PROCESS FOR THE PRODUCTION OF A TERTIARY AMINE SURFACTANT

Abstract

Described herein is a process for the production of a surfactant, as well as a surfactant composition. Also described herein are specific surfactants and compositions thereof, as well as methods of their use in a wide variety of applications such as all purpose cleaning agents.

Claims

1. A process for producing a tertiary amine surfactant of general formula (I) ##STR00007## or a salt thereof, wherein R.sup.1 is selected from the group consisting of C.sub.5-C.sub.17-alkyl and C.sub.5-C.sub.17-alkenyl; R.sup.2 and R.sup.3 are independently selected from the group consisting of C.sub.1-C.sub.8-alkyl and C.sub.3-C.sub.8-alkenyl, wherein C.sub.1-C.sub.8-alkyl and C.sub.3-C.sub.8-alkenyl are each optionally substituted with one or more substituents selected from the group consisting of a hydroxy group, a C.sub.1-C.sub.8-alkoxy group, an amino group, a C.sub.1-C.sub.8-alkylamino group, a thio group and a C.sub.1-C.sub.8-alkylthio group; or wherein R.sup.2 and R.sup.3, together with the nitrogen atom to which they are bound, form a 5- or 6-membered heterocycle, optionally substituted with one or more substituents selected from the group consisting of a hydroxy group, a C.sub.1-C.sub.8-alkoxy group, an amino group, a C.sub.1-C.sub.8-alkylamino group, a thio group and a C.sub.1-C.sub.8-alkylthio group; the process comprising reductive amination of an aldehyde of general formula (II) ##STR00008## wherein R.sup.1 is defined as above; with a secondary amine of general formula (III) ##STR00009## wherein R.sup.2 and R.sup.3 are defined as above; in the presence of molecular hydrogen and a heterogeneous catalyst comprising a group 10 element of the periodic table of the elements; wherein the reductive amination is conducted in feed operation, wherein the secondary amine of general formula (III) is provided, and the aldehyde of general formula (II) is metered thereto; and wherein the reductive amination is performed at a pressure of molecular hydrogen in the range of at least 1 bara to less than 40 bara; and at a temperature in the range of 25 to 70 C.

2. The process according to claim 1, wherein R.sup.1 is C.sub.7-C.sub.17-alkyl; or wherein R.sup.1 is C.sub.9-C.sub.17-alkenyl.

3. The process according to claim 1, wherein R.sup.2 is optionally substituted C.sub.1-C.sub.3-alkyl; and R.sup.3 is optionally substituted C.sub.1-C.sub.3-alkyl.

4. The process according to claim 1, wherein R.sup.2 and R.sup.3, together with the nitrogen atom to which they are bound, form a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, or a 8-oxa-3-azabicyclo[3.2.1]octanyl group, each of which is optionally substituted.

5. The process according to claim 1, wherein the group 10 element is selected from the group consisting of palladium, platinum and nickel.

6. The process according to claim 5, wherein the heterogeneous catalyst is palladium on activated carbon.

7. The process according to claim 1, wherein the process is conducted in the presence of a solvent.

8. The process according to claim 7, wherein the solvent comprises a protic solvent and/or an aprotic solvent comprising an ether moiety.

9. The process according to claim 8, wherein the solvent is selected from the group consisting of an aliphatic alcohol and a mixture of an aliphatic alcohol and water.

10. The process according to claim 7, wherein the solvent dilution ratio is less than 5.0 L per kg, the solvent dilution ratio being the total volume of solvent to the total weight of the aldehyde of general formula (II) and the secondary amine of general formula (III).

11. The process according to claim 1, comprising neutralizing the tertiary amine surfactant of general formula (I) with an acid.

12. The process according to claim 1, wherein the aldehyde of general formula (II) and/or the secondary amine of general formula (III) are bio-based compounds.

13. A surfactant composition, comprising a surfactant of general formula (I) or a salt thereof as defined according to claim 1 in an amount of at least 90 wt.-%, relative to the weight of the surfactant composition, and a compound of general formula (IV) ##STR00010## or a salt thereof in an amount of 0.01 to 5.0 wt.-%, relative to the weight of the surfactant composition, wherein R.sup.2 and R.sup.3 are defined as above; and R.sup.4 is selected from the group consisting of C.sub.10-C.sub.34-alkyl and C.sub.10-C.sub.34-alkenyl, with the proviso that the number of carbon atoms in R.sup.4 differs from the number of carbon atoms in R.sup.1 of the surfactant of general formula (I).

14. A compound selected from the group consisting of 2-[(3,7-dimethyloctyl)(methyl)amino]ethanol, 1-(3,7-dimethyloctyl)pyrrolidine, 3-dodecyl-8-oxa-3-azabicyclo[3.2.1]octane, 3-nonyl-8-oxa-3-azabicyclo[3.2.1]octane, and 3-(3,7-dimethyloctyl)-8-oxa-3-azabicyclo[3.2.1]octane, or a salt thereof.

15. A composition comprising at least one compound according to claim 14.

16. A method of using the compound according to claim 15, the method comprising using the compound as a surfactant.

17. The process according to claim 1, wherein R.sup.1 is a C.sub.8-, C.sub.9- or C.sub.11-alkyl.

18. The process according to claim 1, wherein R.sup.1 is a C.sub.9-alkenyl.

19. The process according to claim 1, wherein R.sup.2 is C.sub.1-C.sub.3-alkyl substituted with a hydroxy group.

20. The process according to claim 1, wherein R.sup.3 is methyl.

Description

EXAMPLES

General Information

[0127] Reductive aminations of an aldehyde with a secondary amine were performed at a temperature of 25 to 50 C. and at a hydrogen pressure of 5 to 10 bar in a 300 mL autoclave in accordance with Table 1 below.

[0128] Analysis was performed via gas chromatography (after silylation) or via gas chromatography-mass spectrometry (GC-MS), and structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy.

Example 1

[0129] Palladium on carbon black (10 wt.-%, 1.9 g) was added to a solution of pyrrolidine (99%, 10 g) and dodecanal (95%, 29 g) in tetrahydrofuran (100 mL) in an autoclave. The reaction vessel was closed and subsequently purged with nitrogen gas (thrice at 5 bar). At an initial hydrogen gas pressure of 5 bar, stirring (700 rpm) was applied. The reaction mixture was warmed to 25 C. and the hydrogen pressure was maintained at 5 bar.

[0130] The reaction mixture was stirred under these conditions for 12 h, then cooled to room temperature and purged with nitrogen gas (thrice at 5 bar). Afterwards, the catalyst was filtered off and the solvent was removed by evaporation, yielding the crude material as a liquid (purity: 71%, 35 g, yield: 75%).

Example 2

[0131] Example 2 was performed analogously to Example 1, as indicated in Table 1.

Example 3

[0132] Palladium on carbon black (10 wt.-%, 1 g) was added to a solution of morpholine (99%, 10 g) in ethanol (90 mL) in an autoclave. The reaction vessel was closed and subsequently purged with nitrogen gas at (thrice at 5 bar). At an initial hydrogen gas pressure of 5 bar, stirring (700 rpm) was applied. The reaction mixture was warmed to 40 C. Subsequently, dodecanal (95%, 25 g) as a solution in ethanol (20 mL) was metered continuously to the reaction mixture over the course of 5 h. The temperature (40 C.) and the hydrogen pressure (5 bar) were maintained.

[0133] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 40 C. and a hydrogen pressure of 5 bar for 1 h, then cooled to room temperature and purged with nitrogen gas (thrice at 5 bar). Afterwards, the catalyst was filtered off and the solvent was removed by evaporation, yielding the crude material as a colourless liquid (purity: 91%, 29 g, yield: 91%).

Example 4

[0134] Palladium on carbon black (10 wt.-%, 1.5 g) was added to a solution of pyrrolidine (99%, 15 g) in a mixture of ethanol (50 mL) and water (40 mL) in an autoclave. The reaction vessel was closed and subsequently purged with nitrogen gas at (thrice at 5 bar). At an initial hydrogen gas pressure of 5 bar, stirring (700 rpm) was applied. The reaction mixture was warmed to 40 C. Subsequently, dodecanal (95%, 45 g) as a solution in ethanol (20 mL) was metered continuously to the reaction mixture over the course of 5 h. The temperature (40 C.) and the hydrogen pressure (5 bar) were maintained.

[0135] After complete addition of the aldehyde solution, the reaction mixture was stirred at a temperature of 40 C. and a hydrogen pressure of 5 bar for 1 h, then cooled to room temperature and purged with nitrogen gas (thrice at 5 bar). Afterwards, the catalyst was filtered off and the solvent was removed by evaporation, yielding the crude material as a yellow liquid (purity: 89%, 46 g, yield: 80%). Distillation (5 mbar, 140-150 C.) yielded the product as a colorless liquid (purity: 99%, 30 g, yield: 59%).

Examples 5 to 8

[0136] Examples 5 to 8 were performed analogously to Example 4, as indicated in Table 1.

Example 9

[0137] Palladium on carbon black (10 wt.-%, 1.5 g) was added to a solution of N-methyl ethanolamine (100%, 15 g) and dodecanal (95%, 43 g) in a mixture of ethanol (70 mL) 5 and water (40 mL) in an autoclave. The reaction vessel was closed and subsequently purged with nitrogen gas (thrice at 5 bar). At an initial hydrogen gas pressure of 20 bar, stirring (700 rpm) was applied. The reaction mixture was warmed to 50 C. and the hydrogen pressure was maintained at 20 bar.

[0138] The reaction mixture was stirred under these conditions for 6 h, then cooled to room temperature and purged with nitrogen gas (thrice at 5 bar). Afterwards, the catalyst was filtered off and the solvent was removed by evaporation, yielding the crude material as a liquid (purity: 93%, yield: 88%).

TABLE-US-00002 TABLE 1 Solvent Dilution .sup.2 Secondary Time H.sub.2 T Yield .sup.3 Purity .sup.3 # Solvent Ratio .sup.1 [MPa.sup.1/2] Catalyst Amine Aldehyde [h] [bara] [ C.] [%] [%] .sup.1 * THF 2.6 18.5 Pd/C .sup.4 pyrrolidine dodecanal 12 5 25 75 71 (100 mL) (1.9 g) (10 g) (29 g) .sup.2 * THF 3.0 18.5 Pd/C .sup.4 piperidine dodecanal 12 5 30 75 77 (100 mL) (2.3 g) (10 g) (23 g) 3 EtOH 3.2 26.2 Pd/C .sup.4 morpholine dodecanal 5 + 1 .sup.5 5 40 91 91 (110 mL) (1.0 g) (10 g) (25 g) 4 EtOH/water 1.8 34.1 Pd/C .sup.4 pyrrolidine dodecanal 5 + 1 .sup.5 5 40 80 89 1.75:1 (1.5 g) (15 g) (45 g) (110 mL) 5 EtOH/water 1.9 34.1 Pd/C .sup.4 N-methyl dodecanal 5 + 1 .sup.5 20 50 93 91 1.75:1 (2.0 g) ethanolamine (43 g) (110 mL) (15 g) 6 EtOH/water 1.7 34.1 Pd/C .sup.4 N-methyl citral .sup.6 5 + 1 .sup.5 20 50 94 96 1.75:1 (2.0 g) ethanolamine (45 g) (110 mL) (20 g) 7 EtOH/water 1.8 34.1 Pt/C .sup.7 pyrrolidine dodecanal 5 + 1 .sup.5 5 40 99 85 1.75:1 (8.0 g) (15 g) (45 g) (110 mL) .sup.8 * EtOH/water 1.9 34.1 Pd/C .sup.4 N-methyl dodecanal 5 + 1 .sup.5 50 80 92 79 1.75:1 (2.0 g) ethanolamine (43 g) (110 mL) (15 g) .sup.9 * EtOH/water 1.9 34.1 Pd/C .sup.4 N-methyl dodecanal 6 20 50 93 88 1.75:1 (2.0 g) ethanolamine (43 g) (110 mL) (15 g) .sup.1 volume contractions were taken into account for mixtures of two solvents .sup.2 Hildebrandt solubility parameter .sup.3 yield and purity refer to the crude product .sup.4 10 wt-% palladium on carbon black (no water content) .sup.5 time for continuous dosing of the aldehyde, plus additional stirring time .sup.6 3,7-dimethylocta-2,6-dienal (mixture of isomers) .sup.7 5 wt-% platinum on carbon black (50 wt-% water content) * comparative example

Example 10-Salt Form of Example 1

[0139] Crude N-dodecyl pyrrolidine as obtained in example 1 (71%, 10 g) was dissolved in tetrahydrofuran (50 mL). Concentrated aqueous hydrochloric acid (37%) was added to the solution until a pH value of 1 was reached. The reaction mixture was stirred at room temperature for 12 h. Afterwards, the solvent was removed by evaporation, and the crude material was recrystallized from heptane/toluene (19:1) at 75 C. (purity: 82%, 10 g, yield: 84%).