ALKOXYLATED ESTERAMINES AND SALTS THEREOF

Abstract

The present invention relates to alkoxylated esteramines of Formula (I) and salts thereof. Esteramines according to the present invention may be used in cleaning composition, for example in liquid laundry detergents. They lead to improved cleaning performance of said compositions, for example when used in cold water washing conditions. They surprisingly boost grease cleaning performance of liquid laundry detergents, especially under cold water washing conditions. Whiteness is also improved. The esteramine according to the present invention show improved compatibility in liquid laundry detergent formulations.

##STR00001##

Claims

1. An esteramine of Formula (I) and salt thereof, ##STR00007## wherein independently from each other n being an integer from 1 to 12, m being an integer for each repetition unit n independently selected from 0 to 12; p being an integer from 0 to 12, o being an integer for each repetition unit p independently selected from 0 to 12; r being an integer from 0 to 12, q being an integer for each repetition unit r independently selected from 0 to 12; s being an integer from 0 to 100; t being an integer from 1 to 100; u being an integer from 0 to 100; v being an integer from 0 to 100; with the sum of s, t, u, and v being equal to or greater than 1; A.sub.1, A.sub.2, A.sub.3, and A.sub.4 are independently from each other and independently for each repetition unit s, t, u, or v, selected from the list consisting of ethyleneoxy group, 1,2-propyleneoxy group, 1,2-butyleneoxy group, 2,3-butyleneoxy group, i-butyleneoxy group, pentyleneoxy group, hexyleneoxy group, styryloxy group, decenyloxy group, dodecenyloxy group, tetradecenyloxy group, and hexadecanyloxy group, wherein for s, t, u, and/or v equal to 1 the oxygen atom of the A.sub.1, A.sub.2, A.sub.3, and A.sub.4 group is bound to the B group and the following A.sub.1, A.sub.2, A.sub.3, and A.sub.4 groups are always bound via the oxygen atom to the previous A.sub.1, A.sub.2, A.sub.3, and A.sub.4 group; B.sub.1, B.sub.2, B.sub.3, and B.sub.4 are independently from each other selected from the group consisting of a bond, linear C.sub.1 to C.sub.12 alkanediyl groups, and branched C.sub.1 to C.sub.12 alkanediyl groups; R.sub.4, R.sub.8, and R.sub.12 being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.1, R.sub.2, and R.sub.3 being independently for each repetition unit m of each repetition unit n being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.5, R.sub.6, and R.sub.7 being independently for each repetition unit o of each repetition unit p being selected from the group consisting of 14, linear alkyl, branched alkyl, and cycloalkyl; R.sub.9, R.sub.10, and R.sub.11 being independently for each repetition unit q of each repetition unit r being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; i) with the provisio that when p and r are both equal to 0, and n being at least 1, Z.sub.1 and Z.sub.2, are independently selected from the group consisting of OH, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and a compound according to Formula (II), wherein said compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, with the provisio that at least one substituent Z.sub.1 and/or Z.sub.2 is not OH, and with the provisio that R.sub.3 contains equal to or more than 2 carbon atoms; ##STR00008## with independently from each other w being an integer from 0 to 12; R.sub.13 and R.sub.14 independently for each repetition unit w being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.15, R.sub.16, R.sub.17, and R.sub.18 being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; ii) with the provisio that when n and p are individually equal to or greater than 1 and r is equal to or greater than 0, Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, independently for each repetition unit n, p, and r, are selected from the group consisting of OH, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and a compound according to Formula (II), wherein said compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, with the provisio that at least one substituent Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, is not OH, and wherein for n and p equal to 1 and r equal to 0 at least one unit A.sub.1, A.sub.2, or A.sub.3 is selected from the group consisting of 1,2-propyleneoxy group, 1,2-butyleneoxy group, 2,3-butyleneoxy group, i-butyleneoxy group, pentyleneoxy group, hexyleneoxy group, styryloxy group, decenyloxy group, dodecenyloxy group, tetradecenyloxy group, and hexadecanyloxy group.

2. The salt of esteramine according to claim 1, wherein the salt is formed by at least partial protonation of the amine group by an acid being a protic organic or inorganic acid.

3. The salt of esteramine according to claim 1, wherein the salt is formed by at least partial protonation of the amine group by an acid being selected from the group consisting methanesulfonic acid, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, citric acid and lactic acid.

4. The esteramine or salt thereof according to claim 1, wherein A.sub.1, A.sub.2, A.sub.3, and A.sub.4 are independently from each other and independently for each repetition unit s, t, u, or v, selected from the list consisting of ethyleneoxy group, 1,2-propyleneoxy group, and 1,2-butyleneoxy group.

5. The esteramine or salt thereof according to claim 1, wherein p and r are both equal to 0, and n being at least 1, Z.sub.1 and Z.sub.2, are independently selected from the group consisting of OH, alanine, glycine, lysine, and a compound according to Formula (II), wherein w is an integer in the range of from 1 to 4, wherein the compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, with the provisio that at least one substituent Z.sub.1 and/or Z.sub.2 is not OFT, and with the provisio that R.sub.3 contains equal to or more than 2 carbon atoms.

6. The esteramine or salt thereof according to claim 1, wherein p and r are both equal to 0, and n being at least 1, wherein m is equal to 1 and R.sub.1 and R.sub.2 are both linear C.sub.2 to C.sub.4 alkyl groups.

7. The esteramine or salt thereof according to claim 1, wherein when n and p are individually equal to or greater than 1 and r is equal to or greater than 0, Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, independently for each repetition unit n, p, and r, are selected from the group consisting of OH, alanine, glycine, lysine, and a compound according to Formula (II), wherein w is an integer in the range of from 1 to 4, wherein the compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, with the provisio that at least one substituent Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, is not OH.

8. The esteramine or salt thereof according to claim 1, wherein n and p are both equal to 1, r is equal to 0, in and o are both equal to 0, B1 is equal to a chemical bond, R.sub.3, R.sub.4, R.sub.7, R.sub.8, and R.sub.12 are all equal to H.

9. The esteramine or salt thereof according to claim 1 any of the preceding claims 1 to 4, wherein n and p are both equal to 1, r is equal to 0, m and o are both equal to 0, B1 is equal to a methylene, R.sub.3, R.sub.1, R.sub.7, and R.sub.8, are all equal to H, and R.sub.12 is equal to ethyl.

10. A process for preparation of esteramine or salt thereof according to claim 1, comprising the steps of a) Reacting an alcohol according to Formula (III) ##STR00009## wherein independently from each other n being an integer from 1 to 12, m being an integer for each repetition unit n independently selected from 0 to 12; p being an integer from 0 to 12, o being an integer for each repetition unit p independently selected from 0 to 12; r being an integer from 0 to 12, q being an integer for each repetition unit r independently selected from 0 to 12; B.sub.1, B.sub.2, B.sub.3, and B.sub.4 are independently from each other selected from the group consisting of a bond, linear C.sub.1 to C.sub.12 alkanediyl groups, and branched C.sub.1 to C.sub.12 alkanediyl groups; R.sub.4, R.sub.8, and R.sub.12 being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.1, R.sub.2, and R.sub.3 being independently for each repetition unit m of each repetition unit n being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.5, R.sub.6, and R.sub.7 being independently for each repetition unit o of each repetition unit p being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.9, R.sub.10, and R.sub.11 being independently for each repetition unit q of each repetition unit r being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; with one or more C.sub.2 to C.sub.16 alkylene oxide, followed by b) at least partial esterification of the alkoxylated alcohol with at least one compound selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, acids according to Formula (IV), and salts thereof; ##STR00010## with w being an integer from 0 to 12, R.sub.13 and R.sub.14 independently for each repetition unit w being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; R.sub.15, R.sub.16, R.sub.17, and R.sub.18 being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl.

11. The process according to claim 10, wherein the molar ratio of alcohol according to Formula (III) to total C.sub.2 to C.sub.12 alkylene oxide is in the range of from 1:1 to 1:400.

12. The process according to claim 10, wherein the molar ratio of the acid to the hydroxyl groups of the alkoxylated alcohol is in the range of from 0.1:1 to 1:1.

13. Use of the esteramine and salt thereof according to claim 1 in personal care, as curing agent for epoxy resins, as reactant in the production of polymers, in polyurethanes, polyureas, or as thermoplastic polyamide adhesives.

14. Use of the esteramine and salt thereof according to claim 13 in shampoo or body wash formulations.

15. A personal care composition comprising the esteramine and salt thereof according to claim 1.

Description

EXAMPLES

Comparative Example 1: Butyltriglycol Ester with 6-amino Hexane Acid, Methane Sulfonic Acid Salt

[0099] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 64.39 g butyltriglycol and 39.35 g 6-amino hexane acid are placed and heated to 90 C. To the mixture 29.4 g methane sulfonic acid is added within 10 minutes. The reaction mixture is heated to 135 C. and is stirred for 4 hours at 135 C. Vacuum (5 mbar) is applied and the reaction mixture is stirred for additional 13.5 hours at 130 C. 122.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 6-amino hexane acid acid-butyltriglycol ester as methane sulfonic acid salt.

Comparative Example 2: Polyethylene Glycol, M.SUB.w .Approx. 200 g/Mol; Ester with 6-amino Hexane Acid, Methane Sulfonic Acid Salt

[0100] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 30.0 g polyethylene glycol (M.sub.w approx. 200 g/mol) and 39.35 g 6-amino hexane acid are placed and heated to 90 C. To the mixture 29.4 g methane sulfonic acid is added within 10 minutes. The reaction mixture is heated to 135 C. and is stirred for 4 hours at 135 C. Vacuum (5 mbar) is applied and the reaction mixture is stirred for additional 22 hours at 135 C. 97.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 6-amino hexane acid acid polyethylene glycol ester as methane sulfonic acid salt.

Example 1 Use as Additives in Detergents

[0101] Technical stain swatches of blue knitted cotton containing Bacon Grease were purchased from Warwick Equest Ltd. The stains were washed for 30 min in a launder-o-meter (manufactured by SDL Atlas) at room temperature using per canister 500 mL of washing solution, 20 metal balls and ballast fabrics. The washing solution contained 5000 ppm of detergent composition DC1 (table 1). Water hardness was 2.5 mM (Ca.sup.2+:Mg.sup.2+ was 4:1). Additives were added to the washing solution of each canister separately and in the amount as detailed below. After addition the pH value was re-adjusted to the pH value of washing solution without additive.

[0102] Standard colorimetric measurement was used to obtain L*, a* and b* values for each stain before and after the washing. From L*, a* and b* values the stain level were calculated as color difference E (calculated according to DIN EN ISO 11664-4) between stain and untreated fabric. Stain removal from the swatches was calculated as follows:

[00001]$\mathrm{Stain}.Math..Math.\mathrm{Removal}.Math..Math.\mathrm{Index}.Math..Math.\left(S.Math..Math.R.Math..Math.I\right)=\frac{.Math..Math.E_{\mathrm{inital}}-.Math..Math.E_{\mathrm{washed}}}{.Math..Math.E_{\mathrm{inital}}}100$

[0103] E.sub.initial=Stain level before washing

[0104] E.sub.washed=Stain level after washing

[0105] Stain level corresponds to the amount of grease on the fabric. The stain level of the fabric before the washing (E.sub.initial) is high, in the washing process stains are removed and the stain level after is smaller (E.sub.washed) The better the stains have been removed the lower the value for E.sub.washed will be and the higher the difference will be to E.sub.initial. Therefore, the value of stain removal index increases with better washing performance.

[0106] The esteramines according to the present invention can be used in the detergent composition of Table 1.

TABLE-US-00001 TABLE 1 Detergent composition DC1 Ingredients of liquid detergent composition DC1 percentage by weight n-C.sub.10-C.sub.13-alkylbenzene 5.3 sulfonic acid coconut C.sub.12-C.sub.18 fatty acid 2.4 sodium laureth sulfate + 2 EO 7.7 potassium hydroxide 2.2 C13C15- oxo alcohol + 7 EO 5.4 1,2 propylene glycol 6 ethanol 2 water To Balance pH of detergent composition DC1 = 8.0

Example 2: Sorbitol, Propoxylated with 12 Mole Propylene Oxide, Ester with 2 Mole 6-aminohexane Acid, Methane Sulfonic Acid Salt

[0107] 2a Sorbitol, Propoxylated with 12 Mole Propylene Oxide:

[0108] In a 2 l autoclave 278.85 g sorbitol and 2.65 g potassium tert-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 1005.4 g propylene oxide is added in portions within 15 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 C. After filtration 1325.0 g of a light yellowish oil is obtained (hydroxy value: 375 mgKOH/g).

[0109] 2b Sorbitol, Propoxylated with 12 Mole Propylene Oxide, Ester with 2 Mole 6-aminohexane Acid, Methane Sulfonic Acid Salt

[0110] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, and stirrer 88.14 g sorbitol propoxylated with 12 mole propylene oxide and 26.0 g 6-amino hexane acid are placed. The mixture is heated to 50 C., and 19.6 g methane sulfonic acid is added within 10 minutes under a constant stream of nitrogen. The temperature is allowed to rise to 60 C. during the addition. The reaction mixture is heated to 135 C. and is stirred for 4 hours at 135 C. Vacuum (5 mbar) is applied and the reaction mixture is stirred for additional 11.0 hours at 130 C. 121.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 33% conversion of hydroxyl groups into esterified hydroxyl groups.

Example 3 Sorbitol, Alkoxylated with 18 Mole Ethylene Oxide and 6 Mole Propylene Oxide, Ester with 2 Mole 6-aminohexane Acid, Methane Sulfonic Acid Salt

[0111] 3a Sorbitol, Alkoxylated with 18 Mole Ethylene Oxide and 6 Mole Propylene Oxide

[0112] In a 2 l autoclave 148.7 g sorbitol and 2.1 g potassium tert.-butylate are placed and the mixture is heated to 130 C. The vessel is purged three times with nitrogen and 634.3 g ethylene oxide is added within 20 h. The mixture is stirred for additional 5 h, followed by the addition of 278.8 g propylene oxide in portions within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 130 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. After filtration 1060.0 g of a light yellowish oil was obtained (hydroxy value: 250 mgKOH/g).

[0113] 3b Sorbitol, Alkoxylated with 18 Mole Ethylene Oxide and 6 Mole Propylene Oxide, Ester with 6 Mole DL-Alanine, Methane Sulfonic Acid Salt

[0114] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, and stirrer 105.8 g sorbitol, alkoxylated with 18 mole ethylene oxide and 6 mole propylene oxide and 42.8 g DL-alanine are placed. The mixture is heated to 50 C., and 47.1 g methane sulfonic acid is added within 10 minutes under a constant stream of nitrogen. The temperature is allowed to rise to 60 C. during the addition. The reaction mixture is heated to 135 C. and is stirred for 13 hours at 135 C. 186.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 100% conversion of hydroxyl groups into esterified hydroxyl groups.

[0115] Use as Additives in Detergents

[0116] Technical stain wfk20D (polyester/cotton 65/35, soil:pigment/sebum) from wfk Testgewebe GmbH, was used. Washing procedure and determination of stain removal index was followed as described above but with 1584 ppm of detergent composition 2 (table 2). The pH of the washing solution prior to washing with and without additives was adjusted in each case to pH=8.0.

TABLE-US-00002 TABLE 2 Detergent composition DC2 Ingredients of liquid detergent composition DC2 percentage by weight linear C.sub.11.8-alkylbenzene 17.6 sulfonic acid C12-C15 alkyl ethoxy (1.8) sulfate 4.4 C12-C14 alcohol + 9 ethylene oxide 0.9 C12-C18 fatty acid 1.1 C12-C14 amine oxide 0.8 chelant 2.8 solvent 14.8 brightener 0.2 sodium hydroxide 1.9 water To Balance Experiment 1 SRI, wfk 20D Without additive 40.3 Example 3: Sorbitol ethoxylated and 45.5 propoxylated, ester with alanine, methane sulfonic acid salt; 0.024 g per wash Experiment 2 SRI, wfk 20D Without additive 42.4 Example 2: Sorbitol propoxylated, ester 47.1 with ester with 6-amino hexane acid, methane sulfonic acid salt; 0.024 g per wash