° C. was continued for another 2 hours. After evaporation, a white solid paste (250 g
)was gotten. The product, ethoxylated Armeen 2HT, is a monoethoxylated amine.
(71.3 mol%), n = 2.7 polyethoxylated amine (26.0 mol%) and unreacted
It consisted of an amine (2.7 mol%).

2. Reaction of ethoxylated Armeen 2HT with succinic acid Under a nitrogen atmosphere, ethoxylated Armeen 2HT (172 g, 0.3 mol), succinic acid (17.
A mixture of 84 g, 0.15 mol) and 50% aqueous hypophosphorous acid (0.74 g) with stirring.
Heat to 0-5 ° C. for 5 hours. An off-white viscous paste was obtained. The product consisted of 90% by weight of the desired diamine ester and a monoamine reported as 10% by weight.

3. Quaternized bis- (ethoxylated Armeen 2HT) succinate diester Quaternized bis- (ethoxylated Armeen 2HT) succinate (89 g, 0.14 eq) in a solution of isopropyl alcohol (20 g) at 75-80 ° C. Dimethyl sulfate (about 17 g, 0.135 mol) was added slowly. Approximately 2 free amines, indicating substantial termination of quaternization.
%Must. Evaporation gave the net ester diquaternary ammonium compound.

Example 8-Bis (2-ethylhexyldimethyla) via bis (Schiff base) intermediate
Overview of the production of (Numonium) -1,6-hexanedi (chloride)

[Chemical 29]

1. Reaction of 2-ethylhexanal with 1,6-hexanediamine Melt 1,6-hexanediamine (58.1 g, 0.5 mol) into 2-ethylhexanal (128.2 g, 1 mol) at about 50 ° C. ) Was added slowly with stirring over 3 hours.
The reaction was exothermic and occasionally required cooling in an ice water bath. ^The reaction was terminated when indicated by the disappearance of the aldehyde carbon in the ¹³ C NMR spectrum. The reaction product was washed several times with deionized water. Evaporation gave a yellow liquid in about quantitative yield (about 160 g).

2. Reduction of the diimine with sodium borohydride To a solution of diimine (I) (141.6 g, 0.38 mol) in methanol (150 g) was added sodium borohydride (about 20 g) in small portions. During the addition, the reaction flask was occasionally cooled in an ice water bath. ^The reaction was terminated when indicated by the disappearance of the imine carbon series at 168 ppm in the ¹³ C NMR spectrum. The reaction mixture was washed several times with deionized water. Evaporation gave a yellowish liquid (~ 138g).

3. N, N′-di (2-ethylhexyl) -1,6-hexanediamine methylation 90% Formic acid is added to diamine (II) (126.3 g, 0.37 mol) with stirring and the temperature As the temperature rose to 75 ° C, a light brown solution was obtained. Once cooled to room temperature, the mixture is
Treated with a% formaldehyde solution (65.8g, 0.814mol) by adding formaldehyde in small portions with stirring. The resulting mixture was evaporated on a rotary evaporator at about 65 ° C. for 2 hours. Then, about 72 g of concentrated HCl was added.
The mixture was heated at 70 ° C. for 3 hours and then neutralized with 25% aqueous NaOH solution. The product was washed several times with water and evaporated to give a pale yellow liquid (~ 150g).

4. Quaternization of di-tertiary amine (III) with methyl chloride In the presence of sodium bicarbonate (1.5 g) at 80 ° C. for about 10 hours, di-tertiary amine (147.5 g , 0.4 mol) was quaternized with methyl chloride. ^The reaction was terminated when indicated by the disappearance of the peak of the methyl carbon on nitrogen at 42.7 ppm in the ¹³ 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 (189g).

Example 9-Bis (2-ethylhexyldimethylammonium) (dimethylammonium
Umm) dihexane trichloride production outline

[Chemical 30]

1. Reaction of di (hexamethylene) triamine with 2 -ethylhexanal 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. "Triamine" (101.4 g, 1.05 equivalent of primary amine) and 2-ethylhexanal (
134.7 g, 1.05 mol) was heated at 70 ° C. for 4 hours. Wash the crude product with water,
Evaporation gave the diimine (V) (220g).

2. Reduction of the diimine (V) with sodium borohydride 220 g of a solution of the diimine (V) in methanol (220 g) reacted when indicated by the disappearance of the imine carbon (168 ppm) in the ¹³ C NMR spectrum. Sodium borohydride powder (20 g) was added in small portions until the end of. The product was washed with water and evaporated.

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

4. Quaternized tris (tertiary amine) compound (VII) Compound VII (140 g, 0.3 mol) dissolved in methanol (140 g) was added to NaHC.
Quaternized with methyl chloride with O ₃ at 80 ° C. for 10 hours. ^The reaction was terminated when indicated by the disappearance of the methyl carbon (CH ₃ —N) peak in the ¹³ C NMR spectrum. Filtration and evaporation of solvent gave a pale yellow solid (VIII) (about 185 g).

Example 10-Preparation of multifunctional amidoamine quaternary ammonium compounds: Duome en CD and dimethyl succinate to form bis-Duomeen CD succinate [bis (secondary amide-secondary amine) compound] Reaction of

[Chemical 31] R = Coco Duomeen ™ CD (490.8 g, 2 eq primary amine) and dimethyl succinate (136
0.08 g, 0.93 mol) was heated under nitrogen at 125-130 ° C. for 5 hours. Further dimethyl succinate (6.8 g, 0.046 mol) was added and heating continued for a further 5 hours. Bis-Duomeen succinate (XXI) (off-white solid) was obtained. The product consisted of bis-secondary amine (95% by weight) and unreacted Duomeen (4%).

Methylation and quaternization of this bis-secondary amine product was performed in a similar manner as described elsewhere herein to give a bis (amido-amine) quaternary ammonium compound. .

Example 11-Alternative Route to Polyfunctional "Internal Esters" Quaternary Ammonium Compounds Step 1: Reaction of primary aliphatic amine compound with formaldehyde forms a hexahydrotriazine intermediate;

Embedded image RNH ₂ + 3HCHO → hexahydrotriazine

[0060] Step 2: reduce hexahydrotriazine to form a secondary amine;

[Chemical 33] Hexahydrotriazine → RNH (Me)

[0061] Step 3: Ethoxylate the secondary amine to form an alcohol amine compound;

Embedded image RNH (Me) + ethylene oxide → RN (Me) CH ₂ CH ₂ OH

Step 4: 2 equivalents of ethoxylated amine reacts with dicarboxylic acid to form gemini tertiary amine;

[Chemical 35]

Step 5: Gemini tertiary amine is quaternized by reaction with a methylating agent (methyl chloride or methyl sulfate).

[Chemical 36]

Example 1 Preparation of 2-ester-functional tris-quaternary ammonium compound

[0065] Step 1: Production of diester amine

[Chemical 37]

[0066] Step 2: Ethoxylation of long chain amino compounds (see Example 7, Step 1).

[Chemical 38]

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

[Chemical Formula 39]

[0068] Step 4: Quaternization of III (see Example 7, Step 3)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 213/08 C07C 213/08 231/02 231/02 233/36 233/36 C09K 3/00 103 C09K 3 / 00 103 C11D 1/62 C11D 1/62 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL , PT, SE), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB , GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU , LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Sperrain, Peter, Jay. United States, New York 10503, Ardsley-On-Hudson, West Ardsley Avenue 100 (72) Inventor Cho, Hee United States, New York 12590, Wappinger Falls, Lenny Court 5F Term (Reference) 4D077 AA04 AA09 AB10 AB11 AB12 AC01 BA14 DC02Y DC42Y DC48Y 4H003 AA03 AE04 DA01 FA03 FA21 4H006 AA01 AA02 AB68 AC52 AC53 BB11 BU32 BU50

Claims (32)

[Claims] 1. A compound of formula I, II or III: Here, each of R _{1 to} R ₂₀ is independently selected from a linear or branched, substituted or unsubstituted C _{1 to} C ₂₂ alkyl or alkenyl group, and the alkyl or alkenyl group is at least one. It may contain ester bonds, at least one amide bond or mixtures thereof; A is of the formula: A spacer group or other ester or amide functional alkyl group of x,
, Y and z are each independently selected from an integer from 1 to 20, and in each of formulas I, II and III Z ⁻ is an anion, provided that R ₁₅ and R ₂₀ are not the same. Wherein _{R 1, R 2, R 7} , R 14, R 15 and R ₂₀ are each independently, C ₁₂ ~
C ₁₈ alkyl group, C ₁₂ -C ₁₈ alkyl groups, and C ₁₂ -C ₁₈ compound of claim 1 wherein is selected from the group consisting of alkyl groups containing an amide bond comprising an ester linkage. 3. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C ₁₃ -C ₁₅ mixed alkyl group,
Dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl,
The compound according to claim 1, which is selected from the group consisting of soyaalkyl, tallowalkyl, hydrogenated tallowalkyl, and mixtures thereof, and n is an integer of 1 to 5. 4. R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C. ₁₃ -C ₁₅ mixed alkyl group, dodecyl alkyl, octadecyl alkyl, oleyl alkyl, coco alkyl, Soyaarukiru, tallow alkyl, selected from hydrogenated tallow alkyl and the group consisting of mixtures thereof, wherein n is an integer of 1 to 5 Item 1. The compound according to Item 1. 5. R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ are each independently
Methyl, ethyl, propyl, 2-ethylhexyl, nonyl - alkyl, C ₁₃ -C ₁₅ mixed alkyl group, dodecyl alkyl, octadecyl alkyl, oleyl alkyl,
The compound of claim 1 selected from the group consisting of cocoalkyl, soyaalkyl, tallowalkyl, hydrogenated tallowalkyl and mixtures thereof, provided that R ₁₅ is not the same as R ₂₀ and n is an integer from 1-20. 6. A surfactant composition comprising at least one of the compounds of claim 1. 7. A process for preparing a polyfunctional quaternary ammonium compound of general formula I, which has the formula: (Wherein each of Q ₁ , Q ₂ and Q ₃ are independently selected from the group consisting of C ₁ -C ₂₂ alkyl groups) and a dialkylalkanolamine of the formula: (Where n is an integer from 1 to 10) reacting to form a reaction mixture and then quaternizing the reaction mixture. 8. The dialkylalkanolamine has the formula: (Here, Z is a C _{12 to} C ₂₂ substituted or unsubstituted saturated or unsaturated linear or branched alkyl group, and Y is a C _{1 to} C ₂₂ substituted or unsubstituted saturated or unsaturated. 8. The method according to claim 7, which is produced by ethoxylating an aliphatic amine compound having a linear or branched alkyl group of 9. The aliphatic amine compound is dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenated tallowalkylamine, dicocoalkylamine, ditallowalkyl. 9. The process of claim 8 wherein the quaternizing agent is a methylating agent selected from the group consisting of amines, dihydrogenated tallow alkyl amines, dioctadecyl amines and mixtures thereof. 10. The dialkylalkanolamine is selected from the group consisting of dimethylethanolamine, diethylethanolamine and mixtures thereof, and the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid. Selected from the group consisting of acids, fumaric acid and mixtures thereof,
The method according to claim 7, wherein the quaternizing agent is a long-chain alkyl halide reagent. 11. The method according to claim 10, wherein the dialkylalkanolamine is dimethylethanolamine and the dicarboxylic acid is adipic acid. 12. A method of making a polyfunctional hydrophilic / hydrophobic compound, which comprises the formula: Diamine or formula: (Wherein Z is a C ₁ -C ₂₂ saturated or unsaturated alkyl group, and m is 1 or 2
A triamine or tetramine of the formula: (Where n is an integer from 1 to 10). 13. Z is selected from cocoalkyl, tallowalkyl or oleylalkyl and the dicarboxylic acid is a group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and mixtures thereof. 13. The method of claim 12 selected from: 14. The amine is N-coco-1,3-diaminopropane, N-tallow-1,3-
Diaminopropane, N, N, N'-trimethyl-N-tallow-1,3-diaminopropane, N-oleyl-1,3-diaminopropane, 3-tallowalkyl-1,3-hexahydropyrimidine, N-tallow Selected from the group consisting of alkyldipropylenetriamine, N-tallowalkyltripropylenetetramine and mixtures thereof, wherein the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and their 14. The method of claim 13 selected from the group consisting of mixtures. 15. R ₁₅ and R ₂₀ are each independently a C ₁₂ -C ₁₈ alkyl group,
Methyl, ethyl, propyl, 2-ethylhexyl, nonyl - alkyl and C ₁₃ -C _{1 5} mixed alkyl group, dodecyl alkyl, octadecyl alkyl, oleyl alkyl, coco alkyl, Soyaarukiru, tallow alkyl, hydrogenated tallow alkyl and esters or amides The compound according to claim 1, wherein n is an integer of 2 to 3 selected from the group consisting of C _{12 to} C ₁₈ alkyl groups having functionality. 16. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl and C ₁₂ -C ₁₈ mixed alkyl groups, The compound according to claim 1, wherein n is an integer of 2 to 3. 17. A viscosity modifier containing the compound according to claim 15. 18. A viscosity modifier containing the compound according to claim 16. 19. R ₁₅ and R ₂₀ are each independently a C ₁₂ -C ₁₈ alkyl group,
Methyl, ethyl, propyl, 2-ethylhexyl, nonyl - selected from the group consisting of C ₁₂ -C ₁₈ alkyl group containing alkyl and C ₁₂ -C _{1 8} mixed alkyl groups as well as ester or amide functionality, n is 5-8 The compound according to claim 1, which is an integer of 20. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl and C ₁₂ -C ₁₈ mixed alkyl groups, The compound according to claim 1, wherein n is an integer of 5 to 8. 21. R ₁₅ and R ₂₀ are each independently a C ₁₂ -C ₁₈ alkyl group,
Methyl, ethyl, propyl, 2-ethylhexyl, nonyl - selected from the group consisting of C ₁₂ -C ₁₈ alkyl group containing alkyl and C ₁₂ -C _{1 8} mixed alkyl groups as well as ester or amide functionality, n is 2-20 The compound according to claim 1, which is an integer of 22. An ore flotation auxiliary agent containing the compound according to claim 21. 23. The compounds, independently R ₁₅ and R ₂₀ are each, C ₁₂ -C ₁₈ containing C _{1 2} -C ₁₈ alkyl group, C ₁₂ -C ₁₈ alkenyl groups and the ester or amide functionality 23. The ore flotation auxiliary agent according to claim 22, which is selected from the group consisting of alkyl groups, R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are methyl groups, and n is an integer of 2 to 12. 24. A calcium ore flotation auxiliary agent containing the compound according to claim 23. 25. The general formula IV: _{(Wherein, R 21, R 22, R} 23, R 24, R 25, R 26, R 27 and R ₂₈ are the same or different, linear or branched, C ₁ substituted or unsubstituted -C ₂₂ Selected from alkyl or alkenyl groups, which may contain at least one ester bond, at least one amide bond or mixtures thereof, wherein x and y are each independently 1-20. Is an integer, n is 1 to 20 and Z ⁻ is an anion), and the method comprises reacting a polyaminoalkyl compound with a multi-equivalent amount of an alkyl or alkenyl aldehyde or an alcohol compound. Method. 26. A diaminoalkyl compound has the formula: Wherein the aldehyde or alcohol compound is selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C ₁₂ -C ₁₈ mixed alkyl groups and mixtures thereof, and n is 1-5. 26. The method of claim 25, which is an integer. 27. The method of claim 25, wherein the diaminoalkyl compound is hexamethylenediamine. 28. Formula IV: _{(Wherein, R 21, R 22, R} 23, R 24, R 25, R 26, R 27 and R ₂₈ are the same or different, linear or branched, C ₁ substituted or unsubstituted -C ₂₂ Selected from alkyl or alkenyl groups, which may contain at least one ester bond, at least one amide bond or mixtures thereof, wherein x and y are each independently from 1 to 20 Is an integer, n is greater than 1 and Z ⁻ is an anion). 29. A composition according to claim 1, in combination with at least one conventional surfactant.
A surfactant composition comprising at least one of the described compounds. 30. The composition according to claim 29, wherein said conventional surfactant is a mono-quaternary ammonium compound. 31. A method according to claim 2 in combination with at least one conventional surfactant.
9. A surfactant composition containing at least one compound according to item 8. 32. The composition according to claim 31, wherein said conventional surfactant is a mono-quaternary ammonium compound.