Polyetheramines based on 1,3-dialcohols

Abstract

This invention relates to polyetheramines based on 1,3-dialcohols, in particular to an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of anamine of Formula (I) and/or (II), wherein R.sub.1-R.sub.12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R.sub.1-R.sub.6 and at least one of R.sub.7-R.sub.12 is different from H, wherein A.sub.1-A.sub.9 are independently selected from linear or branched alkylenes having 2 to 18 carbon atoms, preferably 2-10 carbon atoms, most preferably 2-5 carbon atoms, wherein Z.sub.1-Z.sub.4 are independently selected from OH or NH.sub.2, wherein at least one of Z.sub.1-Z.sub.2 and at least one of Z.sub.3-Z.sub.4 is NH.sub.2, and wherein the sum of x+y is in the range of from 2 to 200, wherein x1 and y1; and x.sub.1+y.sub.1 is in the range of from 2 to 200, preferably 2-20, most preferably 2-10, wherein x.sub.11 and y.sub.11. ##STR00001##

Claims

1. An etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an amine of Formula (I) and (II), ##STR00010## wherein R.sub.1-R.sub.12 are independently H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R.sub.1-R.sub.6 and at least one of R.sub.7-R.sub.12 is not H, wherein A.sub.1-A.sub.9 are independently linear or branched alkylenes having 2 to 18 carbon atoms, wherein Z.sub.1-Z.sub.4 are independently OH, NH.sub.2, NHR or NRR, wherein at least one of Z.sub.1-Z.sub.2 and at least one of Z.sub.3-Z.sub.4 is NH.sub.2, NHR or NRR, wherein R and R are independently alkylenes having 2 to 6 carbon atoms and wherein the sum of x+y is in the range of from 3 to 20, wherein x1 and y1; and x.sub.1+y.sub.1 is in the range of from 2 to 200, wherein x.sub.11 and y.sub.11.

2. The etheramine mixture according to claim 1, wherein the etheramine mixture comprises at least 95% by weight, based on the total weight of the etheramine mixture, of the amine of Formula (I) and (II).

3. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), the degree of amination is in the range of 60% to 100%.

4. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), A.sub.1-A.sub.9 are independently selected from the group consisting of ethylene, propylene, and butylene.

5. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), each of A.sub.1-A.sub.9 is propylene.

6. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.11, and R.sub.12 are H and R.sub.3, R.sub.4, R.sub.9, and R.sub.10 are independently C1-16 alkyl or aryl.

7. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.11, and R.sub.12 are H and R.sub.3, R.sub.4, R.sub.9, and R.sub.10 are independently a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group.

8. The etheramine mixture according to claim 1, wherein in said polyetheramine Formula (I) or Formula (II), R.sub.3 and R.sub.9 are each an ethyl group, R.sub.1, R.sub.2, R.sub.5 R.sub.6, R.sub.7, R.sub.8, R.sub.11, R.sub.12 are each H, R.sub.4 and R.sub.10 are each a butyl group.

9. The etheramine mixture according to claim 1, wherein the polyetheramine of Formula (I) or Formula (II) has a weight average molecular weight of about 290 to about 1000 grams/mole.

10. A process for the manufacture of an etheramine mixture comprising at least 90% by weight, based on the total weight of the etheramine mixture, of an etheramine of Formula (I) and (II) comprising the following steps: a) reacting a 1,3-diol of Formula (III) with C.sub.2-C.sub.18 alkylene oxides, wherein the molar ratio of 1,3-diol to C.sub.2-C.sub.18 alkylene oxides is in the range of 1:3 to 1:8, ##STR00011## wherein R.sub.1-R.sub.6 are independently of one another H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl and at least one group selected from R.sub.1-R.sub.6 is not H, to form an alkoxylated 1,3-diol; and b) aminating the alkoxylated 1, 3-diol with ammonia.

11. The process for the manufacture of an etheramine mixture according to claim 10, further comprising reacting the polyetheramine of Formula (I) or Formula (II) obtained in step b) with an acid.

12. The process according to claim 10, wherein the molar ratio of 1,3-diol to C.sub.2-C.sub.18 alkylene oxides is in the range of 1:3 to 1:8.

13. The process according to claim 10, wherein the molar ratio of 1,3-diol to C.sub.2-C.sub.18 alkylene oxides is in the range of 1:4 to 1:6.

14. The process according to claim 10, wherein the C.sub.2-C.sub.18 alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.

15. The process according to claim 10, wherein the C.sub.2-C.sub.18 alkylene oxide is propylene oxide.

16. The process according to claim 10, wherein the 1,3-diol of formula (III) is selected from the group consisting of 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-phenyl-1,3-propanediol, 2,2-dimethyl-1,3-propandiol, and 2-ethyl-1,3-hexandiol.

17. The process according to claim 10, wherein the amination is carried out in the presence of a copper-, nickel- or cobalt-containing catalyst.

18. The process according to claim 17, wherein the catalytically active material of the catalysts, before the reduction thereof with hydrogen, comprises oxygen compounds of aluminum, of copper, of nickel and of cobalt, and in the range from 0.2 to 5.0% by weight of oxygen compounds of tin, calculated as SnO.

19. A shampoo or body wash formulation comprising the etheramine mixture of claim 1.

20. A curing agent for epoxy resins or a reactant in the production of polymers comprising the etheramine mixture of claim 1.

21. The etheramine mixture of claim 1, wherein A.sub.1-A.sub.9 are independently linear or branched alkylenes having 2 to 10 carbon atoms.

22. The etheramine mixture of claim 1, wherein A.sub.1-A.sub.9 are independently linear or branched alkylenes having 2 to 5 carbon atoms.

23. The etheramine mixture of claim 1, wherein x.sub.1+y.sub.1 is in the range of from 2 to 20.

24. The etheramine mixture of claim 1, wherein x.sub.1+y.sub.1 is in the range of from 2 to 10.

Description

SYNTHESIS EXAMPLES

Example 1

1 mol 2-Butyl-2-ethyl-1,3-propane diol+4 mol propylene oxide, aminated

a) 1 mol 2-Butyl-2-ethyl-1,3-propane diol+4 mol propylene oxide

(1) In a 2 l autoclave 322.6 g 2-Butyl-2-ethyl-1,3-propane diol and 7.9 g KOH (50% in water) were mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave was purged with nitrogen and heated to 140 C. 467.8 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst potassium hydroxide was removed by adding 2.3 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.), stirring at 100 C. for 2 h and filtration. A yellowish oil was obtained (772.0 g, hydroxy value: 248.5 mgKOH/g).

b) 1 mol 2-Butyl-2-ethyl-1,3-propane diol+4 mol propylene oxide, aminated

(2) In a 9 l autoclave 600 g of the resulting diol mixture from example 1-a, 1250 g THF and 1500 g ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 18 h at 205 C., the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 560 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 1.

(3) TABLE-US-00001 TABLE 1 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 277.66 282.50 4.54 0.86 5.70 98.59 98.36

Example 2

1 mol 2,2,4-Trimethyl-1,3-propane diol+4 mol propylene oxide, aminated

a) 1 mol 2,2,4-Trimethyl-1,3-propane diol+4 mol propylene oxide

(4) 327.3 g molten 2,2,4-Trimethyl-1,3-pentane diol and 8.5 g KOH (50% in water) were dewatered for 2 h at 80 C. and <10 mbar in a 2 l autoclave. The autoclave was purged with nitrogen and heated to 140 C. 519.4 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 2.5 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration. A yellowish oil was obtained (825.0 g, hydroxy value: 172.3 mgKOH/g).

b) 1 mol 2,2,4-Trimethyl-1,3-propane diol+4 mol propylene oxide, aminated

(5) In a 9 l autoclave 700 g of the resulting diol mixture from example 2-a, 1000 mL THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 280 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 670 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 2.

(6) TABLE-US-00002 TABLE 2 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 179.70 224.80 0.45 0.21 45.31 79.86 99.75

Example 3

1 mol 2,2-Diethyl-1,3-propane diol+4 mol propylene oxide, aminated

a) 1 mol 2,2-Diethyl-1,3-propane diol+4 mol propylene oxide

(7) 197.4 g molten 2,2-diethyl-1,3-propane diol and 5.4 g KOH (50% in water) were dewatered for 2 h at 80 C. and <10 mbar in a 2 l autoclave. The autoclave was purged with nitrogen and heated to 140 C. 346.4 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 1.6 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration. A yellowish oil was obtained (530.0 g, hydroxy value: 267.8 mgKOH/g).

b) 1 mol 2,2-Diethyl-1,3-propane diol+4 mol propylene oxide, aminated

(8) In a 9 l autoclave 500 g of the resulting diol mixture from example 3-a, 1200 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 470 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 3.

(9) TABLE-US-00003 TABLE 3 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 292.40 300.88 3.78 0.72 9.20 96.95 98.71

Example 4

1 mol 2-Methyl-2-propyl-1,3-propandiol+4 mol propylene oxide, aminated

a) 1 mol 2-Methyl-2-propyl-1,3-propandiol+4 mol propylene oxide

(10) 198.3 g molten 2-methyl-2-propyl-1,3-propanediol and 5.5 g KOH (50% in water) were dewatered for 2 h at 80 C. and <10 mbar in a 2 l autoclave. The autoclave was purged with nitrogen and heated to 140 C. 348.0 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 1.6 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration.

(11) A yellowish oil was obtained (520.0 g, hydroxy value: 308.1 mgKOH/g).

b) 1 mol 2-Methyl-2-propyl-1,3-propandiol+4 mol propylene oxide, aminated

(12) In a 9 l autoclave 500 g of the resulting diol mixture from example 4-a, 1200 ml THF and 1500 g ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 470 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 4.

(13) TABLE-US-00004 TABLE 4 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 292.45 301.76 3.01 1.33 10.64 96.49 98.97

Example 5

1 mol 2-Ethyl-1,3-hexane diol+4 mol propylene oxide, aminated

a) 1 mol 2-Ethyl-1,3-hexane diol+4 mol propylene oxide

(14) A 2 l autoclave was charged with 290.6 g molten 2-Ethyl-1,3-hexane diol and 7.5 g KOH (50% in water). The mixture was dewatered for 2 h at 90 C. and <10 mbar. The autoclave was purged with nitrogen and heated to 140 C. 461.1 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was stirred for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 2.3 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration.

(15) A yellowish oil was obtained (745.0 g, hydroxy value: 229.4 mgKOH/g).

b) 1 mol 2-Ethyl-1,3-hexane diol+4 mol propylene oxide, aminated

(16) In a 9 l autoclave 750 g of the resulting diol mixture from example 5-a, 950 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 710 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 5.

(17) TABLE-US-00005 TABLE 5 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 288.21 301.10 3.32 0.50 13.39 95.56 98.85

Example 6

1 mol 2-Phenyl-2-methyl-1,3-propane diol+4 mol propylene oxide, aminated

a) 1 mol 2-Phenyl-2-methyl-1,3-propane diol+4 mol propylene oxide

(18) A 2 l autoclave was charged with 298.4 g 2-Phenyl-2-methyl-1,3-propane diol and 7.1 g KOH (50% in water) and heated to 120 C. The mixture was dewatered for 2 h at 120 C. and <10 mbar. The autoclave was purged with nitrogen and heated to 140 C. 408.6 g propylene oxide was added in portions within 4 h. To complete the reaction, the mixture was stirred for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 2.1 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration.

(19) A yellowish oil was obtained (690.0 g, hydroxy value: 266.1 mgKOH/g).

b) 1 mol 2-Phenyl-2-methyl-1,3-propane diol+4 mol propylene oxide, aminated

(20) In a 9 l autoclave 600 g of the resulting diol mixture from example 6-a, 1100 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 270 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 570 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 6.

(21) TABLE-US-00006 TABLE 6 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 281.80 287.50 2.91 0.47 6.17 97.86 98.97

Example 7

1 mol 2,2-Dimethyl-1,3-propane diol+4 mol propylene oxide, aminated

a) 1 mol 2,2-Dimethyl-1,3-propane diol+4 mol propylene oxide

(22) A 2 l autoclave was charged with 208.3 g 2,2-Dimethyl-1,3-propane diol and 1.34 g potassium tert.-butylate and heated to 120 C. The autoclave was purged with nitrogen and heated to 140 C. 464 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was stirred for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 1.1 g Macrosorb MP5plus, stirring at 100 C. for 2 h and filtration.

(23) A light yellowish oil was obtained (650.0 g, hydroxy value: 308.6 mgKOH/g).

b) 1 mol 2,2-Dimethyl-1,3-propane diol+4 mol propylene oxide, aminated

(24) In a 9 l autoclave 500 g of the resulting diol mixture from example 6-a, 1200 ml THF and 1500 g Ammonia were mixed in presence of 200 ml of a solid catalyst as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium was in the form of 33 mm tables. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 h at 205 C., the total pressure was maintained at 280 bar by purging hydrogen during the entire reductive amination step. After cooling down the autoclave the final product was collected, filtered, vented of excess ammonia and stripped in a rotary evaporator to remove light amines and water. A total of 450 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 7.

(25) TABLE-US-00007 TABLE 7 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Degree of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 329.86 338.00 1.66 0.90 9.04 97.33 99.50

Example 8

1 mol 2-butyl-2-ethyl-1,3-propanediol+5.6 mol propylene oxide, aminated

a) 1 mol 2-butyl-2-ethyl-1,3-propanediol+5.6 mol propylene oxide

(26) In a 2 l autoclave 313.1 g 2-Butyl-2-ethyl-1,3-propanediol and 3.8 g KOH (50% in water) were mixed and stirred under vacuum (<10 mbar) at 120 C. for 2 h. The autoclave was purged with nitrogen and heated to 140 C. 635.6 g propylene oxide was added in portions within 6 h. To complete the reaction, the mixture was allowed to post-react for additional 5 h at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 C. The catalyst was removed by adding 50.9 g water and 8.2 g phosphoric acid (40% in water) stirring at 100 C. for 0.5 h and dewatering in vacuo for 2 hours. After filtration 930.0 g of light yellowish oil was obtained (hydroxy value: 190 mgKOH/g).

b) 1 mol 2-butyl-2-ethyl-1,3-propanediol+5.6 mol propylene oxide, aminated

(27) The amination of 8a (1 mol 2-butyl-2-ethyl-1,3-propanediol+5.6 mole propylene oxide) was conducted in a tubular reactor (length 500 mm, diameter 18 mm) which had been charged with 15 mL of silica (33 mm pellets) followed by 70 mL (74 g) of the catalyst precursor (containing oxides of nickel, cobalt, copper and tin on gamma-Al.sub.2O.sub.3, 1.0-1.6 mm splitprepared according to WO 2013/072289 A1) and filled up with silica (ca. 15 mL).

(28) The catalyst was activated at atmospheric pressure by being heated to 100 C. with 25 NI/h of nitrogen, then 3 hours at 150 C. in which the hydrogen feed was increased from 2 to 25 NI/h, then heated to 280 C. at a heating rate of 60 C. per hour and kept at 280 C. for 12 hours. The reactor was cooled to 100 C., the nitrogen flow was turned off and the pressure was increased to 120 bar. The catalyst was flushed with ammonia at 100 C., before the temperature was increased to 206 C. and the alcohol feed was started with a WHSV of 0.19 kg/liter*h (molar ratio ammonia/alcohol=55:1, hydrogen/alcohol=11.6:1). The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and reaction water to afford 8 b (1 mol 2-butyl-2-ethyl-1,3-propanediol+5.6 mole propylene oxide, aminated). The analytical data of the reaction product is shown in Table 8.

(29) TABLE-US-00008 TABLE 8 Secondary Primary Total Total and tertiary Tertiary Hydroxyl Grade of Amine in % amine-value acetylatables amine value amine-value value amination of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 222.92 231.50 2.57 0.31 8.89 96.16 98.85
Use as Additives in Laundry Detergents

(30) Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, Sausage Fat, Chicken Fat, Bacon Graese and Napolina Olive Oil were purchased from Warwick Equest Ltd. and washed in conventional western European washing machines (Miele Waschmaschine Softronic W 2241), selecting a 59 min washing cycle without heating and using 75 g of liquid detergent composition LA1 (table 9) together with or without 1.25 g of polyetheramine additive and some hydrochloric acid to readjust the pH after addition of the polyetheramine. The pH of 75 g of LA1 (Tab. 9) in 1 L water should be at pH=8.3. Water hardness was 2.5 mM (Ca.sup.2+: Mg.sup.2+ was 3:1). 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 was calculated.

(31) Stain removal from the swatches was calculated as follows:

(32) $\mathrm{Stain}\mathrm{Removal}\mathrm{Index}\left(SRI\right)=\frac{E_{\mathrm{initial}}-E_{\mathrm{washed}}}{E_{\mathrm{initial}}}100$
E.sub.initial=Stain level before washing
E.sub.washed=Stain level after washing

(33) Four replicates for each stain type have been carried out. Given below are the averaged values. 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.

(34) TABLE-US-00009 TABLE 9 liquid detergent composition LA1 Ingredients of liquid detergent percentage composition LA1 by weight Alkyl Benzene sulfonate.sup.1 7.50% AE3S .sup.2 2.60% AE9 .sup.3 0.40% NI 45-7 .sup.4 4.40% Citric Acid 3.20% C1218 Fatty acid 3.10% Amphiphilic polymer.sup.5 0.50% Zwitterionic dispersant.sup.6 1.00% Ethoxylated Polyethyleneimine .sup.7 1.51% Protease.sup.8 0.89% Enymes.sup.9 0.21% Chelant.sup.10 0.28% Brightener.sup.11 0.09% Solvent 7.35% Sodium Hydroxide 3.70% Fragrance & Dyes 1.54% Water, filler, stucturant To Balance .sup.1Linear alkylbenenesulfonate having an average aliphatic carbon chain length C11-C12 supplied by Stepan, Northfield Illinois, USA .sup.2 AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA .sup.3 AE9 is C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA .sup.4 NI 45-7 is C14-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA .sup.5Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. .sup.6A compound having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)N+CxH2xN+(CH3)-bis((C2H5O)(C2H4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof .sup.7 Polyethyleneimine (MW = 600) with 20 ethoxylate groups per NH .sup.8Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase, Coronase). .sup.9Natalase, Mannaway are all products of Novozymes, Bagsvaerd, Denmark. .sup.10Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) or diethylene triamine penta(methyl phosphonic) acid supplied by Solutia, St Louis, Missouri, USA; .sup.11Fluorescent Brightener 1 is Tinopal AMS, Fluorescent Brightener 2 supplied by Ciba Specialty Chemicals, Basel, Switzerland
Washing Test 1: Initial Water Temperature at 24 C.

(35) TABLE-US-00010 Stain A B C D E Beef Fat 69.1 66.4 76.3 76.2 77.4 Pork Fat 68.2 68.4 77.1 77.2 78.4 Napolina 47.0 47.0 59.8 55.7 57.4 Olive Oil A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive B: liquid detergent composition LA1 (table 8) with polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230. C: liquid detergent composition LA1 (table 8) with polyetheramine of Example 1 D: liquid detergent composition LA1 (table 8) with polyetheramine of Example 4 E: liquid detergent composition LA1 (table 8) with polyetheramine of Example 6
Washing Test 2: Initial Water Temperature at 25 C.

(36) TABLE-US-00011 Stain A B C Sausage 64.6 66.6 73.6 Fat Chicken Fat 63.0 65.9 74.4 Bacon 67.1 72.0 75.5 Grease A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive B: liquid detergent composition LA1 (table 8) with Polyetheramine D230 C: liquid detergent composition LA1 (table 8) with polyetheramine of Example 5

(37) The superior grease cleaning effect obtained with the addition of the claimed 1,3 propandiol-based polyetheramine compounds is clearly shown.

(38) Washing Test 3: Initial Water Temperature at 24.5 C.

(39) TABLE-US-00012 Stain A B Pork Fat 65.3 68.7 Chicken Fat 59.3 68.3 Bacon Graese 64.9 74.1 A: liquid detergent composition LA1 (table 8) without additional polyetheramine additive B: liquid detergent composition LA1 (table 8) with polyetheramine of example 7
Washing Test 4: Initial water temperature at 18 C.

(40) Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat and Chicken Fat were purchased from Warwick Equest Ltd. and washed in conventional western European washing machines (Miele Waschmaschine Softronic W 2241), selecting a 59 min washing cycle without heating (wash at 18 C.) and using 75 g of liquid detergent composition LA1 (see Table 9) together with or without 0.75 g of etheramine additive and some hydrochloric acid to readjust the pH. The pH of 75 g of LA1 (Tab. 9) in 1 L water should be at pH=8.3.

(41) TABLE-US-00013 Stain A B C Beef Fat 73.5 77.4 73.5 Pork Fat 73.3 76.6 72.7 Chicken Fat 75.6 78.4 75.4 A: liquid detergent composition LA1 (see Table 9) without additional etheramine additive B: liquid detergent composition LA1 (see Table 9) with polyetheramine of example 8. C: liquid detergent composition LA1 (see Table 9) with polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230

(42) The cleaning composition with the etheramine according to the invention (see Washing Test 4B) shows superior grease cleaning effects over the detergent composition without etheramines (see Washing Test 4A) and also shows superior grease cleaning effects over the cleaning composition with the etheramine of the comparative example (Washing Test 4C).

Application Tests

(43) In the following examples, the individual ingredients within the cleaning compositions are expressed as percentages by weight of the cleaning compositions.

Example I: Comparative Grease Stain Removal from NA Laundry Detergent Compositions

(44) The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional premium laundry detergent that uses Baxxodur EC301 comprising a linear amine-terminated polyalkylene glycol with the structure of Formula A.

(45) ##STR00006##

(46) Detergent compositions B and C each contain an etheramine mixture comprising 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 (Formula B).

(47) ##STR00007##

(48) TABLE-US-00014 Liquid Liquid Liquid Detergent Detergent Detergent A B C (wt %) (wt %) (wt %) AES C.sub.12-15 alkyl ethoxy (1.8) sulfate 10.9 10.9 10.9 Alkyl benzene sulfonate .sup.2 1.56 1.56 1.56 Sodium formate 2.66 2.66 2.66 Sodium hydroxide 0.21 0.21 0.21 Monoethanolamine (MEA) 1.65 1.65 1.65 Diethylene glycol (DEG) 4.10 4.10 4.10 AE9.sup.3 0.40 0.40 0.40 C16AE7 3.15 3.15 3.15 Baxxodur EC301 1.04 Polyetheramine.sup.11 1.04 2.30 Chelant.sup.4 0.18 0.18 0.18 Citric Acid 1.70 1.70 1.70 C.sub.12-18 Fatty Acid 1.47 1.47 1.47 Borax 1.19 1.19 1.19 Ethanol 1.44 1.44 1.44 Ethoxylated Polyethyleneimine .sup.1 1.35 1.35 1.35 A compound having the following general structure: 0.40 0.40 0.40 bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)N.sup.+C.sub.xH.sub.2xN.sup.+(CH.sub.3)- bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof 1,2-Propanediol 2.40 2.40 2.40 Protease (54.5 mg active/g).sup.9 0.89 0.89 0.89 Mannanase: Mannaway (25.6 mg active/g).sup.5 0.04 0.04 0.04 Amylase: Natalase (29 mg active/g).sup.5 0.14 0.14 0.14 Fluorescent Whitening Agents.sup.10 0.10 0.10 0.10 Water, perfume, dyes & other components Balance .sup.1 Polyethyleneimine (MW = 600) with 20 ethoxylate groups per NH. .sup.2 Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Illinois, USA .sup.3AE9 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA .sup.4Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark .sup.5Natalase, Mannaway are all products of Novozymes, Bagsvaerd, Denmark. 6. Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase, Coronase). .sup.10Suitable Fluorescent Whitening Agents are for example, Tinopal AMS, Tinopal CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland .sup.112-Butyl-2-ethyl-1,3-propane diol + 2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1.

(49) Technical stain swatches of CW120 cotton containing US clay, Frank's Hot Sauce, hamburger grease, Italian dressing, and make up were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The swatches were washed in a Whirlpool front loader washing machine, using 6 grains per gallon water hardness and washed at 100 degrees Fahrenheit. The total amount of liquid detergent used in the test was 49 grams.

(50) Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared.

(51) Stain removal from the swatches was measured as follows:

(52) $\mathrm{Stain}\mathrm{Removal}\mathrm{Index}\left(SRI\right)=\frac{E_{\mathrm{initial}}-E_{\mathrm{washed}}}{E_{\mathrm{initial}}}100$$E_{\mathrm{initial}}=\mathrm{Stain}\mathrm{level}\mathrm{before}\mathrm{washing}$$E_{\mathrm{washed}}=\mathrm{Stain}\mathrm{level}\mathrm{after}\mathrm{washing}$

(53) Stain removal index scores for each stain were calculated and are listed in the table below:

(54) TABLE-US-00015 Composition Composition Composition A B C Stain SRI SRI SRI LSD US Clay 54.4 58.7 57.7 4.0 Frank's Hot Sauce 31.0 34.1 35.3 3.2 Hamburger Grease 60.0 64.6 67.4 3.9 Italian Dressing 77.4 79.4 82.7 2.6 Make-up 37.4 38.4 41.3 2.3

(55) These results illustrate the surprising grease removal benefit of an etheramine compound comprising compounds of Formula I and/or II (as used in Compositions B and C), as compared to a linear polyalkylene glycol with terminal primary amines (Composition A).

Example II: Comparative Grease Removal from Laundry Cleaning Powder Composition

(56) The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional premium laundry detergent that contains no amine-terminated polyalkylene glycol compound. Composition B is a laundry detergent that uses BaxxodurEC301, a linear amine-terminated polyalkylene glycol (see Formula A above).

(57) Composition C is a detergent that uses a polyetheramine comprising 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 (Formula B above).

(58) TABLE-US-00016 Powder Powder Powder Detergent Detergent Detergent A B C (wt %) (wt %) (wt %) Linear alkylbenzenesulfonate.sup.1 8.2 8.2 8.2 AE3S.sup.2 1.9 1.9 1.9 Zeolite A.sup.3 1.8 1.8 1.8 Citric Acid 1.5 1.5 1.5 Sodium Carbonate.sup.5 29.7 29.7 29.7 Silicate 1.6R (SiO.sub.2:Na.sub.2O).sup.4 3.4 3.4 3.4 Soil release agent.sup.6 0.2 0.2 0.2 Acrylic Acid/Maleic Acid Copolymer.sup.7 2.2 2.2 2.2 Carboxymethylcellulose 0.9 0.9 0.9 ProteasePurafect (84 mg active/g).sup.9 0.08 0.08 0.08 AmylaseStainzyme Plus (20 mg active/g).sup.8 0.16 0.16 0.16 LipaseLipex (18.00 mg active/g).sup.8 0.24 0.24 0.24 CellulaseCelluclean (15.6 mg active/g).sup.8 0.1 0.1 0.1 Baxxodur EC301 1.0 Polyetheramine.sup.10 1.0 TAED .sup.11 3.26 3.26 3.26 Percarbonate.sup.12 14.1 14.1 14.1 Na salt of Ethylenediamine-N,N-disuccinic acid, 2.19 2.19 2.19 (S,S) isomer (EDDS).sup.13 Hydroxyethane di phosphonate (HEDP).sup.14 0.54 0.54 0.54 MgSO.sub.4 0.38 0.38 0.38 Perfume 0.38 0.38 0.38 Suds suppressor agglomerate.sup.15 0.04 0.04 0.04 Sulphonated zinc phthalocyanine (active).sup.16 0.0012 0.0012 0.0012 Sulfate/Water & Miscellaneous Balance Balance Balance .sup.1Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Illinois, USA .sup.2AE3S is C.sub.12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA .sup.3Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK .sup.41.6R Silicate is supplied by Koma, Nestemica, Czech Republic .sup.5Sodium Carbonate is supplied by Solvay, Houston, Texas, USA .sup.6Soil release agent is Repel-o-tex PF, supplied by Rhodia, Paris, France .sup.7Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany .sup.8Savinase, Natalase, Stainzyme, Lipex, Celluclean, Mannaway and Whitezyme are all products of Novozymes, Bagsvaerd, Denmark. .sup.9Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase, Coronase). 102-Butyl-2-ethyl-1,3-propane diol + 2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 .sup.11 TAED is tetraacetylethylenediamine, supplied under the Peractive brand name by Clariant GmbH, Sulzbach, Germany .sup.12Sodium percarbonate supplied by Solvay, Houston, Texas, USA .sup.13Na salt of Ethylenediamine-N,N-disuccinic acid, (S,S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK .sup.14Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA .sup.15Suds suppressor agglomerate is supplied by Dow Corning, Midland, Michigan, USA .sup.16Fluorescent Brightener 1 is Tinopal AMS, Fluorescent Brightener 2 is Tinopal CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol Violet BN-Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland

(59) Technical stain swatches of cotton CW120 containing bacon grease, burnt butter, dirty motor oil, hamburger grease, Italian dressing, lipstick, margarine, pizza sauce, taco grease were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The stained swatches were washed in conventional western European washing machines (Meile) using 14 grains per gallon hardness, selecting the cotton cycle at 30 C., using 80 g of each of the respective detergent compositions. Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula shown above.

(60) Key results are summarized in the following table:

(61) TABLE-US-00017 Composition Composition Composition A B C Stain SRI SRI SRI LSD Bacon Grease 88.8 88.6 90.6 1.0 Burnt Butter 95.6 96.1 96.8 0.6 Dirty Motor Oil 31.3 32.6 35.8 2.8 Hamburger Grease 73.6 82.5 85.8 5.8 Italian Dressing 90.2 91.1 92.5 1.2 Lipstick 72.4 70.7 75.2 12.6 Margarine 82.8 88.0 94.1 3.2 Pizza Sauce 70.2 72.6 74.9 11.1 Taco Grease 69.8 77.8 94.0 8.0

(62) These results illustrate the surprising grease removal benefit of the polyetheramine compound comprising compounds of Formula I and/or II (as used in Composition C), as compared to a linear polyalkylene glycol with terminal primary amines (Composition B) and a conventional (nil-polyetheramine) powdered detergent, especially on difficult-to-remove, high-frequency consumer stains like hamburger grease and taco grease.

Example III: Comparative Grease Removal from WE Laundry Liquid Compositions

(63) The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a conventional premium laundry detergent that contains no amine-terminated polyalkylene glycol compound. Composition B is a detergent that uses a polyetheramine comprising two terminal primary amines and two alkyl branches (specifically, 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 Formula B above).

(64) TABLE-US-00018 WE WE Liquid Liquid HDL HDL A B (wt %) (wt %) AE3S.sup.4 2.6 2.6 Alkyl benzene sulfonate .sup.3 7.5 7.5 Sodium formate/Calcium formate 0.4 0.4 Sodium hydroxide 3.7 3.7 Monoethanolamine (MEA) 0.3 0.3 Diethylene glycol (DEG) 0.8 0.8 AE9.sup.6 0.4 0.4 AE7.sup.5 4.4 4.4 Polyetheramine.sup.11 1.0 Chelant.sup.7 0.3 0.3 Citric Acid 3.2 3.2 C.sub.12-18 Fatty Acid 3.1 3.1 Ethanol 2.0 2.0 Ethoxylated Polyethylenimine .sup.1 1.5 1.5 Amphiphilic polymer .sup.2 0.5 0.5 A compound having the following general 1.0 1.0 structure: bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)N.sup.+ C.sub.xH.sub.2xN.sup.+(CH.sub.3)-bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof 1,2-Propanediol 3.9 3.9 Protease (40.6 mg active/g).sup.9 0.6 0.6 Amylase: Stainzyme (15 mg active/g).sup.8 0.2 0.2 Fluorescent Whitening Agents.sup.10 0.1 0.1 Water, perfume, dyes & other components Balance .sup.1 Polyethyleneimine (MW = 600) with 20 ethoxylate groups per NH. .sup.2 Random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. .sup.3 Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Illinois, USA .sup.4AE3S is C.sub.12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA .sup.5AE7 is C.sub.12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA .sup.6AE9 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA .sup.7Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark .sup.8Savinase, Natalase, Stainzyme, Lipex, Celluclean, Mannaway and Whitezyme are all products of Novozymes, Bagsvaerd, Denmark. .sup.9Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase, Coronase). .sup.10Suitable Fluorescent Whitening Agents are for example, Tinopal AMS, Tinopal CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland .sup.112-Butyl-2-ethyl-1,3-propane diol + 2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1.

(65) Technical stain swatches of cotton CW120 containing bacon grease, burnt butter, dirty motor oil, hamburger grease, Italian dressing, lipstick, margarine, pizza sauce, taco grease were purchased from Empirical Manufacturing Co., Inc (Cincinnati). The stained swatches were washed in conventional western European washing machines (Miele) using 14 grains per gallon hardness, selecting the cotton cycle at 30 C., using 80 g of each of the respective detergent composition. Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula shown above.

(66) Key results are summarized in the following table:

(67) TABLE-US-00019 Composition Composition A B Stain SRI SRI LSD Bacon Grease 84.6 90.8 2.8 Burnt Butter 84.9 95.5 2.3 Dirty Motor Oil 53.9 71.4 21.7 Hamburger 61.0 82.7 5.3 Grease Italian Dressing 90.1 92.3 1.8 Makeup 52.6 55.7 2.2 Margarine 74.4 90.6 3.7 Taco Grease 61.7 79.2 3.1

(68) These results illustrate the surprising grease removal benefit of an etheramine mixture comprising compounds of Formula I and/or II (as used in Composition B), as compared to a conventional (nil-polyetheramine) liquid detergent, especially on difficult-to-remove, high-frequency consumer stains like hamburger grease and taco grease.

Example IV: Comparative Grease Removal in a Powder Additive

(69) The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. Composition A is a powder additive that contains no amine-terminated polyalkylene glycol compound. Composition B is a powder additive that uses a polyetheramine comprising 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 Formula B above).

(70) Technical stain swatches were purchased from Warwick Equest Ltd. and washed in conventional western European washing machines (Ariston Hotpoint), selecting the cotton cycle at 30 C., using 80 g of a marketed commercial liquid detergent composition (i.e., Ariel Liquid Actilift) and 30 g of powder additive, Composition A, which contains no amine-terminated polyalkylene glycol compound, or Composition B, a powder additive that uses a polyetheramine comprising 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1, Formula B above).

(71) Image analysis was used to compare each stain to an unstained fabric control. Software converted images taken into standard colorimetric values and compared these to standards based on the commonly used Macbeth Colour Rendition Chart, assigning each stain a colorimetric value (Stain Level). Eight replicates of each were prepared. The stain removal index was then calculated according to the formula above.

(72) Statistical significance on a 95% confidence level was calculated using standard statistical methods (Student's t-test) and is shown with an s nest to the stain removal index.

(73) Key results are summarized in the following tables:

(74) TABLE-US-00020 Powder Powder Powder Additive A Additive B Additive C Ingredients (wt %) (wt %) (wt %) Sodium percarbonate.sup.5 33.0 33.0 33.0 Tetraacetyl ethylene 10.0 10.0 10.0 diamine.sup.4 nonanoyloxybenzene 7.5 7.5 7.5 sulphonate.sup.7 Polyetheramine.sup.3 4.0 Baxxodur EC301 4.0 C12-C16 Alkylbenzene 1.2 1.2 1.2 sulphonic acid C14-C15 alkyl 7- 0.25 0.25 0.25 ethoxylate.sup.6 Mannanase .sup.1 0.2 0.2 0.2 Cellulase .sup.2 0.2 0.2 0.2 Brightener.sup.8 0.1 0.1 0.1 Sodium sulphate Balance Balance Balance .sup.1 Mannaway, from Novozymes (Denmark), 4 mg active enzyme per gram. .sup.2 Celluclean, from Novozymes (Denmark), 15.6 mg active enzyme per gram. .sup.32-Butyl-2-ethyl-1,3-propane diol + 2,0 propylene oxide/OH, aminated, preparation of polyetheramine described in Example 1 .sup.4TAED is tetraacetylethylenediamine, supplied under the Peractive brand name by Clariant GmbH, Sulzbach, Germany .sup.5Sodium percarbonate supplied by Solvay, Houston, Texas, USA .sup.6AE7 is C.sub.14-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA .sup.7NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, Arkansas, USA .sup.8Suitable Fluorescent Whitening Agents are for example, Tinopal AMS, Tinopal CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland

(75) TABLE-US-00021 Liquid Detergent + Liquid Detergent + Powder Additive A Powder Additive B Stain SRI SRI Bacon Grease 39.4 40.5 Lard 41.1 42.3 Beef fat 50.0 52.8 Burnt Butter 46.1 47.0 Hamburger Grease 49.7 51.9 Liquid Detergent + Liquid Detergent + Powder Additive A Powder Additive C Stain SRI SRI Bacon Grease 47.9 63.5s Lard 44.3 58.8s Pork fat 47.1 61.6s Burnt Butter 68.8 76.4s Chicken Fat 46.0 59.5s

(76) These results illustrate the surprising grease removal benefit of an etheramine mixture comprising compounds of Formula I and/or II (as used in Composition B) compared to conventional WE liquid detergent that does not contain branched amine-terminated polyakylene glycols, in 30 C Miele wash cycle.

Application of the Amines as Hardener in Epoxy Systems

Example 1

Preparation of the Reaction Resin Molding Material and Investigation of Reactivity Profile

(77) The compared formulations were prepared by mixing of stoichiometric amounts of amine with a liquid epoxy resin based on bisphenol-A-diglycidyl ether (EEW 182).

(78) The rheological measurements for investigating the reactivity profile of the amines with epoxy resins were carried out at a shear stress controlled plate-plate rheometer (MCR 301, Anton Paar) with a plate diameter of 15 mm and a gap distance of 0.25 mm at different temperatures.

(79) Analysis 1: Comparison of the time to reach a viscosity of 10000 mPa*s at a defined temperature: The measurement was carried out using the before mentioned rheometer at different temperatures (10 C., 23 C., 75 C.) (rotating). Comparison of gel time: The measurement was carried out using the before mentioned rheometer at different temperatures (10 C., 23 C., 40 C., 75 C.) (rotating-oscillating). The gel time is given by the inspection of loss modulus (G) and storage modulus (G).

(80) TABLE-US-00022 1 a Viscosity increase to 10.000 mPas b 23 C. 75 C. Gel time Initial viscosity Initial viscosity 23 C. 75 C. 2-5 min time 2-5 min time time time Name [mPas] [min] [mPas] [min] [min] [min] A 886 478 39 40 1850 60 B 71 737 34 59 1534 90.5 C 304 1269 60 39 2090 52 D 836 721 36 68 2966 104 E 822 762 27 68 3050 99 F 535 471 26 56 2114 124 G 787 709 31 58 2633 85

(81) A: polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230

(82) B: Polyetheramine with the following structure, sold under the tradename XTJ568:

(83) ##STR00008##

(84) C: Poly[oxy(methyl-1,2-ethanediyl)], -hydro--(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1), CAS-Nr.: 39429-51-3, sold under the trade name Polyetheramine T 403 or JEFFAMINE T-403

(85) D: 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, synthesis described in example 1

(86) E: 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, synthesis described in example 1, second batch

(87) F: 1 mol 2-butyl-2-ethyl-1,3-propanediol+1.0 mole propylene oxide, aminated, synthesis described in comparative example 1

(88) G: 2,2-Dimethyl-1,3-propane diol+2 PO/OH, aminated, synthesis described in comparative example 7

Example 2

Exothermic Profile of Reaction Resin Molding Material and Glass Temperatures of the Cured Thermosets

(89) The DSC-measurements of the curing reaction of the amines with a liquid epoxy resin based on bisphenol-A-diglycidyl ether (EEW 182) for determination of onset temperature (T.sub.0), exotherm (E) as well as glass temperature (T.sub.g) was carried out according to ASTM D 3418.

(90) Analysis 2a) Temperature program for the DSC-measurements: 0 C..fwdarw.5K/min 180 C..fwdarw.30 min 180 C..fwdarw.20K/min 0 C..fwdarw.20K/min 220 C.

(91) TABLE-US-00023 a 2 DSC Name Onset [ C.] H [J/g] Tg [ C.] A 83.3 421.9 93 B 91.6 425.9 91.8 C 84.3 399.3 90.3 D 88.2 263.2 67.8 E 90.1 349 67.8 F 80.3 300.2 67.8 G 88.1 372.3 73.9

(92) A: polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230

(93) B: Polyetheramine with the following structure, sold under the tradename XTJ568:

(94) ##STR00009##

(95) C: Poly[oxy(methyl-1,2-ethanediyl)], -hydro--(2-aminomethylethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1), CAS-Nr.: 39429-51-3, sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230.

(96) D: 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, synthesis described in example 1

(97) E: 2-Butyl-2-ethyl-1,3-propane diol+2.0 propylene oxide/OH, aminated, synthesis described in example 1, second batch

(98) F: 1 mol 2-butyl-2-ethyl-1,3-propanediol+1.0 mole propylene oxide, aminated, synthesis described in comparative example 1

(99) G: 2,2-Dimethyl-1,3-propane diol+2 PO/OH, aminated, synthesis described in comparative example 7

(100) Results:

(101) D; E and G show a longer open time at 23 C. compared to F, the time to reach 10.000 mPas is significantly longer. On the other hand, at 75 C., D and E show a faster overall curing which are measured by the gel time. This is an advantage for the workability of the epoxy systems because the reactive components are usually mixed at ambient temperature and cured at higher temperatures later.

(102) D and E show similar Tgs compared to F. This means we have a better reactivity profile with similar thermomechanical properties.