ALKOXYLATED HYDROXYBENZOIC ACID ESTERS OR AMIDES

Abstract

Alkoxylates according to the following formula (I)

##STR00001##

are described, wherein X is selected from ethoxy and mixtures of ethoxy and propoxy groups, T is selected from the group consisting of H, C.sub.1-C.sub.4 alkyl, SO.sub.3.sup.−, CH.sub.2—COO.sup.−, sulfosuccinate and PO.sub.3.sup.2−, R1, R2 and R4 are H, CO—NR8R3 or COO—[X.sub.1].sub.v—R3, whereby two of the substituents R1, R2 and R4 are H and the third of these substituents is CO—NR8R3 or COO—[X.sub.1].sub.v—R3, R8 is H or a linear or branched alkyl group with 1 to 4 C-atoms, R3 is a linear or branched saturated alkyl group with 6 to 30 carbon atoms, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, a group (CH.sub.2CH.sub.2O).sub.maryl, wherein the aryl group comprises 6 to 10 carbon atoms and m, on a molar average, is a number from 1 to 100, or an aryl-substituted linear or branched C.sub.1-C.sub.3 alkyl group wherein the aryl group comprises 6 to 10 carbon atoms, but in the case, that R1 and R4 are H and R2 is COOR3, R3 can only be an alkyl group, an alkenyl group or a group (CH.sub.2CH.sub.2O).sub.maryl as defined above, X.sub.1 is selected from ethoxy and mixtures of ethoxy and propoxy groups, u on a molar average, is a number of from 3 to 100, and v on a molar average, is a number of from 0 to 20.

The compounds of formula (I) may advantageously be used as anti-redeposition agents in laundry applications.

Claims

1. An alkoxylate according to formula (I) ##STR00009## wherein X is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, T is selected from the group consisting of H, C.sub.1-C.sub.4 alkyl, SO.sub.3.sup.−, CH.sub.2—COO.sup.−, sulfosuccinate and PO.sub.3.sup.2−, R1, R2 and R4 are H, CO—NR8R3 or COO—[X.sub.1].sub.v—R3, whereby two of the substituents R1, R2 and R4 are H and the third of these substituents is CO—NR8R3 or COO—[X.sub.1].sub.v—R3, R8 is H or a linear or branched alkyl group with 1 to 4 C-atoms, R3 is a linear or branched saturated alkyl group with 6 to 30 carbon atoms, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30 carbon atoms, an aryl group with 6 to 10 carbon atoms, a group (CH.sub.2CH.sub.2O).sub.maryl, wherein the aryl group comprises 6 to 10 carbon atoms and m, on a molar average, is a number of from 1 to 100, or an aryl-substituted linear or branched C.sub.1-C.sub.3 alkyl group wherein the aryl group comprises 6 to 10 carbon atoms, but in the case, that R1 and R4 are H and R2 is COOR3, R3 can only be an alkyl group, an alkenyl group or a group (CH.sub.2CH.sub.2O ).sub.maryl as defined above X.sub.1 is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, u on a molar average, is a number of from 3 to 100, and on a molar average, is a number of from 0 to 20.

2. The alkoxylate according to claim 1, wherein X is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, T is selected from the group consisting of H, C.sub.1-C.sub.4 alkyl, SO.sub.3.sup.−, CH.sub.2—COO.sup.−, sulfosuccinate and PO.sub.3.sup.2−, R1, R2 and R4 are H, CO—NR8R3 or COO—[X.sub.1].sub.v—R3, whereby two of the substituents R1, R2 and R4 are H and the third of these substituents is CO—NR8R3 or COO—[X.sub.1].sub.v—R3, R8 is H or a linear or branched alkyl group with 1 to 4 C-atoms, R3 is a linear or branched saturated alkyl group with 6 to 30, carbon atoms, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30 carbon atoms or (CH.sub.2CH.sub.2O).sub.mphenyl, wherein m, on a molar average, is a number of from 1 to 100, and in the case, that R1 or R4 is COO—[X.sub.1].sub.v—R3, and the other substituents of R1, R2 and R4 are H R3 may also be phenyl or benzyl, X.sub.1 is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, u on a molar average, is a number of from 3 to 100, and v on a molar average, is a number of from 0 to 20.

3. The alkoxylate according to claim 1 wherein two of the substituents R1, R2 and R4 are H and the third of these substituents is COO—[X.sub.1].sub.v—R3, and the sum u+v, on a molar average, is a number of from 3 to 100.

4. The alkoxylate according to claim 1, wherein two of the substituents R1, R2 and R4 are H and the third of these substituents is COOR3.

5. The alkoxylate according to claim 1, wherein R4 is H.

6. The alkoxylate according to claim 1, wherein X is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, T is H, R1 and R2 are H or COOR3, whereby one of the substituents R1 and R2 is H and the other of these substituents is COOR3, R3 is a linear or branched saturated alkyl group with 6 to 30 carbon atoms, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30, carbon atoms or (CH.sub.2CH.sub.2O).sub.mphenyl, wherein m, on a molar average, is a number of from 1 to 100, and in the case, that R1 is COOR3 and R2 is H, R3 may also be phenyl or benzyl, R4 is H, and on a molar average, is a number of from 3 to 100.

7. The alkoxylate according to claim 1, wherein R1 and R4 are H and R2 is COOR3.

8. The alkoxylate according to claim 1, wherein R1 is COOR3 and R2 and R4 are H.

9. The alkoxylate according to claim 1, wherein R3 is a linear or branched saturated alkyl group with 6 to 30, carbon atoms or a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30, carbon atoms and in the case that R1 is COOR3 and R2 and R4 are H, R3 may also be phenyl or benzyl.

10. The alkoxylate according to claim 1, wherein R3 is a linear or branched saturated alkyl group with 6 to 30, carbon atoms or a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30, carbon atoms or (CH.sub.2CH.sub.2O).sub.mphenyl, wherein m, on a molar average, is a number of from 1 to 100.

11. The alkoxylate according to claim 1, wherein R3 is (CH.sub.2CH.sub.2O).sub.mphenyl, wherein m, on a molar average, is a number of from 1 to 10.

12. The alkoxylate according to claim 1, wherein R3 is a linear or branched saturated alkyl group with 6 to 30, carbon atoms or a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30 carbon atoms.

13. The alkoxylate according to claim 1, wherein R3 is selected from the group consisting of n-hexyl, 3-methyl-3-pentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, lauryl, n-tridecyl, isotridecyl, myristyl, n-pentadecyl, cetyl, palmitoleyl, n-heptadecyl, stearyl, oleyl, n-nonadecyl, arachidyl, heneicosyl, behenyl, erucyl, n-tetracosanyl, ceryl, 1-heptacosanyl, n-octacosanyl, n-nonacosanyl and myricyl.

14. The alkoxylate according to claim 1, wherein R3 is selected from the group consisting of stearyl, oleyl and isotridecyl.

15. The alkoxylate according to claim 1, wherein a) R1 and R4 are H, R2 is COOR3, R3 is oleyl, X is ethoxy, T is H and u, on a molar average, is a number of from 8 to 28, or b) R1 and R4 are H, R2 is COOR3, R3 is isotridecyl, X is ethoxy, T is H and u, on a molar average, is a number of from 8 to 16, or c) R1 and R4 are H, R2 is COOR3, R3 is isotridecyl, X is ethoxy, T is H and u, on a molar average, is a number of from 17 to 28, or d) R1 is COOR3, R2 and R4 are H, R3 is oleyl, X is ethoxy, T is H and u, on a molar average, is a number of from 6 to 12.

16. The alkoxylate according to claim 1, wherein it is a mixture of two or more compounds.

17. A method of preparing an alkoxylate according to claim 1, wherein one of the substituents R1, R2 or R4 in formula (I) is COO—[X.sub.1].sub.v—R3, and that in a first step ortho-, meta- or para-hydroxybenzoic acid is esterified or an ortho-, meta- or para-hydroxybenzoic acid ester of an alcohol with 1 to 4 carbon atoms is transesterified, in each case with an alcohol COO—[X.sub.1].sub.v—R3, wherein X.sub.1 is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, v on a molar average, is a number of from 0 to 20, and R3 is a linear or branched saturated alkyl group with 6 to 30, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30, an aryl group with 6 to 10 carbon atoms, a group (CH.sub.2CH.sub.2O).sub.maryl, wherein the aryl group comprises 6 to 10 carbon atoms and m, on a molar average, is a number of from 1 to 100, or an aryl-substituted linear or branched C1-C3 alkyl group wherein the aryl group comprises 6 to 10 carbon atoms, but in the case, that R1 and R4 are H and R2 is COOR3, R3 can only be an alkyl group, an alkenyl group or a group (CH.sub.2CH.sub.2O).sub.maryl as defined above, at a temperature of from 140 to 250° C. in the presence of a catalyst, and in a second step the ester obtained in the first step is reacted with ethylene oxide and/or propylene oxide in the presence of a catalyst at a pressure of from 1 to 100 bar and at a temperature of from 75 to 220° C. and in an optional third step the reaction product of the second step is reacted with an alkylating agent providing a C.sub.1-C.sub.4 alkyl group, with a carboxymethylating agent, with a sulfating agent, with a phosphating agent or with a sulfosuccinating agent.

18. A method of preparing an alkoxylate according to claim 1, wherein one of the substituents R1, R2 or R4 in formula (I) is CO-NR8R3 and that in a first step ortho-, meta- or para-hydroxybenzoic acid chloride or ortho-, meta- or para-hydroxybenzoic acid methyl ester is reacted with an amine HNR8R3, wherein R3 is a linear or branched saturated alkyl group with 6 to 30, a linear or branched mono- or polyunsaturated alkenyl group with 6 to 30, an aryl group with 6 to 10 carbon atoms, a group (CH.sub.2CH.sub.2O).sub.maryl, wherein the aryl group comprises 6 to 10 carbon atoms and m, on a molar average, is a number of from 1 to 100, or an aryl-substituted linear or branched C1-C3 alkyl group wherein the aryl group comprises 6 to 10 carbon atoms, but in the case, that R1 and R4 are H and R2 is COOR3, R3 can only be an alkyl group, an alkenyl group or a group (CH.sub.2CH.sub.2O).sub.maryl as defined above, and R8 is H or a linear or branched alkyl group with 1 to 4 C-atoms, and in a second step the amide obtained in the first step is reacted with ethylene oxide and/or propylene oxide in the presence of a catalyst at a pressure of from 1 to 100 bar and at a temperature of from 75 to 220° C. and in an optional third step the reaction product of the second step is reacted with an alkylating agent providing a C.sub.1-C.sub.4 alkyl group, with a carboxymethylating agent, with a sulfating agent, with a phosphating agent or with a sulfosuccinating agent.

Description

EXAMPLES

[0098] Benzyl salicylate was used as purchased from Sigma Aldrich.

[0099] Oleyl alcohol (HD-Ocenol® 70/75 V) was used as purchased from BASF. Isotridecyl alcohol (Marlipal® O13) was used as purchased from Sasol.

[0100] Isotridecyl alcohol and oleyl alcohol were used in technical grade quality and their molecular masses were determined prior to use by measuring the hydroxyl value (OH-value) and subsequently calculating the molecular weight (per hydroxyl function, “Gebrauchsmol”). In this case the OH-value may be measured according to DIN 53240.

[0101] The degree of alkoxylation of the inventive alkoxylates may be checked using NMR spectroscopy. The degree of ethoxylation of described examples was checked using .sup.1H-NMR spectroscopy in analogy to the method described in R.

[0102] Stevanova, D. Rankoff, S. Panayotova, S.L. Spassov, J. Am. Oil Chem. Soc., 65, 1516-1518 (1988). For this purpose, the samples are derivatised by reacting them with trichloro acetyl isocyanate and measured as solutions in deuterated chloroform containing 1 weight-% (1 wt.-%) of tetramethyl silane as internal standard.

[0103] Residual contents of salicylic acid and 4-hydroxybenzoic acid were determined by High Performance Liquid Chromatography (HPLC) after calibration with the pure materials. The analyses were conducted using an Ascentis Express RP-Amide column (150 mm length and 4.6 mm diameter with 2.7 μm silica particle size). The compounds were detected using a diode array detector (DAD, λ1=254 nm (hydroxybenzoic acid), λ2=303 nm (hydroxybenzoic acid). An eluent mixture of A: 0.1% (v/v) formic acid in water and B: acetonitrile/methanol 50/50 (v/v) was used in the following profile: 0-3 minutes: 30% (v/v) B, 3-20 minutes: 80% (v/v) B, 20-22 min: 100% (v/v) B, 22-30 minutes: 30% (v/v) B. The system was operated at a temperature of 40° C. with a flow rate of 1.4 ml/minute. For the sample preparation, 50 mg of the sample were dissolved in 10 ml of eluent B.

[0104] The esterification reactions of examples 1-4 were controlled by determining the residual content of oleyl alcohol and isotridecyl alcohol by GC-FID. Calibration was performed with pure starting materials. Gas chromatography (GC) was performed using a Hewlett Packard GC 6890 with autosampler, coupled with a flame-ionisation detector (fid). Samples were separated on a 25 m×0.32 mm, 0.52 μm film DB-5 column. The column temperature was initially held at 40° C. for 2 minutes, then the temperature was raised to 250° C. at a rate of 10° C. per minute and held for 6.5 minutes. The injector temperature was maintained at 250° C., the detector temperature was maintained at 250° C. and the injection volume was 1.0 μL in the split mode. Helium was used as a carrier gas with a constant pressure of 0.9 bar. The samples were prepared by diluting 500 mg of sample with 5 ml of methanol.

[0105] Thin layer chromatography (TLC) was performed using TLC Silica Gel 60 F254 plates from Merck. The aromatic compounds were detected by UV light (254 and 366 nm simultaneously). As the eluent, a mixture of hexanes/ethyl acetate=1:1 was used.

Example 1

[0106] 379.4 g (1.4 mol) of oleyl alcohol, 213.0 g (1.4 mol) of methyl salicylate and 6.0 g (43.4 mmol) of potassium carbonate were dissolved in 200 ml of xylene in a 1 liter round bottom flask equipped with a KPG stirrer, a reflux condenser and a thermometer. The reaction mixture was heated to reflux (150-166° C.) under nitrogen atmosphere for 11 hours. After this time, the status of the reaction was checked by thin layer chromatography (TLC; ethyl acetate:heptane=3:2) and no methyl salicylate was found.

[0107] The reaction mixture was cooled to room temperature, washed three times with 200 ml of saturated aqueous sodium bicarbonate solution and three times with 200 ml of water. The organic phase was dried with MgSO.sub.4 and the solvent was removed under reduced pressure. After the described workup, 409.6 g of the product was obtained as a dark brown oil. The residual content of methyl salicylate was <0.1 wt.-% as determined by gas chromatography (GC).

Example 2

[0108] 352.3 g (1.3 mol) of oleyl alcohol, 179.6 g (1.3 mol) of 4-hydroxybenzoic acid and 1.2 g (6.5 mmol) of p-toluenesulfonic acid were added into a 1 liter round bottom flask equipped with a KPG stirrer, a distillation bridge, a reflux condenser and a thermometer. The reaction mixture was heated to 170° C. under nitrogen atmosphere. The reaction was stirred at 170° C. for 8 hours and during that time the reaction water was distilled off. Afterwards, the reaction mixture was heated to 200° C. The reaction mixture was stirred at 200° C. for 8 hours and during that time the reaction water was distilled off.

[0109] The reaction mixture was cooled to room temperature and 483.1 g of the product were obtained and analysed. The residual content of 4-hydroxybenzoic acid was 0.25 wt.-% as determined by high performance liquid chromatography (HPLC) and the residual content of oleyl alcohol was 0.1 wt.-% as determined by gas chromatography (GC).

Example 3

[0110] 303.8 g (1.5 mol) of isotridecyl alcohol, 207.2 g (1.5 mol) of 4-hydroxybenzoic acid and 1.4 g (7.5 mmol) of p-toluenesulfonic acid were added into a 1 liter round bottom flask equipped with a KPG stirrer, a distillation bridge, a reflux condenser and a thermometer. The reaction mixture was heated to 170° C. under nitrogen atmosphere. The reaction was stirred at 170° C. for 8 hours and during that time the reaction water was distilled off. Afterwards, the reaction mixture was heated to 200° C. The reaction mixture was stirred at 200° C. for 8 hours and during that time the reaction water was distilled off.

[0111] The reaction mixture was cooled to room temperature and 444.1 g of the product were obtained and analysed. The residual content of 4-hydroxybenzoic acid was 0.64 wt.-% as determined by HPLC and the residual content of isotridecyl alcohol was <0.1 wt.-% as determined by gas chromatography (GC).

[0112] General procedure for the ethoxylation of hydroxyaromatic esters: The hydroxyaromatic ester was filled into a dry and clean lab autoclave. Sodium methoxide solution in methanol was added under stirring and then the autoclave was purged with nitrogen. After a successful pressure test, the pressure in the autoclave was again reduced to atmospheric pressure. Then full vacuum was applied and the reaction mixture was heated up to 120° C. for removal of methanol. This drying was continued for 2 hours at 120° C. After that, the vacuum was compensated with nitrogen. The reaction mixture was heated to 140° C. At this temperature a safe amount of ethylene oxide (EO) was added and the pressure observed until the reaction started (pressure decreased). In the following 7 to 17 hours the remaining ethylene oxide was added at 140° C. and stirring was continued for one to two hours to complete the reaction. Then the reaction mixture was cooled down to 100° C. and vacuum was applied for 30 minutes to remove residual ethylene oxide. After that, the vacuum was compensated with nitrogen, the reaction mixture cooled down to 80° C. and filled into a flask.

Example 4

Ethoxylation of Benzyl Salicylate with 10 Equivalents of EO

[0113] 156.8 g of benzyl salicylate and 1.2 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 302.3 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 206.7 g of the product (brown oil) were discharged out of the reactor.

Example 5

Ethoxylation of Benzyl Salicylate with 20 Equivalents of EO

[0114] The remaining product of example 4 (252.4 g, calculated) was reacted with additional 166.2 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 206.9 g of the product (brown oil) were discharged out of the reactor.

Example 6

Ethoxylation of Benzyl Salicylate with 30 Equivalents of EO

[0115] The remaining product of example 5 (211.7 g, calculated) was reacted with additional 84.1 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 295.8 g of the product (brown oil) were obtained.

Example 7

Ethoxylation of the Hydroxyaromatic Ester of Example 1 with 10 Equivalents of EO (DMC (Double Metal Cyanide) Catalysis)

[0116] 165.0 g of the hydroxyaromatic ester of example 1 was filled into a dry and clean lab autoclave. 0.08 g of Arcol Catalyst 3 (Bayer) and two droplets of phosphoric acid (40 wt.-% in water) were added under stirring, and then the autoclave was purged with nitrogen. After a successful pressure test, the pressure in the autoclave was again reduced to atmospheric pressure. Then full vacuum was applied and the reaction mixture was heated up to 140° C. When the temperature was reached, the vacuum was compensated with nitrogen. A safe amount (13 g) of ethylene oxide was added. Additional 0.125 g Arcol Catalyst 3 was added, because no evidence that the reaction had begun (i.e. no temperature increase) was observed. After addition of further 26 g ethylene oxide the typical conversion started and the rest of the 199.0 g ethylene oxide was added. The reaction mixture was stirred for one hour after completed addition. Then the reaction mixture was cooled down to 100° C. and vacuum was applied for 30 minutes to remove residual ethylene oxide. After that, the vacuum was compensated with nitrogen and the reaction mixture cooled down to 80° C. 173.0 g of the product (brown oil) were discharged out of the reactor.

Example 8

Ethoxylation of the Hydroxyaromatic Ester of Example 2 with 10 Equivalents of EO

[0117] 101.5 g of the hydroxyaromatic ester of example 2 and 1.4 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 114.9 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 97.1 g of the product (brown oil) were discharged out of the reactor.

Example 9

Ethoxylation of the Hydroxyaromatic Ester of Example 2 with 20 Equivalents of EO

[0118] The remaining product of example 8 (119.3 g, calculated) was reacted with additional 63.4 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 182.7 g of the product (brown oil) were obtained.

Example 10

Ethoxylation of the Hydroxyaromatic Ester of Example 3 with 10 Equivalents of EO

[0119] 65.4 g of the hydroxyaromatic ester of example 3 and 1.2 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 90.4 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 64.2 g of the product (brown oil) were discharged out of the reactor.

Example 11

Ethoxylation of the Hydroxyaromatic Ester of Example 3 with 20 Equivalents of EO

[0120] The remaining product of example 10 (91.6 g, calculated) was reacted with additional 53.2 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of hydroxyaromatic esters. 144.8 g of the product (brown oil) were obtained.

[0121] An aqueous liquid laundry detergent of the following formulation was prepared:

TABLE-US-00001 TABLE 1 Liquid laundry detergent formulation Ingredient weight-% Mono propylene glycol 2.2 Triethylamine 1.5 C.sub.12-C.sub.15 alcohol ethoxylate with 7 moles of ethylene oxide 1.2 Linear alkyl benzene sulfonate 4.6 Sodium laureth ether sulphate with 1 moles of ethylene 5.8 oxide Citric acid 2.0 CaCl.sub.2 dihydrate 0.2 NaCl 0.2 Tinopal ® CBS-X (fluorescer BASF) 0.3 Sodium Hydroxide to pH = 8.4 Exemplary dispersants see text Water balance

Application Example 1

Anti-Redeposition Benefit

[0122] The formulation was used to wash eight 5×5 cm knitted cotton cloth pieces in a tergotometer set at 200 rpm (revolutions per minute). A one hour wash was conducted in 800 ml of 26° French Hard water at 20° C., with 2.3 g/l of the formulation. To simulate particulate soil that could redeposit 0.04 g/l of 100%) compressed carbon black (ex Alfa Aesar) was added to the wash liquor. To simulate oily sebaceous soil 7.2 g of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.

[0123] Once the wash had been completed the cotton swatches were rinsed once in 400 ml clean water, removed, dried and the colour measured on a reflectometer and expressed as the CIE L*a*b* values. The anti-redeposition benefit was expressed as the ΔL value:

ΔL=L(dispersant)−L(control)

[0124] The larger the ΔL value the greater the prevention of deposition of the carbon black soil. 95% confidence limits based on the 8 separate cotton swatches were calculated. Formulations were made with and without the addition of 8.7 wt.-% of the dispersant of Table 2. The results are given in Table 2.

TABLE-US-00002 TABLE 2 Anti-redeposition benefit Exemplary dispersant ΔL 95% Example 8 9.5 0.4 Example 9 10.7 0.3 Example 10 11.7 0.3 Example 11 4.2 0.2 Example 7 4.1 0.2

[0125] The dispersants enhance anti-redeposition.