Alkoxylated Polycarboxylic Acid Amides

Abstract

Alkoxylated polycarboxylic acid amides are provided obtainable by first reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or anhydrides derived therefrom, preferably an aromatic polycarboxylic acid containing three or four carboxylic acid units or anhydrides derived therefrom, more preferably an aromatic polycarboxylic acid containing three carboxylic acid units or anhydrides derived therefrom, even more preferably trimellitic acid or trimellitic acid anhydride, most preferably trimellitic acid anhydride, with an amine alkoxylate and in a second step reacting the resulting product with an alcohol or amine or a mixture of alcohols and/or amines, preferably with an alcohol.

Claims

1. An alkoxylated polycarboxylic acid amide, prepared by a first step of reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom, with an amine alkoxylate and in a second step reacting the resulting product with an alcohol or a mixture of alcohols.

2. The alkoxylated polycarboxylic acid amide according to claim 1 wherein the amine alkoxylate is described by formula (I), ##STR00005## wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms or an aryl or alkyl aryl group having 6 to 20 carbon atoms, R2 to R5 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, where the substituents R2 to R5 are chosen such that both of either R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, n and m are independently of each other, based on a molar average, numbers of from 0 to 100 such that n+m is of from 4 to 100, where in the case that R2 and R3 are both hydrogen, n is a number of from 4 to 100 and m is a number of from 0 to 50, and when m>0, the ratio of n to m is larger than 1, where in the case that R4 and R5 are both hydrogen, m is a number of from 4 to 100 and n is a number of from 0 to 50, and when n>0, the ratio of m to n is larger than 1, where in the case that both n and m are >0, the units are distributed blockwise, alternating, periodically and/or statistically, R6 and R7 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y is NH.sub.2.

3. The alkoxylated polycarboxylic acid amide according to claim 1, wherein the amine alkoxylate is an ethoxylated amine or an ethoxylated and propoxylated amine, wherein the ratio of ethylene oxide units to propylene oxide units is larger than 1.

4. The alkoxylated polycarboxylic acid amide according to claim 1, wherein the amine alkoxylate of formula (I) is an amine-terminated methyl-ethoxylated-propoxylated polyether where one of R6 and R7 is methyl and the other is hydrogen and the molecular mass Mn is from 381 to 4900.

5. The alkoxylated polycarboxylic acid amide according to claim 1, wherein the alcohol or at least one alcohol from the mixture of alcohols used in step 2 of the reaction is selected from the group consisting of lauryl alcohol (dodecanol), myristyl alcohol (tetradecanol), a mixture of lauryl alcohol and myristyl alcohol, cetearyl alcohol (a mixture of hexadecanol and octadecanol), stearyl alcohol (octadecanol) and coconut fatty alcohol (a mixture of C.sub.6 to C.sub.18 alcohols), phenoxyethanol, phenethyl alcohol and benzyl alcohol.

6. The alkoxylated polycarboxylic acid amide according to claim 1, according to formula (II) ##STR00006## wherein R8, R9 and R10 are selected from the group consisting of (a) and (b) such that at least one of R8, R9 and R10 is (b) and at least one of R8, R9 and R10 is (a), where: (a) is alkylaryloxy having 7 to 10 carbon atoms or unsubstituted alkoxy or alkenyloxy having 12 to 18 carbon atoms, and (b) is an amine alkoxylate group of formula (I′) ##STR00007## wherein R1 is a substituted or unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms or an aryl or alkyl aryl group having 6 to 20 carbon atoms, R2 to R5 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, where the substituents R2 to R5 are chosen such that both of either R2 and R3 or R4 and R5 are hydrogen and at least one of the other substituents is different from hydrogen, n and m are independently of each, based on a molar average, numbers of from 0 to 100 such that n+m is a number of from 4 to 100, where in the case that R2 and R3 are both hydrogen, n is a number of from 4 to 100 and m is a number of from 0 to 50, and when m>0, the ratio of n to m is larger than 1, where in the case that R4 and R5 are both hydrogen, m is a number of from 4 to 100 and n is a number of from 0 to 50, and when n>0, the ratio of m to n is larger than 1, where in the case that both n and m are >0, the units can be distributed blockwise, alternating, periodically and/or statistically, R6 and R7 are independently of each other hydrogen or an alkyl group having 1 to 4 carbon atoms, and at least one of R6 and R7 is methyl, and Y′ is NH.

7. The alkoxylated polycarboxylic acid amide according to claim 6, where R8 is equal to one of R9 or R10 and is an alkylaryloxy having 7 to 10 carbon atoms.

8. The alkoxylated polycarboxylic acid amide according to claim 6 wherein R8 is equal to one of R9 or R10 and is a substituted or unsubstituted ethoxylated aromatic alcohol residue having 8 to 16 carbon atoms.

9. The alkoxylated polycarboxylic acid amide according to claim 6, wherein (b) is an amine-terminated methyl-ethoxylated-propoxylated polyether residue where one of R6 and R7 is methyl and the other is hydrogen and the molecular mass Mn is from 381 to 4900.

10. A process for producing an alkoxylated polycarboxylic acid amide comprising the steps of firstly reacting an aromatic polycarboxylic acid containing at least three carboxylic acid units or an anhydride derived therefrom with an amine alkoxylate, and secondly reacting the resulting product with an alcohol or a mixture of alcohols.

11. The process according to claim 10, wherein the reaction of step 1 is conducted with 0.7 to 1.5 molar equivalents of the amine alkoxylate.

12. The process according to claim 10, wherein the reaction of step one is performed at a temperature of 50 to 150° C.

13. The process according to claim 10, wherein the reaction of step 2 is conducted with 1.8 to 3.5 molar equivalents of the alcohol or mixture of alcohols.

Description

EXAMPLES

[0077] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto.

[0078] Trimellitic acid was used as purchased from ACROS Organics. Trimellitic acid anhydride and pyromellitic acid was used as purchased from Alfa Aesar. Phenoxyethanol, para-toluene sulfonic acid and titanium isopropoxide were used as purchased from Merck. Methanesulfonic acid, 4-dodecylbenzenesulfonic acid mixture of isomers and benzyl alcohol were used as purchased from Sigma Aldrich.

[0079] Lauryl/myristyl alcohol and cetearyl 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 mass (per hydroxyl function, “Gebrauchsmol”). In this case the OH-value may be measured according to DIN 53240.

[0080] The acid number (acid value) may be measured according to DIN EN ISO 2114.

[0081] The degree of alkoxylation of the used amine alkoxylates may be checked using NMR spectroscopy, for example 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 an internal standard.

[0082] The esterification reactions were controlled by determining the residual content of alcohol (e.g. benzyl alcohol, phenoxyethanol, lauryl/myristyl alcohol and cetearyl 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).

[0083] For the quantification of benzyl alcohol, samples were separated on a 50 m×0.2 mm, 0.33 μm film column. The column temperature was initially held at 50° C., then the temperature was raised to 175° C. at a rate of 5° C. per minute and from 175° C. to 300° C. at a rate of 25° C. per minute. The injector 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 1.8 bar. The samples were prepared by diluting 500 mg of sample (duplicate analysis) with 5 ml of methanol.

[0084] For the quantification of phenoxyethanol, cetearyl alcohol and lauryl/myristyl alcohol, samples were separated on a 25 m×0.32 mm, 0.52 μm film column. The column temperature was initially held at 50° C., 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. 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 (duplicate analysis) with 5 ml of methanol.

[0085] 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).

[0086] All examples, unless otherwise stated, were performed according to a standard procedure. All reagents and quantities are listed in Table I.

[0087] The amine alkoxylate of choice was heated to 80° C. with stirring under nitrogen. The polycarboxylic acid or acid anhydride of choice was added in portions over 5 minutes. The reaction mixture was then stirred for 2.5 hours at 80° C. The product, henceforth termed precursor, was isolated and the acid number determined these are listed in Table I in the column AN1.

[0088] Some amount of the precursor (listed in the column “PC” of Table I) was mixed with the alcohol and catalyst of choice and heated to the temperature listed in Table I while stirring under nitrogen. The reaction mixture was stirred at the temperature listed for the time denoted in Table I and water was distilled off.

[0089] The abbreviations used in Table I are as follows: [0090] AA amine alkoxylate [0091] PCA polycarboxylic acid [0092] PC precursor [0093] BA benzyl alcohol [0094] PE phenoxyethanol [0095] C16/18 cetearyl alcohol [0096] C12/14 lauryl/myristyl alcohol [0097] AN1 acid number of the precursor [0098] AN2 acid number of the final product [0099] M41 amine-terminated methyl-ethoxylated-propoxylated polyether with an average molecular mass of 2000 g/mol, an average molar ratio of EO to PO of 4 to 1 with the EO and PO units distributed statistically [0100] TMAA trimellitic acid anhydride [0101] pTsOH p-toluene sulfonic acid

TABLE-US-00001 TABLE I Examples of Alkoxy Polycarbolxylic Acid Amides of the Invention Residual PC/ BA/ PE/ C16/18/ C12/C14/ Temp/ Time/ AN1/mg AN2/mg Alcohol/ AA PCA g g g g g Cat ° C. hr KOH/g KOH/g wt.-% 1 M41, TMAA, 215.0 20.2 pTsOH, 180 43 48.7 14.0 5.3 470 g 42.71 g 0.24 g 2 M41, TMAA, 215.0 20.2 pTsOH, 200 43 48.7 8.5 3 470 g 42.71 g 0.24 g 3 M41, TMAA, 340.6 40.8 pTsOH, 180 40 48.6 15.1 2.1 1005 g 91.36 g 0.36 g 4 M41, TMAA, 325.9 74.3 pTsOH, 180 42 48.6 8.9 11 1005 g 91.36 g 0.40 g 5 M41, TMAA, 334.6 54 pTsOH, 180 42 48.6 9.2 9.5 1005 g 91.36 g 0.39 g C1 M41, TMAA, — — — 2.5 48.7 — — 470 g 42.71 g

[0102] As a comparative example, sample Cl from Table I was isolated after the first synthesis step and no reaction with alcohol was performed.

[0103] An aqueous liquid laundry detergent of the following formulation was prepared:

TABLE-US-00002 TABLE II Liquid laundry detergent formulation Ingredient weight-% Mono propylene glycol 2.2 Triethanolamine 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 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 EXEMPLARY alkoxylated polycarboxylic acid amides of see text the invention Water balance

Application Example 1—Anti-Redeposition Benefit

[0104] The formulations of Table II were 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 water with 26° French hardness at 20° C., with 2.3 g/l of the formulation shown in Table II. 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.

[0105] 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)

[0106] 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 dispersants of Table I. The results are given in Table III.

TABLE-US-00003 TABLE III Anti-redeposition benefit Exemplary dispersant ΔL 95% Example 3 1.63 0.35 Example 4 3.58 0.19 Example 5 3.84 0.19 Comparative Example C1 0.31 0.06

[0107] The alkoxylated polycarboxylic acid amides of the invention enhance anti-redeposition.