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) or salt thereof, ##STR00007## wherein independently from each other t being an integer from 1 to 100; A.sub.1 is independently for each repetition unit t 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 t equal to 1 the oxygen atom of the A.sub.1 group is bound to the B group and the following A.sub.1 group is always bound via the oxygen atom to the previous A.sub.1 group; B.sub.1 is 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; with the provisio that Z.sub.1 is 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, 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 of at least one group R.sub.4, R.sub.8, and/or R.sub.12 containing at least 7 or more 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.

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 is independently for each repetition unit t 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 Z.sub.1 is selected from the group consisting of alanine, glycine, lysine, and a compound according to Formula (II), wherein w is an integer in the range of from 1 to 4, and wherein the compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, with the provisio of at least one group R.sub.4, R.sub.8, and/or R.sub.12 containing at least 7 or more carbon atoms.

6. A process for preparation of the 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 B.sub.1 is 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; 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.

7. The process according to claim 6, 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.

8. The process according to claim 6, 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.

9. Use of the esteramine or 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.

10. Use of the esteramine or salt thereof according to claim 9 in shampoo or body wash formulations.

11. A personal care composition comprising the esteramine or salt thereof according to claim 1.

Description

EXAMPLES

Example 1: 2-Propylheptanol, Ethoxylated with 3 Mole Ethylene Oxide, Ester with 6-Amino Hexane Acid, Methane Sulfonic Acid Salt

[0048] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 58.1 g 2-Propylheptanol, ethoxylated with 3 mole ethylene oxide and 26.2 g 6-amino hexane acid are placed and heated to 90 C. To the mixture 19.6 g methane sulfonic acid is added within 10 minutes. The reaction mixture is heated to 130 C. and is stirred for 0.5 hours at 130 C. Vacuum (2 mbar) is applied and the reaction mixture is stirred for additional 10 hours at 130 C. 90.5 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 6-amino hexane acid acidtriethylene glycol 2-propyl-heptylether ester as methane sulfonic acid salt.

Example 2: C.SUB.13.Oxoalkohol Ethoxylated with 3 Mole Ethylene Oxide, Ester with 6-Amino Hexane Acid, Methane Sulfonic Acid Salt

[0049] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 65.93 g C.sub.13 oxoalkohol ethoxylated with 3 mole ethylene oxide and 26.23 g 6-amino hexane acid are placed and heated to 90 C. To the mixture 19.6 g methane sulfonic acid is added within 10 minutes. The reaction mixture is heated to 135 C. and is stirred for 7.0 hours at 135 C. Vacuum (5 mbar) is applied and the reaction mixture is stirred for additional 3 hours at 130 C. 101.95 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 6-amino hexane acid acidtriethylene glycol C.sub.13-oxoalkohol ester as methane sulfonic acid salt.

Example 3

[0050] 3a: C12/C14 fatty alcohol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide In a 2 I autoclave 573.6 g C12/C14 fatty alcohol and 2.4 g potassium tert.-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 348.5 g propylene oxide is added within 5 h. The mixture is stirred for additional 6 h, followed by the addition of 264.3 g ethylene oxide within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. After filtration 1178.0 g of a light yellowish oil was obtained (hydroxy value: 141.8 mgKOH/g).

[0051] 3b: C12/C14 fatty alcohol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt

[0052] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 59.3 g C12/C14 fatty alcohol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide and 17.9 g 6-amino hexane acid are placed and heated to 60 C. To the mixture 13.4 g methane sulfonic acid is added within 10 minutes. The temperature is allowed to rise to 70 C. during the addition. The reaction mixture is heated to 130 C. and is stirred for 13 hours at 130 C. Volatile compounds are removed in vacuo (2 mbar) at elevated temperature (135 C.) and 81.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to C.sub.12/C.sub.14 fatty alcohol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt.

Example 4

[0053] 4a 2-ethyl-hexanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide

[0054] In a 2 I autoclave 390.7 g 2-ethylhexanol and 2.0 g potassium tert.-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 348.5 g propylene oxide is added within 4 h. The mixture is stirred for additional 6 h, followed by the addition of 264.3 g ethylene oxide within 3 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. 1024.0 g of a light yellowish oil was obtained (hydroxy value: 164.0 mgKOH/g).

[0055] 4b: 2-ethylhexanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt

[0056] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 50.2 g 2-ethylhexanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide and 17.9 g 6-amino hexane acid are placed and heated to 60 C. To the mixture 13.4 g methane sulfonic acid is added within 10 minutes. The temperature is allowed to rise to 70 C. during the addition. The reaction mixture is heated to 130 C. and is stirred for 13 hours at 130 C. Volatile compounds are removed in vacuo (2 mbar) at elevated temperature (135 C.) and 72.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 2-ethylhexanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt.

Example 5

[0057] 5a: 2-propylheptanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide

[0058] In a 2 I autoclave 474.0 g 2-ethylhexanol and 2.4 g potassium tert.-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 348.5 g propylene oxide is added within 4 h. The mixture is stirred for additional 6 h, followed by the addition of 264.3 g ethylene oxide within 3 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. 1065.0 g of a light yellowish oil was obtained (hydroxy value: 152.0 mgKOH/g).

[0059] 5b: 2-propylheptanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt

[0060] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 59.8 g 2-propylheptanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide and 19.7 g 6-amino hexane acid are placed and heated to 60 C. To the mixture 14.7 g methane sulfonic acid is added within 10 minutes. The temperature is allowed to rise to 70 C. during the addition. The reaction mixture is heated to 130 C. and is stirred for 5 hours at 130 C. Then, vacuum is applied (800 mbar) and the mixture is stirred for 2 hours under these conditions. Volatile compounds are removed in vacuo (2 mbar) at elevated temperature (140 C.) and 86.9 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 2-propylheptanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt.

Example 6

[0061] 6a: 2-ethyl-hexanol, ethoxylated with 1 mol ethylene oxide

[0062] In a 2 I autoclave 651.1 g 2-ethylhexanol and 1.74 g potassium tert.-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 220.3 g ethylene oxide is added within 4 h. The mixture is stirred for additional 5 h at 140 C. to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. 870.0 g of a light yellowish oil was obtained (hydroxy value: 321.0 mgKOH/g).

[0063] 6b: 2-ethylhexanol, ethoxylated with 1 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt

[0064] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 38.3 g 2-ethylhexanol, ethoxylated with 1 mol ethylene oxide and 26.2 g 6-amino hexane acid are placed and heated to 60 C. To the mixture 19.6 g methane sulfonic acid is added within 10 minutes. The temperature is allowed to rise to 70 C. during the addition. The reaction mixture is heated to 130 C. and is stirred for 4 hours at 130 C. Vacuum is applied and volatile compounds are removed in vacuo (5 mbar) at elevated temperature (135 C.) for 2 hours. 72.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 2-ethylhexanol, ethoxylated with 1 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt.

Example 7

[0065] 7a: 2-propylheptanol, ethoxylated with 1 mol ethylene oxide

[0066] In a 2 I autoclave 794.0 g 2-propylheptanol and 2.0 g potassium tert.-butylate are placed and the mixture is heated to 140 C. The vessel is purged three times with nitrogen and 220.9 g ethylene oxide is added within 4 h. The mixture is stirred for additional 5 h at 140 C. to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 65 C. 1010.0 g of a light yellowish oil was obtained (hydroxy value: 275.0 mg KOH/g).

[0067] 7b: 2-propylheptanol, ethoxylated with 1 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt

[0068] In a 4-neck vessel with thermometer, reflux condenser, nitrogen inlet, dropping funnel, and stirrer, 44.5 g 2-propylheptanol, ethoxylated with 1 mol ethylene oxide and 26.2 g 6-amino hexane acid are placed and heated to 60 C. To the mixture 19.6 g methane sulfonic acid is added within 10 minutes. The temperature is allowed to rise to 70 C. during the addition. The reaction mixture is heated to 130 C. and is stirred for 4 hours at 130 C. Vacuum is applied and volatile compounds are removed in vacuo (4 mbar) at elevated temperature (135 C.) for 6 hours. 80.0 g of a light brown solid is obtained. .sup.1H-NMR in MeOD indicates complete conversion to 2-propylheptanol, ethoxylated with 1 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt.

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

[0069] 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

[0070] 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 8 Use as Additives in Detergents

[0071] 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.

[0072] 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.

[0073] Stain removal from the swatches was calculated as follows:

[00001]$\begin{array}{c}\mathrm{Stain}.Math..Math.\mathrm{Removal}.Math..Math.\mathrm{Index}\\ \left(\mathrm{SRI}\right)=\end{array}.Math.\frac{.Math..Math.E_{\mathrm{initial}}-.Math..Math.E_{\mathrm{washed}}}{.Math..Math.E_{\mathrm{initial}}}100$

E.sub.initial=Stain level before washing
E.sub.washed=Stain level after washing

[0074] 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 washing 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.

TABLE-US-00001 TABLE 1 Detergent composition DC1 Ingredients of liquid detergent percentage composition DC1 by weight n-C.sub.10-C.sub.13-alkylbenzene sulfonic acid 5.3 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 pH of detergent To Balance composition DC1 = 8.0

TABLE-US-00002 TABLE 2 Washing Experiment with Example 2 SRI, Bacon Graese Cleaning Without additive 26.1 Example 2: C.sub.13 Oxoalkohol ethoxylated 31.9 with 3 mole ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt; 0.045 g per wash Example 1: C.sub.10-Guerbetalkohol 31.8 (2-Propylheptanol) with 3 mole ethylenoxide, ester with 6-amino hexane acid, methane sulfonic acid salt; 0.046 g per wash Comparitive example 1: Butyltriglycol 28.0 ester with 6-amino hexane acid, methane sulfonic acid salt; 0.049 g per wash Comparitive example 2: Polyethylenglycol, 28.1 M.sub.w approx. 200 g/mol; ester with 6-amino hexane acid, methane sulfonic acid salt; 0.057 g per wash

TABLE-US-00003 TABLE 3 Washing Experiment with Example 5b: 2-propylheptanol, alkoxylated with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt SRI, Bacon Graese Cleaning Without additive 8.5 Example 5b: 2-propylheptanol, alkoxylated 17.5 with 2 mol propylene oxide and 2 mol ethylene oxide, ester with 6-amino hexane acid, methane sulfonic acid salt; 0.099 g per wash

[0075] Use as Additives in Detergents

[0076] 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 4). The pH of the washing solution prior to washing with and without additives was adjusted in each case to pH=8.0.

TABLE-US-00004 TABLE 4 Detergent composition DC2 Ingredients of liquid detergent percentage composition DC2 by weight linear C.sub.11.8-alkylbenzene sulfonic acid 17.6 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