POLYETHERAMINES BASED ON 1,3-DIALCOHOLS

Abstract

Described herein is an etheramine mixture including at least 90% by weight, based on the total weight of the etheramine mixture, of an amine of Formula (I) and/or (II),

##STR00001##

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 alkanediyl groups having 2 to 18 carbon atoms,
wherein Z.sub.1-Z.sub.4 are independently selected from OH and linear OCH.sub.2CH.sub.2CH.sub.2NH.sub.2, wherein the degree of amination of each of the etheramines of Formula (I) and Formula (II) is at least 50%, 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, wherein x.sub.11 and y.sub.11.

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/or (II), ##STR00009## 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 alkanediyl groups having 2 to 18 carbon atoms, wherein Z.sub.1-Z.sub.4 are independently selected from OH and linear OCH.sub.2CH.sub.2CH.sub.2NH.sub.2, wherein the degree of amination of each of the etheramines of Formula (I) and Formula (II) is equal to or greater than 50%, 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, 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/or (II).

3. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), x+y is in the range of from 2 to 20.

4. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), x+y is in the range of from 3 to 20.

5. The etheramine mixture according to claim 1, wherein in said polyetheramine of Formula (I) or Formula (II), the degree of amination lies in the range of from 60% to 95%.

6. 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, or butylene.

7. 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.

8. 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 selected from C1-16 alkyl or aryl.

9. 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 selected from a butyl group, an ethyl group, a methyl group, a propyl group, or a phenyl group.

10. The etheramine mixture according to any 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.

11. 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.

12. The etheramine mixture according to claim 1, wherein the polyetheramine of Formula (I) or Formula (II) is reacted with an acid.

13. A method of using the etheramine mixture of claim 1, the method comprising using the etheramine mixture in personal care.

14. A method of using the etheramine mixture of claim 1, the method comprising using the etheramine mixture in shampoo and body wash formulations.

15. A method of using the etheramine mixture of claim 1, the method comprising using the etheramine mixture as curing agent for epoxy resins or as a reactant in the production of polymers.

16. A method of using the etheramine mixture of claim 1, the method comprising using the etheramine mixture in polyurethanes, polyureas, and as thermoplastic polyamide adhesives.

17. The etheramine mixture according to claim 1, wherein A.sub.1-A.sub.9 are independently selected from linear or branched alkanediyl groups having 2-10 carbon atoms.

18. The etheramine mixture according to claim 17, wherein A.sub.1-A.sub.9 are independently selected from linear or branched alkanediyl groups having 2-5 carbon atoms.

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

20. The etheramine mixture according to claim 19, wherein and x.sub.1+y.sub.1 is in the range of from 2 to 10.

Description

EXAMPLES

[0081] .sup.1H-NMR and .sup.13C-NMR measurements were carried out in CDCl.sub.3 with a Bruker 400 MHz spectrometer.

[0082] Unless specified otherwise herein, the degree of amination is calculated from the total amine value (AZ) divided by sum of the total acetylables value (AC) and tertiary amine value (tert. AZ) multiplicated by 100:

(Total AZ:(AC+tert.AZ)100).

[0083] The total amine value (AZ) is determined according to DIN 16945.

[0084] The total acetylables value (AC) is determined according to DIN 53240.

[0085] The secondary and tertiary amine are determined according to ASTM D2074-07.

The primary amines value is calculated as follows: primary amine value=AZsecondary+tertiary amine value.

[0086] Primary amine in % of total amine is calculated as follows:

Primary amine in %=((AZsecondary+tertiary amine value)/AZ)*100

The hydroxyl value is calculated from(total acetylables value+tertiary amine value)total amine value.

1. EXPERIMENTAL PART

Example 1 a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 mol propylene oxide

[0087] In a 2 l autoclave 495.7 g 2-butyl-2-ethyl-1,3-propane diol and 1.7 g potassium tert.-butylate were mixed. The autoclave was purged three times with nitrogen and heated to 140 C. 359.3 g propylene oxide was added within 5 hours. The mixture was allowed to post-react for 4 hours 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 26.2 g Macrosorb MP5plus, stirring at 100 C. for 2 hours and filtration. A yellowish oil was obtained (873.0 g, hydroxyl value: 386.6 mgKOH/g).

Example 1 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 mol propylene oxide+2 mol acrylonitrile

[0088] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 276.4 g of product from example 1 a was placed. 2.3 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 109.3 g acrylonitrile was added dropwise at 60 C. After stirring for 1.5 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (370.0 g, water 0.1%). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3.

Example 1 c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 mol propylene oxide+2 mol acrylonitrile, Hydrogenated

[0089] Representative Procedure for the hydrogenation of cyanoethylated polyoxyalkylenes:

[0090] The hydrogenation of example 1 b was conducted in a tubular reactor (length 500 mm, diameter 18 mm) filled with a splitted cobalt catalyst prepared as described in EP636409.

[0091] At a temperature of 110 C. and a pressure of 160 bar the nitrile (20 wt.-% in THF) was together with ammonia and hydrogen continuously fed into the reactor at such a rate that full conversion of the nitrile was assured. The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and THF to afford the hydrogenated material. The analytical data of the reaction product are shown below.

TABLE-US-00001 Secondary + tertiary Total amine value amine value Tertiary amine value [mg KOH/g] [mg KOH/g] [mg KOH/g] 264.8 1.17 0.66

Example 2 a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide

[0092] In a 2 l autoclave 411.0 g 2-butyl-2-ethyl-1,3-propane diol and 2.0 g potassium tert.-butylate were mixed. The autoclave was purged three times with nitrogen and heated to 140 C. 596.8 g propylene oxide was added within 8 hours. The mixture was allowed to post-react for 6 hours 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 30.2 g Macrosorb MP5plus, stirring at 100 C. for 2 hours and filtration. A yellowish oil was obtained (1001.0 g, hydroxyl value: 273.1 mgKOH/g).

Example 2 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+1.2 mol acrylonitrile

[0093] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 314.1 g of product from example 2 a was placed. 6.0 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 89.0 g acrylonitrile was added dropwise at 60 C. After stirring for 3 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (354.0 g). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3. The degree of functionalization with acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3 (peak at 2.6 ppm).

Example 2 c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+1.2 mol acrylonitrile, Hydrogenated

[0094] Example 2 b was hydrogenated according to the representative procedure described in example 1 c. The analytical data of the reaction product are shown below.

TABLE-US-00002 Total amine value Secondary + tertiary amine value Tertiary amine value [mg KOH/g] [mg KOH/g] [mg KOH/g] 145.2 3.83 3.19

Comparative Example 3 a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide

[0095] 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, hydroxyl value: 248.5 mgKOH/g).

Comparative Example 3 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide, Aminated

[0096] In a 9 l autoclave 600 g of the resulting diol mixture from example 3 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 below.

TABLE-US-00003 Total Total Secondary Tertiary Primary amine- acetylatables and tertiary amine- Hydroxyl Degree of Amine value value value amine value value value amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 278.21 287.70 6.96 4.60 14.09 95.18 97.50

Comparative Example 4 a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+5.6 mol propylene oxide

[0097] In a 2 l autoclave 313.1 g 2-Butyl-2-ethyl-1,3-propane diol 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 a light yellowish oil was obtained (hydroxyl value: 233 mgKOH/g).

Comparative Example 4 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+5.6 mol propylene oxide, partially Aminated

[0098] The amination of example 4 a 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 gama-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).

[0099] The catalyst was activated at atmospheric pressure by being heated to 100 C. with 25 norm litre (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.

[0100] The catalyst was flushed with ammonia at 100 C., before the temperature was increased to 184 C. and the alcohol feed was started with a WHSV of 0.44 kg/liter*h (molar ratio ammonia/alcohol=27:1, hydrogen/alcohol=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 the aminated material. The analytical data of the reaction product is shown below.

TABLE-US-00004 Total Total Secondary Tertiary Primary amine- acetylatables and tertiary amine- Hydroxyl Degree of Amine value value value amine value value value amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 111.80 236.80 0.14 0.00 125.00 47.21 99.87

Comparative Example 5 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+0.8 mol acrylonitrile

[0101] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 392.1 g of product from example 2 a was placed. 4.7 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 61.3 g acrylonitrile was added dropwise at 60 C. After stirring for 6 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (414.0 g). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3. The degree of functionalization with acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3 (peak at 2.6 ppm).

Comparative Example 5 c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+0.8 mol acrylonitrile, Hydrogenated

[0102] Compound 5 b was hydrogenated over Raney cobalt in a continuously operated autoclave. At a temperature of 110 C. and a pressure of 160 bar the nitrile (10 wt.-% in ethanol) was together with ammonia and hydrogen continuously fed into the reactor at such a rate that full conversion of the nitrile was assured (controlled by NMR spectroscopy). The crude material was collected and stripped on a rotary evaporator to remove excess ammonia, light weight amines and ethanol to afford the hydrogenated material. The analytical data of the reaction product is shown below.

TABLE-US-00005 Total Total Secondary Tertiary Primary amine- acetylatables and tertiary amine- Hydroxyl Degree of Amine value value amine value value value amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 90.24 278.8 1.98 1.66 190.2 32.2 97.8

Example 6 b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+2 mol acrylonitrile

[0103] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 39.3 g of product from example 2 a was placed. 0.23 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 10.9 g acrylonitrile was added dropwise at 60 C. After stirring for 1.5 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (36.5 g). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3.

Example 6 c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol propylene oxide+2 mol acrylonitrile, Hydrogenated

[0104] Example 6 b was hydrogenated according to the representative procedure described in example 1 c. The analytical data of the reaction product are shown below.

TABLE-US-00006 Total amine value Secondary + tertiary amine value Tertiary amine value [mg KOH/g] [mg KOH/g] [mg KOH/g] 204.70 1.21 1.09

Example 7 a: 1 mol 2-ethyl-1,3-hexane diol+4 mol propylene oxide

[0105] In a 2 l autoclave 150.0 g 2-ethyl-1,3-hexane diol and 1.5 g potassium hydroxide (50% aqueous solution) were mixed. The mixture was heated to 110 C. and the water was removed in vacuo for 2 hours at 30 mbar. The autoclave was purged three times with nitrogen and heated to 140 C. 231.2 g propylene oxide was added within 2 hours. The mixture was allowed to post-react for 4 hours 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 11.4 g Macrosorb MP5plus, stirring at 100 C. for 2 hours and filtration. A yellowish oil was obtained (373.6 g, hydroxyl value: 245.0 mgKOH/g).

Example 7 b: 1 mol 2-ethyl-1,3-hexane diol+4 mol propylene oxide+2 mol acrylonitrile

[0106] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 151.3 g of product from example 7 was placed. 3.6 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 64.1 g acrylonitrile was added dropwise at 60 C. After stirring for 3 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (174.0 g). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3. The degree of functionalization with acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3 (peak at 2.6 ppm).

Example 7 c: 1 mol 2-ethyl-1,3-hexane diol+4 mol propylene oxide+2 mol acrylonitrile, Hydrogenated

[0107] Example 7 b was hydrogenated according to the representative procedure described in example 1 c. The analytical data of the reaction product are shown below.

TABLE-US-00007 Total amine value Secondary + tertiary amine value Tertiary amine value [mg KOH/g] [mg KOH/g] [mg KOH/g] 218.7 5.76 1.02

Example 8 b: 1 mol 2-ethyl-1,3-hexane diol+4 mol propylene oxide+1.2 mol acrylonitrile

[0108] In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogen inlet, and dropping funnel 151.3 g of product from example 7 a was placed. 4.8 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammonium hydroxide was added at room temperature. The mixture was heated to 60 C. and 29.3 g acrylonitrile was added dropwise at 60 C. After stirring for 3 hours at given temperature the mixture was stirred for additional 14 hours at room temperature. The reaction product was filtered and excess acrylonitrile was removed in vacuo. An orange liquid was obtained (160.0 g). Complete conversion of acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3. The degree of functionalization with acrylonitrile was detected by .sup.1H-NMR in CDCl.sub.3 (peak at 2.6 ppm).

Example 8 c: 1 mol 2-ethyl-1,3-hexane diol+4 mol propylene oxide+1.2 mol acrylonitrile, Hydrogenated

[0109] Example 8 b was hydrogenated according to the representative procedure described in example 1 c. The analytical data of the reaction product are shown below.

TABLE-US-00008 Total amine value Secondary + tertiary amine value Tertiary amine value [mg KOH/g] [mg KOH/g] [mg KOH/g] 146.9 4.52 0.82

2. Use as Additives in Laundry Detergent

2.1 Stain Removal Index

[0110] Technical stain swatches of blue knitted cotton containing grease stains 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 steel balls (weight of 1 ball is 1 g) 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+ molar ratio 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.

[0111] 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.

[0112] Stain removal from the swatches was calculated as follows:

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

[0113] E.sub.initial=Stain level before washing

[0114] E.sub.washed=Stain level after washing

[0115] Stain level corresponds to the amount of grease on the fabric. The stain level of the fabric before the washing (E.sub.intial) 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.intial. Therefore, the value of stain removal index increases with better washing performance.

TABLE-US-00009 TABLE 1 Detergent composition DC1 Ingredients of liquid detergent composition DC1 percentage by weight n-C10-C13-alkylbenzene sulfonic acid 5.3 coconut C12-C18 fatty acid 2.4 sodium laureth sulfate + 2 EO 7.7 potassium hydroxide 2.2 C13C15-oxo alcohol + 7 EO 5.4 1,2 propylene glycol 6 ethanol 2 water to balance pH of detergent composition DC1 = 8.4

TABLE-US-00010 TABLE 2 Washing Test 1: SRI, additive/ stain: Beef [g] Fat without additive 25.6 with Example 1 c 0.0375 36.9 with Comparitive Example 3 b 0.0375 32.1 with Comparitive Example 5 c 0.0375 29.5

TABLE-US-00011 TABLE 3 Washing Test 2: SRI, additive/ stain: Chicken Additive [g] Fat without additive 24.3 with Example 2 c 0.0375 33.1 with Comparitive Example 4 b 0.0375 28.0

[0116] All washing tests with Examples 1 and 2 (Table 2 and Table 3) show improved stain removal compared to Comparative Examples 3, 4, and 5.

2.2 Anti-Redeposition Methodology

[0117] The Anti-Redeposition Methodology uses a grease-soluble fluorescent dye to mimic the redeposition behavior of grease. To summarize the method, the dye is incorporated in bacon grease and the fluorescent dye-doped bacon grease is applied to fabrics to create a fluorescent grease stain. The fluorescent grease stain is incorporated into a wash system with a NIL-polymer detergent. The grease stains are washed for 12 mins. This creates a suspension of fluorescent grease. Then the wash system is paused and the anti-redeposition technology is added to the wash system. The wash system is stirred and clean white tracer fabrics are added to the wash system and the wash is restarted. At the end of the wash the tracers are removed from the wash, dried and evaluated to measure the fluorescent signal on the tracer fabrics. The intensity of the fluorescent signal is correlated to the power of the anti-redeposition technology to suspend greasy soils. The lower the intensity of the fluorescent signal on the tracer fabric, the greater the power of the anti-redeposition technology for suspending grease.

[0118] To make stains with bacon grease doped with fluorescent dye start by doping the fluorescent dye into bacon grease. The dye doped grease is made at least one day before applying to fabric. To solubilize the fluorescent dye (Fluorol 555 CAS#19125-99-6, from Exciton Dayton, Ohio), into the grease, completely melt bacon grease (from EMC) in a 50 OC oven or water bath. Then add 0.1 g of Fluorol 555 to 100 g melted bacon grease and stir. If possible, it is ideal to follow with sonication will improve the uniformity of solubilization and this will reduce noise level of the method.

[0119] After at least one day, heat the bacon grease again in a 50 C. oven or water bath until completely melted. Lay fabric swatches (cotton or polycotton) out onto a weight cup to keep fabric suspended. Suspending the fabric over a cup, stops grease loss from bleeding through the fabric onto another surface while the grease cools on the fabric. With a 1 ml pipette apply three 250 ul spots (approximately 0.25 g) to 1 cotton swatch spaced far enough to ensure the grease spots remain separate and don't wick into each other. Applying three small stains enables emulsification of the grease during the wash process. Keep the bacon grease fluid while applying, reintroduce into the oven or water bath if the bacon grease begins to congeal to re-fluidize it. Let the stains rest over the weigh cup for several hours until these are thoroughly solidified. If stains will be stored before use, the cooled stains can be layered with wax paper between the stains and wrapped in aluminum foil, then stored in the refrigerator until time to use the stains. It is important to protect the stains from light, and keep these cool to prevent photo-oxidation of the fluorescent dye and oxidation/microbial contamination of the bacon grease. Stains can be stored in this manner for 1 month. Expired stains should be discarded.

TABLE-US-00012 TABLE 4 Detergent composition DC2. Raw Material % C12-15 alkyl ethoxy (1.8) sulfate 11.27 Nonionic C24 EO9.sup.1 1.04 DTPA.sup.2 0.30 1,2 Propylene Glycol 3.72 Monoethanolamine 3.17 Sodium Hydroxide 0.69 Sodium Tetraborate 2.03 Alkyl benzene sulfonic acid 10.01 Sodium Formate 0.11 Citric Acid 2.87 C1218 Fatty Acid 1.11 Calcium Formate 0.10 Ethanol 1.49 Water Balance to 100% .sup.1Nonionic 24-9 is a C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9 .sup.2DTPA is diethylenetetraamine pentaacetic acid

[0120] To create the wash suspension of fluorescent dye-doped grease, start with a 5.29 g of a detergent containing surfactant and NIL-polymer (detergent composition DC2 of Table 4). Add two soiled fabrics with 3 spots each of dyed grease (approximately 1.5 g of fluorescent dye-doped grease) in 7.5 L of water in a mini-washer washing machine tub. Add 200 g of clean terry ballast. Set wash conditions at 30.5 C., 119.7 ppm of a 3:1 Ca.sup.2+/Mg.sup.2+ (0.98 moles Ca.sup.2+) mix to simulate water hardness.

[0121] After 12 min., remove the dyed grease stains and add the three polycotton 50/50 tracers and the anti-redeposition technology and agitate for 30 s. After agitation, complete another 12 min. wash cycle and 2 min. rinse (21.1 C.). Dry each test load plus ballast (in separate dryers) for 50 min (normal dryer cycle). To improve signal sensitivity, run the test swatches through 2 more cycles w/the test technology to created 3 cycles of deposition of dyed grease.

[0122] Cut samples from the traces to fit into a 12-24 well plate. Place cut samples in the bottom of the well and use o-rings to hold the swatches flat in the well. Read 3-6 spots per treatment. Sample the most uniform, representative parts of the tracer swatch. Read the fluorescence intensity on the samples using a reflectance fluorescence spectrometer (BMG Fluostar).

[0123] Index the test samples to the control samples (NIL-polymer detergent) equation: (test signalcontrol signal)/control signal=index. If the index is a negative number, the test sample provides improved anti-redeposition vs. the control. If the test sample is positive, it is causing deposition versus control.

TABLE-US-00013 TABLE.5 The index is more negative for examples 1c & 6c over Comparative example 9. Examples 1c and 6c provide improved anti-redeposition vs. Comparative example 9. Molecule Anti-redepo- Name Molecular Structure sition Index Comparative example 9 [00006] 14.75 Example 1c; (2-Butyl-2- Ethyl-Propane- diol)(PO/OH)1 (CAN/)H)1 hydrogenated [00007] 17.14 Example 6c (2-Butyl-2- Ethyl-Propane- diol)(PO/OH)2 (CAN/)H)1 hydrogenated [00008] 19.88

[0124] Comparative example 9 was prepared by a reaction sequence similar to the one described for comparative example 4b but conditions were adapted to obtain a high amination degree.