Alkoxylated polyethyeneimine with a low melting point

Abstract

The present invention relates to water-soluble alkoxylated polyalkyleneimines having an inner block of polyethylene oxide comprising 5 to 18 polyethylene oxide units, a middle block of polyalkylene oxide comprising 1 to 5 polyalkylene oxide units and an outer block of polyethylene oxide comprising 2 to 14 polyethylene oxide units. The middle block is formed from polypropylene oxide units, polybutylene oxide units and/or polypentene oxide units. In addition, the present invention relates to water-soluble alkoxylated polyamines.

Claims

1. A water-soluble alkoxylated polyalkylenimine or polyamine of the general formula I ##STR00016## in which the variables are each defined as follows: R represents identical or different, linear or branched C.sub.2-C.sub.12 alkylene radicals or an etheralkyl unit of the following formula: ##STR00017## in which the variables are each defined as follows: R.sup.10, R.sup.11, R.sup.12 represent identical or different, linear or branched C.sub.2-C.sub.6-alkylene radicals and d is an integer having a value in the range of from 0 to 50; B represents a continuation of the alkoxylated polyalkylenimine by branching E is an alkylenoxy unit of the formula II ##STR00018## in which the variables are each defined as follows: R.sup.1 represents 1,2-propylene, 1,2-butylene and/or 1,2-pentene; R.sup.2 represents hydrogen and/or C.sub.1-C.sub.22-alkyl and/or C.sub.7-C.sub.22 aralkyl; y and z are each from 0 to 150, m is an integer having a value in the range of from 5 to 18; n is an integer having a value in the range of from 1 to 5; p is an integer having a value in the range of from 2 to 14.

2. The polyalkylenimine or polyamine according to claim 1, wherein R represents identical or different, linear or branched C.sub.2-C.sub.12-alkylene radicals.

3. The polyalkylenimine or polyamine according to claim 1, wherein R is ethylene or hexamethylene.

4. The polyalkylenimine or polyamine according to claim 1, wherein the sum of y+z is at least 1 or wherein y and z are 0.

5. The polyamine according to claim 1, wherein y and z are both 0, d is from 1 to 5, and R.sup.10, R.sup.11, R.sup.12 are independently selected from linear or branched C.sub.3 to C.sub.4 alkylene radicals.

6. The polyalkylenimine or polyamine according to claim 1, wherein m and p have a value in the range of from 5 to 14.

7. The polyalkylenimine or polyamine according to claim 1, wherein up to 100% of the nitrogen atoms present in the polyalkylenimine or polyamine are quaternized.

8. The polyalkylenimine or polyamine according to claim 1, wherein the degree of quaternization of the nitrogen atoms present in the polyalkylenimine or polyamine lies in the range of from 10% to 95%.

9. The polyalkylenimine or polyamine according to claim 7, wherein the quaternized polyalkylenimine or polyamine is sulfatized or transsulfatized.

10. A cosmetic formulation, a crude oil emulsion breaker, a pigment dispersion for ink jet inks, a formulation for electro plating, or a cementitious composition which comprises the polyalkylenimine or polyamine according to claim 1.

11. A process for preparing the alkoxylated polyalkyleneimine or the polyamine according to claim 1, which comprises first reacting a polyalkyleneimine or a polyamine with ethylene oxide than with propylene oxide or butylene oxide and then with ethylene oxide.

12. The process according to claim 11 in which per mol of N—H functionalities in the polyalkyleneimine or polyamine the polyalkyleneimine or polyamine is reacted with 5 to 18 moles ethylene oxide then with 1 to 5 moles propylenoxide or butylene oxide and then with 2 to 14 moles ethylene oxide.

13. The process according to claim 11 in which the polyalkyleneimine is a polyethyleneimine or the polyamine is a hexamethylenediamine.

14. The process according to claim 11 in which the alkoxylated polyalkyleneimine or the alkoxylated polyamine is additionally quaternized and/or sulfatized.

15. The polyalkylenimine or polyamine according to claim 1, wherein the polyalkyleneimine or polyamine has a backbone molecular weight Mw in the range of from 50 to 10 000 g/mol.

Description

EXAMPLES

(1) In the examples, the following abbreviations are used: EO ethylene oxide PO propylene oxide PEI600 polyethylenimine with an average molecular weight of 600 g/mol x EO/NH x mole ethylene oxide per mole of NH-functionality y PO/NH y mole propylene oxide per mole of NH-functionality

Example 1

(2) PEI600+17 EO/NH+2 PO/NH+2 EO/NH

(3) a) PEI600+1 EO/NH

(4) A 5 l autoclave was charged with 1943.0 g of a polyethylenimine with an average molecular weight of 600 g/mol and 97.0 g water. The reactor was purged three times with nitrogen and heated to 110° C. 1789.0 g ethylene oxide were added within 14 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours. Water and volatile compounds were removed in vacuo at 90° C. A highly viscous yellow oil (3688.0 g, water content: 2.6%, pH: 11.05 (5% in water)) was obtained.

(5) b) PEI600+17 EO/NH+2 PO/NH+2 EO/NH

(6) Product from example 1a) (76.3 g) and 3.58 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 637.6 g ethylene oxide were added within 7 hours, followed by addition of 104.4 g propylene oxide within 1.5 hours and afterwards 79.2 g ethylene oxide within 1.5 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 890.0 g of a slightly turbid liquid were obtained (melting point: 19.1° C.). Melting points were measured according to DIN 51007.

Example 2

(7) PEI600+13 EO/NH+2 PO/NH+6 EO/NH

(8) Product from example 1a) (80.0 g) and 3.75 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 502.2 g ethylene oxide were added within 6 hours, followed by addition of 109.4 g propylene oxide within 1.5 hours and afterwards 249.0 g ethylene oxide within 3.5 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 938.0 g of a slightly turbid liquid were obtained (melting point: 6.8° C.).

Example 3

(9) PEI600+11 EO/NH+2 PO/NH+8 EO/NH

(10) Product prepared as described in example 1a) (80.2 g, 92.7% in water) and 3.58 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 399.9 g ethylene oxide were added within 5 hours, followed by addition of 104.4 g propylene oxide within 1.5 hours and afterwards 316.8 g ethylene oxide within 3.5 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 895.0 g of a slightly turbid liquid were obtained (melting point: 8.3° C., viscosity (20° C.) 2126 mPas, cloud point: 87° C. Cloud points were measured according to DIN EN 1890, method B.

Example 4

(11) a) PEI600+11 EO/NH+3 PO/NH+8 EO/NH

(12) Product prepared as described in example 1a) (76.3 g, 97.4% in water) and 3.8 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C., 400.0 g ethylene oxide were added within 6 hours, followed by addition of 156.6 g propylene oxide within 2 hours and afterwards 316.8 g ethylene oxide within 5 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 945.0 g of a light brown liquid were obtained (melting point: 3.8° C.)

(13) b) PEI600+11 EO/NH+3 PO/NH+8 EO/NH, Quaternized with Dimethylsulfate

(14) In a 500 ml reaction vessel with a nitrogen inlet, 160.0 g product from example 4a) (PEI600+11 EO/NH+3 PO/NH+8 EO/NH) was heated to 70° C. under a constant stream of nitrogen. 17.40 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, the pH was adjusted with 3.7 g sodium hydroxide (50% in water) to 9.2 (measured 10% in water). 185.0 g of a yellow liquid were obtained (amine value: 0.03 mgKOH/g, melting point: 5.0° C.). The degree of quaternization was 96%.

(15) c) PEI600+11 EO/NH+3 PO/NH+8 EO/NH, Quaternized with Dimethylsulfate, Transsulfatized

(16) In a reaction vessel 70.0 g of product obtained in example 4b) was heated under nitrogen atmosphere to 60° C. 2.0 g sulfuric acid (96%) was added at 60° C. to adjust the pH to 2.0 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 5.4 g sodium hydroxide (50% solution in water) to 9.3. 69.0 g of a brown liquid were obtained (melting point: 7.0° C., water: 0.5%)

Example 5

(17) PEI600+9 EO/NH+2 PO/NH+10 EO/NH

(18) Product from example 1a) (76.3 g, 97.4% in water) and 3.58 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 320.7 g ethylene oxide were added within 4 hours, followed by addition of 104.4 g propylene oxide within 1.5 hours and afterwards 396.0 g ethylene oxide within 6 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 895.0 g of a slightly brown liquid were obtained (melting point: 7.7° C.).

Example 6

(19) PEI600+5 EO/NH+2 PO/NH+14 EO/NH

(20) Product from example 1a) (76.3 g, 97.4% in water) and 3.6 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 162.4 g ethylene oxide were added within 2 hours, followed by addition of 104.4 g propylene oxide within 1.5 hours and afterwards 554.4 g ethylene oxide within 8 h. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 896.0 g of a slightly turbid liquid were obtained (melting point: 17.7° C.).

Comparative Example 1 (CE 1)

(21) PEI600+20 EO/NH

(22) Product prepared as described in example 1a) (144.6 g, 92.7% in water) and 4.34 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 1470.7 g ethylene oxide were added within 14 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 1615.0 g of a slightly brown solid were obtained (melting point: 35.4° C.).

Comparative Example 2 (CE 2)

(23) PEI600+19 EO/NH+2 PO/NH

(24) Product prepared as described in example 1a) (80.2 g, 92.7% in water) and 3.58 g potassium hydroxide (50% in water) was placed in a 21 autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 716.8 g ethylene oxide were added within 8 hours, followed by addition of 104.4 g propylene oxide within 1 hour. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 897.0 g of a slightly brown solid were obtained (melting point: 28.7° C.).

Comparative Example 3 (CE 3)

(25) PEI600+2.5 EO/NH+2 PO/NH+16.5 EO/NH

(26) Product similar to example 1a) (80.2 g, 92.7% in water) and 3.58 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 63.4 g ethylene oxide were added within 1 hour, followed by addition of 104.4 g propylene oxide within 1 hour and followed by addition of 653.4 g ethylene oxide within 6 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 896.0 g of a slightly brown solid were obtained (melting point: 27.2° C.).

Comparative Example 4 (CE 4)

(27) PEI600+2 PO/NH+19 EO/NH

(28) a) PEI600+1 PO/NH

(29) A 2 l autoclave was charged with 430.0 g of a polyethylenimine with an average molecular weight of 600 g/mol and 21.5 g water. The reactor was purged three times with nitrogen and heated to 110° C. 522.0 g propylene oxide were added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours. Water and volatile compounds were removed in vacuo at 90° C. A highly viscous yellow oil (970.0 g, water content: 2.6%) was obtained.

(30) b) PEI600+2 PO/NH+19 EO/NH

(31) Product from example 5a) (76.2 g, 97.4% in water) and 3.18 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 51.04 g propylene oxide were added within 10 minutes, followed by addition of 668.8 g ethylene oxide within 10 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 793.0 g of a light brown solid were obtained (melting point: 35.8° C.).

Comparative Example 5 (CE 5)

(32) HMDA+24 EO/NH

(33) a) HMDA+1 EO/NH

(34) A 2 l autoclave was charged with 408.0 g hexamethylene diamine (HMDA) and 20.4 g water. The autoclave was purged three times with nitrogen and heated to 110° C. 618.0 g ethylene oxide were added within 6 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110° C. Water and volatile compounds were removed in vacuo at 90° C. A highly viscous yellow oil (1019 g, water content: 0.2%, pH: 11.05 (5% in water)) was obtained.

(35) b) HMDA+5 EO/NH

(36) Product from comparative example 5a) (292.2 g) and 8.8 g potassium hydroxide (50% in water) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 2 hours to remove water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 704.0 g ethylene oxide were added within 7 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo, 999.0 g of a brown liquid were obtained.

(37) c) HMDA+24 EO/NH

(38) Product from comparative example 5b) (348.7 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 1171.7 g ethylene oxide were added within 10 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 1515.0 g of a light brown solid were obtained (melting point: 42.4° C.).

(39) d) HMDA+24EO/NH, Quaternized with Dimethyl Sulfate

(40) Product from comparative example 5 c) was quaternized as described in WO 04/024858. A brown solid was obtained (melting point 43.6° C.).

(41) e) HMDA+24EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(42) Product from comparative example 5 c) was quaternized and transsulfatized as described in WO 04/024858. A brown solid was obtained (melting point 41.5° C.).

Comparative Example 6 (CE 6)

(43) HMDA+2 PO/NH+22 ED/H

(44) a) HMDA+1 PO/NH

(45) A 2 l autoclave was charged with 232.4 g hexamethylene diamine (HMDA) and 11.6 g water. The autoclave was purged three times with nitrogen and heated to 110° C. 464.0 g propylene oxide were added within 6 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110° C. Water and volatile compounds were removed in vacua at 90° C. A highly viscous yellow oil (696.5 g, water content:amine value: 320 mgKOH/g) was obtained.

(46) b) HMDA+2 PO/NH+4 EO/NH

(47) Product from comparative example 6a) (350.0 g) and 2.58 g potassium t-butoxide was placed in a 3.5 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 233.2 g propylene oxide were added within 2 hours, followed by addition of 704.0 g ethylene oxide. To complete the reaction, the mixture was allowed to post-react for 5 hours at 140° C. Volatile compounds were removed in vacuo. 1291.0 g of a light brown liquid were obtained (amine value: 88.5 mgKOH/g).

(48) c) HMDA+2 PO/NH+22 EO/NH

(49) Product from comparative example 6b) (263.0 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 648.8 g ethylene oxide were added within 710 hours. To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 909.0 g of a light brown solid were obtained (melting point: 42.1° C., amine value: 25.2 mgKOH/g).

(50) d) HMDA+2 PO/NH+22 EO/NH, Quaternized with Dimethyl Sulfate

(51) In a 500 ml reaction vessel with a nitrogen inlet, 160.0 g product from example 6 c) (HMDA+2 PO/NH+22 EO/NH) was heated to 70° C. under a constant stream of nitrogen. 9.08 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, the pH was adjusted with 1.7 g sodium hydroxide (50% in water) to 9.2 (measured 10% in water). 1.54 g of a light brown solid was obtained (amine value: 0.12 mgKOH/g, melting point: 37.8° C.). The degree of quaternization was 100%.

(52) e) HMDA+2 PO/NH+22 EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(53) In a reaction vessel 70.0 g of product obtained in example 6 d) was heated under nitrogen atmosphere to 60° C. 2.0 g Sulfuric acid (96%) was added at 60° C. to adjust the pH to 2.0 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 2.2 g sodium hydroxide (50% solution in water) to 9.2. 65.0 g of a brown solid were obtained (melting point: 40.3° C., water: 0.5%)

Example 7

(54) a) HMDA+12 EO/NH+2 PO/NH+12 EO/NH

(55) Product from comparative example 5b) (199.2 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 246.2 g ethylene oxide were added within 3 hours, followed by addition of 92.8 g propylene oxide within 1 hours and afterwards 422.4 g ethylene oxide within 5 h.

(56) To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 960.0 g of a light brown liquid were obtained (melting point: 20.2° C., amine value: 23.0 mgKOH/g).

(57) b) HMDA+12 EO/NH+2 PO/NH+12 EO/NH, Quaternized with Dimethyl Sulfate

(58) In a 500 ml reaction vessel with a nitrogen inlet, 350.0 g product from example 7a) was heated to 70° C. under a constant stream of nitrogen. 17.7 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, 360 g of a brown liquid were obtained (amine value: 0.02 mgKOH/g, pH: 8.45 (10% in water), melting point: 19.9° C.). The degree of quaternization was 95%.

(59) c) HMDA+12 EO/NH+2 PO/NH+12 EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(60) In a reaction vessel 200.0 g of product obtained in example 7b) was heated under nitrogen atmosphere to 60° C. 1.0 g Sulfuric acid (96%) was added at 60° C. to adjust the pH to 2.15 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 2.0 g sodium hydroxide (50% solution in water) to 8.7. 200.0 g of a brown liquid were obtained (melting point: 22.1° C., water: 0.5%)

Example 8

(61) a) HMDA+11 EO/NH+2 PO/NH+11 EO/NH

(62) Product from comparative example 5b) (199.2 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 211.2 g ethylene oxide were added within 2.5 hours, followed by addition of 92.8 g propylene oxide within 1 hours and afterwards 387.2 g ethylene oxide within 4 h.

(63) To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 888.0 g of a light brown liquid were obtained (melting point: 17.7° C., amine value: 25.8 mgKOH/g).

(64) b) HMDA+11 EO/NH+2 PO/NH+11 EO/NH, Quaternized with Dimethyl Sulfate

(65) In a 500 ml reaction vessel with a nitrogen inlet, 350.0 g product from example 8a) was heated to 70° C. under a constant stream of nitrogen. 19.9 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, 365 g of a yellow liquid were obtained (amine value: 0.5 mgKOH/g, pH: 8.0 (10% in water), melting point: 16.4° C.). The degree of quaternization was 98%.

(66) c) HMDA+11 EO/NH+2 PO/NH+11 EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(67) In a reaction vessel 200.0 g of product obtained in example 8b) was heated under nitrogen atmosphere to 60° C. 1.0 g sulfuric acid (96%) was added at 60° C. to adjust the pH to 2.15 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 1.5 g sodium hydroxide (50% solution in water) to 8.7. 200.0 g of a brown liquid were obtained (melting point: 19.2° C., water: 0.5%)

Example 9

(68) a) HMDA+13 EO/NH+2 PO/NH+9 EO/NH

(69) Product from comparative example 5b) (199.2 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 281.6 g ethylene oxide were added within 3 hours, followed by addition of 92.8 g propylene oxide within 1 hours and afterwards 316.8 g ethylene oxide within 4 h.

(70) To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 890.0 g of a light brown liquid were obtained (melting point: 18.7° C., amine value: 26.9 mgKOH/g, viscosity: 351 mPas (50° C.)).

(71) b) HMDA+13 EO/NH+2 PO/NH+9 EO/NH, Quaternized with Dimethyl Sulfate

(72) In a 250 ml reaction vessel with a nitrogen inlet, 160.0 g product from example 9a) was heated to 70° C. under a constant stream of nitrogen. 9.21 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, the pH was adjusted to 8.0 with 0.3 g sodium hydroxide (50% solution in water). 156.0 g of a yellow liquid were obtained (amine value: 1.1 mgKOH/g, pH: 8.0 (10% in water), melting point: 14.7° C.). The degree of quaternization was 98%.

(73) c) HMDA+13 EO/NH+2 PO/NH+9 EO/NH, Quaternized with Dimethyl Sulfate, Transulfatized

(74) In a reaction vessel 70.0 g of product obtained in example 9b) was heated under nitrogen atmosphere to 60° C. 2.0 g Sulfuric acid (96%) was added at 60° C. to adjust the pH to 1.9 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 4.1 g sodium hydroxide (50% solution in water) to 9.1. 66.0 g of a brown liquid were obtained (melting point: 17.6° C.)

Example 10

(75) a) HMDA+11 EO/NH+2.5 PO/NH+11 EO/NH

(76) Product from comparative example 5b) (199.2 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C. 211.2 g ethylene oxide were added within 3 hours, followed by addition of 116.0 g propylene oxide within 1 hours and afterwards 387.2 g ethylene oxide within 4 h.

(77) To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 912.0 g of a light brown liquid were obtained (melting point: 16.6° C., amine value: 24.1 mgKOH/g, viscosity: 380 mPas (50° C.)).

(78) b) HMDA+11 EO/NH+2.5 PO/NH+11 EO/NH, Quaternized with Dimethyl Sulfate

(79) In a 250 ml reaction vessel with a nitrogen inlet, 160.0 g product from example 10a) was heated to 70° C. under a constant stream of nitrogen. 8.2 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, 153.0 g of a yellow liquid were obtained (amine value: 1.1 mgKOH/g, pH: 7.6 (10% in water), melting point: 13.9° C.). The degree of quaternization was 95.1%.

(80) c) HMDA+11 EO/NH+2.5 PO/NH+11 EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(81) In a reaction vessel 70.0 g of product obtained in example 10b) was heated under nitrogen atmosphere to 60° C. 2.0 g Sulfuric acid (96%) was added at 60° C. to adjust the pH to 2.0 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 3.9 g sodium hydroxide (50% solution in water) to 8.4. 66.0 g of a brown liquid were obtained (melting point: 12.9° C.)

Example 11

(82) a) HMDA+12 EO/NH+3 PO/NH+12 EO/NH

(83) Product from comparative example 5b) (150.0 g) was placed in a 2 l autoclave. The mixture was heated under vacuum (<10 mbar) to 100° C. and stirred for 0.5 hours to remove traces of water. The reactor was purged three times with nitrogen and the mixture was heated to 140° C.

(84) 185.5 g ethylene oxide were added within 3 hours, followed by addition of 104.8 g propylene oxide within 1 hours and afterwards 318.1 g ethylene oxide within 4 h.

(85) To complete the reaction, the mixture was allowed to post-react for 5 hours. Volatile compounds were removed in vacuo. 912.0 g of a light brown liquid were obtained (melting point: 18.6° C., amine value: 22.4 mgKOH/g, viscosity: 415 mPas (50° C.)).

(86) b) HMDA+12 EO/NH+3 PO/NH+12 EO/NH, Quaternized with Dimethyl Sulfate

(87) In a 250 ml reaction vessel with a nitrogen inlet, 160.0 g product from example 11a) was heated to 70° C. under a constant stream of nitrogen. 8.1 g dimethyl sulfate was added dropwise at 70-75° C. and the reaction mixture was stirred for two hours at 70° C. under nitrogen. After cooling to room temperature, the pH was adjusted to 9.1 with 1.3 g sodium hydroxide (50% solution in water). 150.0 g of a light brown liquid were obtained (amine value: 1.1 mgKOH/g, melting point: 15.2° C.). The degree of quaternization was 94.7%.

(88) c) HMDA+12 EO/NH+3 PO/NH+12 EO/NH, Quaternized with Dimethyl Sulfate, Transsulfatized

(89) In a reaction vessel 70.0 g of product obtained in example 11b) was heated under nitrogen atmosphere to 60° C. 3.1 g Sulfuric acid (96%) was added at 60° C. to adjust the pH to 1.8 (measured 10% in water). The temperature was raised to 90° C. and the mixture was set under vacuum (15 mbar) for 3 hours. After cooling to 60° C. the pH was adjusted with 3.2 g sodium hydroxide (50% solution in water) to 9.3. 69.0 g of a brown liquid were obtained (melting point: 14.8° C.)

(90) TABLE-US-00001 TABLE 1 Results melting point per DSC (peak Example temperature) N.sup.o Polymer-type (° C.) CE1 PEI600 + 20 EO/NH 34 CE2 PEI600 + 19 EO/NH + 2 PO/NH 28.7 1 PEI600 + 17 EO/NH + 2 PO/NH + 2 EO/NH 19.1 2 PEI600 + 13 EO/NH + 2 PO/NH + 6 EO/NH 6.8 3 PEI600 + 11 EO/NH + 2 PO/NH + 8 EO/NH 8.3 4 a) PEI600 + 11 EO/NH + 3 PO/NH + 8 EO/NH) 3.8 4 b) PEI600 + 11 EO/NH + 3 PO/NH + 8 EO/NH, 5.0 quaternized with dimethylsulfate 4 c) PEI600 + 11 EO/NH + 3 PO/NH + 8 EO/NH, 7.0 quaternized with dimethylsulfate, transsulfatized 5 PEI600 + 9 EO/NH + 2 PO/NH + 10 EO/NH 7.7 6 PEI600 + 5 EO/NH + 2 PO/NH + 14 EO/NH 17.7 CE3 PEI600 + 2.5 EO/NH + 2 PO/NH + 16.5 27.2 EO/NH CE4 PEI600 + 2 PO/NH + 19 EO/NH 35.8 CE5 c) HMDA + 24 EO/NH 42.4 CE5 d) HMDA + 24 EO/NH, quaternized with 43.6 dimethylsulfate CE5 e) HMDA + 24 EO/NH, quaternized with 41.5 dimethylsulfate, transsulfatized CE6 c) HMDA + 2 PO/NH + 22 EO/NH 42.1 CE6 d) HMDA + 2 PO/NH + 22 EO/NH, quaternized 37.8 with dimethylsulfate CE6 e) HMDA + 2 PO/NH + 22 EO/NH, quaternized 40.3 with dimethylsulfate, transsulfatized 7 a) HMDA + 12 EO/NH + 2 PO/NH + 12 EO/NH 20.2 7 b) HMDA + 12 EO/NH + 2 PO/NH + 12 EO/NH, 19.9 100% quat. DMS 7 c) HMDA + 12 EO/NH + 2 PO/NH + 12 EO/NH, 22.1 100% quat. DMS, transsulfat. 8 a) HMDA + 11 EO/NH + 2 PO/NH + 11 EO/NH 17.7 8 b) HMDA + 11 EO/NH + 2 PO/NH + 11 EO/NH, 16.4 100% quat DMA 8 c) HMDA + 11 EO/NH + 2 PO/NH + 11 EO/NH, 19.2 100% quat. DMS, transsulfat. 9 a) HMDA + 13 EO/NH + 2 PO/NH + 9 EO/NH 18.7 9 b) HMDA + 13 EO/NH + 2 PO/NH + 9 EO/NH 14.7 quat. DMS 9 c) HMDA + 13 EO/NH + 2 PO/NH + 9 EO/NH 17.6 quat. DMS, transsulfat. 10 a) HMDA + 11 EO/NH + 2.5 PO/NH + 11 16.6 EO/NH 10 b) HMDA + 11 EO/NH + 2.5 PO/NH + 11 13.9 EO/NH quat. DMS 10 c) HMDA + 11 EO/NH + 2.5 PO/NH + 11 12.9 EO/NH quat. DMS, transsulfat. 11 a) HMDA + 12 EO/NH + 3 PO/NH + 12 EO/NH 18.6 11 b) HMDA + 12 EO/NH + 3 PO/NH + 12 EO/NH 15.2 quat. DMS 11 c) HMDA + 12 EO/NH + 3 PO/NH + 12 EO/NH 14.8 quat. DMS, transsulfat.

(91) Melting points are determined according to DIN 51007 with a differential scanning calorimeter 823/700/229 from Mettler Toledo

(92) Examples for the Use in Laundry Detergents

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

(94) The following laundry detergent compositions are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients.

Formulation Example 1

NA Laundry Detergent Composition

(95) TABLE-US-00002 Liquid Detergent (wt %) AES C.sub.12-15 alkyl ethoxy (1.8) sulfate 10.9 Alkyl benzene sulfonate.sup.2 1.56 Sodium formate 2.66 Sodium hydroxide 0.21 Monoethanolamine (MEA) 1.65 Diethylene glycol (DEG) 4.10 AE9.sup.3 0.40 C16AE7 3.15 Chelant.sup.4 0.18 Citric Acid 1.70 C.sub.12-18 Fatty Acid 1.47 Borax 1.19 Ethanol 1.44 One of the inventive alkoxylated polyalkylenimines.sup.1 1.35 A compound having the following general structure: 0.40 bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)—N.sup.+—C.sub.xH.sub.2x—N.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 Protease (54.5 mg active/g).sup.6 0.89 Mannanase: Mannaway ® (25.6 mg active/g).sup.5 0.04 Amylase: Natalase ® (29 mg active/g).sup.5 0.14 Fluorescent Whitening Agents.sup.7 0.10 Water, perfume, dyes & other components .sup.1One of the inventive alkoxylated polyalkylenimines, for example the alkoxylated polyethyleneimine described in example 2 (PEI600 + 13 EO/NH + 2 PO/NH + 6 EO/NH) or the alkoxylated polyethyleneimine described in example 3 (PEI600 + 11 EO/NH + 2 PO/NH + 8 EO/NH) or the alkoxylated polyethyleneimine described in example 4 (PEI600 + 11 EO/NH + 3 PO/NH + 8 EO/NH) or the alkoxylated polyethyleneimine described in example 5 (PEI600 + 9 EO/NH + 2 PO/NH + 10 EO/NH) or described in any of the other examples above. .sup.2Linear 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. .sup.6Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime ®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ®, Coronase ®). .sup.7Suitable Fluorescent Whitening Agents are for example, Tinopal ® AMS, Tinopal ® CBS-X, Sulphonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland

Formulation Example 2

WE Laundry Liquid Composition

(96) TABLE-US-00003 WE Liquid HDL (wt %) AE3S.sup.4 2.6 Alkyl benzene sulfonate.sup.3 7.5 Sodium formate/Calcium formate 0.4 Sodium hydroxide 3.7 Monoethanolamine (MEA) 0.3 Diethylene glycol (DEG) 0.8 AE9.sup.6 0.4 AE7.sup.5 4.4 Chelant.sup.7 0.3 Citric Acid 3.2 C.sub.12-18 Fatty Acid 3.1 Ethanol 2.0 One of the inventive alkoxylated polyalkylenimines.sup.1 1.5 Amphiphilic polymer.sup.2 0.5 A compound having the following general structure: 1.0 bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)—N.sup.+—C.sub.xH.sub.2x—N.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 Protease (40.6 mg active/g).sup.9 0.6 Amylase: Stainzyme ® (15 mg active/g).sup.8 0.2 Fluorescent Whitening Agents.sup.10 0.1 Water, perfume, dyes & other components .sup.1One of the inventive alkoxylated polyalkylenimines, for example the alkoxylated polyethyleneimine described in example 2 (PEI600 + 13 EO/NH + 2 PO/NH + 6 EO/NH) or the alkox-ylated polyethyleneimine described in example 3 (PEI600 + 11 EO/NH + 2 PO/NH + 8 EO/NH) or the alkoxylated polyethyleneimine described in example 4 (PEI600 + 11 EO/NH + 3 PO/NH + 8 EO/NH) or the alkoxylated polyethyleneimine described in example 5 (PEI600 + 9 EO/NH + 2 PO/NH + 10 EO/NH). .sup.2Random 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.3Linear 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