AMPHIPHILIC ALKOXYLATED POLYALKYLENE IMINES OR ALKOXYLATED POLYAMINES

Abstract

Disclosed herein are novel alkoxylated polyalkylene imines or alkoxylated polyamines having amphiphilic properties. Additionally disclosed 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. Further disclosed herein are those compositions or products as such.

Claims

1. An alkoxylated polyalkylene imine or alkoxylated polyamine obtainable by a process comprising the steps a) to d) as follows: a) reaction of i) at least one polyalkylene imine or at least one polyamine with ii) at least one first alkylene oxide (AO1), wherein 0.25 to 7.0 mol of alkylene oxide (AO1) is employed per mol of NH-functionality of polyalkylene imine or of polyamine, in order to obtain a first intermediate (I1), b) reaction of the first intermediate (I1) with at least one lactone and/or at least one hydroxy carbon acid, wherein 0.25 to 10 mol of lactone and/or of hydroxy carbon acid is employed per mol of NH-functionality of polyalkylene imine or of polyamine as employed in step a), in order to obtain a second intermediate (I2), c) reaction of the second intermediate (I2) with ethylene oxide, wherein 1 to 100 mol of ethylene oxide is employed per mol of NH-functionality of polyalkylene imine or of polyamine as employed in step a), in order to obtain a third intermediate (I3), and d) reaction of the third intermediate (I3) with at least one second alkylene oxide (AO2), wherein at least 1 mol of alkylene oxide (AO2) is employed per mol of NH functionality of polyalkylene imine or of polyamine as employed in step a), in order to obtain the alkoxylated polyalkylene imine or the alkoxylated polyamine, and wherein the second alkylene oxide (AO2) is different to ethylene oxide in case only one second alkylene oxide (AO2) is employed in step d).

2. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein the at least one polyalkylene imine or the at least one polyamine as employed in step a) is defined according to general formula (I) ##STR00011## 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): ##STR00012## in which the variables are each defined as follows: R.sup.10, R.sup.11, R.sup.12 represent identical or different, linear or branched C.sub.2-C.sub.6-alkylene radicals and d is an integer having a value in the range of 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; and B represents a continuation of the polyalkylene imine by branching; y and z are each an integer having a value in the range of 0 to 150.

3. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1 containing at least one residue according to general formula (IIa) ##STR00013## 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; R.sup.3 represents linear or branched C.sub.1-C.sub.22-alkylene radicals; R.sup.4 represents C.sub.2-C.sub.22-(1,2-alkylene) radicals; R.sup.5 represents 1,2-ethylene; m is an integer having a value of at least 1 to 10; n is an integer having a value of at least 5 to 100; o is an integer having a value of at least 1 to 100; and p is an integer having a value of at least 1 to 5.

4. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1 containing at least one residue according to general formula (IIb) ##STR00014## 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; R.sup.3 represents linear or branched C.sub.1-C.sub.22-alkylene radicals; R.sup.5 represents 1,2-ethylene; m is an integer having a value of at least 1 to 10; n is an integer having a value of at least 5 to 100; and o is an integer having a value of at least 1 to 100.

5. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1 containing at least one residue according to general formula (IIc) ##STR00015## in which the variables are 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; R.sup.5 represents 1,2-ethylene; n is an integer having a value of at least 5 to 100; and o is an integer having a value of at least 0 to 100.

6. The alkoxylated imine or alkoxylated polyamine according to claim 3, wherein the residue (IIa) accounts for at least 80 wt.-% of all residues (IIa), (IIb) and (IIc) attached to the amino groups of the polyalkylene imine or polyamine as employed in step a).

7. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 2, wherein i) step a) is carried out in the presence of water and/or in the presence of a base catalyst, and/or ii) the weight-average molecular weight (Mw) of the polyalkylene imine or of the polyamine employed in step a) lies in the range of 50 to 10 000 g/mol, iii) at least two different alkylene oxides are employed as second alkylene oxide (AO2) in step d) in consecutive order, and/or iv) in step d) the second alkylene oxide (AO2) comprises >80% by weight of propylene oxide and/or 1,2-butylene oxide; and/or v) residues according to general formula (IIc) do not account for >50% of all residues on the alkoxylated polyalkylene imine or alkoxylated polyamine.

8. The alkoxylated polyalkylene imine according to claim 2, wherein the variables are each defined as follows: R is ethylene and/or propylene; and the sum of y+z is an integer having a value in the range of 9 to 120.

9. The alkoxylated polyamine according to claim 2, wherein y is an integer having a value in the range of 0 to 10; z is 0; and 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 and branched C.sub.3 to C.sub.4 alkylene radicals.

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

11. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein i) in step b) the lactone is caprolactone, and/or ii) in step b) the hydroxy carbon acid is lactic acid or glycolic acid, and/or iii) in step a) the first alkylene oxide (AO1) is at least one C.sub.2-C.sub.22-epoxide, and/or iv) in step d) the second alkylene oxide (AO2) comprises propylene oxide, and/or v) in step d) the second alkylene oxide (AO2) comprises >80% by weight of propylene oxide and/or 1,2-butylene oxide.

12. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 1, wherein i) in step a) 0.5 to 2 mol of alkylene oxide (AO1) is employed per mol of NH-functionality of polyalkylene imine or of polyamine, and/or ii) in step b) 0.5 to 3 mol of lactone and/or of hydroxy carbon acid is employed per mol of NH-functionality of polyalkylene imine or of polyamine as employed in step a), and/or iii) in step c) 10 to 50 mol of ethylene oxide is employed per mol of NH-functionality of polyalkylene imine or of polyamine as employed in step a), and/or iv) in step d) 10 to 50 mol of alkylene oxide (AO2) is employed per mol of NH-functionality of polyalkylene imine or of polyamine as employed in step a), and/or v) the alkyoxylated polyalkylene imine or alkoxylated polyamine is amphiphilic.

13. A method of using the alkoxylated polyalkylene imine or alkoxylated polyamine of claim 1, the method comprising using the alkoxylated polyalkylene imine or alkoxylated polyamine 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. The method according to claim 13, wherein the method comprises using the alkoxylated polyalkylene imine or alkoxylated polyamine in cleaning compositions and/or in fabric and home care products.

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

16. The cleaning composition according to claim 15, wherein the cleaning composition is a cleaning composition for i) clay removal, and/or ii) soil removal of particulate stains, and/or iii) dispersion and/or emulsification of soils, and/or iv) modification of treated surface to improve removal upon later re-soiling, and/or v) whiteness improvement and/or vi) when at least one enzyme selected from the group consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, is presentadditionally for improvement of oily/fatty stains, food stain removal and/or removal of complex stains, and/or vii) additionally comprising at least one enzyme selected from the group consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, and/or viii) for oily/fatty stain removal, food stain removal and/or removal of complex stains, when at least one enzyme according to vii) is present.

17. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 2, 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.

18. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 3, wherein the variables within general formula (IIa) are defined as follows: R.sup.1 represents 1,2-ethylene, 1,2-propylene and/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 R.sup.4 represents 1,2-ethylene and/or 1,2-propylene; and/or R.sup.5 represents 1,2-ethylene; and/or m is an integer having a value in the range of 1 to 5; and/or n is an integer having a value in the range of 10 to 50; and/or o is an integer having a value in the range of 10 to 50; and/or p is 1 or 2.

19. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 4, wherein the variables within general formula (IIb) are defined as follows: R.sup.1 represents 1,2-ethylene, 1,2-propylene and/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 R.sup.5 represents 1,2-ethylene; and/or m is an integer having a value in the range of 1 to 5; and/or n is an integer having a value in the range of 10 to 50; and/or o is an integer having a value in the range of 10 to 50.

20. The alkoxylated polyalkylene imine or alkoxylated polyamine according to claim 5, wherein preferably the variables within general formula (IIc) are defined as follows: R.sup.1 represents 1,2-ethylene, 1,2-propylene and/or 1,2-butylene; and/or R.sup.2 represents hydrogen and/or C.sub.1-C.sub.4-alkyl; and/or R.sup.5 represents 1,2-ethylene; and/or n is an integer having a value in the range of 10 to 50; and/or o is an integer having a value in the range of 10 to 50.

Description

SYNTHESIS EXAMPLES

[0428] In all the examples, step b) is begun after step a) is ended, step c) is begun after step b) is ended and step d) is begun after step c) is ended.

1) Synthesis of Compounds According to the Present Invention

Example 1: (PEI 800+0.9 PO/NH+0.9 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

Example 1a: PEI 800+0.9 PO/NH

[0429] 302 g of PEI 800 and 30.2 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 368 g of propylene oxide are dosed into the reactor within 14 hours. After that, the reaction mixture is kept at 100? C. for post reaction. Volatile compounds are removed under vacuum and 668 g of a yellow and highly viscous product is removed from the reactor.

Example 1b: (PEI 800+0.9 PO/NH)+0.9 CL/NH

[0430] 90 g of the previously obtained product are charged into a four-necked round bottom flask equipped with a cooler and a dripping funnel under nitrogen atmosphere. The reaction mixture is heated to 80? C. and 97 g of caprolactone are added slowly at 80? C. After caprolactone addition, the temperature is increased slowly to 120? C. and the mixture is allowed to post-react for 24 hours at 120? C. 182 g of a brownish, highly viscous liquid were obtained.

Example 1c: (PEI 800+0.9 PO/NH+0.9 CL/NH)+20 EO/NH

[0431] 153 g of the previously obtained product are filled into a steel pressure reactor and 5.0 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at mbars at 80? C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1.5 bars is set. The reactor is heated to 120? C. and 682 g of ethylene oxide are dosed into the reactor within 12 hours. The mixture is allowed to post react for seven hours at 120? C. 790 g of a light brown solid were obtained as product.

Example 1d: (PEI 800+0.9 PO/NH+0.9 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

[0432] 380 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 2.5 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at 20 mbars at 110? C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1 bars is set. The reactor is heated to 130? C. and 62 g of ethylene oxide are dosed into the reactor within one hour. The mixture is allowed to post react for two hours at 130? C. Subsequently, 327 g of propylene oxide are dosed into the reactor at 130? C. within six hours. The mixture is allowed to post-react for six hours at 130? C. 778 g of an orange viscous liquid were obtained as product.

Example 2: (PEI 800+0.9 PO/NH+1.8 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

Example 2a: PEI 800+0.9 PO/NH

[0433] 302 g of PEI 800 and 30.2 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 368 g of propylene oxide are dosed into the reactor within 14 hours. After that, the reaction mixture is kept at 100? C. for post reaction. Volatile compounds are removed under vacuum and 668 g of a yellow and highly viscous product is removed from the reactor.

Example 2b: (PEI 800+0.9 PO/NH)+1.8 CL/NH

[0434] 70 g of the previously obtained product are charged into a four-necked round bottom flask equipped with a cooler and a dripping funnel under nitrogen atmosphere. 2.9 g of tin-II (ethylhexanoate).sub.2 (1 mol %) are charged to the reactor. The reaction mixture is heated to 80? C. and 169 g of caprolactone are added slowly at 80? C. After caprolactone addition, the temperature is increased slowly to 120? C. and the mixture is allowed to post-react four hours at 120? C. 236 g of an orange, highly viscous liquid were obtained.

Example 2c: (PEI 800+0.9 PO/NH+1.8 CL/NH)+20 EO/NH

[0435] 105 g of the previously obtained product are filled into a steel pressure reactor and 2.5 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at 20 mbars at 80? C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1.5 bars is set. The reactor is heated to 120? C. and 308 g of ethylene oxide are dosed into the reactor within six hours. The mixture is allowed to post react for 12 hours at 120? C. 406 g of a light brown solid were obtained as product.

Example 2d: (PEI 800+0.9 PO/NH+1.8 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

[0436] 140 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 0.8 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at 20 mbars at 110? C. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 3 bars is set. The reactor is heated to 130? C. and 21 g of ethylene oxide are dosed into the reactor ten minutes. The mixture is allowed to post react for two hours at 130? C. Subsequently, 110 g of propylene oxide are dosed into the reactor at 130? C. within two hours. The mixture is allowed to post-react for five hours at 130? C. 262 g of an orange viscous liquid were obtained as product.

Example 3: (PEI 800+0.92 EO/NH+0.92 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

Example 3a: PEI 800+0.92 EO/NH

[0437] 800 g of PEI 800 and 80 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 755 g of ethylene oxide are dosed into the reactor within 13 hours. After that, the reaction mixture is kept at 100? C. for post reaction for six hours. Volatile compounds are removed under vacuum and 1550 g of a yellow and highly viscous product is removed from the reactor.

Example 3b: (PEI 800+0.92 EO/NH)+0.92 CL/NH

[0438] 150 g of the previously obtained product are charged into a four-necked round bottom flask equipped with a cooler and a dripping funnel under nitrogen atmosphere. 0.36 g of tin-II (ethylhexanoate).sub.2 are charged to the reactor. The reaction mixture is heated to 80? C. and 207 g of caprolactone are added slowly at 80? C. After caprolactone addition, the temperature is slowly increased to 160? C. and the mixture is allowed to post-react at 160? C. over-night. 345 g of a brown, highly viscous liquid were obtained.

Example 3c: (PEI 800+0.92 EO/NH+0.92 CL/NH)+20 EO/NH

[0439] 150 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 1.64 g of potassium tert-butoxide are added. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 2.5 bars is set. The reactor is heated to 120? C. and 669 g of ethylene oxide are dosed into the reactor within ten hours. The mixture is allowed to post react for 12 hours at 120? C. 821 g of a light brown solid were obtained as product.

Example 3d: (PEI 800+0.92 EO/NH+0.92 CL/NH+20 EO/NH)+4 EO/NH+16 PO/NH

[0440] 380 g of the previously obtained ethoxylate are filled into a steel pressure reactor and 3.3 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at 20 mbars 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 62 g of ethylene oxide are dosed into the reactor thirty minutes. The mixture is allowed to post react for two hours at 130? C. Subsequently, 327 g of propylene oxide are dosed into the reactor at 130? C. within six hours. The mixture is allowed to post-react for five hours at 130? C. 770 g of an orange viscous liquid were obtained as product.

Example 4: (PEI 800+1.1 BuO/NH+1.1 CL/NH+27 EO/NH)+18 PO/NH

Example 4a: PEI 800+1.1 BuO/NH

[0441] 250 g of PEI 800 and 25 g water are charged to a steel pressure reactor. The reactor is purged with nitrogen to remove air and a nitrogen pressure of 1.5 bar is set. The reactor is heated to 100? C. and 461 g of butylene oxide are dosed into the reactor within 14 hours. After that, the reaction mixture is kept at 100? C. for post reaction. Volatile compounds are removed under vacuum and 702 g of a light yellow and highly viscous product is removed from the reactor.

Example 4b: (PEI 800+1.1 BuO/NH)+1.1 CL/NH

[0442] 180 g of the previously obtained product are charged into a four-necked round bottom flask equipped with a cooler and a dripping funnel under nitrogen atmosphere. The product is heated to 80? C. and 190 g of caprolactone are added slowly at 80? C. After caprolactone addition, the temperature is increased slowly to 160? C. and the mixture is allowed to post-react thirty hours at 160? C. 360 g of a light brown, slightly viscous liquid were obtained.

Example 4c: (PEI 800+1.1 BuO/NH+1.1 CL/NH)+27 EO/NH+18 PO/NH

[0443] 100 g of the previously obtained product are filled into a steel pressure reactor and 6.2 g of potassium methanolate (32.5 wt % in methanol) are added. Methanol is removed at 20 mbar at 90? 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 481 g of ethylene oxide are dosed into the reactor within ten hours. The mixture is allowed to post react for 6 hours at 130? C. Subsequently, 423 g of propylene oxide are dosed into the reactor within eight hours. The mixture is allowed to post react for 6 hours at 130? C. After evaporation of residual alkylene oxides, 1002 g of a dark orange highly viscous liquid were obtained as product.

2) Comparative Examples

Comparative Example 1: PEI 600, Ethoxylated and Propoxylated (24 EO-16 PO)

[0444] This example is prepared as described in WO 95/32272 by a two-step alkoxylation.

3 Application Experiments

[0445] Primary Cleaning Performance on Oily/Fatty Stains

[0446] 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.

[0447] 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 polyalkylene imine or alkoxylated polyamine or comparative polymer, respectively, vs. the laundry detergent w/o any inventive amphiphilic alkoxylated polyalkylene imine or alkoxylated polyamine or comparative polymer, respectively.

[0448] 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 amphiphilic alkoxylated polyalkylene imine or alkoxylated polyamine or comparative polymer, respectively, on the cleaning performance.

TABLE-US-00005 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-00006 TABLE 6 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 polyalkylene imine or detergent) of the polymer, 100% active alkoxylated polyamine ingredient 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-00007 TABLE 7 Results from washing tests (primary cleaning performance on oily/fatty stains). Standardized cleaning Concentration of performance (sum delta Detergent Example polymeric additive * delta E) LLD.1 #1 2.83 wt % 51.6 LLD.1 #2 2.83 wt % 42.7 LLD.1 #3 2.83 wt % 10.8 LLD.1 #4 2.83 wt % 47.2 LLD.1 Comparative 2.83 wt % 106.9 example 1 * All data are wt % active ingredient, independent of the respective product form.

[0449] Test Results:

[0450] The error of the measurement is +/?10 delta delta E units. Therefore, any value >10 (sum delta delta E) means that the respective polymer exhibits a directional and visible contribution to the overall cleaning performance of the respective detergent formulation; Any value >20 (sum delta delta E) means that the respective polymer exhibits even a significant contribution to the overall cleaning performance, i.e., the respective polymer leads to a significant improvement of the formulation.

[0451] Biodegradation Data:

[0452] Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen. To a measured volume of medium, 100 mg/L test substance, which is the nominal sole source of carbon is added along with the inoculum (30 mg/L, aerated sludge taken from Mannheim wastewater treatment plant). This is stirred in a closed flask at a constant temperature (20? C.) for 28 days. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop? C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Evolved carbon dioxide is absorbed in a solution of sodium hydroxide. Nitrification inhibitors are added to the flask to prevent usage of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD (Theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control Glucose/Glucosamine is run along with the test samples for each cabinet.

TABLE-US-00008 TABLE 8 Biodeg tests Example Biodeg data #1 39.4% #2 54.8% #3 79.9% #4 45.4% Comparative 5.1% example 1

[0453] Test Results:

[0454] Only the inventive materials (polymers 1-4) exhibit significant biodegradation properties (>10%) in the OECD 301F test after 28 days. Therefore, only the inventive materials (polymers 1-4) show a good combination of cleaning performance (i.e., visible improvement of the formulation) and biodegradation.