Etheramines based on 1,2-dialcohols

Abstract

The invention relates to etheramines of formula (I) or formula (II) or a mixture of etheramines of formula (I) and formula (II) based on 1,2-dialcohols, wherein R.sub.1 is a linear or branched alkyl group with 2 to 16 carbon atoms, R.sub.2 is a hydrogen or an alkyl group with 1 to 16 carbon atoms, x1 and y1 and the sum of x+y is between 2 and 10, and A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from the group consisting of linear and/or branched alkylenes having 2 to 18 carbon atoms and wherein Z.sub.1-Z.sub.4 are independently selected from 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 selected from alkylenes having 2 to 6 carbon atoms. ##STR00001## The invention further relates to etheramines obtainable by the alkoxylation and amination of 1,2-dialcohols.

Claims

1. A composition comprising etheramines of formula (I) and formula (II), ##STR00006## wherein R.sub.1 is a linear or branched alkyl group with 2 to 16 carbon atoms, R.sub.2 is a hydrogen or an alkyl group with 1 to 16 carbon atoms, x1 and y1 and the sum of x+y is between 2 and 10, and A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from the group consisting of linear and/or branched alkylenes having 2 to 18 carbon atoms, wherein Z.sub.1-Z.sub.4 are independently selected from OH, NH.sub.2, NHR or NRR, wherein at least one of Z.sub.1 or Z.sub.2 and at least one of Z.sub.3 or Z.sub.4 is NH.sub.2, NHR or NRR, wherein R and R are independently selected from alkylenes having 2 to 6 carbon atoms.

2. The composition according to claim 1, wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from 1,2-propylene or 1,2-butylene.

3. The composition according to claim 1, wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are each 1,2-propylene.

4. The composition according to claim 1, wherein x+y is in the range of from 3 to 6.

5. The composition according to claim 1, wherein R.sub.1 is a linear or branched alkyl group with 3 to 16 carbon atoms and R.sub.2 is hydrogen or an alkyl group with 1 to 16 carbon atoms.

6. The composition according to claim 1, wherein R.sub.1 is a linear alkyl group with 3 to 8 carbon atoms and R.sub.2 is hydrogen.

7. The composition according to claim 1, wherein Z.sub.1 to Z.sub.4 are each NH.sub.2.

8. The composition according to claim 1, wherein the etheramine of formula (I) and formula (II) has a weight average molecular weight of from about 270 to about 1000 grams/mole.

9. The composition according to claim 1, wherein the etheramines of formula (I) and formula (II) are reacted with an acid.

10. A process for the manufacture of a composition comprising etheramines of formula (I) and formula (II) according to claim 1 comprising the following steps: alkoxylation of a 1,2-dialcohol of formula (III) with C.sub.2-C.sub.18 alkylene oxides, wherein the molar ratio of the 1,2-dialcohol of formula (III) to C.sub.2-C.sub.18 alkylene oxides is in the range of 1:2 to 1:10, ##STR00007## wherein R.sub.1 is a linear or branched alkyl group with 3 to 16 carbon atoms and R.sub.2 is a hydrogen or an alkyl group with 1 to 16 carbon atoms, amination of the alkoxylated 1,2-dialcohol with ammonia.

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

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

13. The process according to claim 10, wherein the C.sub.2-C.sub.18 alkylene oxides are selected from propylene oxide, butylene oxide or a mixture thereof.

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

15. The process according to claim 10, wherein the 1,2-dialcohol of formula (III) is selected from the group consisting of 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecandiol, 1,2 hexadecandiol and 1,2 octadecandiol.

16. The process according to claim 10, wherein the amination is carried out in the presence of a catalyst that comprises at least one of copper, nickel or cobalt.

17. The process according to claim 16, wherein the catalyst, 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.

18. A personal care product comprising the composition of claim 1.

19. The personal care product of claim 18 selected from a shampoo or a body wash formulation.

20. A curing agent for epoxy resins comprising the composition of claim 1.

21. A polymer selected from a polyurethane, a polyurea, or a thermoplastic polyamide adhesive comprising the composition of claim 1.

22. A composition comprising etheramines of formula (I) and formula (II), ##STR00008## wherein R.sub.1 is a linear or branched alkyl group with 2 to 16 carbon atoms, R.sub.2 is a hydrogen or an alkyl group with 1 to 16 carbon atoms, x1 and y1 and the sum of x+y is between 2 and 10, and A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from 1,2-propylene or 1,2-butylene, and at least one of A.sub.1, A.sub.2, A.sub.3 or A.sub.4 is 1,2-propylene, wherein Z.sub.1 to Z.sub.4 are independently selected from OH, NH.sub.2, NHR or NRR, wherein at least one of Z.sub.1 or Z.sub.2 and at least one of Z.sub.3 or Z.sub.4 is NH.sub.2, NHR or NRR, wherein R and R are independently selected from alkylenes having 2 to 6 carbon atoms.

23. The composition according to claim 22, wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are each 1,2-propylene, and x+y is in the range of from 3 to 6.

24. The composition according to claim 23, wherein R.sub.1 is a linear alkyl group with 3 to 8 carbon atoms, R.sub.2 is hydrogen, and Z.sub.1 to Z.sub.4 are each NH.sub.2.

Description

SYNTHESIS EXAMPLES

Example 1

1 mol 1,2-pentanediol+3.4 mol propylene oxide, Aminated

1a) 1 mol 1,2-pentanediol+3.4 mol propylene oxide

(1) In a 2 l autoclave 208.3 g 1,2-pentanediol and 6.03 g potassium hydroxide (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. 394.2 g propylene oxide was added in portions within 5 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. Potassium hydroxide was removed by adding 18.1 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.). The mixture was stirred for 2 h at 90 C. and <10 mbar. After filtration 605.5 g of a light yellowish oil was obtained (hydroxy value: 336.3 mgKOH/g).

1b) 1 mol 1,2-pentanediol+3.4 mol propylene oxide, Aminated

(2) In a 9 l autoclave 500.0 g of the resulting alkoxylated dialcohol from example 1-a, 1200 mL of THF and 1500.0 g of ammonia were mixed in the presence of 500 mL of a solid catalyst. The catalyst containing oxides of nickel, copper and molybdenum on zirconium dioxide was in the form of 33 mm tablets. The autoclave was purged with hydrogen and pressurized to 20 bar before the mixture was heated to 205 C. The pressure was increased to 280 bar and the reaction mixture was stirred for 15 hours at 205 C. and the total pressure was maintained at 280 bar. After 15 hours the autoclave was cooled to ambient temperature, the product was collected, filtered, and stripped on a rotary evaporator to remove light amines and water. A total of 450.0 g of a low-color etheramine mixture was isolated. The analytical results thereof are shown in Table 1.

(3) TABLE-US-00001 TABLE 1 Total Total Tertiary Hy- Grade Primary amine- acetylata- Secondary amine- droxyl of Amine value bles and tertiary value value amina- in % of mg mg amine value mg mg tion total KOH/g KOH/g mg KOH/g KOH/g KOH/g in % amine 372.40 379.50 5.87 0.43 7.53 98.02 98.42

Example 2

1 mol 1,2-hexanediol+3.4 mol propylene oxide, Aminated

2a) 1 mol 1,2-hexanediol+3.4 mol propylene oxide

(4) In a 2 l autoclave 236.3 g 1,2-hexanediol and 6.3 g potassium hydroxide (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. 394.2 g propylene oxide was added in portions within 5 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. Potassium hydroxide was removed by adding 19.0 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.). The mixture was stirred for 2 h at 90 C. and <10 mbar. After filtration 631.0 g of a light yellowish oil was obtained (hydroxy value: 315.4 mgKOH/g).

2b) 1 mol 1,2-hexanediol+3.4 mol propylene oxide, Aminated

(5) In a 9 l autoclave 500.0 g of the resulting alkoxylated dialcohol from example 2-a, 1200 mL of THF and 1500.0 g of ammonia were mixed in the presence of 200 mL of a solid catalyst. The catalyst containing oxides of nickel, copper and molybdenum on zirconium dioxide was in the form of 33 mm tablets. The autoclave was purged with hydrogen and pressurized to 20 bar before the mixture was heated to 205 C. The pressure was increased to 280 bar and the reaction mixture was stirred for 15 hours at 205 C. and the total pressure was maintained at 280 bar. After 15 hours the autoclave was cooled to ambient temperature, the product was collected, filtered, and stripped on a rotary evaporator to remove light amines and water. A total of 450.0 g of a low-color etheramine mixture was isolated. The analytical results thereof are shown in Table 2.

(6) TABLE-US-00002 TABLE 2 Total Total Tertiary Hy- Grade Primary amine- acetylata- Secondary amine- droxyl of Amine value bles and tertiary value value amina- in % of mg mg amine value mg mg tion total KOH/g KOH/g mg KOH/g KOH/g KOH/g in % amine 350.40 357.50 7.03 1.85 8.95 97.51 97.99

Example 3

1 mol 1,2-octanediol+3.4 mol propylene oxide, Aminated

3a) 1 mol 1,2-octanediol+3.4 mol propylene oxide

(7) In a 2 l autoclave 248.6 g 1,2-octanediol and 5.8 g potassium hydroxide (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. 335.2 g Propylene oxide was added in portions within 5 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. Potassium hydroxide was removed by adding 17.5 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.). The mixture was stirred for 2 h at 90 C. and <10 mbar. After filtration 585.0 g of a yellowish oil was obtained (hydroxy value: 293.2 mgKOH/g).

3b) 1 mol 1,2-octanediol+3.4 mol propylene oxide, Aminated

(8) In a 9 l autoclave 500 mL of the resulting alkoxylated dialcohol from example 3-a, 1200 mL of THF and 1500.0 g of ammonia were mixed in the presence of 200 mL of a solid catalyst. The catalyst containing oxides of nickel, copper and molybdenum on zirconium dioxide was in the form of 33 mm tablets. The autoclave was purged with hydrogen and pressurized to 20 bar before the mixture was heated to 205 C. The pressure was increased to 280 bar and the reaction mixture was stirred for 15 hours at 205 C. and the total pressure was maintained at 280 bar. After 15 hours the autoclave was cooled to ambient temperature, the product was collected, filtered, and stripped on a rotary evaporator to remove light amines and water. A total of 450.0 g of a low-color etheramine mixture was isolated. The analytical results thereof are shown in Table 3.

(9) TABLE-US-00003 TABLE 3 Total Total Tertiary Hy- Grade Primary amine- acetylata- Secondary amine- droxyl of Amine value bles and tertiary value value amina- in % of mg mg amine value mg mg tion total KOH/g KOH/g mg KOH/g KOH/g KOH/g in % amine 299.20 308.40 6.68 1.19 10.39 96.64 97.77

Example 4

1 mol 1,2-decanediol+3.4 mol propylene oxide, Aminated

4a) 1 mol 1,2-decanediol+3.4 mol propylene oxide

(10) In a 2 l autoclave 278.8 g 1,2-decanediol and 5.9 g potassium hydroxide (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. 315.5 g Propylene oxide was added in portions within 5 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. Potassium hydroxide was removed by adding 18.0 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.). The mixture was stirred for 2 h at 90 C. and <10 mbar. After filtration 595.0 g of a yellow oil was obtained (hydroxy value: 278.4 mgKOH/g).

4b) 1 mol 1,2-decanediol+3.4 mol propylene oxide, Aminated

(11) In a 9 l autoclave 500 mL of the resulting alkoxylated dialcohol from example 4-a, 1200 mL of THF and 1500 g of ammonia were mixed in the presence of 200 mL of a solid catalyst. The catalyst containing oxides of nickel, copper and molybdenum on zirconium dioxide was in the form of 33 mm tablets. The autoclave was purged with hydrogen and pressurized to 20 bar before the mixture was heated to 205 C. The pressure was increased to 280 bar and the reaction mixture was stirred for 15 hours at 205 C. and the total pressure was maintained at 280 bar. After 15 hours the autoclave was cooled to ambient temperature, the product was collected, filtered, and stripped on a rotary evaporator to remove light amines and water. A total of 400 g of a low-color etheramine mixture was isolated. The analytical results thereof are shown in Table 4.

(12) TABLE-US-00004 TABLE 4 Total Total Tertiary Hy- Grade Primary amine- acetylata- Secondary amine- droxyl of Amine value bles and tertiary value value amina- in % of mg mg amine value mg mg tion total KOH/g KOH/g mg KOH/g KOH/g KOH/g in % amine 319.15 328.00 6.90 0.73 9.58 97.09 97.84

Example 5

1 mol 1,2-dodecanediol+3.4 mol propylene oxide, Aminated

5a) 1 mol 1,2-dodecanediol+3.4 mol propylene oxide

(13) In a 2 l autoclave 337.2 g 1,2-dodecanediol and 6.0 g potassium hydroxide (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. 295.8 g Propylene oxide was added in portions within 5 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. Potassium hydroxide was removed by adding 19.1 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.). The mixture was stirred for 2 h at 90 C. and <10 mbar. After filtration 636.0 g of a yellow oil was obtained (hydroxy value: 275.5 mgKOH/g).

5b) 1 mol 1,2-dodecanediol+3.4 mol propylene oxide, Aminated

(14) In a 9 l autoclave 500 g of the resulting alkoxylated dialcohol from example 5-a, 1200 mL of THF and 1500 g of ammonia were mixed in the presence of 200 mL of a solid catalyst. The catalyst containing oxides of nickel, copper and molybdenum on zirconium dioxide was in the form of 33 mm tablets. The autoclave was purged with hydrogen and pressurized to 20 bar before the mixture was heated to 205 C. The pressure was increased to 280 bar and the reaction mixture was stirred for 15 hours at 205 C. and the total pressure was maintained at 280 bar. After 15 hours the autoclave was cooled to ambient temperature, the product was collected, filtered, and stripped on a rotary evaporator to remove light amines and water. A total of 450.0 g of a low-color etheramine mixture was isolated. The analytical results thereof are shown in Table 5

(15) TABLE-US-00005 TABLE 5 Total Total Tertiary Hy- Grade Primary amine- acetylata- Secondary amine- droxyl of Amine value bles and tertiary value value amina- in % of mg mg amine value mg mg tion total KOH/g KOH/g mg KOH/g KOH/g KOH/g in % amine 282.86 289.50 5.27 2.50 9.14 96.87 98.14
Use as Additives in Laundry Detergents

(16) Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, and Bacon Graese 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 6) together with or without 1.25 g of the etheramine additive and some hydrochloric acid to readjust the pH after addition of the polyetheramine. (pH of 75 g of LA1 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.

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

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

(19) The value of stain removal index increases with better washing performance.

(20) TABLE-US-00006 TABLE 6 liquid detergent composition LA1 Ingredients of liquid detergent composition LA1 percentage 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% C12-18 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.5Amphilic polymer 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) .sup.9Natalase, is a product of Novozymes, Bagsvaerd, Denmark. .sup.10A suitable chelant is 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

(21) TABLE-US-00007 TABLE 7 Wash Results: Stain A B C D E Beef Fat 61.1 63.4 67.8 69.5 69.9 Pork Fat 58.5 61.2 67.6 71.3 71.2 Bacon Grease 62.4 64.9 71.2 73.3 73.7 A: liquid detergent composition LA1 (see Table 6) without additional etheramine additive B: liquid detergent composition LA1 (see Table 6) with 1.25 g polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230 (Comparative example) C: liquid detergent composition LA1 (see Table 6) with 1.25 g of the etheramine described in Example 1 D: liquid detergent composition LA1 (see Table 6) with 1.25 g of the etheramine described in Example 2 E: liquid detergent composition LA1 (see Table 2) with 1.25 g of the etheramine described in Example 3