WO1993016157A1

WO1993016157A1 - Process for producing low-viscosity aqueous esterquat concentrates

Info

Publication number: WO1993016157A1
Application number: PCT/EP1993/000203
Authority: WO
Inventors: Oriol Ponsati; Joaquim Bigorra; Nuria Bonastre
Original assignee: Henkel Kommanditgeselschaft Auf Aktien
Priority date: 1992-02-07
Filing date: 1993-01-29
Publication date: 1993-08-19
Also published as: DE4203489A1; DE59301215D1; EP0625184B1; ES2081719T3; EP0625184A1; JPH07503503A

Abstract

Low-viscosity aqueous esterquat concentrates are obtained by adding to aqueous solutions of quaternised di-fatty acid trialkanol amine esters of formula (I), in which R?1CO is an aliphatic, linear or branched saturated acyl radical with 6 to 22 carbon atoms, [Z] is an ethylene, propylene or isopropylene group and X is chloride, bromide, sulphate, methosulphate or phosphate, at least one viscosity regulator selected from the group formed by a) quaternised unsaturated di-fatty acid trialkanol amine ester salts, b) quaternised fatty acid amidoamine salts, c) diquaternised fatty acid triethanol amine ester salts.

Description

Process for the preparation of low-viscosity aqueous ester quat concentrates

Field of the Invention

The invention relates to a process for the preparation of low-viscosity aqueous ester quat concentrates, in which aqueous solutions of quaternized di-fatty acid trialkanolamine ester salts are mixed with selected viscosity regulators.

State of the art

For the treatment of textile fibers, yarns or fabrics, a large number of compounds or mixtures of substances are proposed which impart the desired properties to the textiles treated therewith or which are components of agents for textile care. Depending on the type of active ingredients used, the processing properties, the wearing properties of the textiles and their care can be improved.

For example, the American patent US 23 40 881 describes aqueous dispersions of condensation products, Made from a hydroxyalkyl poly in and a fatty acid glyceride, which improve the lubricity and the softness of the textiles treated with it.

In recent years, products which contain essentially quaternized ester salts of fatty acids with alkanolamines, so-called “ester quats”, have gained importance in the field of textile treatment agents as a cationic surfactant component. As representative of the extensive state of the art, reference is made to the documents US 3,915,867, US 4,370,272, EP 0 239 910 A2, EP 0 293 955 A2, EP 0 295 739 A2 and EP 0 309 052 A2.

Esterquats are not only characterized by excellent anti-static and anti-static properties, but also have a surprisingly good biodegradability for cationic surfactants. It is disadvantageous, however, that aqueous esterquat concentrates behave dilutantly at low shear forces and are structurally viscous only when shear is strong. In practice, this means that the viscosity of aqueous ester quat concentrates increases by leaps and bounds when pumping, and conveying these products through pipelines is therefore extremely problematic.

In European patent application EP 0 165 138 A2 it is proposed to regulate the viscosity of ester quats based on triethanolamine by adding organic salts such as sodium gluconate or short-chain quaternary ammonium compounds. The reduction in viscosity that can be achieved with this method when pumping is for Most of the technical applications, however, are in no way sufficient.

The object of the invention was therefore to develop a new process for producing low-viscosity textile treatment agents which is free from the disadvantages described.

Beachreibunσ of the invention

The invention relates to a process for the preparation of low-viscosity aqueous ester quat concentrates, which is characterized in that aqueous solutions of quaternized di-fatty acid trialkanolamine ester salts of the formula (I)

CH ₃

1+ [RiCO-O-EZJ-N-CZl-O-OCR ¹ ] X "(I)

I [Z] -OH

in the

R ¹ CO is an aliphatic, linear or branched saturated acyl radical having 6 to 22 carbon atoms,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate stands ,

mixed with at least one viscosity regulator, which is selected from the group consisting of

a) quaternized unsaturated di-fatty acid trialkanolamine ester salts,

b) quaternized or pseudoquaternized fatty acid amido amine salts,

c) long chain quaternized ammonium compounds and

d) diquaternized fatty acid trialkola inester salts

is formed.

Surprisingly, it was found that when the selected regulators are added, the viscosity of ester quat concentrates is reduced to such an extent, even with short-term and low shear, that pump delivery is possible without any problems.

Quaternized di-fatty acid tialkanolamine ester salts are known substances which are accessible by the relevant methods of preparative organic chemistry. They are usually prepared from fatty acids which are esterified in the first step with trialkanolamines, such as, for example, triethanolamine, tripropanolamine or triisopropanolamine. The difatty acid ester formed can then, for example, in a manner known per se Methyl chloride or dimethyl sulfate can be quaternized. In this context, the term "concentrate" includes 12 to 40, preferably 15 to 25% by weight solutions of the ester quat base in water and the term "ester quat base" 70 to 95, preferably 80 to 90% by weight. To understand% solutions of the ester quats in isopropyl alcohol.

Typical examples of the fatty acid components of these compounds are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid and behenic acid, as well as their technical mixtures, which are obtained, for example, from the splitting of vegetable oils or animal fats.

Textile treatment agents with a particularly low viscosity under shear can be produced by using quaternized di-fatty acid trialkanolamine ester salts of the formula (I) in which R ^ -CO is an acyl radical having 12 to 18 carbon atoms, Z is an ethylene group and / or X represents chloride or methosulfate.

Suitable viscosity regulators a) are quaternized unsaturated di-fatty acid trialkanolamine ester salts which follow the formula (II)

CH ₃

1+ [R ^ OO-CZJ-N- Zl-O-OCR ¹ ] X- (II)

I [Z] -OH in the

R ² CO is an aliphatic, linear or branched acyl radical having 16 to 22 carbon atoms and 1, 2 or 3 double bonds,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands.

To produce these known substances, one can start from unsaturated fatty acids, for example palmoleic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid and / or erucic acid and their technical mixtures, which in the first stage are mixed with trialkanolamines, such as ethanol be implemented in, propanolamine or isopropanolamine. The resulting difatty acid esters can then be quaternized in a manner known per se, for example with methyl chloride or dimethyl sulfate. Preferred viscosity regulators are quaternized unsaturated di-fatty acid trialkanolamine ester salts of the formula (II), the fatty acid components of which are derived from oleic acid and / or elaidic acid.

Quaternized or pseudoquaternized fatty acid amidoamines of the formula (purple), (Illb) and / or (IIIc) can be used as viscosity-regulating component b), CH ₃

1 ⁺ [R ³ CO-NH- [Z] -NH ₂ ] X- (purple)

CH ₃

1 ⁺ [R ³ CO-NH- [Z] -NH] X- (Ulb)

I CH ₃

CH ₃

1 ⁺ [R ³ CO-NH- [Z] -N-CH ₃ ] x- (HIc)

I.

CH ₃

in the

R ³ CO is an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands.

These substances are also known compounds which are obtained by esterifying fatty acids with Diamines, for example ethylene or propylene diamine, dimethylamine methylamine (DAMA), diethylamine ethyl in (DAEA) or dimethylamine propylamine (DAPA) and subsequent methylation can be obtained. The components (purple), (Illb) and (IIIc) can be present side by side in a mixture, the weight ratio within the mixture triangle being 1: 1: 8; 1: 8: 1 and 8: 1: 1 may vary.

It has proven to be advantageous to use quaternized fatty acid amidoamines of the formulas (purple), (Illb) and / or (IIIc), the fatty acid components of which have 12 to 18 and in particular 12 to 14 or 16 to 18 carbon atoms. Quaternized fatty acid amido acids are also particularly preferred, the fatty acid components of which are derived from oleic acid and / or elaidic acid.

Finally, long-chain quaternized ammonium compounds of the formula (IV) are suitable as viscosity-regulating component c),

(IV)

R ⁴ for alkyl and / or alkenyl radicals with 12 to 22 carbon atoms and for chloride, bromide, sulfate, methosulfate or phosphate

stands.

For quaternary ammonium compounds which have a particularly advantageous viscosity-reducing effect, R ⁴ in the formula (IV) represents alkyl radicals having 16 to 18 carbon atoms and X represents chloride.

Possible viscosity-regulating component d) are diquaterized fatty acid trialkanolamine ester salts of the formula (V),

CH ₃ CH ₃

1+ 1+

R ⁵ C0-0- [Z] -N- [Z] -00C- [Y] -CCX- [Z] -N- [Z] -0-Cκ3l ⁵ (V)

I I

[Z] -OH [Z] -OH

in the

R ⁵ CO is an aliphatic, linear or branched acyl radical having 12 to 18 carbon atoms,

[Z] for an ethylene, propylene or isopropylene group and

[Y] for an alkylene group with 0 or 1 to 18 carbon atoms

stands. The viscosity regulators can be added to the aqueous esterquat concentrates in amounts of 0.1 to 10, preferably 1 to 8 and in particular 3 to 7% by weight, based on the 100% by weight di-fatty acid trialkanoamine salt. The mixing can take place mechanically, for example by stirring or dispersing; a chemical reaction does not take place.

Industrial applicability

The aqueous ester quat concentrates obtainable by the process according to the invention are low-viscosity, easily pumpable even with short, low shear and have excellent anti-static and anti-static properties. They are therefore suitable for the production of textile treatment agents in which they can be present in amounts of 5 to 95, preferably 10 to 90% by weight, based on the agent.

The following examples are intended to explain the subject matter of the invention in more detail without restricting it.

Examples

J. Substances used

A) Esterquats

Quaternized di-fatty acid triethanolamine ester salts of the formula (I)

CH ₃

1+ [R ¹ CO-0-CH2CH2-N-CH2CH2-0-OCR ² ] GH ₃ S04 "(I)

I CH2CH ₂ OH

AI) product based on cig / ig tallow fatty acid, 90% by weight solution in water; Sales product of Pulcra s.a., Barcelona

A2) Product based on Ci6 / 18 ~ ^al 9 ^{fatty acid '90 wt} .-% solution in water; STEPANTEX ( ^R ) VS 90, sales product from Stefan B) Viscosity regulators

Bl) reaction product of di-oleic acid triethanolamine ester with dimethyl sulfate.

B2) reaction product of Ci2 l8 " ^coconut ^{fatty acid with} DAPA quaternized with dimethyl sulfate.

B3) reaction product of Cχs / ιg-tallow fatty acid with DAPA, quaternized with dimethyl sulfate.

B4) Cetyltrimethylammonium chloride.

B5) bis (Cχg / g-tallow fatty acid triethanolamine) adipate, quaternized with dimethyl sulfate.

II. Application examples

Preparation of the test mixtures. 177 g of quaternized di-fatty acid triethanolamine ester salt (Al, A2, in each case calculated as 100% by weight of solid) and 2 g of magnesium chloride were placed in a 1 l flask and dissolved in 813 g of deionized water. The mixture was heated to 50 ° C. and adjusted to pH = 3.0 with sodium hydroxide. After cooling to 37 ° C., 8 g of perfume oil were added.

Pump test. The test mixtures were optionally tempered to 20 ° C. after addition of the viscosity regulators and pumped in a circle over a period of 30 min using a peristaltic pump (Heidolph RZR2, 800 rpm). The viscosity of the mixtures was determined using a Brookfield RVT viscometer (spindle 2 to 7, 10 rpm) before carrying out the test and after the pumping tests had ended. The results are summarized in Table 1.

Tab. 1: Viscosity measurements in the pump test Percentages as% by weight

Legend: EQ = ester quat

VR = viscosity regulator c (VR) = concentration viscosity regulator Homogenizer test. After the addition of the viscosity regulators, the test mixtures were placed in a homogenizer of the rotor-stator mixer type, where they were mixed at 20 ° C. initially five times for 5 minutes and finally once for 15 minutes. The viscosities of the mixtures were determined before the start and after the end of each mixing period using the Brookfield method (see pump test). The results are summarized in Table 2.

Tab. 2: Viscosity measurements in the homogenizer test Percentages as% by weight

Claims

1. A process for the preparation of low-viscosity aqueous ester quat concentrates, characterized in that aqueous solutions of quaternized di-fatty acid trialkanolamine ester salts of the formula (I)

1 +

[RicO-O-Zl- -CZJ-O-OCR ¹ ] x- (I)

I.

[Z] -OH

in the

R ¹ CO is an aliphatic, linear or branched saturated acyl radical with 6 to 22 carbon atoms,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands, mixed with at least one viscosity regulator, which is selected from the group of

a) quaternized unsaturated di-fatty acid trialkanolamine ester salts, b) quaternized or pseudoquatated fatty acid amidoamine salts,

c) long chain quaternized ammonium compounds and

d) diquatated fatty acid trialkanolamine ester salts

is formed.

2. The method according to claim 1, characterized in that quaternized di-fatty acid trialkanol amine ester salts of the formula (I) are used as ester quats, in which R ^ CO for an acyl radical having 12 to 18 carbon atoms, Z for an ethylene group and / or X represents chloride or methosulfate.

3. The method according to claim 1, characterized in that quaternized unsaturated di-fatty acid trialkanolamine ester salts of the formula (II) are used as viscosity regulators,

CH ₃

1+ [R2CO-0- Z3-N- Z3-0-OCR ¹ ] x- (II)

I.

[Z] -OH

in the R ^ CO for an aliphatic, linear or branched acyl radical with 16 to 22 carbon atoms and 1, 2 or 3 double bonds,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands.

4. The method according to claim 3, characterized in that quaternized unsaturated di-fatty acid trialkanolamine ester salts of the formula (II) are used as viscosity regulators, the fatty acid components of which are derived from oleic acid and / or elaidic acid.

5. The method according to claim 1, characterized in that quaternized or pseudo-quaternized fatty acid amidoamines of the formula (purple), (Illb) and / or (IIIc) are used as viscosity regulators,

v _-- α

1+

[R ³ CO-NH- [Z] -NH2] X ~ (purple) CH ₃

1+ [R ³ CO-NH- [Z] -NH] X- (Illb)

CH ₃

1+ [R ³ CO-NH- [Z] -N-CH ₃ ] X "(IIIc)

CH ₃

in the

R CO is an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds,

[Z] for an ethylene, propylene or isopropylene group and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands.

6. The method according to claim 5, characterized in that quaternized fatty acid amidoamines of the formulas (purple), (Illb) and / or (IIIc) are used as viscosity regulators, the fatty acid components of which have 12 to 18 carbon atoms.

7. The method according to claim 5, characterized in that quaternized fatty acid amidoamines of the formulas (purple), (Illb) and / or (IIIc) are used as viscosity regulators, the fatty acid components of which have 12 to 14 carbon atoms.

8. The method according to claim 5, characterized in that quaternized fatty acid amidoamines of the formulas (purple), (Illb) and / or (IIIc) are used as viscosity regulators, the fatty acid components of which have 16 to 18 carbon atoms.

9. The method according to claim 5, characterized in that quaternized fatty acid amidoamines of the formulas (purple), (Illb) and / or (IIIc) are used as viscosity regulators, the fatty acid components of which are derived from oleic acid and / or elaidic acid.

10. The method according to claim 1, characterized in that long-chain quaternized ammonium compounds of the formula (IV) are used as viscosity regulators,

I.

[R4 - N-CH ₃ ] x- (IV)

I CH ₃

in the R ⁴ for alkyl and / or alkenyl radicals with 12 to 22 carbon atoms and

X for chloride, bromide, sulfate, methosulfate or phosphate

stands.

11. The method according to claim 10, characterized in that viscosity regulators of the formula (IV) are used in which R ^{4 is} alkyl radicals having 16 to 18 carbon atoms and X is chloride.

12. The method according to claim 1, characterized in that diquaternized fatty acid triethanolamine ester salts of the formula (V) are used as viscosity regulators,

CH ₃ CH ₃

1+ 1+

R ⁵ CO-0- [Z] -N- [Z] -OOC- [Y] -COO- [Z] -N- [Z] -0-OCR ⁵ (V)

I I

[Z] -OH [Z] -OH

in the

R ^ CO represents an aliphatic, linear or branched acyl radical having 12 to 18 carbon atoms,

[Z] for an ethylene, propylene or isopropylene group and [Y] for an alkylene group with 0 or 1 to 18 carbon atoms

stands.

13. The method according to claim 12, characterized in that viscosity regulators of the formula (V) are used in which R ⁵ CO for an acyl radical having 16 to 18 carbon atoms, [Y] for an alkylene group having 4 to 8 carbon atoms and [ZJ stands for an ethylene group.

14. The method according to claim 1, characterized in that the viscosity regulator to the aqueous ester quat concentrates in amounts of 0.1 to 10 wt .-% - based on the 100 wt .-% di-fatty acid trialkanoamine salt ¬ sets.