AMPHIPHILIC ALKOXYLATED POLYETHYLENE/-PROPYLENE IMINE COPOLYMERS FOR MULTI-BENEFIT DETERGENT FORMULATIONS

Abstract

Described herein is an amphiphilic alkoxylated polyethylene/-propylene imine copolymer. Also described herein is a process for manufacturing the amphiphilic alkoxylated polyethylene/-propylene imine copolymer and a method of using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer.

Claims

1. An amphiphilic alkoxylated polyethylene/-propylene imine copolymer, comprising in condensed form repeating units of monomer (A), optionally monomer (B), and/or optionally monomer (C), wherein monomer (A) is represented by the formula ##STR00015## monomer (B) is represented by the formula ##STR00016## and monomer (C) is represented by the formula ##STR00017## wherein m is in a range from 1 to 4, 1 is in a range from 1 to 3, is 0 or 1 o is 0 or 1, and R is a C.sub.1 to C.sub.18 alkyl moiety, and wherein each NH-functional group has been directly linked by a covalent bond to an alkoxy chain (A) of the composition
-(A.sup.1O).sub.a-(A.sup.2O).sub.b-(A.sup.3O).sub.c—R′, and wherein A.sup.1 is C.sub.3-C.sub.12 alkylene, a is in a range from 0 to 2, A.sup.2 is ethylene, b is in a range from 5 to 50, A.sup.3 is 1,2-propylene, c is in a range from 5 to 50, R′ is selected from the group consisting of H and C.sub.1-C.sub.4 alkyl.

2. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, comprising in condensed form repeating units of monomer (A) and either monomer (B) or monomer (C).

3. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, comprising in condensed form repeating units of monomer (A) and monomer (B) and monomer (C).

4. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, wherein m is 1, 2 or 3, and/or wherein l is 1, and/or wherein k is 1, and/or wherein o is 1, and/or wherein R is a C.sub.1 to C.sub.4 alkyl moiety, and/or wherein R′ is hydrogen.

5. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, wherein a weight-average molecular weight M.sub.w of a backbone of the polyethylene/-propylene imine copolymer without alkoxy chains is at least 300 g/mol.

6. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, wherein a is 0, and/or b is in a range from 10 to 40, and/or c is 5 to 40, and/or wherein a molar ratio EO/PO >0.8.

7. The amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 3, wherein m is 1, k is 1, o is 1, 1 is l, R is methyl, R′ is hydrogen, and wherein an amount of monomer (A), monomer (B) and monomer (C) in a backbone of the polyethylene/-propylene imine copolymer without alkoxy chains is each at least 10 wt % and at most 50 wt %.

8. A polyethylene/-propylene imine copolymer before alkoxylation, comprising in condensed form repeating units of monomer (A) and monomer (B) and monomer (C), according to claim 1.

9. A process for manufacturing the amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, wherein (I) ##STR00018## wherein m is in a range from 1 to 4, l is in a range from 1 to 3, k is 0 or 1, o is 0 or 1, and R is a C.sub.1 to C.sub.19 alkyl moiety, is catalytically reacted with hydrogen, optionally purified, then (II) reacted with ethylene oxide, followed by reaction with propylene oxide.

10. The process for manufacturing the amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 9, wherein the catalyst for the reaction with hydrogen contains cobalt and/or manganese and/or wherein the catalyst is a fixed bed catalyst, and/or wherein a reaction temperature during the reaction with hydrogen is in a range from 50 to 200° C., and/or wherein a pressure during the reaction with hydrogen is between 30 and 100 bar.

11. An amphiphilic alkoxylated polyethylene/-propylene imine copolymer, obtainable by the process according to claim 9.

12. Detergent A detergent composition, comprising (i) at least one amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, and (ii) at least one surfactant.

13. The detergent composition according to claim 12, wherein the composition is liquid or solid.

14. The detergent composition according to claim 12, further comprising at least one anionic surfactant as at least one of the at least one the surfactant and water.

15. The detergent composition according to claim 12, further comprising at least one polymer selected from the group consisting of multifunctional polyethylene imines, multifunctional diamines, and mixtures thereof.

16. The detergent composition according to claim 12, further comprising at least one 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.

17. The detergent composition according to claim 12, further comprising 2-phenoxyethanol and/or 4,4′-dichloro-2-hydroxydiphenylether.

18. A method of using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, the method comprising using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer for laundry care or manual dishwashing.

19. The method of using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer* copolymer according to claim 18, further comprising using the the amphiphilic alkoxylated polyethylene/-propylene imine copolymer for oily and/or fatty soil removal and whiteness improvement.

20. A method of using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer according to claim 1, the method comprising using the amphiphilic alkoxylated polyethylene/-propylene imine copolymer as an additive for detergent formulations.

Description

EXAMPLES

[0300] In the following paragraphs, some experimental examples are given in order to illustrate some aspects of the present invention.

[0301] Synthesis of Inventive and Comparative Examples

[0302] Synthesis of Polyamines

[0303] “N,N′-Bis-(3-aminopropyl)-ethylene diamine” is abbreviated as “N4-Amine” or “N4”, “N,N-Bis-(3-aminopropyl)methylamine” is abbreviated as “BAPMA”, “1,3-propylene diamine” is abbreviated as “1,3-PDA” or just “PDA” and “ethylene diamine” is abbreviated as “EDA” in the following.

Example 1: Synthesis of Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4) Homopolymer) (A.1)

[0304] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, N4-Amine was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 170° C. N4-amine was fed into the reactor with 0.3 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

Example 2: Synthesis of Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA) Copolymer) (A.2)

[0305] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, premixed 1,3-PDA and N4-Amine in a ratio of 3:1 wt % was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 165° C. The premixed starting materials were fed into the reactor with 0.2 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

Example 3: Synthesis of Linear polyethylene/-propylene Imine Copolymer (Poly(N4-co-PDA) Copolymer) (A.3)

[0306] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, premixed 1,3-PDA and N4-Amine in a ratio of 3:1 wt % was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 170° C. The premixed starting materials were fed into the reactor with 0.2 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

Example 4: Synthesis of Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA-co-BAPMA) Terpolymer) (A.4)

[0307] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, premixed 1,3-PDA, N4-Amine and BAPMA in a ratio of 4:3:3 wt % was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 170° C. The premixed starting materials were fed into the reactor with 0.28 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

Comparative Example 1: Transamination of a Mixture Containing EDA and PDA (A.5)

[0308] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, premixed 1,3-PDA and EDA in a ratio of 1:1 wt % was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 170° C. The premixed starting materials were fed into the reactor with 0.28 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

Comparative example 2: Synthesis of Linear Polypropylene Imine Homopolymer (Poly(PDA) Homopolymer) (A.6)

[0309] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, 1,3-PDA was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 165° C. 1,3-PDA was fed into the reactor with 0.4 kg/L.sub.cat*h. The desired product was directly obtained as a water white solid without any purification step in between.

Comparative Example 3: Synthesis of Linear Polypropylene Imine Homopolymer (Poly(PDA) Homopolymer) (A.7)

[0310] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, 1,3-PDA was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 170° C. 1,3-PDA was fed into the reactor with 0.3 kg/L.sub.cat*h. The desired product was directly obtained as a water white solid without any purification step in between.

Comparative Example 4: Synthesis of Linear Polypropylene Imine Homopolymer (Poly(BAPMA) Homopolymer) (A.8)

[0311] In a tubular reactor with an inner diameter of 10 mm equipped with an inner thermowell of 3.17 mm, BAPMA was continuously led, together with 15 NI/h hydrogen gas, over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar, the temperature 160° C. BAPMA was fed into the reactor with 0.2 kg/L.sub.cat*h. The desired product was directly obtained as a water white liquid without any purification step in between.

[0312] Synthesis of Polyalkoxylates

Example 1: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4) Homopolymer) (P.1)

[0313] 180 g of the Poly(N4) Homopolymer (A.1) and 18 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 156 g of ethylene oxide are dosed into the reactor within three hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 328.5 g of a yellow and highly viscous product is removed from the reactor.

[0314] 100 g of the previously obtained product are filled into a steel pressure reactor and 4.9 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 120° C. and 1114 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for three hours. Volatile compounds are removed under vacuum and 1242.3 g of a dark yellow solid were obtained.

[0315] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 1.1 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 130° C. and 287 g of propylene oxide are dosed into the reactor within five hours. The mixture is allowed to post react for three hours. Volatile compounds are removed under vacuum and 635.7 g of a yellow viscous liquid were obtained.

Example 2: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA) Copolymer) (P.2)

[0316] 214.1 g of the Poly(N4-co-PDA) Copolymer (A.2) and 10.7 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 171 g of ethylene oxide are dosed into the reactor within ten hours. After that, the reaction mixture is kept at 100° C. for post reaction.

[0317] Volatile compounds are removed under vacuum and 383 g of a yellow and highly viscous product is removed from the reactor.

[0318] 50 g of the previously obtained product are filled into a steel pressure reactor and 4.2 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 120° C. and 532.8 g of ethylene oxide are dosed into the reactor within ten hours. The mixture is allowed to post react for three hours. 582.7 g of the previously obtained ethoxylate are kept in the steel pressure reactor and the reactor is heated to 130° C. 476 g of propylene oxide are dosed into the reactor within seven hours. The mixture is allowed to post react for six hours. Volatile compounds are removed under vacuum and 1047 g of a yellow highly viscous liquid were obtained.

Example 3: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA) Copolymer) (P.3)

[0319] 493.1 g of the Poly(N4-co-PDA) Copolymer (A.3) and 24.7 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 335 g of ethylene oxide are dosed into the reactor within six hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 520 g of a yellow and highly viscous product is removed from the reactor.

[0320] 55 g of the previously obtained product are filled into a steel pressure reactor and 2.4 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bars is set. The reactor is heated to 120° C. and 556 g of ethylene oxide are dosed into the reactor within ten hours. The mixture is allowed to post react for three hours. 612 g of the previously obtained ethoxylate are kept in the steel pressure reactor and the reactor is heated to 130° C. 477 g of propylene oxide are dosed into the reactor within seven hours. The mixture is allowed to post react for six hours. Volatile compounds are removed under vacuum and 1095 g of a brown highly viscous liquid were obtained.

Example 4: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA-co-BAPMA) Terpolymer) (P.4)

[0321] 400 g of the Poly(N4-co-PDA-co-BAPMA) Terpolymer (A.4) and 40 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 265 g of ethylene oxide are dosed into the reactor within five hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 664 g of a yellow and highly viscous product is removed from the reactor.

[0322] 120 g of the previously obtained product are filled into a steel pressure reactor and 5.1 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 120° C. and 1148 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for four hours. Volatile compounds are removed under vacuum and 1281 g of a brownish solid were obtained.

[0323] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 1.1 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 130° C. and 283 g of propylene oxide are dosed into the reactor within five hours. The mixture is allowed to post react for three hours. Volatile compounds are removed under vacuum and 625 g of a yellow viscous liquid were obtained.

Example 5: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4) Homopolymer) (P.5)

[0324] 180 g of the Poly(N4) Homopolymer (A.1) and 18 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 156 g of ethylene oxide are dosed into the reactor within three hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 328.5 g of a yellow and highly viscous product is removed from the reactor.

[0325] 100 g of the previously obtained product are filled into a steel pressure reactor and 4.9 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 120° C. and 1114 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for three hours. Volatile compounds are removed under vacuum and 1242.3 g of a dark yellow solid were obtained.

[0326] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 3.3 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 130° C. and 167 g of ethylene oxide are dosed into the reactor within two hours. The mixture is allowed to post-react for four hours, then, 662 g of propylene oxide are dosed into the reactor within eight hours. The mixture is allowed to post react for five hours. Volatile compounds are removed under vacuum and 1188 g of a yellow glassy solid were obtained.

Example 6: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA) Copolymer) (P.6)

[0327] 493.1 g of the Poly(N4-co-PDA) Copolymer (A.3) and 24.7 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 335 g of ethylene oxide are dosed into the reactor within six hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 520 g of a yellow and highly viscous product is removed from the reactor.

[0328] 73 g of the previously obtained product are filled into a steel pressure reactor and 4.6 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bars is set. The reactor is heated to 120° C. and 1072 g of ethylene oxide are dosed into the reactor within 15 hours. The mixture is allowed to post react for six hours. 1149 g of a brownish solid was obtained after removal of volatile compounds under vacuum.

[0329] 70 g of the previously obtained ethoxylate charged into a steel pressure reactor and the reactor is heated to 130° C. The reactor is degassed with nitrogen and a pre-pressure of 2 bar ist set. 17 g of propylene oxide are dosed into the reactor within one hour. The mixture is allowed to post react for one hour. Volatile compounds are removed under vacuum and 82 g of a yellow highly viscous liquid were obtained.

Example 7: Synthesis of Ethoxylated and Propoxylated Linear Polyethylene/-Propylene Imine Copolymer (Poly(N4-co-PDA-co-BAPMA) Terpolymer) (P.7)

[0330] 400 g of the Poly(N4-co-PDA-co-BAPMA) Terpolymer (A.4) and 40 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 265 g of ethylene oxide are dosed into the reactor within five hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 664 g of a yellow and highly viscous product is removed from the reactor.

[0331] 120 g of the previously obtained product are filled into a steel pressure reactor and 5.1 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 120° C. and 1148 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for four hours. Volatile compounds are removed under vacuum and 1281 g of a brownish solid were obtained.

[0332] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 3.3 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 130° C. and 165 g of ethylene oxide is dosed into the reactor within two hours. After post reaction time of four hours, 653 g of propylene oxide are dosed into the reactor within eight hours. The mixture is allowed to post react for four hours. Volatile compounds are removed under vacuum and 1180 g of a yellow viscous liquid were obtained.

Comparative Example 1: Synthesis of the Ethoxylated and Propoxylated Transamination Product of EDA and PDA (CP.1)

[0333] 95 g of the transamination product of EDA and PDA (A.5) and 9.5 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 100° C. and 149 g of ethylene oxide are dosed into the reactor within three hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 234 g of a yellow, viscous product is removed from the reactor.

[0334] 91 g of the previously obtained product are filled into a steel pressure reactor and 5.7 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 120° C. and 1334 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for four hours. Volatile compounds are removed under vacuum and 1434 g of a dark yellow solid were obtained.

[0335] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 1.2 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 130° C. and 293 g of propylene oxide are dosed into the reactor within five hours. The mixture is allowed to post react for three hours. Volatile compounds are removed under vacuum and 643 g of a yellow viscous liquid were obtained.

Comparative example 2: Synthesis of Ethoxylated and Propoxylated Linear Polypropylene Imine Homopolymer (Poly(PDA) Homopolymer) (CP.2)

[0336] 200 g of the Poly(PDA) Homopolymer (A.6) and 19 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is heated to 120° C. and 187 g of ethylene oxide are dosed into the reactor within six hours. After that, the reaction mixture is kept at 120° C. for post reaction. Volatile compounds are removed under vacuum and 390 g of a brown, highly viscous product is removed from the reactor.

[0337] 44 g of the previously obtained product are filled into a steel pressure reactor and 4.0 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 120° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is kept at 120° C. and 507 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for four hours. The reactor is heated to 130° C. and 453 g of propylene oxide are dosed into the reactor within twelve hours. The mixture is allowed to post react for six hours at 130° C. Volatile compounds are removed under vacuum and 1010 g of a brown viscous liquid were obtained.

Comparative Example 3: Synthesis of Ethoxylated and Propoxylated Linear Polypropylene Imine Homopolymer (Poly(PDA) Homopolymer) (CP.3)

[0338] 167 g of the Poly(PDA) Homopolymer (A.7) and 14 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 4 bar is set. The reactor is heated to 120° C. and 106 g of ethylene oxide are dosed into the reactor within two hours. After that, the reaction mixture is kept at 120° C. for post reaction. Volatile compounds are removed under vacuum and 270 g of a brown, highly viscous product is removed from the reactor.

[0339] 76 g of the previously obtained product are filled into a steel pressure reactor and 5.5 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 120° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1.5 bar is set. The reactor is kept at 120° C. and 705 g of ethylene oxide are dosed into the reactor within 10 hours. The mixture is allowed to post react for ten hours. The reactor is kept at 120° C. and 604 g of propylene oxide are dosed into the reactor within ten hours. The mixture is allowed to post react for four hours at 120° C. Volatile compounds are removed under vacuum and 1390 g of a yellow viscous liquid were obtained.

Comparative example 4: Synthesis of Ethoxylated and Propoxylated Linear Polypropylene Imine Homopolymer (Poly(BAPMA) Homopolymer) (CP.4)

[0340] 344 g of the Poly(BAPMA) Homopolymer (A.8) and 34.4 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 4 bar is set. The reactor is heated to 100° C. and 132 g of ethylene oxide are dosed into the reactor within six hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 462 g of a brown, highly viscous product is removed from the reactor.

[0341] 140 g of the previously obtained product are filled into a steel pressure reactor and 4.3 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bar is set. The reactor is kept at 120° C. and 928 g of ethylene oxide are dosed into the reactor within 15 hours. The mixture is allowed to post react for two hours. 1072 g of a brown solid was obtained as product.

[0342] 350 g of the obtained ethoxylate is charged into a steel pressure reactor and 1.1 g of potassium hydroxide (50 wt % aqueous solution) is added. Water is removed from the reactor at 110° C. under reduced pressure. The reactor is purged with nitrogen and is heated to 130° C. 272 g of propylene oxide are dosed into the reactor within six hours. The mixture is allowed to post react for four hours at 130° C. Volatile compounds are removed under vacuum and 612 g of a yellow viscous liquid were obtained.

Comparative Example 5: Synthesis of Ethoxylated and Propoxylated Ethylene Diamine (CP.5)

[0343] 300.5 g of EDA and 30 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 4 bar is set. The reactor is heated to 100° C. and 705 g of ethylene oxide are dosed into the reactor within twelve hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 1010 g of a yellow, viscous product is removed from the reactor.

[0344] 40 g of the previously obtained product are filled into a steel pressure reactor and 5.3 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 100° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 130° C. and 677 g of ethylene oxide are dosed into the reactor within six hours. The mixture is allowed to post react for three hours. Then, 604 g of propylene oxide are dosed into the reactor at 130° C. within six hours. The mixture is allowed to post react for four hours at 130° C. Volatile compounds are removed under vacuum and 1330 g of a orange viscous liquid were obtained.

Comparative Example 6: Synthesis of Ethoxylated and Propoxylated Propylenediamine (CP.6)

[0345] 356.5 g of PDA and 18 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 100° C. and 679 g of ethylene oxide are dosed into the reactor within ten hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 996 g of a yellow, viscous product is removed from the reactor.

[0346] 70 g of the previously obtained product are filled into a steel pressure reactor and 4.7 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 120° C. and 1102 g of ethylene oxide are dosed into the reactor within 15 hours. The mixture is allowed to post react for three hours at 120° C. Volatile compounds are removed under vacuo and 1157 g of a brown solid was obtained as product.

[0347] 337.7 g of the previously obtained ethoxylated are charged into a glass flask and 0.6 g potassium methanolate are added. Methanol is removed from the mixture at 90° C. and 20 mbar. This mixture is then charged to a steel pressure reactor and the reactor is purged with nitrogen. A pre-pressure of 2 ar is set to the reactor and the reactor is heated to 130° C. Then, 284 g of propylene oxide are dosed into the reactor at 130° C. within six hours. The mixture is allowed to post react for four hours at 130° C. Volatile compounds are removed under vacuum and 608 g of yellow viscous liquid were obtained.

Comparative Example 7: Synthesis of Ethoxylated and Propoxylated N4-Amine (CP.7)

[0348] 146 g of N4-Amine and 15 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 100° C. and 178 g of ethylene oxide are dosed into the reactor within ten hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 312 g of a yellow, viscous product is removed from the reactor.

[0349] 70 g of the previously obtained product are filled into a steel pressure reactor and 4.0 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 120° C. and 919 g of ethylene oxide are dosed into the reactor within 12 hours. The mixture is allowed to post react for six hours at 120° C. Volatile compounds are removed under vacuo and 1005 g of a brown solid was obtained as product.

[0350] 546 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 4.0 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 100° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 130° C. and 453 g of propylene oxide are dosed into the reactor within six hours. The mixture is allowed to post react for six hours at 130° C. Volatile compounds are removed under vacuo and 1013 g of a brown solid was obtained as product.

Comparative Example 8: Synthesis of Ethoxylated and Propoxylated Polyethylene Imine (PEI) (CP.8)

[0351] 340 g of PEI (M.sub.w=600 g/mol) and 34 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2 bar is set. The reactor is heated to 100° C. and 331 g of ethylene oxide are dosed into the reactor within six hours. After that, the reaction mixture is kept at 100° C. for post reaction. Volatile compounds are removed under vacuum and 666 g of a yellow, viscous product is removed from the reactor.

[0352] 110 g of the previously obtained product are filled into a steel pressure reactor and 4.8 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 120° C. and 1088 g of ethylene oxide are dosed into the reactor within 14 hours. The mixture is allowed to post react for four hours at 120° C. Volatile compounds are removed under vacuo and 1015 g of a brown solid was obtained as product.

[0353] 350 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 1.1 g of potassium hydroxide (50 wt % aqueous solution) are added. Water is removed under reduced pressure at 110° C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 0.5 bar is set. The reactor is heated to 130° C. and 286 g of propylene oxide are dosed into the reactor within five hours. The mixture is allowed to post react for six hours at 130° C. Volatile compounds are removed under vacuo and 632 g of a brown highly viscous liquid was obtained as product.

Comparative Example 9: Synthesis of Ethoxylated and Propoxylated Polyethylene Imine (PEI) (CP.9)

[0354] Synthesis was performed as described in EP 2209837 B1, example 1. Comparative example 10: Synthesis of ethoxylated polyethylene imine (PEI) (CP.10)

[0355] Synthesis was performed as described in EP 3039057 B1, example CE 1.

[0356] Characterization of Polymers

[0357] Molecular weights of the polyamine starting materials were determined by gel permeation chromatography (GPC). The measurements were carried out on a column combination of three following columns: HFIP-LG Guard, PL HFIPGEL and PL HFIPGel. Elution was performed at a constant flow rate of 1 mL/min with Hexafluoroisopropanol and 0.05 wt % Potassium trifluroroacetate. The injected sample was prefiltered over a Millipore Millex FG (0.2 μm), 50 μl were injected with a concentration of 1.5 mg/mL (diluted in eluent). The effluent was monitored by the UV detector DRI Agilent 1100 at λ=230 and 280 nm. The calibration was carried out using PMMA standards (PSS, Mainz, Germany) with a molecular weight from 800 to 2 200 000 g/mol. Values outside of the calibration range were extrapolated.

[0358] Molecular weights of the di- and oligoamines (for preparation of the comparative polymers) were not measured since those materials were used in high purity (>99%), therefore their molecular weights are available based on their known molecular structure.

[0359] Molecular weights of the polyalkoxylates (both inventive and comparative) were obtained by theoretical calculations, using the determined weight-average molecular weights of the polyamine starting materials (or known molecular weights of the pure di-/oligoamines, respectively) and assuming complete conversion during the alkoxylation step (II). The calculations were performed as follows:

[0360] In case of co-/terpolymer backbones, first the molar ratio of the monomers in the polymer backbone has been calculated, based on the wt % composition of the materials. Subsequently, the average number of monomer-repeating units in the backbone has been calculated, based on the weight-average molecular weights of the polyamine starting materials (from GPC data, see above), the known molecular weights of the employed monomers and their molar ratio. Based on the known structural information of the employed monomers and their individual number of NH-functional groups, the total number of NH-functional groups of the polyamine starting materials has been obtained accordingly, which represent the sum of the NH-functional groups of all primary and secondary amino groups in the polymer backbone. In the second step, the average theoretical molecular weight of one polyalkoxylate chain has been calculated, using the employed molar amount of both EO and PO per NH-functional group and assuming complete conversion during the alkoxylation step (II). In the third step, the overall molecular weight of the inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymers and the comparative polymers, respectively, has been calculated, by (a) multiplication of the number of NH-functional groups of the polymer backbone and the average molecular weight of one polyalkoxylate chain—assuming that on average each polyalkoxylate chain has been attached to one available NH-functional group of the backbone—and (b) adding the molecular weight of the polymer backbone (from GPC data, see above) itself.

[0361] Composition and analytical data of the inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymers and comparative polymers are summarized in Table 1.

[0362] “EO/NH” means ethylene oxide (EO) repeating units per NH group of the core amine, “PO/NH” means propylene oxide (PO) repeating units per NH group of the core amine. EO and PO units are attached to form EO/PO block structures, with EO units being directly linked to the amine core.

TABLE-US-00001 TABLE 1 Composition and physicochemical characterization of inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymers and comparative polymers. Molecular Molecular weight Alkoxylate Amine starting Monomer ratio weight M.sub.w (Alkoxylate Polymer material (Amine) [wt %] (Amine) [g/mol] EO/NH PO/NH Polymer) [g/mol] P.1 Poly(N4) N4: 100 700 20 13 25200 Homopolymer (A.1) P.2 Poly(N4-co-PDA) N4:PDA 25:75 767 20 13 28600 Copolymer (A.2) P.3 Poly(N4-co-PDA) N4:PDA 25:75 1272 20 13 44600 Copolymer (A.3) P.4 Poly(N4-co-PDA- N4:PDA:BAPMA 980 20 13 33000 co-BAPMA) 30:40:30 Terpolymer (A.4) P.5 Poly(N4) N4: 100 700 30 30 46700 Homopolymer (A.1) P.6 Poly(N4-co-PDA) N4:PDA 25:75 1272 30 30 82500 Copolymer (A.3) P.7 Poly(N4-co-PDA- N4:PDA:BAPMA 980 30 30 52800 co-BAPMA) 30:40:30 Terpolymer (A.4) CP.1 Transamination EDA:PDA 50:50 124 20 13 8300 product of EDA and PDA (A.5) CP.2 Poly(PDA) PDA: 100 459 20 13 15500 Homopolymer (=PPI) (A.6) CP.3 Poly(PDA) PDA: 100 1072 20 13 31600 Homopolymer (=PPI) (A.7) CP.4 Poly(BAPMA) BAPMA: 100 1630 20 13 26700 Homopolymer (A.8) CP.5 EDA * — 60 20 13 6600 CP.6 PDA * — 74 20 13 6600 CP.7 N4 * — 174 20 13 10000 CP.8 PEI ** — 600 20 13 27100 CP.9 PEI ** — 600 24 16 32900 CP.10 PEI ** — 600 20 0 14600 * EDA, PDA and N4-Amine, commercially available from BASF SE, Ludwigshafen, Germany. ** Lupasol ® FG, commercially available from BASF SE, Ludwigshafen, Germany. CP1: Amphiphilic alkoxylate, based on the transamination product of EDA and 1,3-PDA. The transamination is only leading to cyclic and acyclic oligoamine mixtures containing homopiperazine and/or homopiperazine moieties, as described in EP2638020B1. No polyamine formation observed (M.sub.w (core) <150 g/mol). CP.2/CP.3: Polymers similar to the polymers described in EP2961821B1 (GC.4/GC.5), i.e. amphiphilic alkoxylated polyamines based on PPI homopolymers CP.4: Amphiphilic alkoxylated polyamine based on a Poly(BAPMA) homopolymer, i.e. homopolymer based on monomer (C), as described in WO2017009220 CP.5/CP.6/CP.7: Amphiphilic alkoxylated di- and oligoamines: The specific di- and oligoamines are identical to the monomer repeating units in the backbone of the inventive polymers, however, the transamination step to yield high M.sub.w polyamine backbones has been skipped CP.8: Amphiphilic alkoxylated PEI, similar to the polymers described in EP2209837B1, but having a PEO-b-PPO modification which is identical to inventive polymers P.1-P.4 CP.9: Amphiphilic alkoxylated PEI, as described in EP2209837B1, example 1 CP.10: PEI ethoxylate, as described in EP 3039057 B1, example CE 1

[0363] Application Experiments

[0364] Primary Cleaning Performance on Oily/Fatty Stains

[0365] 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.

[0366] 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 amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, vs. the laundry detergent w/o any inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively.

[0367] Table 2 shows the composition of the laundry detergent, Table 3 shows the washing test conditions and Table 4 summarizes the obtained standardized cleaning performance. The standardized cleaning performance shown in Table 4 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 amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, on the cleaning performance.

TABLE-US-00002 TABLE 2 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 C.sub.12-C.sub.18 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-00003 TABLE 3 Washing conditions for evaluation 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 2.5 mmol/L (4:1:8) (14° dH) (Ca:Mg:HCO3) Fabric to liquor ratio 1:10 Amphiphilic alkoxylated 2.83% by weight (vs. liquid laundry detergent) polyethylene/-propylene of the polymer, 100% active ingredient imine copolymer 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-00004 TABLE 4 Results from washing tests (primary cleaning performance on oily/fatty stains). Concentration Standardized of polymeric cleaning performance Detergent Polymer additive * (sum delta delta E) LLD.1 P.1 2.83 wt % 46.9 LLD.1 P.2 2.83 wt % 68.3 LLD.1 P.3 2.83 wt % 59.7 LLD.1 P.4 2.83 wt % 56.0 LLD.1 P.5 2.83 wt % 87.1 LLD.1 P.6 2.83 wt % 101.5 LLD.1 P.7 2.83 wt % 100.5 LLD.1 CP.1 2.83 wt % 42.1 LLD.1 CP.2 2.83 wt % 36.0 LLD.1 CP.3 2.83 wt % 45.8 LLD.1 CP.4 2.83 wt % 19.3 LLD.1 CP.5 2.83 wt % 22.4 LLD.1 CP.6 2.83 wt % 32.4 LLD.1 CP.7 2.83 wt % 9.1 LLD.1 CP.8 2.83 wt % 72.3 LLD.1 CP.9 2.83 wt % 88.2 LLD.1 CP.10 2.83 wt % −8.2 * All data are wt % active ingredient, independent of the respective product form.

[0368] The results from the washing tests clearly demonstrate the superior performance of the inventive polymers vs. the comparative polymers CP.1-CP.7 described in the state of the art. More specifically, it can be clearly seen that the inventive polymers P.1-P.4 containing the monomer (A) as a building block exhibit a significantly better performance than comparative polymers CP.2-CP.4 based on a homopolymer made only from monomer (B) or only from monomer (C), at identical type of modification (20 EO/13 PO). In addition, it can be seen that the polymers CP.1 and CP.5-CP.7 based on low M.sub.w oligoamine mixtures or specific di- and oligoamines do not lead to the same performance level as the inventive polymers, based on higher M.sub.w polyamines, at identical type of modification (20 EO/13 PO). Only the comparative polymers based on PEI and having an amphiphilic type of modification (CP.8 and CP.9) are showing a cleaning performance benefit on oily/fatty stains which is similar to the inventive structures, however, still worse compared to inventive polymers P.6 and P.7, which have longer EO/PO chains attached to their polyamine backbone.

[0369] Secondary Cleaning Performance, Mixed Stains

[0370] To determine the secondary detergency, the whiteness of 7 different test fabrics was measured by determining the color difference (delta E) between the test fabrics after wash and the unsoiled (white) test fabric before wash, using a reflectometer (Datacolor SF600 plus).

[0371] By using these delta E values, the so-called “standardized cleaning performance” (delta delta E) has been calculated for each individual fabric. The “standardized cleaning performance” (delta delta E) is the difference of the performance of the laundry detergent including the respective inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, vs. the laundry detergent w/o any inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively.

[0372] Table 2 shows the composition of the laundry detergent, Table 5 shows the washing test conditions and Table 6 summarizes the obtained standardized cleaning performance. The standardized cleaning performance shown in Table 6 is the sum of the standardized cleaning performance of all 7 test fabrics. The bigger the sum of the delta delta E value, the whiter the fabrics after wash and therefore the bigger the positive contribution (anti-redeposition benefit) of the respective inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, on the secondary cleaning performance.

TABLE-US-00005 TABLE 5 Washing conditions for evaluation of secondary cleaning performance. Washing conditions Device Linitest+ from SDL Atlas, Rock Hill, USA Washing liquor 200 mL Washing time 30 minutes Washing temperature 40° C. Detergent concentration 3.0 g/L Water hardness 2.5 mmol/L (4:1:8) (14° dH) (Ca:Mg:HCO3) Fabric to liquor ratio 1:10 Washing cycles * 2 Amphiphilic alkoxylated 2.83% by weight (vs. liquid laundry detergent) polyethylene/-propylene of the polymer, 100% active ingredient imine copolymer or comparative polymer addition Test fabric ** 7 different test fabrics (in total: ca 7.8 g): 1.0 g WFK 10A (standard cotton), 2.0 g WFK 12A (cotton terry cloth), 0.9 g WFK 80A (cotton knit) (fabrics from WFK Testgewebe GmbH, Brueggen, Germany), 1.1 g EMPA 221 (cotton fabric, cretonne, bleached, without optical brightener; EMPA Testmaterials, St. Gallen, Switzerland), 1.0 g WFK20A (polyester 65%, cotton 35%), 1.0 g WFK30A (polyester), 0.8 g EMPA 406 (polyamide 6.6 spun, type 200, plain weave, ISO 105-F03) Soiled fabric *** 3 pieces of a circular red poterry clay stain on knitted cotton (diameter: 2 cm; weight: each ca. 3.2 g; CFT, Vlaardingen, The Netherlands); +2.5 g SBL 2004 (Soil Ballast Fabric ‘Formula 2004’ that simulates sebum grease stains; WFK Testgewebe GmbH, Brueggen, Germany) * After each cycle, the test fabrics were rinsed with 14° dH water (2 times), followed by drying at ambient room temperature overnight. ** After the end of 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. *** New soiled fabric was used for each cycle.

TABLE-US-00006 TABLE 6 Results from washing tests (secondary cleaning performance, mixed stains). Concentration Standardized of polymeric cleaning performance Detergent Polymer additive * (sum delta delta E) LLD.1 P.1 2.83 wt % 17.5 LLD.1 P.2 2.83 wt % 33.3 LLD.1 P.3 2.83 wt % 22.8 LLD.1 P.4 2.83 wt % 17.4 LLD.1 P.5 2.83 wt % 18.5 LLD.1 P.6 2.83 wt % 11.9 LLD.1 P.7 2.83 wt % 21.4 LLD.1 CP.1 2.83 wt % −5.6 LLD.1 CP.2 2.83 wt % 15.4 LLD.1 CP.3 2.83 wt % 30.8 LLD.1 CP.4 2.83 wt % 17.0 LLD.1 CP.5 2.83 wt % 7.0 LLD.1 CP.6 2.83 wt % 4.4 LLD.1 CP.7 2.83 wt % 12.2 LLD.1 CP.8 2.83 wt % 9.0 LLD.1 CP.9 2.83 wt % 7.0 LLD.1 CP.10 2.83 wt % 8.8 * All data are wt % active ingredient, independent of the respective product form.

[0373] The results from the washing tests clearly demonstrate the superior performance of the inventive polymers vs. the benchmark polymer for secondary cleaning performance/whiteness maintenance in general (ethoxylated PEI, CP.10) and also vs. the comparative polymers based on PEI (CP.8 and CP.9) described in the state of the art. It can be clearly seen that the comparative polymer based on the low M.sub.w transamination product of EDA and 1,3-PDA (CP.1) leads to very poor secondary cleaning performance—in fact, the comparative polymer CP.1 even leads to more soil on the fabric compared to the experiment w/o polymer (negative sum delta delta E). In contrast, the comparative polymers CP.2/CP.3 and CP.7 lead to a secondary cleaning performance level similar to that of the inventive polymers, however, their primary cleaning performance on oily/fatty stains was already distinctively worse (cf. Table 4).

[0374] Primary Cleaning Performance on Particulate Stains

[0375] To determine the primary detergency, the cleaning performance on 4 different particulate stains on a polyester fabric (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 4 different circular particulate stains (Clay ground soil, Standard clay, Red pottery clay, Tennis court clay; All 4 stains on one polyester fabric, 2 of those fabrics per wash) was repeated 3 times, and the obtained data was used to calculate the average delta E value.

[0376] 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 respective inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, vs. the laundry detergent w/o any inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively.

[0377] Table 2 shows the composition of the laundry detergent, Table 7 shows the washing test conditions and Table 8 summarizes the obtained standardized cleaning performance. The standardized cleaning performance shown in Table 8 is the sum of the standardized cleaning performance of all 4 stains. The bigger the sum of the delta delta E value, the bigger the positive contribution of the respective inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer or comparative polymer, respectively, on the cleaning performance.

TABLE-US-00007 TABLE 7 Washing conditions for evaluation of primary cleaning performance on particulate stains. Washing conditions Device Launder-O-Meter from SDL Atlas, Rock Hill, USA Washing liquor 250 mL Washing time 30 minutes Washing temperature 30° C. Detergent concentration 3.0 g/L Water hardness 2.5 mmol/L (4:1:8) (14° dH) (Ca:Mg:HCO3) Fabric to liquor ratio 1:10 Amphiphilic alkoxylated 3.33% by weight (vs. liquid laundry detergent) polyethylene/-propylene of the polymer (or combination of imine copolymers or polymers), 100% comparative polymer addition active ingredient Test fabric * 4 different circular particulate stains (P-H018, P-H115, P-H144, P-H145) (CFT, Vlaardingen, The Netherlands) on one polyester fabric; 2 stained fabrics per wash Ballast fabric 2.5 g SBL 2004 (Soil Ballast Fabric ‘Formula 2004’ that simulates sebum grease stains; WFK Testgewebe GmbH, Brueggen, Germany); +additional white 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 8 Results from washing tests (primary cleaning performance on particulate stains). Concen- Concen- Standardized tration of tration non- cleaning inventive Non- inventive performance Deter- Inventive polymeric inventive polymeric (sum delta gent Polymer additive * Polymer additive * delta E) LLD.1 P.4 3.33 wt % — — 5.6 LLD.1 — — CP.10 3.33 wt % 4.8 LLD.1 — — Sokalan ® 3.33 wt % 4.9 HP96 LLD.1 P.4 1.67 wt % CP.10 1.67 wt % 5.9 LLD.1 P.4 1.67 wt % Sokalan ® 1.67 wt % 7.6 HP96 * All data are wt % active ingredient, independent of the respective product form.

[0378] The results from the washing tests demonstrate that the inventive polymer P.4 exhibits slightly better primary cleaning performance for particulate stains than the comparative polymer CP.10 (multifunctional polyethyleneimine) or than a known multifunctional diamine from the state-of-the-art (commercially available as Sokalan® HP96, BASF SE, Ludwigshafen, Germany). It can be also clearly seen that a 1:1 (by weight) combination of the inventive polymer P.4 and one of the two non-inventive polymers, known in the state-of-the-art for their excellent primary cleaning performance for particulate stains, leads to further improved benefits (synergistic effects), at identical concentrations.

[0379] Manual Dish Wash Detergent Formulations

[0380] A range of different inventive liquid manual dish wash formulations have been prepared, using the inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymer P.7. The details of the detergent compositions are shown in Table 9 below.

TABLE-US-00009 TABLE 9 Compositions of inventive liquid manual dish wash detergents. Ingredients MDW.1 MDW.2 MDW.3 MDW.4 MDW.5 MDW.6 MDW.7 MDW.8 Linear C.sub.12C.sub.14- 8 0 6 0 6 0 6 0 alkylbenzenesulfonic acid C.sub.12-fatty alcohol × 8 16 6 12 6 12 6 12 2 EO sulfate Cocamidopropyl 0 0 4 4 0 0 2 2 betaine Lauramine oxide 0 0 0 0 4 4 2 2 2-Propylheptanol × 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 4 EO Amphiphilic 1 1 1 1 1 1 1 1 alkoxylated polyethylene/- propylene imine copolymer P.7 Ethanol 2 2 2 2 2 2 2 2 2-Phenoxyethanol 1 1 1 1 1 1 1 1 (preservative) Sodium chloride 1 1 1 1 1 1 1 1 Demin, water add 100 add 100 add 100 add 100 add 100 add 100 add 100 add 100 Sodium hydroxide add pH 8 add pH 8 add pH 8 add pH 8 add pH 8 add pH 8 add pH 8 add pH 8 *) All data are wt % active ingredient, independent of the respective product form.

[0381] Melting Point of Amine Starting Materials

[0382] The melting point of the amine starting materials was measured with a TA Instruments Q2000 device, following DIN EN 11357-3.

TABLE-US-00010 TABLE 10 Melting points of polyamines (starting materials). Molecular Monomer ratio weight M.sub.w Melting Amine starting (Amine) (Amine) Point material [wt %] [g/mol] [° C.] Poly(N4) N4: 100 700 13.0 Homopolymer (A.1) Poly(N4-co-PDA) N4:PDA 25:75 767 26.3 Copolymer (A.2) Poly(N4-co-PDA-co- N4:PDA:BAPMA 980 −2.9 BAPMA) Terpolymer 30:40:30 (A.4) Poly(PDA) PDA: 100 459 35.3 Homopolymer (=PPI) (A.6) Poly(PDA) PDA: 100 1072 44.4 Homopolymer (=PPI) (A.7) Poly(BAPMA) BAPMA: 100 1630 1.0 Homopolymer (A.8)

[0383] The analytical data demonstrate that the polyamine backbones of the inventive polymers (A.1, A.2, A.4) have significantly lower melting points than the polyamine backbones of the comparative polymers in case they are solely based on 1,3-PDA (i.e. homopolymers A.6, A.7). The melting point of the polyamine backbone A.8 based on monomer (C) alone, which is further used for preparation of comparative polymer CP.4, is even lower than some of the inventive polyamine backbones, however, the primary cleaning performance of CP.4 is extremely poor (cf. Table 4).

[0384] Summary of the Application Examples:

[0385] The experimental examples show that only the inventive polymers exhibit very good cleaning benefits for primary cleaning of oily/fatty stains (specifically vs. comparative polymers based on other polypropylene imines or di-/oligoamines) and at the same time also for secondary cleaning performance/whiteness maintenance (specifically vs. comparative polymers based on polyethylene imines). Furthermore, the polyamine backbones of the inventive amphiphilic alkoxylated polyethylene/-propylene imine copolymers exhibit significantly lower melting points compared to other polypropylene imines, thus enabling a better handling in the production process. The inventive polymers are therefore ideally suitable for preparation of multi-benefit detergent formulations, and specifically for improved oily soil removal in laundry care and improved degreasing properties in manual dishwashing.