ALKOXYLATED POLYALKYLENE IMINES OR ALKOXYLATED POLYAMINES WITH IMPROVED BIODEGRADABILITY

Abstract

Described herein is an alkoxylated polyalkylene imine or an alkoxylated polyamine according to the general formula (I)

##STR00001##

Also described herein is a process for preparing such alkoxylated polyalkylene imines or alkoxylated polyamines as well as a method of using such compounds within, for example, cleaning compositions and/or in fabric and home care products. Also described herein are compositions or products that include the alkoxylated polyalkylene imine or the alkoxylated polyamine.

Claims

1. An alkoxylated polyalkylene imine or an alkoxylated polyamine of the general formula (I) ##STR00013## in which the variables are each defined as follows: R represents identical or different, i) linear or branched C.sub.2-C.sub.12-alkylene radicals or ii) an etheralkyl unit of the following formula (III): ##STR00014## 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 a range of 0 to 50 or iii) C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl; B represents a continuation of the alkoxylated polyalkylene imine by branching; y and z are each an integer having a value in a range of 0 to 150, under the provisio that both z and y are 0 in case R are C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl; E1, E2 and E4 represent an identical or different residue according to formula (IIa) or an identical or different residue according to formula (IIb), wherein the residue according to formula (IIa) is an alkylenoxy unit defined as follows ##STR00015## in which the variables are each defined as follows: R.sup.1 represents C.sub.2-C.sub.22-(1,2-alkylene) radicals; R.sup.2 represents hydrogen and/or C.sub.1-C.sub.22-alkyl and/or C.sub.7-C.sub.22-aralkyl in case z is an integer ≥1 within general formula (I), or R.sup.2 represents hydrogen and/or C.sub.1-C.sub.4-alkyl and/or C.sub.7-C.sub.22-aralkyl in case z is 0 within general formula (I); R.sup.3 represents linear or branched C.sub.1-C.sub.22-alkylene radicals; m is an integer having a value of 1 to 10; n is an integer having a value of 5 to 100; and wherein the residue according to formula (IIb) is an alkylenoxy unit defined as follows ##STR00016## in which the variables are defined as follows: R.sup.l represents C.sub.2-C.sub.22-(1,2-alkylene) radicals; R.sup.2 represents hydrogen and/or C.sub.1-C.sub.22-alkyl and/or C.sub.7-C.sub.22-aralkyl; n is an integer having a value of 5 to 100; E3 is hydrogen in case E2 is a residue according to formula (IIa) or E3 is a residue according to formula (IIb); E5 is hydrogen in case E4 is a residue according to formula (IIa) or E5 is a residue according to formula (IIb); wherein 20 to 100% of a total amount of E2 and E4 is a residue according to formula (IIa) and 50 to 100% of a total amount of E1 is a residue according to formula (IIb).

2. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein R represents identical or different, i) linear or branched C.sub.2-C.sub.12-alkylene radicals, or ii) C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl.

3. The alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, wherein within formulas (IIa) and/or (IIb) the variables are each defined as follows: R.sup.1 represents 1,2-ethylene, 1,2-propylene or 1,2-butylene; and/or R.sup.2 represents hydrogen and/or C.sub.1-C.sub.4-alkyl; and/or R.sup.3 represents linear or branched C.sub.2-C.sub.10-alkylene radicals; and/or m is an integer having a value in a range of 1 to 5; and/or n is an integer having a value in a range of 8 to 40; and/or 50 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa) and 80 to 100% of the total amount of E1 is a residue according to formula (IIb).

4. The alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, wherein a weight average molecular weight (Mw) of a polyalkylene imine backbone or of a polyamine backbone lies in a range of 50 to 10 000 g/mol.

5. The alkoxylated polyalkylene imine according to claim 1, wherein the variables are each defined as follows: R is ethylene or propylene; the sum of y+z is an integer having a value in a range of 9 to 120.

6. The alkoxylated polyalkylene imine according to claim 5, wherein R is ethylene or propylene; the sum of y+z is an integer having a value in the range of 9 to 120; R.sup.1 represents 1,2-ethylene; R.sup.2 represents hydrogen and/or C.sub.1-C.sub.4-alkyl; R.sup.3 represents linear or branched C.sub.2-C.sub.10-alkylene radicals; m is an integer having a value in a range of 1 to 5; n is an integer having a value in a range of 8 to 40; 50 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa) and 80 to 100% of the total amount of E1 is a residue according to formula (IIb).

7. The alkoxylated polyalkylene imine according to claim 5, wherein the variables are each defined as follows: R is ethylene; the sum of y+z is an integer having a value in a range of 10 to 20; R.sup.1 represents 1,2-ethylene; R.sup.2 represents hydrogen; R.sup.3 represents linear or branched C.sub.2-C.sub.5-alkylene radicals; m is an integer having a value in a range of 1 to 3; n is an integer having a value in a range of 10 to 25; wherein 90 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa) and 85 to 95% of the total amount of E1 is a residue according to formula (IIb).

8. The alkoxylated polyamine according to claim 1, wherein y is an integer having a value in a range of 0 to 10; z is 0; R represents identical or different, linear or branched C.sub.2-C.sub.12-alkylene radicals or an etheralkyl unit according to formula (III), wherein d is from 1 to 5, and R.sup.10, R.sup.11, R.sup.12 are independently selected from the group consisting of linear or branched C3 to C4 alkylene radicals.

9. The alkoxylated polyamine according to claim 8, wherein R.sup.1 represents 1,2-ethylene; R.sup.2 represents hydrogen and/or C.sub.1-C.sub.4-alkyl; R.sup.3 represents linear or branched C.sub.2-C.sub.10-alkylene radicals; m is an integer having a value in a range of 1 to 5; n is an integer having a value in the range of 8 to 40; y is an integer having a value in the range of 1 to 10; wherein 50 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa) and 80 to 100% of the total amount of E1 is a residue according to formula (IIb).

10. The alkoxylated polyamine according to claim 8, wherein R is ethylene or propylene; R.sup.1 represents 1,2-ethylene; R.sup.2 represents hydrogen; R.sup.3 represents linear or branched C.sub.2-C.sub.5-alkylene radicals; m is an integer having a value in a range of 1 to 3; n is an integer having a value in a range of 10 to 25; y is an integer having a value in a range of 2 to 4; wherein 90 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa) and 90 to 100% of the total amount of E1 is a residue according to formula (IIb).

11. The alkoxylated polyamine according to claim 1, wherein y is 0; z is 0; and R represents identical or different C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl.

12. The alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, wherein up to 100% of nitrogen atoms present in the alkoxylated polyalkylene imine or the alkoxylated polyamine are quaternized

13. A method of using the alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, the method comprising: using the alkoxylated polyalkylene imine or the alkoxylated polyamine in laundry detergents, in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions and/or as dispersant for agrochemical formulations.

14. A process for preparing the alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, wherein a polyalkylene imine backbone or a polyamine backbone is first reacted with at least one lactone and/or at least one hydroxy carbon acid and then with at least one C.sub.2-C.sub.22-epoxide in order to obtain the respective alkoxylated compounds.

15. The process according to claim 14 wherein, per mol of N—H functionalities in the polyalkylene imine or the polyamine, the respective polyalkylene imine backbone or polyamine backbone is reacted with at least 0.05 moles of at least one lactone and/or at least one hydroxy carbon acid and then with at least 5 moles of least one C.sub.2-C.sub.22-epoxide.

16. The process according to claim 14, wherein the alkoxylated polyalkylene imine or the alkoxylated polyamine is additionally quaternized.

17. The process according to claim 14, wherein the lactone is caprolactone, the hydroxy carbon acid is lactic acid and/or the C.sub.2-C.sub.22-epoxide is ethylene oxide.

18. A laundry detergent, a cleaning composition, a fabric and home care product, a cosmetic formulation, a crude oil emulsion breaker, a pigment dispersion for ink jet inks, a formulation for electro plating, a cementitious composition and/or a dispersant for agrochemical formulations, comprising at least one alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1.

19. The alkoxylated polyamine according to claim 1, wherein y is 0; z is 0; and R is at least one C.sub.6-C.sub.7-cycloalkylene radical substituted with at least one methyl or ethyl.

20. The alkoxylated polyalkylene imine or the alkoxylated polyamine according to claim 1, wherein up to 100% of nitrogen atoms present in the alkoxylated polyalkylene imine or the alkoxylated polyamine are quaternized, and wherein the degree of quaternization of the nitrogen atoms present in the alkoxylated polyalkylene imine or the alkoxylated polyamine lies in a range of 10% to 95%.

Description

EXAMPLES

Example 1

[0230] Polyethylene imine, molecular weight 800 g/mole, reacted with 0.5 mole caprolactone per mol of NH-functionality, ethoxylated with 20 mole ethylene oxide per mol of NH-functionality.

1 a Polyethylene Imine, Molecular Weight 800 g/Mole Reacted with 0.5 Mole Caprolactone per mol of NH-Functionality

[0231] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 129.0 g polyethylene imine are placed and heated to 50° C. At this temperature 171.2 g caprolactone is added within 1 hour. Temperature of the reaction mixture rises during the addition of caprolactone to 80° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 15 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 295.0 g of a light orange oil is obtained. .sup.13C-NMR shows all primary amines are converted to amides, and 10% of total amount of secondary amines (E1) are reacted with caprolactone. The saponification value is 52 mgKOH/g.

1 b Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 0.5 Mole Caprolactone per mol of NH-Functionality, Ethoxylated with 10 Mole Ethylene Oxide per mol of NH-Functionality

[0232] In a 2 l autoclave 120.0 g polyethylene imine, molecular weight 800 g/mole, reacted with 0.5 mole caprolactone per mol of NH-functionality (example 1a) and 1.3 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 528.6 g ethylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 645.0 g of a light brown oil is obtained

1 c Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 0.5 Mole Caprolactone per mol of NH-Functionality, Ethoxylated with 20 Mole Ethylene Oxide per mol of NH-Functionality

[0233] In a 2 l autoclave 250.0 g Polyethylene imine, molecular weight800 g/mole reacted with 0.5 mole caprolactone per mol of NH-functionality, ethoxylated with 10 mole ethylene oxide per mol of NH-functionality (example 1b) and 0.4 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 203.7 g ethylene oxide is added within 2 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 450.0 g of a light brown solid is obtained (saponification value: 9.0 mgKOH/g).

Example 2

[0234] Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, ethoxylated with 10 mole ethylene oxide per mol of NH-functionality

2 a Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality

[0235] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 86.0 g polyethylene imine are placed and heated to 90° C. At this temperature 228.3 g caprolactone is added within 1 hour. Temperature of the reaction mixture rises during the addition of caprolactone to 100° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 11 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 310.0 g of a light orange oil is obtained (saponification value: 195 mgKOH/g). .sup.13C-NMR shows all primary amines are converted to amides, and 15% of total amount of secondary amines (El) are reacted with caprolactone.

[0236] 2 b Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 1.0 Mole Caprolactone per mol of NH-Functionality, Ethoxylated with 10 Mole Ethylene Oxide per mol of NH-Functionality

[0237] In a 2 l autoclave 120.0 g polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality (example 2a) and 0.9 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 352.2 g ethylene oxide is added within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 440.0 g of a light brown oil is obtained.

Example 3

[0238] Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, ethoxylated with 20 mole ethylene oxide per mol of NH-functionality

[0239] In a 2 l autoclave 100.0 g Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality (example 2a) and 1.3 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 560.7 g ethylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 659.0 g of a light brown solid is obtained (saponification value: 28.4 mg KOH/g).

Example 4

[0240] Polyethylene imine, molecular weight 800 g/mole, reacted with 2.0 mole caprolactone per mol of NH-functionality, ethoxylated with 20 mole ethylene oxide per mol of NH-functionality

4 a Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 2.0 Mole Caprolactone per mol of NH-Functionality

[0241] In a 0.5 l four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 47.3 g polyethylene imine are placed and heated to 90° C. At this temperature 251.1 g caprolactone is added within 1 hour. Temperature of the reaction mixture rises during the addition of caprolactone to 100° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 35 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 295.0 g of a light orange oil is obtained (saponification value: 302 mgKOH/g).

[0242] .sup.13C-NMR shows all primary amines are converted to amides, and 10% of total amount of secondary amines (El) are reacted with caprolactone.

4 b Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 2.0 Mole Caprolactone per Mole of NH-Functionality, Ethoxylated with 20 Mole Ethylene Oxide per Mole of NH-Functionality

[0243] In a 2 l autoclave 139.0 g polyethylene imine, molecular weight 800 g/mole, reacted with 2.0 mole caprolactone per mol of NH-functionality (example 4a) and 1.2 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 451.4 g ethylene oxide is added within 8 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 590.0 g of a viscous light brown oil is obtained (saponification value: 65.7 mgKOH/g).

Example 5

[0244] Polyethylene imine, molecular weight 800 g/mole, reacted with 0.25 mole lactide per mol of NH-functionality, ethoxylated with 20 mole ethylene oxide per mole of NH-functionality

5 a Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 0.25 Mole Lactide Per Mole of NH-Functionality

[0245] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 172.3 g polyethylene imine are placed and heated to 90° C. At this temperature 145.6 g lactide is added within 1 hour. Temperature of the reaction mixture rises during the addition of lactide to 110° C. After complete addition of lactide, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of lactide. 290 g of a light orange oil is obtained.

5 b Polyethylene imine, molecular weight 800 g/mole, reacted with 0.25 mole lactide per mole of NH-functionality, ethoxylated with 20 mole ethylene oxide per mole of NH-Functionality

[0246] In a 2 l autoclave 71.1 g polyethylene imine, molecular weight 800 g/mole, reacted with 0.25 mole lactide per mol of NH-functionality (example 5a) and 1.7 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 792.9 g ethylene oxide is added within 15 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 860.0 g of a light brown viscous oil is obtained (saponification value: 13.1 mgKOH/g).

Example 6

[0247] Polyethylene imine, molecular weight 800 g/mole, reacted with 0.5 mole γ-butyrolactone per mole of NH-functionality, ethoxylated with 20 mole ethylene oxide per mol of NH-functionality

6 a Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 0.5 Mole γ-Butyrolactone Per Mole of NH-Functionality

[0248] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 172.0 g polyethylene imine are placed and heated to 50° C. At this temperature 172.2 g γ-butyrolactone is added within 0.5 hours. Temperature of the reaction mixture rises during the addition of γ-butyrolactone to 55° C. After complete addition of γ-butyrolactone, the reaction mixture is heated to 100° C. and is stirred for 18 hours at 100° C. .sup.1H-NMR in MeOD indicates complete conversion of γ-butyrolactone. 340.0 g of a yellow viscous oil is obtained (saponification value: 100.6 mgKOH/g). .sup.13C-NMR shows all primary amines are converted to amides, and 13% of total amount of secondary amines (El) are reacted with γ-butyrolactone.

6 b Polyethylene Imine, Molecular Weight 800 g/Mole, Reacted with 0.5 Mole γ-butyrolactone Per Mole of NH-Functionality, Ethoxylated with 20 Mole Ethylene Oxide Per Mole of NH-Functionality

[0249] In a 2 l autoclave 82.0 g polyethylene imine, molecular weight 800 g/mole, reacted with 0.5 mole γ-butyrolactone per mol of NH-functionality (example 6a) and 1.8 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 840 g ethylene oxide is added within 12 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 924.0 g of a light brown solid is obtained (saponification value: 8.7 mgKOH/g).

Example 7

[0250] N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 4 mole caprolactone/mole, ethoxylated with 80 mole ethylene oxide/mole

7 a N4 Amine (N,N-bis(3-aminopropyl)ethylene diamine), Reacted with 4 Mole Caprolactone/Mole

[0251] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 319.6 g caprolactone are placed and heated to 80° C. At this temperature 122.0 g N4 amine (N,N-bis(3-aminopropyl)ethylene diamine) is added within 1 hour. Temperature of the reaction mixture rises during the addition of caprolactone to 110° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 21 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 435.0 g of a light yellow oil is obtained (saponification value: 167.3 mgKOH/g). .sup.13C-NMR shows all primary amines are converted to amides, and no secondary amines are reacted with caprolactone.

7 b N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), Reacted with 4 mole caprolactone/mole, ethoxylated with 80 mole ethylene oxide/mole

[0252] In a 2 l autoclave 100.0 g N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 4 mole caprolactone/mole (example 7a) and 1.4 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 583.2 g ethylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 680.0 g of a viscous light brown oil is obtained (saponification value: 21.1 mgKOH/g).

Example 8

[0253] Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, ethoxylated with 24 mole ethylene oxide per mol of NH-functionality and propoxylated with 16 mole propylene oxide per mol of NH functionality

8 a Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, ethoxylated with 5 mole ethylene oxide per mol of NH-functionality

[0254] In a 2 l autoclave 192.0 g Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality (example 2a) and 0.92 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 269.1 g ethylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 464.0 g of a light brown viscous oil is obtained (saponification value: 80.0 mgKOH/g).

8 b Polyethylene imine, Molecular Weight 800 g/mole, Reacted with 1.0 mole caprolactone per mol of NH-functionality, ethoxylated with 24 mole ethylene oxide per mol of NH-Functionality and propoxylated with 16 mole propylene oxide per mol of NH Functionality

[0255] In a 2 l autoclave 150.9 g Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, and ethoxylated with 5 mole ethylene oxide per mole NH functionality (example 8a) and 1.4 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 334.8 g ethylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 2 h at 120° C. 371.7 g propylene oxide is added within 5 hours, followed by 5 hours post-reaction time. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 464.0 g of a light brown viscous oil is obtained (saponification value: 14.1 mgKOH/g).

Example 9

[0256] Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, propoxylated with 15 mole propylene oxide per mol of NH functionality

[0257] In a 2 l autoclave 105.0 g Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality (example 2a) and 1.4 g potassium tert. butoxide are placed and the mixture is heated to 140° C. The vessel is purged three times with nitrogen. 582.3 g propylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 663.0 g of a light brown viscous oil is obtained.

Example 10

[0258] Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, propoxylated with 15 mole propylene oxide per mole of NH functionality and ethoxylated with 24 mole ethylene oxide per mole of NH- functionality

[0259] In a 2 l autoclave 205.7 g Polyethylene imine, molecular weight 800 g/mole, reacted with 1.0 mole caprolactone per mol of NH-functionality, and propoxylated with 15 mole propylene oxide per mole NH functionality (example 9) and 0.42 g potassium tert. butoxide are placed and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 211.4 g ethylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 415.0 g of a light brown solid is obtained.

Example 11

[0260] Hexamethylene diamine, reacted with 0.25 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

11 a Hexamethylene diamine, Reacted with 0.25 mole caprolactone/mole

[0261] In a 0.5 l four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 612.4 g hexamethylene diamine and 5.4 g potassium methylate (30% in methanol) are placed and heated to 120° C. At this temperature 150.4 g caprolactone is added within 0.5 hour. After complete addition of caprolactone, the reaction mixture is stirred at 120° C. for 3 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 750.0 g of a light yellow oil, which solidifies at room temperature, is obtained.

11 b Hexamethylene diamine, reacted with 0.25 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0262] A 2 l autoclave is filled with 145.4 g hexamethylene diamine, reacted with 0.25 mole caprolactone/mole (example 11 a) and heated to 110° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 696.9 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 7 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 840.0 g of a highly viscous light yellow oil is obtained (saponification value: 5.5 mgKOH/g).

Example 12

[0263] Hexamethylene diamine, reacted with 0.25 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0264] A 2 l autoclave is filled with 252.5 g hexamethylene diamine, reacted with 0.25 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 11 b) and 0.97 g potassium tert. butoxide. The mixture is heated to 110° C., and the vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 348.5 g propylene oxide is added within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 600.0 g of a highly viscous light brown oil is obtained (saponification value: 4.8 mgKOH/g).

Example 13

[0265] Hexamethylene diamine, reacted with 0.25 mole caprolactone/mole, propoxylated with 60 mole propylene oxide/mole

[0266] A 2 l autoclave is filled with 168.3 g hexamethylene diamine, reacted with 0.25 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 11 b) and 1.3 g potassium tert. butoxide. The mixture is heated to 110° C., and the vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 557.6 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 730.0 g of a highly viscous light brown oil is obtained (saponification value: 1.7 mgKOH/g).

Example 14

[0267] Hexamethylene diamine, reacted with 0.25 mole caprolactone/mole, propoxylated with 60 mole propylene oxide/mole and ethoxylated with 40 mole ethylene oxide/mol

[0268] A 2 l autoclave is filled with 151.5 g hexamethylene diamine, reacted with 0.25 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 11b) and 1.8 g potassium tert. butoxide. The mixture is heated to 110° C., and the vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 502.0 g propylene oxide is added within 8 h. To complete the reaction, the mixture is allowed to post-react for additional 2 h at 140° C. 317.2 g ethylene oxide is added within 5 hours, followed by 5 hours post-reaction time. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 960.0 g of a highly viscous light brown oil is obtained.

Example 15

[0269] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

15 a Hexamethylene diamine, reacted with 1 mole caprolactone/mole

[0270] In a 2.0 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 631.0 g hexamethylene diamine is placed and heated to 50° C. 20.8 g potassium methylate (30% in methanol) is added. 619.0 g caprolactone is added within 0.5 hour, the temperature is allowed to rise to 114° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours. 1240.0 g of an orange viscous oil is obtained.

15 b Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0271] A 2 l autoclave is filled with 190.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole (example 15 a) and heated to 110° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 572.4 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 7 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 760.0 g of a highly viscous yellow oil is obtained (saponification value: 12.0 mgKOH/g).

Example 16

[0272] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0273] A 2 l autoclave is filled with 94.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole (example 15 a) and heated to 110° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 758.9 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 7 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 850.0 g of a highly viscous yellow oil is obtained (saponification value: 7.9 mgKOH/g).

Example 17

[0274] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 60 mole propylene oxide/mole

[0275] A 2 l autoclave is filled with 139.1 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 15b) and 0.94 g potassium tert. butoxide. The mixture is heated to 110° C., and the vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 418.2 g propylene oxide is added within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 7 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 556.0 g of a highly viscous brown oil is obtained (saponification value: 5.4 mgKOH/g).

Example 18

[0276] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole and ethoxylated with 32 mole ethylene oxide/mol

[0277] A 2 l autoclave is filled with 231.8 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and propoxylated with 12 mole propylene oxide /mole (example 15 b) and 1.5 g potassium tert. butoxide. The mixture is heated to 110° C., and the vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 290.4 g propylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 2 h at 140° C. 352.4 g ethylene oxide is added within 7 hours, followed by 5 hours post-reaction time. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 870.0 g of a highly viscous light brown oil is obtained.

Example 19

[0278] Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

19 a Hexamethylene diamine, reacted with 4 mole caprolactone/mole

[0279] In a 2 l four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 232.4 g hexamethylene diamine and 19.1 g potassium methylate (30% in methanol) are placed and heated to 120° C. At this temperature 913.4 g caprolactone is added within 0.5 hour. After complete addition of caprolactone, the reaction mixture is stirred for 4 hours at 120° C. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 1130.0 g of a light yellow oil is obtained.

19 b Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0280] A 2 l autoclave is filled with 402.0 g hexamethylene diamine, reacted with 4 mole caprolactone/mole (example 19 a) and heated to 80° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 486.8 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 7 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 880.0 g of a highly viscous yellow oil is obtained (saponification value: 87.5 mgKOH/g).

Example 20

[0281] Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 20 mole propylene oxide/mole

[0282] A 2 l autoclave is filled with 96 g hexamethylene diamine, reacted with 4 mole caprolactone/mole (example 19 a) and heated to 80° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 193.7 g propylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 274.0 g of a highly viscous yellow oil is obtained (saponification value: 72.2 mgKOH/g).

Example 21

[0283] Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0284] A 2 l autoclave is filled with 96.0 g hexamethylene diamine, reacted with 4 mole caprolactone/mole (example 19 a) and heated to 80° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 310.4 g propylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 366.0 g of a highly viscous light yellow oil is obtained (saponification value: 56.9 mgKOH/g).

Example 22

[0285] N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

22 a N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole

[0286] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 348.6 g N4 amine (N,N-bis(3-aminopropyl)ethylene diamine) and 13.4 g potassium methoxide (30% in methanol) are placed. 456.6 g caprolactone is added within 0.75 hours. Temperature of the reaction mixture rises during the addition of caprolactone to 110° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 801.0 g of a light yellow oil is obtained

22 b N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0287] In a 2 l autoclave 296.0 g N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole (example 22 a) is placed and heated to 140° C. The vessel is purged three times with nitrogen. 512.5 g propylene oxide is added within 8 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 798.0 g of a viscous light brown oil is obtained.

Example 23

[0288] N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole, propoxylated with 64 mole propylene oxide/mole

[0289] In a 2 l autoclave 217.6.0 g N4 amine (N,N-bis(3-aminopropyl)ethylene diamine), reacted with 2 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole (example 22 b) and 1.3 g potassium tert. butoxide is placed and heated to 140° C. The vessel is purged three times with nitrogen. 606.3 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 825.0 g of a viscous light brown oil is obtained.

Example 24

[0290] DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

24 a DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole

[0291] In a 1 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 309.5 g DETA (Bis(2-aminoethyl)amine) and 13.7 g potassium methoxide (30% in methanol) are placed. 513.6 g caprolactone is added within 0.75 hours. Temperature of the reaction mixture rises during the addition of caprolactone to 70° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours..sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 801.0 g of a light yellow oil is obtained

24 b DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0292] In a 2 l autoclave 219.5 g DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole (example 24 a) is placed and heated to 140° C. The vessel is purged three times with nitrogen. 557.6 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 767.0 g of a viscous light brown oil is obtained.

Example 25

[0293] DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole, propoxylated with 48 mole propylene oxide/mole

[0294] In a 2 l autoclave 239.9 g DETA (Bis(2-aminoethyl)amine), reacted with 1.5 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole (example 24 b) and 1.2 g potassium tert. butoxide are placed and heated to 140° C. The vessel is purged three times with nitrogen. 525.6 g propylene oxide is added within 8 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 770.0 g of a viscous light brown oil is obtained.

Example 26

[0295] 1,3-Propane diamine, reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

26 a 1,3-Propane diamine, reacted with 1 mole caprolactone/mole

[0296] In a 1 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 370.6 g 1,3-propane diamine and 15.7 g potassium methoxide (30% in methanol) are placed. 570.7 g caprolactone is added within 0.75 hours. Temperature of the reaction mixture rises during the addition of caprolactone to 60° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours..sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 935.0 g of a light yellow oil is obtained.

26 b 1,3-Propane diamine, reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0297] In a 2 l autoclave 188.3 g 1,3-propane diamine, reacted with 1 mole caprolactone/mole (example 26 a) is placed and heated to 140° C. The vessel is purged three times with nitrogen. 696.9 g propylene oxide is added within 12 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 881.0 g of a viscous light brown oil is obtained.

Example 27

[0298] 1,3-Propane diamine, reacted with 1 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0299] In a 2 l autoclave 309.8 g 1,3-propane diamine, reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole (example 26 b) and 1.1 g potassium tert. butoxide are placed and heated to 140° C. The vessel is purged three times with nitrogen. 406.6 g propylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 718.0 g of a viscous light brown oil is obtained.

Example 28

[0300] MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

28 a MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole

[0301] In a 1 l four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 128.4 g MCDA (methylcyclohexyl diamine, mixture of isomers) and 4.0 g potassium methoxide (30% in methanol) are placed. 114.1 g caprolactone is added within 0.5 hour. Temperature of the reaction mixture rises during the addition of caprolactone to 60° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 242.0 g of a light yellow oil is obtained.

28 b MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole

[0302] In a 2 l autoclave 241.2 g MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole (example 28 a) is placed and heated to 140° C. The vessel is purged three times with nitrogen. 348.5 g propylene oxide is added within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C.

[0303] The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 585.0 g of a viscous light brown oil is obtained.

Example 29

[0304] MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0305] In a 2 l autoclave 353.8 g MCDA (methylcyclohexyl diamine, mixture of isomers), reacted with 1 mole caprolactone/mole, propoxylated with 12 mole propylene oxide/mole (example 28 b) and 1.1 g potassium tert. butoxide are placed and heated to 140° C. The vessel is purged three times with nitrogen. 348.5 g propylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 700.0 g of a viscous light brown oil is obtained.

Example 30

[0306] Hexamethylene diamine, reacted with 1 mole g-butyrolactone/mole, propoxylated with 12 mole propylene oxide/mole cl 30 a Hexamethylene diamine, reacted with 1 mole g-butyrolactone /mole

[0307] In a 2.0 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 232.4 g hexamethylene diamine is placed and heated to 45° C. 6.7 g potassium methylate (30% in methanol) is added. 172.2 g g-butyrolactone is added within 1 hour, the temperature is allowed to rise to 118° C. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 2 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 hours. 404.5 g of a light brown solid is obtained.

30 b Hexamethylene diamine, reacted with 1 mole g-butyrolactone /mole, propoxylated with 12 mole propylene oxide/mole

[0308] A 2 l autoclave is filled with 203.0 g hexamethylene diamine, reacted with 1 mole g-butyrolactone /mole (example 30 a) and 1.8 g potassium butoxide and heated to 110° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 696.9 g propylene oxide is added within 15 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 899.0 g of a highly viscous brown oil is obtained.

Example 31

[0309] Hexamethylene diamine, reacted with 1 mole g-butyrolactone /mole, propoxylated with 32 mole propylene oxide/mole

[0310] A 2 l autoclave is filled with 224.8 g hexamethylene diamine, reacted with 1 mole g- butyrolactone /mole and propoxylated with 12 mole propylene oxide/mole (example 30 b) and heated to 110° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 290.4 g propylene oxide is added within 5 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 515.0 g of a viscous brown oil is obtained.

Example 32

[0311] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 60 mole propylene oxide/mole and ethoxylated with 90 mole ethylene oxide/mol

[0312] A 2 l autoclave is filled with 209.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and propoxylated with 32 mole propylene oxide /mole (example 16) The mixture is heated to 140° C., and the vessel is purged three times with nitrogen. 162.6 g propylene oxide is added within 10 h. To complete the reaction, the mixture is allowed to post-react for additional 23 h at 140° C. 369.5 g ethylene oxide is added within 7 hours, followed by 10 hours post-reaction time. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 735.0 g of a highly viscous light brown oil is obtained.

Example 33

[0313] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, ethoxylated with 90 mole ethylene oxide/mol, and propoxylated with 60 mole propylene oxide/mole

33 a Hexamethylene diamine, reacted with 1 mole caprolactone/mole, ethoxylated with 30 mole ethylene oxide/mole

[0314] A 2 l autoclave is filled with 120.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole (example 15 a) and heated to 140° C. The vessel is purged three times with nitrogen. 685.0 g ethylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 785.0 g of a highly viscous brown oil is obtained.

33 b Hexamethylene diamine, reacted with 1 mole caprolactone/mole, ethoxylated with 90 mole ethylene oxide/mole, and propoxylated with 60 mole propylene oxide/mole

[0315] A 2 l autoclave is filled with 120.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and ethoxylated with 30 ethylene oxide/mole (example 33 a) and 1.1 g potassium tert. butoxide and heated to 140° C. The vessel is purged three times with nitrogen. 510.0 g ethylene oxide is added within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. 672.6 g propylene oxide are added within 15 h, followed by 15 h post reaction time at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 1466.0 g of a highly viscous brown oil is obtained.

Example 34

[0316] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, alkoxylated with a mixture of 90 mole ethylene oxide/mole, and 60 mole propylene oxide/mole

34 a Hexamethylene diamine, reacted with 1 mole caprolactone/mole, alkoxylated with a mixture of 15 mole ethylene oxide/mole, and 10 mole propylene oxide/mole

[0317] A 2 l autoclave is filled with 115.8 g hexamethylene diamine, reacted with 1 mole caprolactone/mole (example 15 a) and heated to 140° C. The vessel is purged three times with nitrogen. A mixture of 330.4 g ethylene oxide and 290.4 g propylene oxide is added within 7 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 736.0 g of a highly viscous brown oil is obtained.

34 b Hexamethylene diamine, reacted with 1 mole caprolactone/mole, alkoxylated with a mixture of 90 mole ethylene oxide/mole, and 60 mole propylene oxide/mole

[0318] A 2 l autoclave is filled with 120.0 g Hexamethylene diamine, reacted with 1 mole caprolactone/mole, alkoxylated with a mixture of 15 mole ethylene oxide/mole, and 10 mole propylene oxide/mole (example 34 a) and 0.6 g potassium tert. butoxide and heated to 140° C. The vessel is purged three times with nitrogen. A mixture of 314.3 g ethylene oxide and 276.3 g propylene oxide is added within 7 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 718.0 g of a highly viscous brown oil is obtained.

Example 35

[0319] Hexamethylene diamine, reacted with 1 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole and ethoxylated with 48 mole ethylene oxide/mol

[0320] A 2 l autoclave is filled with 211.0 g hexamethylene diamine, reacted with 1 mole caprolactone/mole and propoxylated with 32 mole propylene oxide /mole (example 16). The mixture is heated to 140° C., and the vessel is purged three times with nitrogen. 214.0 g ethylene oxide is added within 3 h. To complete the reaction, the mixture is allowed to post-react for additional 5 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 420.0 g of a light brown solid is obtained.

Example 36

[0321] Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

36 a Hexamethylene diamine, reacted with 4 mole caprolactone/mole

[0322] In a 0.5 I four-neck vessel equipped with stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet 66.2 g hexamethylene diamine and 5.4 g potassium methylate (30% in methanol) are placed and heated to 90° C. At this temperature 260.2 g caprolactone is added within 0.5 hour. After complete addition of caprolactone, the reaction mixture is heated to 120° C. and is stirred for 7 hours at 120° C. .sup.1H-NMR in MeOD indicates complete conversion of caprolactone. 320.0 g of a light yellow oil is obtained (saponification value: 221.4 mgKOH/g). .sup.13C-NMR shows 87.5% of primary amines are converted to amides, and 12.5% of primary amines remain unmodified.

36 b Hexamethylene diamine, reacted with 4 mole caprolactone/mole, propoxylated with 32 mole propylene oxide/mole

[0323] A 2 l autoclave is filled with 96.0 g hexamethylene diamine, reacted with 4 mole caprolactone/mole (example 8a) and heated to 80° C. The vessel is purged three times with nitrogen. The vessel is heated to 140° C. and 310.4 g propylene oxide is added within 4 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 366.0 g of a highly viscous light yellow oil is obtained (saponification value: 56.9 mgKOH/g).

Comparative Example 1

[0324] PE1800+20 EO/NH, synthesized as described in WO9532272

[0325] Comparative Example

[0326] Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 20 mole ethylene oxide per mole of NH-functionality

Comparative Example 1a

[0327] Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 1 mole ethylene oxide per mole of NH-functionality

[0328] A 5 I autoclave is charged with 1943.0 g of a polyethylenimine with an average molecular weight of 800 g/mol and 97.0 g water. The reactor is purged three times with nitrogen and heated to 110° C. 1789.0 g ethylene oxide is added within 14 hours. To complete the reaction, the reaction mixture is allowed to post-react for 5 hours. Water and volatile compounds are removed in vacuo at 90° C. A highly viscous yellow oil (3688.0 g, water content: 2.6%, pH: 11.05 (5% in water)) is obtained.

Comparative Example 1 b

[0329] Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 20 mole ethylene oxide per mole of NH-functionality

[0330] Product similar to comparative example 1 a (144.6 g, 92.7% in water) and 4.34 g potassium hydroxide (50% in water) are placed in a 2 l autoclave. The mixture is heated under vacuum (<10 mbar) to 120° C. and stirred for 2 hours to remove water. The reactor is purged three times with nitrogen and the mixture is heated to 140° C. 1470.7 g ethylene oxide is added within 14 hours. To complete the reaction, the mixture is allowed to post-react for 5 hours. Volatile compounds are removed in vacuo. 1615.0 g of a slightly brown solid were obtained (melting point: 35.4° C.).

[0331] Biodegradation

[0332] Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg/mL test substance is inoculated into wastewater taken from Mannheim Wastewater Treatment Plant and incubated in a closed flask at 25° C. for 28 days. The consumption of oxygen during this time is measured as the change in pressure inside the flask using an OxiTop® C (Xylem Analytics Germany Sales GmbH & Co KG). Evolved CO.sub.2 is absorbed using an NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance, after correction using a blank, is expressed as a % of the ThOD (Theoretical Oxygen Demand).

TABLE-US-00001 TABLE 1a Saponification Biodegradation value 28 days 56 days [mgKOH/g] [%] [%] Comparative PEI800 + 20 EO/NH 0 <20 <20 example 1b Example 1 PEI800 + 9.0 28 34 0.5 Caprolactone/NH + 20 EO/NH Example 2 PEI800 + n.a. 43 46 1.0 Caprolactone/NH + 10 EO/NH Example 3 PEI800 + 28.4 38 43 1.0 Caprolactone/NH + 20 EO/NH Example 4 PEI800 + 65.7 50 52 2.0 Caprolactone/NH + 20 EO/NH Example 5 PEI800 + 13.1 43 47 0.25 lactide/NH + 20 EO/NH Example 6 PEI800 + 8.7 23 28 0.5 γ-Butyrolactone/NH + 20 EO/NH Example 7 N4 amine + 21.1 43 49 4.0 caprolactone/mole + 80 EO/mole

TABLE-US-00002 TABLE 1b Biodegradation 28 days [%] Comparative PEI800 + 20 EO/NH <20 example 1b Example 8  PEI800 + 1,0 Caprolacton/NH + 5 EO/NH + 34 19 EO/NH + 16 PO/NH Example 9  PEI800 + 1,0 Caprolacton/NH + 15 PO/NH 27 Example 10 (PEI800 + 1,0 Caprolacton/NH + 15 PO/NH) + 24 EO/NH Example 11 HMDA + 0,25 Caprolacton/mol + 12 PO/mol 37 Example 12 HMDA + 0,25 Caprolacton/mol + 32 PO/mol 49 Example 13 HMDA + 0,25 Caprolacton/mol + 60 PO/mol 16 Example 14 HMDA + 0,25 Caprolacton/mol + 60 PO/mol + 40 EO/mol Example 15 HMDA + 1 Caprolacton/mol + 12 PO/mol 50 Example 16 HMDA + 1 Caprolacton/mol + 32 PO/mol 60 Example 17 HMDA + 1 Caprolacton/mol + 60 PO/mol 23 Example 18 HMDA + 1 Caprolacton/mol + 32 PO/mol + 32 EO/mol Example 19 HMDA + 4 Caprolacton/mol + 12 PO/mol 75 Example 20 HMDA + 4 Caprolacton/NH + 20 PO/mol 72 Example 21 HMDA + 4 Caprolacton/mol + 32 PO/mol 74 Example 22 N4 amin + 2 Caprolacton/mol + 12 PO/mol Example 23 N4 amin + 2 Caprolacton/mol + 64 PO/mol Example 24 DETA + 1,5 Caprolacton/mol + 12 PO/mol Example 25 DETA + 1,5 Caprolacton/mol + 48 PO/mol Example 26 1,3-Propandiamin + 1 Caprolacton/mol + 12 PO/mol Example 27 1,3-Propandiamin + 1 Caprolacton/mol + 32 PO/mol Example 28 MCDA + 1 Caprolacton/mol + 12 PO/mol Example 29 MCDA + 1 Caprolacton/mol + 32 PO/mol Example 30 HMDA + 1 g-Butyrolactone/mol + 12 PO/mol Example 31 HMDA + 1 g-Butyrolactone/mol + 32 PO/mol Example 32 HMDA + 1 Caprolacton/mol + 60 PO/mol + 16 90 EO/mol Example 33 (HMDA + 1 Caprolacton/mol) + 90 EO/mol + 17 60 PO/mol Example 34 (HMDA + 1 Caprolacton/mol) + 90 EO/mol + 11 60 PO/mol random Example 35 (HMDA + 1 Caprolacton/mol + 32 PO/mol) + 13 48 EO/mol

[0333] Application Test for Washing Machine

[0334] The soiled swatches are washed together with cotton ballast fabric (3.5 kg) and 1 soil ballast sheet wfk SBL 2004 in a Miele Household washing machine with cotton shirt program 30° C. After the wash the fabrics are dried in the air.

[0335] The washing performance is determined using the MACH5 multi area color measurement which gives LAB values and ΔE calculated between unwashed and washed stain. The higher the value, the better is the performance.

TABLE-US-00003 TABLE 2 Washing conditions Test equipment Miele Softtronic W1935 WTL Washing program Cotton short 30° C., 1200 U/min. Dosage 30 ml Test detergent Washing cycles 1 Water hardness 2.5 mmol/l Ca.sup.2+:Mg.sup.2+:HCO.sub.3.sup.− 4:1:8 Ballast fabric 3.5 kg cotton towels 1 SBL 2004 .sup.3) Soiled fabric CFT- .sup.1) CFT- .sup.2) .sup.1) 2) Producer: Center for Testmaterials BV, NL-3130 AC Vlaardingen .sup.3) Producer: wfk Testgewebe GmbH, Christenfeld 10, D-41379 Brueggen

TABLE-US-00004 TABLE 3 Composition of the test detergent [% weight] calculated Ingredient 100% active C.sub.13C.sub.15-Oxo alcohol with 7 EO 5.4 Linear C.sub.10C.sub.13 alkyl benzene 5.5 sulfonic acid Coco fatty acid K 12-18 2.4 C.sub.12C.sub.14-Fatty alcohol ethersulfate 5.4 (2EO), Na- NaOH 2.2 1,2 Propylene glycol 6.0 Ethanol 2.0 Water Up to 100

TABLE-US-00005 TABLE 4 Applications Example 2 Example 3 No polymer PEI800 + PEI800 + added 1.0 Caprolactone/NH + 1.0 Caprolactone/NH + 10 EO/NH 20 EO/NH soil Δ E Δ E PCH144 red 18.8 21.4 21.0 pottery clay C-S-01 blood, 12.5 13.8 13.8 aged C-S-70 chocolate 23.3 25.0 24.5 mousse

[0336] Primary Cleaning Performance on Oily/Fatty Stains

[0337] To determine the primary detergency, the cleaning performance on 16 different oily/fatty stains on cotton, polycotton and polyester fabrics (CFT, Vlaardingen, The Netherlands) was measured by determining the color difference (delta E) between the stains after wash and the unsoiled white fabric using a reflectometer (Datacolor SF600 plus). Each experiment containing the 16 different circular oily/fatty stains (Lipstick, Make-Up, Beef Fat, Frying Fat, Burnt Butter, Palm Oil, Sebum BEY, Sebum Tefo, Collar Stain; All on different fabrics) was repeated 6 times, and the obtained data was used to calculate the average delta E value.

[0338] By using these delta E values, the so-called “standardized cleaning performance” (delta delta E) has been calculated for each individual stain. The “standardized cleaning performance” (delta delta E) is the difference of the performance of the laundry detergent including the inventive biodegradable amphiphilic alkoxylated polyalkylene imine or alkoxylated polyamine polymer or comparative polymer, respectively, vs. the laundry detergent w/o any inventive biodegradable amphiphilic alkoxylated polyalkylene imine or alkoxylated polyamine polymer or comparative polymer, respectively.

[0339] Table 5 shows the composition of the laundry detergent, Table 6 shows the washing test conditions and Table 7 summarizes the obtained standardized cleaning performance. The standardized cleaning performance shown in Table 7 is the sum of the standardized cleaning performance of all 16 stains. The bigger the sum of the delta delta E value, the bigger the positive contribution of the inventive biodegradable amphiphilic alkoxylated polyalkylene imine or alkoxylated polyamine polymer or comparative polymer, respectively, on the cleaning performance.

TABLE-US-00006 TABLE 5 Composition of the liquid laundry detergent. Ingredients LLD.1 * Linear C.sub.12C.sub.14-alkylbenzenesulfonic acid 5.50 C.sub.12-fatty alcohol × 2 EO sulfate 5.40 C.sub.12C.sub.15-fatty alcohol × 7 EO 5.40 Coconut C12-C18 fatty acid 2.40 Sodium hydroxide 2.20 1,2-Propylene glycol 6.00 Ethanol 2.00 Sodium citrate 3.00 Demin. water add 100 pH value 8.5 * All data are wt % active ingredient, independent of the respective product form.

TABLE-US-00007 TABLE 6 Washing conditions forevaluation of primary cleaning performance on oily/fatty stains. Washing conditions Device Launder-O-Meter from SDL Atlas, Rock Hill, USA Washing liquor 250 mL Washing time 60 minutes Washing temperature 30° C. Detergent concentration 3.0 g/L Water hardness (Ca:Mg:HCO3) 2.5 mmol/L (4:1:8) (14 °dH) Fabric to liquor ratio 1:10 Biodegradable amphiphilic alkoxylated 2.83% by weight (vs. liquid laundry detergent) of the polyalkylene imine polymer or polymer, 100% active ingredient alkoxylated polyamine or comparative polymer addition Test fabric * 16 different circular oily/fatty stains (KC-H122, KC- H176, KC-H015, KC-H187, PC-H082, PC-H212, PC-H210, PC-H252, P-H122, P-H129, P-H015, P- H187, P-H082, P-H212, P-H210, P-H252) (CFT, Vlaardingen, The Netherlands) Ballast fabric Polyester and cotton ballast, to yield a 1:1 ratio of polyester/cotton fabric per experiment * After the washing experiment, the test fabrics were rinsed with 14 °dH water (2 times), followed by drying at ambient room temperature overnight, prior to the measurement with the reflectometer.

TABLE-US-00008 TABLE 7 Results from washing tests (primary cleaning performance on oily/fatty stains). Concentration of Standardized cleaning Detergent Polymer polymeric additive * performance (sum delta delta E) LLD.1 Example 8  2.83 wt % 47.3 LLD.1 Example 9  2.83 wt % 40.2 LLD.1 Example 10 2.83 wt % 17.5 LLD.1 Comp. Ex. 1b 2.83 wt % 0.2 * All data are wt % active ingredient, independent of the respective product form.

[0340] A standardized cleaning performance lower than 10 (sum delta delta E) is not significant/not visible.