ALKOXYLATED PHENOL DERIVATIVES

Abstract

Alkoxylates are described that are obtainable by (i) in a first step reacting a) one or more compounds selected from the group consisting of phenols that are substituted with one substituent, wherein the one substituent is in the ortho-, meta- or para-position to the OH group of the phenol and is selected from the group consisting of OH, R8, OR8, F, Cl, Br, I, CN, NO.sub.2 or COOR9, wherein R8 is a linear or branched alkyl group with 1 to 4 C-atoms and R9 is a linear or branched alkyl group comprising 1 to 22 C-atoms or a linear or branched mono- or polyunsaturated alkenyl group comprising 2 to 22 C-atoms with b) an aryl-substituted linear or branched C.sub.1-C.sub.3 alkyl alcohol or an aryl-substituted linear or branched C.sub.2- or C.sub.3-alkene, and (ii) in a second step alkoxylating the reaction product of the first step and (iii) in an optional third step reacting the reaction product of step (ii) 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.

These alkoxylates may advantageously be used as anti-redeposition agents in laundry applications.

Claims

1. An alkoxylate prepared by (i) in a first step reacting a) one or more compounds selected from the group consisting of phenols that are substituted with one substituent, wherein the one substituent is in the ortho-, meta- or para-position to the OH group of the phenol and is selected from the group consisting of OH, R8, OR8, F, CI, Br, I, CN, NO.sub.2 or COOR9, wherein R8 is a linear or branched alkyl group with 1 to 4 C-atoms and R9 is a linear or branched alkyl group comprising 1 to 22 C-atoms or a linear or branched mono- or polyunsaturated alkenyl group comprising 2 to 22 C-atoms, b) an aryl-substituted linear or branched C.sub.1-C.sub.3 alkyl alcohol or an aryl-substituted linear or branched C.sub.2- or C.sub.3-alkene, and (ii) in a second step alkoxylating the reaction product of the first step and (iii) in an optional third step reacting the reaction product of step (ii) 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.

2. The alkoxylate according to claim 1, wherein the molar ratio of the aryl-substituted linear or branched C.sub.1-C.sub.3 alkyl alcohols or the aryl-substituted linear or branched C.sub.2- or C.sub.3-alkenes mentioned under b) of the first step, to the one or more compounds selected from the group consisting of the substituted phenols mentioned under a) of the first step is of from 1:1 to 3:1.

3. The alkoxylate according to claim 1 wherein the molar ratio of alkoxylation agent to the one or more compounds selected from the group consisting of the substituted phenols mentioned under a) of the first step is of from 5:1 to 100:1.

4. The alkoxylate according to claim 1, wherein the one or more compounds selected from the group consisting of the substituted phenols mentioned under a) of the first step are selected from the group consisting of ortho-dihydroxybenzene, meta-dihydroxybenzene, para-dihydroxybenzene, ortho-methoxyphenol, meta-methoxyphenol and para-methoxyphenol.

5. The alkoxylate according to claim 1, wherein the alkoxylation of the second step is a reaction with ethylene oxide or with ethylene oxide and propylene oxide.

6. The alkoxylate according to claim 1, wherein the alkoxylate is prepared by (i) in a first step reacting a) one or more compounds selected from the group consisting of ortho-dihydroxybenzene, meta-dihydroxybenzene, para-dihydroxybenzene, ortho-methoxyphenol, meta-methoxyphenol and para-methoxyphenol, with b) styrene and (ii) in a second step alkoxylating the reaction product of the first step.

7. An alkoxylate according to formula (I) ##STR00007## 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−, R3-R7 are independently of one another H, Y, aryl, aryl-substituted linear or branched C.sub.1 to C.sub.3 alkyl or O(Z).sub.mT.sub.1, Y is R8, OR8, F, Cl, Br, I, CN, NO.sub.2 or COOR9, wherein R8 is a linear or branched alkyl group with 1 to 4 C-atoms and R9 is a linear or branched alkyl group comprising 1 to 22 C-atoms or a linear or branched mono- or polyunsaturated alkenyl group comprising 2 to 22 C-atoms, Z is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, T.sub.1 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−, n+m on a molar average, is a number of from 5 to 100, wherein exactly one of the substituents R3-R7 is O(Z).sub.mT.sub.1 or Y, and one to three of the other substituents R3-R7 are aryl or aryl-substituted linear or branched C.sub.1 to C.sub.3 alkyl.

8. The alkoxylate according to claim 7, wherein X is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, T is H, R3-R7 are independently of one another H, OCH.sub.3, C.sub.6H.sub.5CHCH.sub.3 or O(Z).sub.mH, Z is selected from the group consisting of ethoxy and mixtures of ethoxy and propoxy groups, n+m on a molar average, is a number of from 5 to 100, and that exactly one of the substituents R3-R7 is O(Z).sub.mH or OCH.sub.3.

9. The alkoxylate according to claim 7, wherein n+m, on a molar average, is a number of from 5 to 100.

10. The alkoxylate according to claim 7, wherein one of the substituents R3-R7 is Y, and n, on a molar average, is a number of from 5 to 100.

11. The alkoxylate according to claim 7, wherein one of the substituents R3-R7 is O(Z).sub.mT.sub.1, and n and m, on a molar average and independently of one another, are numbers of from 1 to 75.

12. The alkoxylate according to claim 7, wherein two of the substituents R3-R7 are aryl or aryl-substituted linear or branched C.sub.1 to C.sub.3 alkyl.

13. The alkoxylate according to claim 7, wherein X is ethoxy, T is H, R3 is O(Z).sub.mH, Z is ethoxy, n+m, on a molar average, is a number of from 5 to 35, two of the substituents R4, R5, R6 and R7 are H and the other two of these substituents are C.sub.6H.sub.5CHCH.sub.3.

14. The alkoxylate according to claim 7, wherein X is ethoxy, T is H, R4 is O(Z).sub.mH, Z is ethoxy, n+m, on a molar average, is a number of from 5 to 35, two of the substituents R3, R5, R6 and R7 are H and the other two of these substituents are C.sub.6H.sub.5CHCH.sub.3.

15. The alkoxylate according to claim 7, wherein X is ethoxy, T is H, R5 is O(Z).sub.mH, Z is ethoxy, n+m, on a molar average, is a number of from 5 to 35, two of the substituents R3, R4, R6 and R7 are H and the other two of these substituents are C.sub.6H.sub.5CHCH.sub.3.

16. The alkoxylate according to claim 7, wherein X is ethoxy, T is H, n, on a molar average, is a number of from 5 to 35, R3 is OCH.sub.3, two of the substituents R4 to R7 are H and the other two of these substituents are C.sub.6H.sub.5CHCH.sub.3.

17. The alkoxylate according to claim 7, wherein X is ethoxy, T is H, n, on a molar average, is a number of from 5 to 35, R5 is OCH.sub.3, two of the substituents R3, R4, R6 and R7 are H and the other two of these substituents are C.sub.6H.sub.5CHCH.sub.3.

18. The alkoxylate according to claim 17, wherein X is ethoxy, T is H, n, on a molar average, is a number of from 5 to 35, R3 and R7 are C.sub.6H.sub.5CHCH.sub.3, R4 and R6 are H and R5 is OCH.sub.3.

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

Description

EXAMPLES

[0094] 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. 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.

[0095] GC-MS spectra were recorded using an Agilent Technologies HP6890 gas chromatograph coupled with an HP 5973 series mass selective detector. Samples were separated on a 15 m×0.25 mm, 0.1 mm film DB-1 UI column. The column temperature was initially held at 40° C. for 2 minutes, then the temperature was raised to 320° C. at a rate of 10° C. per minute and held for 10 minutes. The injector temperature was maintained at 260° C., and the injection volume was 1.0 μL in the split mode. Helium was used as a carrier gas at a pressure of 20 kPa. Mass spectra were scanned from m/z 40-800. The ionization method was El+. All samples were dissolved in organic solvents and filtrated before injection into the GC-system.

[0096] The analysis of the reaction mixture was performed by identifying the species by GC-MS and quantification of the peaks by GC FID. The quantification for these compounds is given in GC area percent.

[0097] Gas chromatography was performed using a Hewlett Packard GC 6890 with autosampler, coupled with a flame-ionisation detector (fid). Samples were separated on a 15 m×0.32 mm, 0.25 μm film DB-5 column. The column temperature was initially held at 40° C. for 2 minutes, then the temperature was raised to 350° C. at a rate of 25° C. per minute and held for 5 minutes. The injector temperature was maintained at 250° C., the detector temperature was maintained at 330° 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 0.5 bar. The samples were prepared by diluting 10 mg of sample with 1.5 ml of dichloromethane.

Example 1

Reaction of Resorcinol with 3 Equivalents of Styrene

[0098] In a 500 ml 3 necked round bottom flask, 110.1 g (1.0 mol) resorcinol and 1.0 g (5.46 mmol) para-toluenesulfonic acid were heated to 120° C. with stirring under nitrogen atmosphere. At 120° C., 312.5 g (3.0 mol) styrene were added dropwise over 1.5 hours. After the addition was completed, the reaction mixture was stirred for 6 hours at 130° C. After cooling down to room temperature, 365.8 g of an orange red solid were obtained.

[0099] The composition of the obtained mixture was analyzed by GC-MS and GC. It contained 0.8% distyrenated resorcinol, 93.7% tristyrenated resorcinol and 1.6% tetrastyrenated resorcinol (percentages given are GC area percent).

Example 2

Reaction of Resorcinol with 2 Equivalents of Styrene

[0100] In a 500 ml 3 necked round bottom flask, 137.6 g (1.25 mol) resorcinol and 1.3 g (6.88 mmol) para-toluenesulfonic acid were heated to 120° C. with stirring under nitrogen atmosphere. At 120° C., 260.4 g (2.5 mol) styrene were added dropwise over 1.5 hours. After the addition was completed, the reaction mixture was stirred for 6 hours at 130° C. After cooling down to room temperature, 379.0 g of a dark red solid were obtained.

[0101] The composition of the obtained mixture was analyzed by GC-MS and GC. It contained 9.1% monostyrenated resorcinol, 63.6% distyrenated resorcinol and 25.1% tristyrenated resorcinol (percentages given are GC area percent).

Example 3

Reaction of 4-Methoxyphenol with 2 Equivalents of Styrene

[0102] In a 500 ml 3 necked round bottom flask, 155.2 g (1.25 mol) 4-methoxyphenol and 1.3 g (6.88 mmol) para-toluenesulfonic acid were heated to 120° C. with stirring under nitrogen atmosphere. At 120° C., 260.4 g (2.5 mol) styrene were added dropwise over 1.5 hours. After the addition was completed, the reaction mixture was stirred for 2.5 hours at 130° C. After cooling down to room temperature, 407.3 g of a dark orange solid were obtained.

[0103] The composition of the obtained mixture was analyzed by GC-MS and GC. It contained 5.0% monostyrenated 4-methoxyphenol, 88.0% distyrenated 4-methoxyphenol and 5.1% tristyrenated 4-methoxyphenol (percentages given are GC area percent).

Example 4

Reaction of Catechol with 2 Equivalents of Styrene

[0104] In a 500 ml 3 necked round bottom flask, 137.6 g (1.25 mol) catechol and 1.3 g (6.88 mmol) para-toluenesulfonic acid were heated to 120° C. with stirring under nitrogen atmosphere. At 120° C., 260.4 g (2.5 mol) styrene were added dropwise over 1.5 hours. After the addition was completed, the reaction mixture was stirred for 1.5 hours at 130° C. After cooling down to room temperature, 375.6 g of a brown-red solid were obtained.

[0105] The composition of the obtained mixture was analyzed by GC-MS and GC. It contained 4.9% monostyrenated catechol, 88.3% distyrenated catechol and 4.1% tristyrenated catechol (percentages given are GC area percent).

[0106] General procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols:

[0107] The styrenated phenol 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 100° C. for removal of methanol. This drying was continued for 2 hours at 100° C. After that, the vacuum was compensated with nitrogen. The reaction mixture was heated to 160° 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 20 hours the rest of ethylene oxide was added at 160° C. (4-5 bar) 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 5

Ethoxylation of the Product of Example 1 with 10 Equivalents of EO

[0108] 202.7 g of the product of example 1 and 1.3 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 203.7 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 155.9 g of the product (brown oil) were discharged out of the reactor.

Example 6

Ethoxylation of the Product of Example 1 with 20 Equivalents of EO

[0109] The remaining product of example 5 (250.7 g, calculated) was reacted with additional 125.7 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 182.2 g of the product (brown oil) were discharged out of the reactor.

Example 7

Ethoxylation of the Product of Example 1 with 30 Equivalents of EO

[0110] The remaining product of example 6 (194.2 g, calculated) was reacted with additional 64.9 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 259.1 g of the product (brown oil) were obtained.

Example 8

Ethoxylation of the Product of Example 4 with 10 Equivalents of EO

[0111] 206.6 g of the product of example 4 and 1.7 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 280.3 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 212.0 g of the product (brown oil) were discharged out of the reactor.

Example 9

Ethoxylation of the Product of Example 4 with 20 Equivalents of EO

[0112] The remaining product of example 8 (274.9 g, calculated) was reacted with additional 158.3 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 198.2 g of the product (brown oil) were discharged out of the reactor.

Example 10

Ethoxylation of the Product of Example 4 with 30 Equivalents of EO

[0113] The remaining product of example 9 (235.0 g, calculated) was reacted with additional 85.9 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 320.9 g of the product (brown oil) were obtained.

Example 11

Ethoxylation of the Product of Example 2 with 10 Equivalents of EO

[0114] 192.3 g of the product of example 2 and 1.5 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 248.3 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 175.4 g of the product (brown oil) were discharged out of the reactor.

Example 12

Ethoxylation of the Product of Example 2 with 20 Equivalents of EO

[0115] The remaining product of example 11 (265.2 g, calculated) was reacted with additional 149.4 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 179.1 g of the product (brown oil) were discharged out of the reactor.

Example 13

[0116] Ethoxylation of the Product of Example 2 with 30 Equivalents of EO

[0117] The remaining product of example 12 (235.5 g, calculated) was reacted with additional 84.9 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 320.4 g of the product (brown oil) were obtained.

Example 14

[0118] Ethoxylation of the Product of Example 3 with 10 Equivalents of EO

[0119] 208.5 g of the product of example 3 and 1.7 g of sodium methoxide solution (30 wt.-% in methanol) were reacted with 272.3 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 127.8 g of the product (brown oil) were discharged out of the reactor.

Example 15

Ethoxylation of the Product of Example 3 with 20 Equivalents of EO

[0120] The remaining product of example 14 (353.0 g, calculated) was reacted with additional 199.9 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 410.0 g of the product (brown oil) were discharged out of the reactor.

Example 16

Ethoxylation of the Product of Example 3 with 30 Equivalents of EO

[0121] The remaining product of example 15 (142.9 g, calculated) was reacted with additional 51.7 g of ethylene oxide (10 mol EO/mol) as described in the general procedure for the ethoxylation of styrenated derivatives of hydroxy or alkoxy phenols. 194.6 g of the product (brown oil) were obtained.

[0122] 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 1.2 oxide Linear alkyl benzene sulfonate 4.6 Sodium laureth ether sulphate with 1 mole 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 ASP dispersant see text Water balance

[0123] ASP: alkoxylated and styrenated phenol derivative

Application Example 1

Anti-Redeposition Benefit

[0124] 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 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.

[0125] 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)

[0126] 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 Example ΔL 95% 11 5.85 0.48 14 4.40 0.44 15 2.29 0.45 16 4.04 0.43

[0127] The dispersants enhance anti-redeposition.

Application Example 2

Stain Removal Benefit

[0128] The formulations of Table 1 including exemplary dispersants of Table 2 were used to wash eight 5×5 cm EMPA 117 stain swatches (blood/milk/ink stain on polycotton) in a tergotometer set at 200 rpm. A 60 minute wash was conducted in 800 ml of 26° French Hard water at 20° C., with 2.3 g/l of the formulation. To simulate oily sebaceous soil 7.2 g of an SBL2004 soil strip (ex Warwick Equest) was added to the wash liquor.

[0129] 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.

[0130] The cleaning benefit was expressed as the ΔL value:

ΔL=L(dispersant)−L(control)

[0131] 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 3. The results are given in Table 3.

TABLE-US-00003 TABLE 3 Stain removal benefit Example ΔL 95% 14 0.49 0.43 15 1.45 0.26 16 0.96 0.32

[0132] The dispersants enhance stain removal.