PREPARATION METHOD FOR ESTERQUATS BASED ON OIL

Abstract

The present invention relates to a process for producing an esterquat by a transesterification reaction of a fatty acid oil or a mixture comprising one or more fatty acid oils and one or more fatty acids with a tertiary hydroxy amine and then a quaternization reaction. Esterquats obtained by the method of the invention show beneficial properties in particular when used as active component in fabric softener materials.

Claims

1-16. (canceled)

17. A process for producing a quaternary ammonium compound of Formula I: ##STR00003## wherein A and B each independently represents (CH.sub.2CHR.sub.2O).sub.n2H or (CH.sub.2CHR.sub.2O).sub.n3OCR.sub.3; and C represents methyl, ethyl or benzyl; n1, n2 and n3 each independently represents an integer from 1 to 20, wherein if A and B both are (CH.sub.2CHR.sub.2O).sub.n2H or both are (CH.sub.2CHR.sub.2O).sub.n3OCR.sub.3, n2 and n3 may be different or identical in A and B; R.sub.2 each independently represents H or an alkyl group with from 1 to 6 carbon atoms; R.sub.1 and R.sub.3 are each independently selected from the group consisting of: linear or branched C7-C21 alkyl groups, and linear or branched C7-C21 alkenyl groups; X.sup.− represents a counter ion; and wherein the process comprises: step a), wherein a hydroxy alkyl tertiary amine of Formula II ##STR00004## in which A and B each independently represents (CH.sub.2CHR.sub.2O).sub.n2H or (CH.sub.2CHR.sub.2O).sub.n3H and n1, n2, n3 and R.sub.2 are defined as for Formula I above, is reacted with one or more fatty acid oils or a mixture comprising one or more fatty acid oils and one or more fatty acids, wherein the alkyl or alkylene chains of the fatty acid residues correspond to R.sub.1 and R.sub.3 as defined for Formula I above; and wherein the process further comprises: step b), wherein the reaction product of step a) is reacted with a quaternization agent C-X, in which C and X are defined as for Formula I above, to obtain the quaternary ammonium compound of Formula I; wherein the total amount of the oils to be added in step a) is divided into at least two portions, wherein portion 1 is added to the hydroxy alkyl tertiary amine of Formula II at the start of step a) and portion 2, as well as any further portion, is added to the reaction mixture after at least some of the oil of portion 1 has reacted with the hydroxy alkyl tertiary amine according to Formula II.

18. The process of claim 17, wherein: a) n1, n2 and n3 each independently represents an integer from 1-6; b) R.sub.2 is H, methyl or ethyl; c) R.sub.1 and R.sub.3 are each independently selected from the group consisting of: linear or branched C11-C21 alkyl groups, and linear or branched C11-C21 alkenyl groups; d) X.sup.− represents an alkyl sulfate group, a halide anion or an alkyl carbonate.

19. The process of claim 17, wherein: a) n1, n2 and n3 each independently represents an integer from 1-3; b) R.sub.2 is H; c) R.sub.1 and R.sub.3 are each independently selected from the group consisting of linear or branched C11-C17 alkyl groups and linear or branched C11-C17 alkenyl groups; d) X.sup.− represents MeSO4-, EtSO4-, Cl—, methyl carbonate or ethyl carbonate.

20. The process of claim 17, wherein, in step a), the molar ratio of the alkyl carbonyl group of portion 1 of the fatty acid oil or the mixture comprising one or more fatty acid oils and one or more fatty acids and the hydroxyalkyl tertiary amine according to Formula II, at the time portion 1 is added, is 0.3-2.4:1.

21. The process of claim 17, wherein, when the decrement of free hydroxyalkyl tertiary amine according to Formula II is more than 25 wt % based on the initial amount of hydroxyalkyl tertiary amine, the portion 2 of the fatty acid oil or the mixture comprising one or more fatty acid oils and one or more fatty acids is added.

22. The process of claim 17, wherein the molar ratio of the alkyl carbonyl group of the total fatty acid oil or the mixture comprising one or more fatty acid oils and one or more fatty acids (total oil) and hydroxyalkyl tertiary amine is 0.9-3.0:1.

23. The process of claim 17, wherein the oil used in step a) is selected from the group consisting of: triglyceride oils; diglyceride oils; monoglyceride oils; or mixtures thereof.

24. The process of claim 17, wherein the oil added as portion 1 in step a) is different from the oil added as portion 2 or a further portion.

25. The process of claim 17, wherein the oil used as portion 1 has a lower iodine value than the oil used as portion 2 or a further portion.

26. The process of claim 17, wherein the tertiary hydroxyalkyl amines according to formula II are selected from the group consisting of: triethanolamine; ethanol diisopropanolamine; and combinations thereof.

27. The process of claim 17, wherein none or only a part of glycerin and/or glycerides are separated or removed from the reaction mixture; and/or the reaction in step a) and/or b) is conducted under an inert atmosphere; and/or no solvent is added in step b) before the quaternization reaction is conducted.

28. The method of claim 17, wherein a vacuum is not applied in step a).

29. The process of claim 17, wherein the temperature of the reaction mixture in step a) is in a range of from 140 to 180° C.

30. The process of claim 17, wherein the temperature of the reaction mixture in step a) is in a range of 162 to 168° C.

31. The process of claim 17, wherein the reaction mixture comprises an alkali catalyst during step a).

32. The process of claim 17, wherein the reaction mixture comprises a catalyst selected from the group consisting of: sodium alkoxide; titanium oxide; zinc oxide; an alkali catalyst; an alkali alcohol salt; a hypophosphite salt; and mixtures thereof.

33. The process of claim 32, wherein the catalyst is an alkali alcohol salt in a range of from 0.1 to 0.3 wt %, based on the total weight of the reaction mixture at the time.

34. The process of claim 17, wherein step b) is conducted when the decrement of the trialkanolamine in the reaction mixture of step a) is more than 70 wt %, based on the initial amount of hydroxyalkyl tertiary amine in step a).

35. A process of producing a fabric softener material comprising the reaction steps of claim 17.

36. A fabric softener material comprising esterquats prepared by the process of claim 17.

Description

EXAMPLE 1

[0067] Triethanolamine (326.6 g, 2.189 mol) and a first portion of oil, hardened palm oil (IV20, 880 g, 1.076 mol) were charged into a 2 L reactor. The mixture was heated and stirred at 80° C. for 0.5 hr under nitrogen atmosphere. The reactants were heated to 160° C. and stirred for 3 hrs after the addition of sodium hypophosphite (1.4 g) and sodium hydroxide (2.8 g). The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 3 hs of reaction were shown in Table 1 below:

TABLE-US-00001 TABLE 1 Components Mol % Components Mol % 1,2,3-triglyceride 0 TEA 20 1,3-diglyceride 5 mono ester 28 1,2-diglyceride 3 di ester 23 monoglyceride 15 tri ester 6

[0068] When the GC results showed that the decrement of TEA was above 50 wt %, then the second portion of oil, hardened palm oil (IV20, 320 g, 0.391 mol) was charged into the 2 L reactor. The mixture was stirred 160° C. for 2.5 hrs. The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 5.5 hs (3+2.5 hrs) of reaction were shown in Table 2 below.

TABLE-US-00002 TABLE 2 H-NMR results: Components Mol % Components Mol % 1,2,3-triglyceride 0 TEA 13 1,3-diglyceride 9 mono ester 22 1,2-diglyceride 5 di ester 31 monoglyceride 15 tri ester 6

[0069] The first portion of the oil accounted for 73 mol % of the total oil used in the process.

[0070] When the GC results showed that the decrement of TEA was more than 75 wt %, the resulted ester (696.9 g, 0.99 mol) was charged into a 1 L reactor. The mixture was heated and stirred at 65° C. Then, dimethyl sulfate (122.2 g, 0.97 mol) was slowly introduced below 90° C. The reaction mixture was stirred for 0.5 hr after the addition of DMS. Propylene glycol (91 g) was added into reactor and stirred for another 0.5 hr.

[0071] As shown in the H-NMR results, the contents of the target compounds of the transesterification reaction: mono ester and di ester was 53 mol % based on the total molar amount of the composition, or 89.8 mol % based on the total molar amount of all triethanolamine fatty esters in example 1. In addition, the content of di ester was higher than that of mono ester.

COMPARATIVE EXAMPLE 1

[0072] Triethanolamine (157 g, 1.052 mol), hardened palm oil (IV20, 300 g, 0.367 mol) and hardened palm oil (IV45, 309 g, 0.367 mol) were charged into a 1 L reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium methylate (25%, 5 g) was charged as the catalyst. Then, the reactants were heated to 140° C. and stirred for 4 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. The composition of the fatty acid hydroxyl alkylamine ester was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 3 below:

TABLE-US-00003 TABLE 3 Components Mol % Components Mol % 1,2,3-triglyceride 1 TEA 12 1,3-diglyceride 5 mono ester 22 1,2-diglyceride 5 di ester 25 monoglyceride 20 tri ester 10

[0073] When the GC results showed that the decrement of TEA was 84.4 wt %, the resulted ester (242.8 g, 0.34 mol) was charged into a 500 mL reactor. The mixture was heated and stirred at 55° C. Then, dimethyl sulfate (41.9 g, 0.33 mol) was slowly introduced below 70° C. The reaction mixture was stirred for 1 hr after the addition of DMS. Propylene glycol (31.5 g) was added into reactor and stirred for another 0.5 hr. Sodium chlorite (30%, 0.9 g) was added for bleaching.

[0074] The contents of the target compounds mono ester and di ester was 47 mol % based on the total molar amount of the composition, or 82.4 mol % based on the total molar amount of all triethanolamine fatty esters.

EXAMPLE 2

[0075] Triethanolamine (157 g, 1.052 mol), hardened palm oil (IV20, 300 g, 0.367 mol) and hardened palm oil (IV45, 154.5 g, 0.184 mol) were charged into a 1 L reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium methylate (25%, 5 g) was charged as the catalyst. The reactants were heated to 140° C. and stirred for 2 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. When the GC results showed that the decrement of TEA was more than 50 wt %, then the second portion of oil, hardened palm oil (IV45, 154.5 g, 0.184 mol) was charged into the reactor and the reaction mixture was stirred at 140° C. for another 2 hrs. The GC results of a sample taken at 4 hs of reaction showed that the decrement of TEA was 83.6 wt %.

[0076] The composition of the fatty acid hydroxyl alkylamine ester was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 4 below:

TABLE-US-00004 TABLE 4 Components Mol % Components Mol % 1,2,3-triglyceride 2 TEA 12 1,3-diglyceride 5 mono ester 26 1,2-diglyceride 4 di ester 24 monoglyceride 19 tri ester 8

[0077] When the GC results showed that the decrement of TEA was 83.6 wt %, the resulted ester (242.8 g) was charged into a 500 mL reactor. The mixture was heated and stirred at 55° C. Then, dimethyl sulfate (41.9 g, 0.33 mol) was slowly introduced below 70° C. The reaction mixture was stirred for 1 hr after the addition of DMS. Propylene glycol (31.5 g) was added into reactor and stirred for another 0.5 hr. Sodium chlorite (30%, 0.9 g) was added for bleaching.

[0078] Table 5 shows the comparison between one step and two steps reaction regarding contents and selectivity of TEA esters according to example 2 and comparative example 1.

TABLE-US-00005 TABLE 5 Mono- and di-ester in total Tri-ester in total TEA ester (Mol %) TEA ester (mol %) Comparative 82.46 17.54 example 1 Example 2 86.21 13.79

[0079] As shown in Table 5, the selectivity of target compounds of the transesterification reaction, mono- and di-esters were higher in example 2 compared with comparative example 1.

[0080] As shown in the H-NMR results, the content of the target compounds of the transesterification reaction: mono ester and di ester was higher in example 2 (50 mol %) than that of comparative example 1 (47 mol %). In addition, the content of tri ester in example 2 was lower than that of comparative example 1.

COMPARATIVE EXAMPLE 2

[0081] Triethanolamine (78 g, 0.523 mol), hardened palm oil (IV20, 150 g, 0.183 mol) and hardened palm oil (IV45, 154.5 g, 0.183 mol) were charged into a 500 mL reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium methylate (25%, 2.5 g) was charged as the catalyst. Then, the reactants were heated to 165° C. and stirred for 4 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 6 below:

TABLE-US-00006 TABLE 6 Components Mol % Components Mol % 1,2,3-triglyceride 1 TEA 11 1,3-diglyceride 4 mono ester 24 1,2-diglyceride 7 di ester 23 monoglyceride 20 tri ester 10

[0082] When the GC results showed that the decrement of TEA was 83.4 wt %, the resulted ester (250.0 g) was charged into a 500 mL reactor. The mixture was heated and stirred at 55° C. Then, dimethyl sulfate (43.2 g, 0.34 mol) was slowly introduced below 70° C. The reaction mixture was stirred for 1 hr after the addition of DMS. Propylene glycol (31.4 g) was added into reactor and stirred for another 0.5 hr.

EXAMPLE 3

[0083] Triethanolamine (78 g, 0.523 mol), hardened palm oil (IV20, 150 g, 0.183 mol) and hardened palm oil (IV45, 77.3 g, 0.092 mol) were charged into a 500 mL reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium hypophosphite 0.4 g (as color stabilizer) and sodium methylate (25%, 2.5 g) was charged as the catalyst. The reactants were heated to 165° C. and stirred for 2 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. When the GC results showed that the decrement of TEA was more than 50 wt %, then the second portion of oil, hardened palm oil (IV45, 77.3 g, 0.092 mol) was charged into the reactor and the reaction mixture was stirred at 165° C. for another 2 hrs. The GC results of a sample taken at 4 hs of reaction showed that the TEA content was 3.21 wt %.

[0084] The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 7 below:

TABLE-US-00007 TABLE 7 Components Mol % Components Mol % 1,2,3-triglyceride 2 TEA 10 1,3-diglyceride 5 mono ester 21 1,2-diglyceride 4 di ester 29 monoglyceride 21 tri ester 9

[0085] When the GC results showed that the decrement of TEA was 84.3 wt %, the resulted ester (117.9 g, 0.17 mol) was charged into a 500 mL reactor. The mixture was heated and stirred at 55° C. Then, dimethyl sulfate (20.5 g, 0.16 mol) was slowly introduced below 70° C. The reaction mixture was stirred for 1 hr after the addition of DMS. Propylene glycol (15.0 g) was added into reactor and stirred for another 0.5 hr.

[0086] Table 8 shows the comparison between one step and two steps reaction regarding contents and selectivity of TEA esters according to example 3 and comparative example 2.

TABLE-US-00008 TABLE 8 Mono- and di-ester in total Tri-ester in total TEA ester (Mol %) TEA ester (mol %) Comparative 82.46 17.54 example 2 Example 3 84.75 15.25

[0087] As shown in Table 8, the selectivity of target compounds of the transesterification reaction, mono- and di-esters were higher in example 3 compared with comparative example 2.

[0088] In comparative example 2, the contents of the target compounds mono ester and di ester was 47 mol % based on the total molar amount of the reaction product of the transesterification reaction, in contrast, in example 3, the contents of the target compounds mono ester and di ester was 50 mol % based on the total molar amount of the reaction product of the transesterification reaction. Particularly, the most important target compounds of the transesterification reaction, di ester increased from 23 mol % in comparative example 2 to 29 mol % in example 3. The content of tri ester in example 3 was lower compared with that of comparative example 2.

EXAMPLE 4

[0089] Triethanolamine (62.8 g, 0.421 mol), hardened palm oil (IV20, 120 g, 0.147 mol) and hardened palm oil (IV45, 61.8 g, 0.073 mol) were charged into a 500 mL reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium hypophosphite 0.3 g and sodium methylate (25%, 2.0 g) was charged as the catalyst. The reactants were heated to 150° C. and stirred for 2 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. When the GC results showed that the decrement of TEA was more than 50 wt %, then the second portion of oil, hardened palm oil (IV45, 77.3 g, 0.092 mol) was charged into the reactor and the reaction mixture was stirred at 150° C. for another 2 hrs. The GC results of a sample taken at 4 hs of reaction showed that the decrement of TEA was 84.3 wt %.

[0090] The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 9 below:

TABLE-US-00009 TABLE 9 Components Mol % Components Mol % 1,2,3-triglyceride 3.7 TEA 10.5 1,3-diglyceride 5.5 mono ester 21.8 1,2-diglyceride 3.5 di ester 26.5 monoglyceride 18.4 tri ester 10.2

EXAMPLE 5

[0091] Triethanolamine (62.8 g, 0.421 mol), hardened palm oil (IV20, 120 g, 0.147 mol) and hardened palm oil (IV45, 61.8 g, 0.073 mol) were charged into a 500 mL reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium hypophosphite 0.3 g and sodium methylate (25%, 2.0 g) was charged as the catalyst. The reactants were heated to 180° C. and stirred for 2 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. When the GC results showed that the decrement of TEA was more than 50 wt %, then the second portion of oil, hardened palm oil (IV45, 77.3 g, 0.092 mol) was charged into the reactor and the reaction mixture was stirred at 180° C. for another 2 hrs. The GC results of a sample taken at 4 hs of reaction showed that the decrement of TEA was 86.5 wt %.

[0092] The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 10 below:

TABLE-US-00010 TABLE 10 Components Mol % Components Mol % 1,2,3-triglyceride 1.7 TEA 8.6 1,3-diglyceride 6.0 mono ester 19.7 1,2-diglyceride 3.2 di ester 29.3 monoglyceride 16.5 tri ester 15.1

EXAMPLE 6

[0093] Triethanolamine (62.8 g, 0.421 mol), hardened palm oil (IV20, 120 g, 0.147 mol) and hardened palm oil (IV45, 61.8 g, 0.073 mol) were charged into a 500 mL reactor. The mixture was heated and stirred at 70° C. and the reactor was vacuumed and connected with nitrogen as inert-blanketing gas. Sodium hypophosphite 0.3 g and sodium methylate (25%, 2.0 g) was charged as the catalyst. The reactants were heated to 200° C. and stirred for 2 hrs. The extent of reaction was monitored by the content of residual triethanolamine, which was analyzed by GC. When the GC results showed that the decrement of TEA was more than 50 wt %, then the second portion of oil, hardened palm oil (IV45, 77.3 g, 0.092 mol) was charged into the reactor and the reaction mixture was stirred at 200° C. for another 2 hrs. The GC results of a sample taken at 4 hs of reaction showed that the decrement of TEA was 86.5 wt %.

[0094] The composition of the fatty acid hydroxyl alkylamine ester reaction products was analyzed with H-NMR. The H-NMR results of a sample taken at 4 hs of reaction were shown in Table 11 below:

TABLE-US-00011 TABLE 11 Components Mol % Components Mol % 1,2,3-triglyceride 1.5 TEA 5.7 1,3-diglyceride 6.5 mono ester 16.5 1,2-diglyceride 2.9 di ester 35.2 monoglyceride 12.5 tri ester 19.3

[0095] It was surprising to found that the selectivity to the most important target compounds of the transesterification reaction, di ester in all the three esters (mono, di and tri esters) peaked at around the reaction temperature of 165° C. (see Table 12). The selectivity to di ester increased substantially when the reaction temperature increased from 150° C. to 165° C., and decreased substantially when the reaction temperature further increased to 180° C. Although the amount of di ester was higher in Example 6 than Example 3, the amount of tri ester which was an undesirable byproduct was much higher.

TABLE-US-00012 TABLE 12 Example 4 Example 3 Example 5 Example 6 Reaction temperature 150 165 180 200 (° C.) mono ester 21.8 21 19.7 16.5 di ester 26.5 29 29.3 35.2 tri ester 10.2 9 15.1 19.3 Selectivity (mono + 82.6 84.7 76.4 72.8 di)/total ester (%) Selectivity (di)/ 45.30% 49.15% 45.71% 49.58% total ester (%) Selectivity (tri)/ 17.4% 15.25% 23.55% 27.2% total ester (%) mono + di esters 48.3 50 49 51.7