Etheramines based on alkoxylated glycerine or trimethylolpropane

Abstract

This invention relates to an etheramine of formula (I) based on glycerine or trimethylolpropane and its manufacturing process, ##STR00001## wherein R=H or ethyl, k=0 or 1 A represents a linear or branched alkylene group having C.sub.2-C.sub.18 carbon atoms, A may be the same as or different from one another, at least one A represents a linear or branched C.sub.4-alkylene group, the sum of x, y and z lies in the range of 3 to 100, x?y?1 and z?1, Z=NH2 or OH but at least two Z per molecule are NH2.

Claims

1. An etheramine of formula (I), ##STR00003## wherein R=H or ethyl, k=0 or 1 A represents a linear or branched alkylene group having C.sub.2-C.sub.18 carbon atoms, A may be the same as or different from one another, at least one A represents a linear or branched C.sub.4-alkylene group, the sum of x, y and z lies in the range of 5 to 10, x?1, y?1 and z?1, Z=NH2 or OH but at least two Z per molecule are NH.sub.2.

2. The etheramine according to claim 1, wherein at least three A represent a linear or branched C.sub.4-alkylene group.

3. The etheramine according to claim 1, wherein all A groups represent a linear or branched C.sub.4-alkylene group.

4. The etheramine according to claim 1, wherein Z is NH.sub.2.

5. The etheramine according to claim 1, wherein the etheramine of formula (I) is reacted with an acid.

6. A process for the manufacture of an etheramine of formula (I) ##STR00004## wherein R=H or ethyl, k=0 or 1 A represents a linear or branched alkylene group having C.sub.2-C.sub.18 carbon atoms, A may be the same as or different from one another, at least one A represents a linear or branched C.sub.4-alkylene group, the sum of x, y and z lies in the range of 5 to 10, x?1, y?1 and z?1, Z=NH2 or OH but at least two Z per molecule are NH.sub.2, comprising the following steps: a) reacting glycerine or 1,1,1-trimethylolpropane with C.sub.4-alkylene oxide and optionally with C.sub.2-C.sub.18 alkylene oxide, wherein the molar ratio of glycerine or 1,1,1-trimethylolpropane to C.sub.4 alkylene oxide is in the range of 1:3 to 1:10, and b) aminating the alkoxylated glycerine or alkoxylated 1,1,1-trimethylolpropane with ammonia.

7. The process according to claim 6, wherein the molar ratio of glycerine or 1,1,1-trimethylolpropane to C.sub.4 alkylene oxide is in the range of 1:3 to 1:6.

8. The process according to claim 6, wherein the C.sub.2-C.sub.18 alkylene oxide is ethylene oxide, propylene oxide or a mixture thereof.

9. The process according to claim 6, wherein the amination is carried out in the presence of copper-, nickel- or cobalt-containing catalyst.

10. The process according to claim 6, 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 is in the range from 0.2 to 5.0% by weight of oxygen compounds of tin, calculated as SnO.

11. A personal care product which comprises the polyetheramine of claim 1.

12. A shampoo and body wash formulation which comprises the polyetheramine of claim 1.

13. A curing agent for epoxy resins or as a reactant in the production of polymers which comprises the polyetheramine of claim 1.

14. A polyurethane, polyurea, or a thermoplastic polyamide adhesive which comprises the polyetheramine of claim 1.

Description

SYNTHESIS EXAMPLES

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

(2) BuO butylene oxide

(3) PO propylene oxide

Example 1: 1 Mole Glycerine+3 Mole BuO+3 Mole PO, Aminated

(4) a) 1 mole Glycerine+3 mole BuO+3 mole PO

(5) In a 3.5 L autoclave 95.0 g glycerine and 1.0 g potassium tert.-butylate were mixed. The auto-clave was purged three times with nitrogen and heated to 140? C. 223.0 g butylene oxide was added within 90 minutes. The mixture was allowed to post-react for 5 hours at 140? C. Then, 179.7 g propylene oxide was added in portions within 1 hour. To complete the reaction, the mixture was allowed to post-react for additional 3 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 4.9 g synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.) stirring at 100? C. for 2 hours and filtration.

(6) A yellowish oil was obtained (490.0 g, hydroxy value: 314.5 mgKOH/g).

(7) b) 1 mole Glycerine+3 mole BuO+3 mole PO, aminated

(8) In a 9 L autoclave 350 mL of the resulting triol mixture from example 1-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 3?3 mm tablets. 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 350-400 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 1.

(9) TABLE-US-00001 TABLE 1 Analytical results of etheramine of example 1 Primary Total Secondary Tertiary Amine amine- Total and tertiary amine- Hydroxyl Grade of in % of value acetylatables amine value value value amination total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 352.30 357.43 3.43 0.75 5.88 98.77 99.03

Example 2: 1 Mole Glycerine+3 Mole PO+3 Mole BuO, Aminated

(10) a) 1 mole Glycerine+3 mole PO+3 mole BuO

(11) In a 3.5 L autoclave 88.1 g glycerine and 0.9 g potassium tert.-butylate were mixed. The auto-clave was purged three times with nitrogen and heated to 140? C. 166.6 g propylene oxide was added within 1 hour. The mixture was allowed to post-react for 3 hours at 140? C. Then, 206.8 g butylene oxide was added in portions within 1 hours. To complete the reaction, the mixture was allowed to post-react for additional 3 hours at 140? C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacua at 80? C. The catalyst was removed by adding 4.4 g Macrosorb MP5plus, stirring at 100? C. for 2 hours and filtration. A yellowish oil was obtained (410.0 g, hydroxy value: 336.5 mgKOH/g).

(12) b) 1 mole Glycerine+3 mole PO+3 mole BuO, aminated

(13) In a 9 L autoclave 350 mL of the resulting triol mixture from example 2-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 3?3 mm tablets. 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 300-350 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 2.

(14) TABLE-US-00002 TABLE 2 Analytical results of etheramine of example 2 Primary Total Secondary Tertiary Amine amine- Total and tertiary amine- Hydroxyl Grade of in % of value acetylatables amine value value value amination total mg KOH/g mg KOH/g mg KOH/g mg KOH /g mg KOH/g in % amine 373.88 377.50 1.33 0.66 4.28 99.21 99.64

Example 3: 1 Mole Glycerine+6 Mole BuO, Aminated

(15) a) 1 mole Glycerine+6 mole BuO

(16) In a 3.5 L autoclave 103.4 g glycerine and 1.2 g potassium tert-butylate were mixed. The auto-clave was purged three times with nitrogen and heated to 140? C. 485.5 g butylene oxide was added within 2 hours. To complete the reaction, the mixture was allowed to post-react for additional 7 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 5.9 g Macrosorb MP5plus, stirring at 100? C. for 2 hours and filtration.

(17) A yellowish oil was obtained (589.0 g, hydroxy value: 285.0 mgKOH/g).

(18) a) Glycerine+6 mole BuO, aminated

(19) In a 9 L autoclave 500 g of the resulting triol 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 3?3 mm tablets. 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 3.

(20) TABLE-US-00003 TABLE 3 Analytical results of etheramine of example 3. Primary Total Secondary Tertiary Amine amine- Total and tertiary amine- Hydroxyl Grade of in % of value acetylatables amine value value value amination total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 313.30 327.30 1.54 0.22 14.22 95.66 99.51

Example 4: 1 Mole Glycerine+4.2 Mole PO+1.8 Mole BuO, Aminated

(21) a) 1 mole Glycerine+4.2 mole PO+1.8 mole BuO

(22) In a 3.5 L autoclave 88.9 g glycerine and 0.9 g potassium tert.-butylate were mixed. The auto-clave was purged three times with nitrogen and heated to 140? C. 235.4 g propylene oxide was added within 1.5 hour. The mixture was allowed to post-react for 3 hours at 140? C. Then, 125.2 g butylene oxide was added in portions within 1 hour. To complete the reaction, the mixture was allowed to post-react for additional 5 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 4.7 g Macrosorb MP5plus, stirring at 100? C. for 2 hours and filtration.

(23) A yellowish oil was obtained (470.0 g, hydroxy value: 312.1 mgKOH/g).

(24) b) 1 mole Glycerine+4.2 mole PO+1.8 mole BuO, aminated

(25) In a 9 L autoclave 350 mL of the resulting triol 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 3?3 mm tablets. 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 350-400 grams of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 4.

(26) TABLE-US-00004 TABLE 4 Analytical results of etheramine of example 4. Primary Total Secondary Tertiary Amine amine- Total and tertiary amine- Hydroxyl Grade of in % of value acetylatables amine value value value amination total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in % amine 343.96 347.12 3.26 0.76 3.92 99.31 99.05

Example 5 (Comparative): 1 Mole Glycerine+6 Mole PO, Aminated

(27) a) 1 mole Glycerine+6 mole PO

(28) In a 2 L autoclave 276.3 g glycerine and 2.6 g potassium tert.-butylate were mixed. The auto-clave was purged three times with nitrogen and heated to 140? C. 1044.0 g propylene oxide was added within 10 hours. The mixture was allowed to post-react for 9.5 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 21.1 g Macrosorb MP5plus, stirring at 100? C. for 2 hours and filtration.

(29) A light yellow oil was obtained (1300.0 g, hydroxy value: 320.2 mgKOH/g).

(30) b) 1 mole Glycerine+6 mole PO, aminated

(31) In a 9 L autoclave 750 mL of the resulting polyol mixture from example 5-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 3?3 mm tablets. 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 250 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. 720 g of a low-color etheramine mixture was recovered. The analytical results thereof are shown in Table 5.

(32) TABLE-US-00005 TABLE 5 Total Secondary Tertiary Primary amine- Total and tertiary amine- Hydroxyl Grade of Amine value acetylatables 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 368.70 380.00 2.85 0.00 11.30 97.03 99.23

(33) Use as Additives in Laundry Detergents

(34) Technical stain swatches of blue knitted cotton containing Beef Fat, Pork Fat, Sausage Fat, Bacon Grease and Anchor Butter 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 (table 8) together with or without 1.25 g of etheramine additive and some hydrochloric acid to readjust the pH after addition of the etheramine. 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.

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

(36) ?E.sub.initial=Stain level before washing

(37) ?E.sub.washed Stain level after washing

(38) 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.inital) 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.

(39) TABLE-US-00006 TABLE 8 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% 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.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.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.7Polyethyleneimine (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

(40) TABLE-US-00007 TABLE 9 results Stain A B C D Beef Fat 75.3 80.2 78.8 75.1 Pork Fat 70.2 77.7 77.7 72.7 Sausage Fat 72.9 79.5 77.0 75.9 Bacon Grease 74.5 79.1 80.3 75.3 Anchor Butter 60.6 69.1 66.9 63.6 A: liquid detergent composition LA1 (table 8) without additional etheramine additive B: liquid detergent composition LA1 (table 8) with the etheramine described in Example 1 (1 mole Glycerine + 3 mole BuO + 3 mole PO, aminated) C: liquid detergent composition LA1 (table 8) with the etheramine described in Example 3 (1 mole Glycerine + 6 mole BuO, aminated) D: liquid detergent composition LA1 (table 8) with the etheramine described in comparitive Example 5 (1 mole Glycerine + 6 mole PO, aminated)

(41) All three etheramines in the test have a molecular ratio of alkylene oxide:glycerol of 6:1. For all the five grease stains a superior cleaning effect of the butylene-oxide containing etheramines (B and C) over the non-butylene oxide containing etheramine (D) and over the liquid detergent composition without etheramine (A) is seen.