Etheramines based on dialcohols

Abstract

This invention relates to etheramines based on dialcohols, wherein the etheramines comprise at least three linear or branched C.sub.4-alkylene groups and a process for the manufacture of these etheramines.

Claims

1. A mixture of etheramines of formula (I) ##STR00008## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H, a methyl group and an ethyl group; A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from the group consisting of linear alkylenes having 2 to 18 carbon atoms and branched alkylenes having 2 to 18 carbon atoms; wherein at least three selected from the group consisting of A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are linear or branched butylene; the sum of x+y is in the range of 3 to 100 and x1 and y1; 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.

2. The mixture according to claim 1, wherein x+y is in the range of from 3 to 10.

3. The mixture according to claim 1, wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are linear or branched butylene.

4. The mixture according to claim 1, wherein R.sub.1 is a methyl group and R.sub.2, R.sub.3 and R.sub.4 are H.

5. The mixture according to claim 1, wherein Z.sub.1-Z.sub.4 are NH.sub.2.

6. The mixture according to claim 1, wherein said etheramine of formula (I) or formula (II) has a weight average molecular weight of about 250 to about 700 grams/mole.

7. A composition comprising the mixture as defined in claim 1 and further comprises an etheramine of formula (VI) ##STR00009## and/or an etheramine of formula (VII) ##STR00010## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H, a methyl group and an ethyl group; A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from the group consisting of linear alkylenes having 2 to 18 carbon atoms and branched alkylenes having 2 to 18 carbon atoms; wherein at least one of A.sub.1, A.sub.2, A.sub.3 and A.sub.4 is linear or branched butylene; the sum of k+m is below 3 and wherein k1 and m1; 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.

8. The mixture according to claim 1, wherein the etheramine mixture is reacted with an acid.

9. A process for the manufacture of the mixture as defined in claim 1 comprising the following steps: a) reacting a dialcohol of Formula (III) with C.sub.2-C.sub.18 alkylene oxides, wherein the molar ratio of dialcohol to C.sub.2-C.sub.18 alkylene oxides is in the range of from 1:3 to 1:10, ##STR00011## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H, a methyl group or an ethyl group; and b) aminating the alkoxylated dialcohols with ammonia.

10. The process according to claim 9, wherein the molar ratio of dialcohol to C.sub.2-C.sub.18 alkylene oxides is in the range of 1:3 to 1:4.

11. The process according to claim 9, wherein the C.sub.2-C.sub.18 alkylene oxides are selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide or a mixture thereof.

12. The process according to claim 9, wherein the C.sub.2-C.sub.18 alkylene oxide is butylene oxide.

13. The process according to claim 9, wherein the dialcohol of formula (III) is selected from the group consisting of 1,2-propanediol, 1,2-butanediol, 1,2-ethanediol, 3,4-hexanediol and 2,3-pentanediol.

14. The process according to claim 9, wherein the amination is carried out in the presence of copper-containing catalyst, nickel-containing catalyst or cobalt-containing catalyst.

15. A personal care composition comprising the mixture as defined in claim 1.

16. A shampoo and/or body wash formulation comprising the mixture as defined in claim 1.

17. A curing agent for epoxy resins or as a reactant in the production of polymers comprising the mixture as defined in claim 1.

18. A polyurethane, polyurea, or a thermoplastic polyamide adhesives comprising the mixture as defined in claim 1.

19. The mixture according to claim 3, wherein R.sub.1 is a methyl group and R.sub.2, R.sub.3 and R.sub.4 are H and Z.sub.1-Z.sub.4 are NH.sub.2.

Description

SYNTHESIS EXAMPLES

(1) In the examples, the following abbreviations are used:

Example 1: 1 Mole 1,2-Propanediol+4 Mole Butylene Oxide, Aminated

(2) a) 1 Mole 1,2-Propandiol+4 Mole Butylene Oxide

(3) A 2 L autoclave was charged with 152.2 g 1,2-propanediol and 1.5 g potassium tert.-butylate and heated to 120 C. The autoclave was purged three times with nitrogen and heated to 140 C. 576.0 g butylene oxide was added in portions within 10 h. To complete the reaction, the mixture was stirred and allowed to post-react for additional 8 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 23.0 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.), stirring at 100 C. for 2 hours and filtration.

(4) A light yellowish oil was obtained (730.1 g, hydroxy value: 251.7 mgKOH/g).

(5) b) 1 Mole 1,2-Propanediol+4 Mole Butylene Oxide, Aminated

(6) In a 9 L autoclave 650 g of the resulting liquid diol mixture from example 1-a, 1050 mL THF and 1500 g ammonia were mixed in presence of 200 mL of a solid catalyst as described in EP 0 696 572 B1. The catalyst containing nickel, copper, molybdenum and zirconium was in the form of 33 mm tablets. The autoclave was purged with hydrogen and the reaction was started by heating the autoclave. The reaction mixture was stirred for 15 hours 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 on a rotary evaporator to remove light amines and water. A total of 500 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 1.

(7) TABLE-US-00001 TABLE 1 Analytical results of the etheramine of Example 1 Total Secondary Tertiary Primary amine- Total and tertiary amine- Hydroxyl Grade of Amine value acetylatables amine value value value amination in % of mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % total amine 294.00 301.30 0.46 0.19 7.49 97.52 99.84

Comparative Example 1

(8) Polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)poly(oxy(methyl-1,2-ethandlyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230 by Huntsman, Tex., United States of America.

Comparative Example 2

(9) 1,2-Bis(2-aminoethoxy)ethane 97%, CAS-NR: 929-59-9, purchased from ABCR GmbH, Germany.

Comparative Example 3

(10) Ethylene glycol bis(2-aminopropyl)ether 98%, CAS-NR: 2997-01-5, purchased from ABCR GmbH, Germany.

(11) Use as Additives in Laundry Detergents

(12) Stain removal from the swatches was calculated as follows:
Stain Removal Index (SRI)=(E.sub.initialE.sub.washed)*100/E.sub.initial

(13) E.sub.initial=Stain level before washing

(14) E.sub.washed=Stain level after washing

(15) E is calculated as CIE 1976 color difference according to DIN EN ISO 11664-4 (June 2012). E.sub.initial is calculated with L*, a*, b* values measured on fabric without stain and the L*, a*, b* values measured on the greasy stain before washing. E.sub.washed is calculated with L, a, b* values measured on fabric without stain and the L*, a*, b* values measured on the greasy stain after washing. Standard colorimetric measurement was used to obtain L, a* and b* values.

Application Example 1

(16) Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat and Bacon Grease 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 17 C.) and using 75 g of liquid detergent composition LA1 (see Table 2) together with or without 1.25 g of etheramine additive and some hydrochloric acid to readjust the pH after addition of the etheramine (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).

(17) Six 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 diminished 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.

(18) TABLE-US-00002 TABLE 2 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% 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% Natalase.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.2AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA .sup.3AE9 is C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA .sup.4NI 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 poly-ethylene 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.7Polyethyleneimine (MW = 600) with 20 ethoxylate groups per NH .sup.8Protease may be supplied by Genencor International, Palo Alto, California, USA .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

(19) TABLE-US-00003 TABLE 3 Wash results (given in SRI units) Beef Fat Pork Fat Bacon Grease Composition A 70.2 70.1 69.2 Composition B 72.1 70.9 71.4 Composition C 78.3 76.3 80.0 Composition A: liquid detergent composition LA1 (see Table 2) without additional etheramine additive Composition B: liquid detergent composition LA1 (see Table 2) with Comparative Example 1, polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230 or JEFFAMINE D-230 Composition C: liquid detergent composition LA1 (see Table 2) with 1,2-Propanediol + 4 butylene oxide, aminated, preparation of etheramine described in Example 1

(20) The cleaning composition with the etheramine according to the invention (see Table 3: Composition C) shows superior grease cleaning effects over the detergent composition without etheramines (see Table 3: Composition A) and also shows superior grease cleaning effects over the cleaning composition with the etheramine of the Comparative Example 1 (see Table 3: B).

Application Example 2

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

(22) Liquid Detergent A (see Table 4) is a conventional laundry detergent that uses the Comparative Example 1, Polyetheramine D 230; Liquid Detergent B (see Table 4) contains instead the etheramine described by Example 1.

(23) Technical stain swatches of cotton CW120 containing burnt butter, hamburger grease, margarine, taco grease were purchased from Empirical Manufacturing Co., Inc (Cincinnati, Ohio). The swatches were washed in a Miele front loader washing machine, using 14 grains per gallon water hardness and washed at 15 C. The total amount of liquid detergent used in the test was 80 grams. 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.

(24) TABLE-US-00004 TABLE 4 composition of the liquid detergents Liquid Detergent A Liquid Detergent B (%) (%) AES C.sub.12-15 alkyl ethoxy 14.0 14.0 (1.8) sulfate Alkyl benzene sulfonic acid 2.0 2.0 Nonionic 24-9.sup.4 1.0 1.0 C12/14 Amine Oxide 0.2 0.2 Etheramine.sup.2 1.0 Polyetheramine.sup.3 1.0 Citric Acid 3.4 3.4 Borax 2.8 2.8 Zwitterionic dispersant.sup.5 1.1 1.1 Ethoxylated 1.5 1.5 Polyethyleneimine.sup.1 Sodium hydroxide 3.7 3.7 DTPA.sup.6 0.3 0.3 Protease 0.8 0.8 Amylase: Natalase 0.14 0.14 1,2-Propanediol 3.9 3.9 Monoethanolamine (MEA) 0.3 0.3 Sodium Cumene Sulfonate 0.9 0.9 Water & other components Balance Balance pH 8.3 8.3 .sup.1Polyethyleneimine (MW = 600) with 20 ethoxylate groups per NH .sup.2The etheramine composition as described in Example 1 .sup.3Polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy(methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine D 230. .sup.4Nonionic 24-9 is a C12-14 alcohol ethoxylate, with an average degree of ethoxylation of 9 .sup.5A 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.6DTPA is diethylenetetraamine pentaacetic acid

(25) Stain removal index scores for each stain were calculated as described above and are listed in Table 5.

(26) TABLE-US-00005 TABLE 5 Cleaning Results Liquid Detergent B (results given as delta SRI vs. Liquid Soils Liquid Detergent A Detergent A) Margarine 88.2 1.7 Grease burnt 76.7 5.1 butter Grease hamburger 68.0 8.2 Grease taco 55.2 7.4

(27) These results illustrate the surprising grease removal benefit of the etheramine of Example 1 as compared to the Comparative Example 1, Polyetheramine D 230 especially on difficult-to-remove, high-frequency consumer stains like hamburger grease and taco grease.

Application Example 3

(28) Technical stain swatches of blue knitted cotton containing Sausage Fat, Chicken Fat and Bacon Grease 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 2 of Application Example 1). To assess the performance of the polyetheramine additive there were added to the detergent composition 1.125 g of polyetheramine additive of Example 1 or 1.160 g of polyetheramine of Comparative Example 2 or 1.148 g of polyetheramine of Comparative Example 3 and some hydrochloric acid to re-adjust 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).

(29) 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.

(30) TABLE-US-00006 TABLE 6 Wash results (given in SRI units) Sausage Fat Chicken Fat Bacon Grease Composition D 61.2 59.0 58.8 Composition E 69.2 67.7 68.0 Composition F 63.2 61.5 60.3 Composition G 63.2 62.3 62.2 Composition D: Liquid detergent composition LA1 (see Table 2) without additional etheramine additive Composition E: Liquid detergent composition LA1 (see Table 2) with polyetheramine of Example 1 Composition F: Comparative example: Liquid detergent composition LA1 (see Table 2) with polyetheramine Comparative Example 2 (1,2-Bis(2-aminoethoxy)ethane) Composition G: Comparative example: Liquid detergent composition LA1 (see Table 2) with polyetheramine Comparative Example 3 (Ethylene glycol bis(2-aminopropyl)ether)

(31) The cleaning composition with the etheramine according to the invention (see Table 6: Composition E) shows superior grease cleaning effects over the detergent composition without etheramines (see Table 6: Composition D) and also shows superior grease cleaning effects over the cleaning composition with the etheramine of the Comparative Example 2 and 3 (see Table 6: Composition F and G).