AMPHIPHILIC STAR-LIKE POLYETHER

Abstract

The present invention relates to amphiphilic star-like polyether. The core molecule is an aliphatic hyperbranched polyether polyol, which is further alkoxylated, first with ethylene oxide or combinations of ethylene oxide and C.sub.3-C.sub.20 alkylene oxide, preferably propylene oxide, and/or glycidol, and then with a C.sub.3-C.sub.20 alkylene oxide, preferably propylene oxide, or combination of ethylene oxide and propylene oxide, then optionally anionically modified. The resulting amphiphilic star-like polyether thus has an inner core based on an aliphatic hyperbranched polyether polyol, an inner shell predominantly containing polyethylene oxide units, the inner shell comprising at least 3 ethylene oxide units and an outer shell predominantly containing polypropylene oxide units, the outer shell comprising at least 3 propylene oxide units. They optionally contain anionic groups instead of hydroxyl groups on the periphery of the macromolecule. The invention further relates to their use as additive in laundry formulations and to their manufacturing process.

Claims

1. An amphiphilic star-like polyether obtainable by the process of: i) step i: preparation of an aliphatic hyperbranched polyether polyol (core compound A) by one of a) reacting an aliphatic alcohol α with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20, and 3≦n≦10 with itself and/or optionally with a di-, tri-, tetra- or higher functional aliphatic alcohol β with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 2≦x≦8, 0≦y≦20, 0≦z≦20, 2≦n≦10, in the presence of a catalyst, and removing the water formed during the reaction (polycondensation approach i)a)); b) reacting an aliphatic alcohol ω with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 1≦x≦6, 0≦y≦20, 0≦z≦20 and 1≦n≦10 with at least one cyclic carbonate based on an aliphatic polyol with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20, and 3≦n≦10, in the presence of a base as catalyst, and removing the carbon dioxide formed during the reaction (ring-opening polycondensation approach i)b)); and c) reacting an aliphatic alcohol ω with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 1≦x≦6, 0≦y≦20, 0≦z≦20 and 1≦n≦10 with at least one epoxide based on an aliphatic polyol with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20 and 3≦n≦10, in the presence of either a base or an acid as catalyst (ring-opening polyaddition approach i)c)), ii) step ii: reacting core compound A with one of ethylene oxide; ethylene oxide and glycidol; ethylene oxide and C.sub.3-C.sub.20 alkylene oxide; and ethylene oxide, glycidol and C.sub.3-C.sub.20 alkylene oxide, leading to compound B, and iii) step iii: reacting compound B with one of a C.sub.3-C.sub.20 alkylene oxide; and a mixture of ethylene oxide and a C.sub.3-C.sub.20 alkylene oxide, leading to compound C.

2. The amphiphilic star-like polyether according to claim 1, wherein the aliphatic alcohol α or ω is selected from the group consisting of glycerol, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, pentaerythritol f and dipentaerythritol.

3. The amphiphilic star-like polyether according to claim 1, wherein in the polycondensation approach i)a), the aliphatic alcohol α is pentaerythritol and pentaerythritol is reacted with at least one additional di-, tri-, tetra- or higher functional aliphatic alcohol β having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 2≦x≦8, 0≦y≦20, 0≦z≦20, 2≦z≦10.

4. The amphiphilic star-like polyether according to claim 1, wherein the aliphatic alcohol ω is glycerol.

5. The amphiphilic star-like polyether according to claim 1, wherein in the polycondensation approach i)a), the additional di-, tri-, tetra- or higher functional aliphatic alcohol β is an ethoxylated ethylene glycol.

6. The amphiphilic star-like polyether according to claim 1, wherein in the polycondensation approach i)a), the additional di-, tri-, tetra- or higher functional aliphatic alcohol β is triethylene glycol.

7. The amphiphilic star-like polyether according to claim 1, wherein in the ring-opening polycondensation approach i) b), the cyclic carbonate based on an aliphatic polyol having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20 and 3≦n≦10 is glycerol carbonate.

8. The amphiphilic star-like polyether according to claim 1, wherein in the ring-opening polyaddition approach i) c), the epoxide is glycidol.

9. The amphiphilic star-like polyether according to claim 1, wherein core compound A has an OH number of from 400 to 1000 mg KOH per g of polymer and a weight-average molecular weight (Mw) of from 2000 g/mol to 100000 g/mol.

10. The amphiphilic star-like polyether according to claim 1, wherein in step ii the C.sub.3-C.sub.20 alkylene oxide is propylene oxide.

11. The amphiphilic star-like polyether according to claim 1, wherein in step iii the C.sub.3-C.sub.20 alkylene oxide is propylene oxide.

12. The amphiphilic star-like polyether according to claim 1, wherein in step ii, 1 mole of hydroxyl groups of core compound A is reacted with at least 3 moles ethylene oxide molecules, and in step iii 1 mole of hydroxyl groups of compound B is reacted with at least 3 moles propylene oxide molecules.

13. The amphiphilic star-like polyether according to claim 1, wherein in step ii, 1 mole of hydroxyl groups of core compound A is reacted with at least 3 moles ethylene oxide, and in step iii 1 mole of hydroxyl groups of compound B is reacted with at least 3 moles propylene oxide.

14. The amphiphilic star-like polyether according to claim 1, wherein compound D contains terminal sulphate groups.

15. An additive for use in laundry detergents, the additive comprising the amphiphilic star-like polyether according to claim 1.

16. A dispersant for hydrophobic soil, the dispersant comprising the amphiphilic star-like polyether according to claim 1.

17. An agent for anti-redeposition or anti-greying, the agent comprising the amphiphilic star-like polyether according to claim 1.

18. Laundry compositions containing the amphiphilic star-like polyether of claim 1.

19. Liquid laundry compositions comprising water, 0.1-60 wt % surfactants, and 0.1-10 wt % amphiphilic star-like polyether according to claim 1.

20. A process for the manufacture of an amphiphilic star-like polyether, the process comprising: i) step i: preparing an aliphatic hyperbranched polyether polyol (core compound A) by one of: a) reacting an aliphatic alcohol α having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20, and 3≦n≦10 with itself and/or optionally with a di-, tri-, tetra- or higher functional aliphatic alcohol β having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 2≦x≦8, 0≦y≦20, 0≦z≦20, 2≦n≦10, in the presence of a catalyst, and removing the water formed during the reaction (polycondensation approach i)a)); b) reacting an aliphatic alcohol ω having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 1≦x≦6, 0≦y≦20, 0≦z≦20 and 1≦n≦10 with a cyclic carbonate based on an aliphatic polyol having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20, and 3≦n≦10, in the presence of a base as catalyst, and removing the carbon dioxide formed during the reaction (ring-opening polycondensation approach i)b)); and c) reacting an aliphatic alcohol ω with the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 1≦x≦6, 0≦y≦20, 0≦z≦20 and 1≦n≦10 with an epoxide based on an aliphatic polyol having the general formula [C.sub.nH.sub.(2n+2)−xOH.sub.x][EO].sub.y[PO].sub.z, wherein 3≦x≦6, 0≦y≦20, 0≦z≦20 and 3≦n≦10, in the presence of either a base or an acid as catalyst (ring-opening polyaddition approach i)c)), ii) step ii: reacting core compound A with one of ethylene oxide; ethylene oxide and glycidol; ethylene oxide and C.sub.3-C.sub.20 alkylene oxide; and ethylene oxide, glycidol and C.sub.3-C.sub.20 alkylene oxide, leading to compound B, and iii) step iii: reacting compound B with one of a C.sub.3-C.sub.20 alkylene oxide; and a mixture of ethylene oxide and a C.sub.3-C.sub.20 alkylene oxide, leading to compound C.

Description

EXAMPLES (SYNTHESIS OF POLYMERS, APPLICATION EXPERIMENTS)

Synthesis of Polymers

Example 1: Synthesis of Dendritic Polyether Core Molecule C.1

[0125] The polycondensation was performed in a 2 L glass flask equipped with a stirrer, reflux condenser and a distillation system with vacuum connection. A mixture of 675 g pentaerythritol, 745 g triethylene glycol (molar ratio pentaerythritol/triethylene glycol 1:1) and 2.2 g paratoluenesulfonic acid (catalyst) was evacuated and heated gradually to 185° C. by means of an oil bath at a pressure of 200-300 mbar. On attainment of the reaction temperature, the reaction mixture was stirred for 11 hours and the water formed in the reaction was distilled off. The distillate passing over was collected in a cooled round-bottom flask and weighed.

[0126] After the removal of 293 g water, the reaction mixture was cooled down in vacuo and neutralized by the addition of an aqueous potassium hydroxide solution. Finally, all volatile by-products were removed in vacuo and the obtained polyether core C.1, a yellowish, highly viscous liquid, was cooled down to room temperature.

Example 2: Synthesis of Dendritic Polyether Core Molecule C.2

[0127] The polycondensation was performed in a 4 L glass flask equipped with a stirrer, reflux condenser and a distillation system with vacuum connection. A mixture of 1225 g pentaerythritol, 1351 g triethylene glycol (molar ratio pentaerythritol/triethylene glycol 1:1) and 4.0 g paratoluenesulfonic acid (catalyst) was evacuated and heated gradually to 185° C. by means of an oil bath at a pressure of 200-300 mbar. On attainment of the reaction temperature, the reaction mixture was stirred for 11.5 hours and the water formed in the reaction was distilled off. The distillate passing over was collected in a cooled round-bottom flask and weighted.

[0128] After the removal of 555 g water, the reaction mixture was cooled down in vacuo and neutralized by the addition of an aqueous potassium hydroxide solution. Finally, all volatile by-products were removed in vacuo and the obtained polyether core C.2, a yellowish, highly viscous liquid, was cooled down to room temperature.

Example 3: Synthesis of Dendritic Polyether Core Molecule C.3

[0129] The polycondensation was performed in a 4 L glass flask equipped with a stirrer, reflux condenser and a distillation system with vacuum connection. A mixture of 1225 g pentaerythritol, 1351 g triethylene glycol (molar ratio pentaerythritol/triethylene glycol 1:1) and 4.0 g methanesulfonic acid (catalyst) was evacuated and heated gradually to 180° C. by means of an oil bath at a pressure of 200-300 mbar. On attainment of the reaction temperature, the reaction mixture was stirred for 6 hours and the water formed in the reaction was distilled off. The distillate passing over was collected in a cooled round-bottom flask and weighted.

[0130] After the removal of 478 g water, the reaction mixture was cooled down in vacuo and neutralized by the addition of an aqueous potassium hydroxide solution. Finally, all volatile by-products were removed in vacuo and the obtained polyether core C.3, a yellowish, highly viscous liquid, was cooled down to room temperature.

Example 4: Synthesis of Dendritic Polyether Core Molecule C.4

[0131] To 4.6 g of glycerol 280 mg potassium tert-butoxide were added and heated to 170° C. under stirring. On attainment of the reaction temperature, 164 g of glycerol carbonate (90% by weight) were added during a period of 8 hours. Upon completion of the addition, the mixture was stirred for further 2 hours at 170° C. Thereafter, the reaction mixture was cooled down to 80° C. and neutralized with acetic acid. Finally, 97 g of the polyether core C.3 were obtained as a brownish, highly viscous liquid.

Example 5: Synthesis of Star-Like Polyether S.1

[0132] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 50.0 g polyether core C.1 and 4.8 g of an aqueous solution of KOH (50% by weight) were charged at a temperature of 110° C. Water was removed in vacuo (<20 mbar). After purging with nitrogen the mixture was heated to 130° C. and 612 g ethylene oxide were added during a period of 12 hours. Subsequently 539 g propylene oxide were added during a period of 5 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1225 g of the star-like polyether S.1 were obtained as a brownish, highly viscous liquid.

Example 6: Synthesis of Star-Like Polyether S.2

[0133] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 25.0 g polyether core C.1 and 1.6 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 612 g ethylene oxide were added during a period of 12 hours. Subsequently 538 g propylene oxide was added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1190 g of the star-like polyether S.2 were obtained as a yellowish, highly viscous liquid.

Example 7: Synthesis of Star-Like Polyether S.3

[0134] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 56.0 g polyether core C.1 and 3.7 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 120° C. and 1032 g ethylene oxide were added during a period of 12 hours. Upon completion of the addition, the reaction mixture was reacted for further 2 hours at 120° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. 1077 g of the polyether ethoxylate were obtained as a brownish, highly viscous liquid.

[0135] 542 g of the polyether ethoxylate were then charged in another 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection. After purging with nitrogen the mixture was heated to 130° C. and 452 g propylene oxide were added during a period of 5 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1011 g of the star-like polyether S.3 were obtained as a brownish, highly viscous liquid.

Example 8: Synthesis of Star-Like Polyether S.4

[0136] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 56.0 g polyether core C.1 and 3.7 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 120° C. and 1032 g ethylene oxide were added during a period of 5 hours. Upon completion of the addition, the reaction mixture was reacted for further 10 hours at 120° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. 1077 g of the polyether ethoxylate were obtained as a brownish, highly viscous liquid.

[0137] 100 g of the polyether ethoxylate and 2.6 g potassium tert-butoxide were then charged in another 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection at 80° C. After purging with nitrogen the mixture was heated to 130° C. and 95 g ethylene oxide were added during a period of 3 hours. Subsequently 167 g propylene oxide were added during a period of 5 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 363 g of the star-like polyether S.4 were obtained as a brownish, highly viscous liquid.

Example 9: Synthesis of Star-Like Polyether S.5

[0138] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 50.0 g polyether core C.2 and 2.8 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 528 g ethylene oxide were added during a period of 12 hours. Subsequently 464 g propylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1042 g of the star-like polyether S.5 were obtained as a yellowish, highly viscous liquid.

Example 10: Synthesis of Star-Like Polyether S.6

[0139] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 25.0 g polyether core C.2 and 2.7 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 530 g ethylene oxide were added during a period of 12 hours. Subsequently 464 g propylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1021 g of the star-like polyether S.6 were obtained as a yellowish, highly viscous liquid.

Example 11: Synthesis of Star-Like Polyether S.7

[0140] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 30.0 g polyether core C.4 and 100 mg potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 455 g ethylene oxide were added during a period of 12 hours. Subsequently 400 g propylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 889 g of the star-like polyether S.7 were obtained as a yellowish, highly viscous liquid.

Example 12. Synthesis of Star-Like Polyether S.8

[0141] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 40.9 g polyether core C.3 and 3.8 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 792 g ethylene oxide were added during a period of 12 hours. Subsequently 397 g propylene oxide were added during a period of 12 hours. Upon completion of the addition, the reaction mixture was reacted for further 10 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1544 g of the star-like polyether S.8 were obtained as a brown solid.

Example 13: Synthesis of Star-Like Polyether S.9

[0142] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 30.0 g polyether core C.3 and 2.12 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 548 g ethylene oxide were added during a period of 6 hours. Subsequently 482 g propylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 1088 g of the star-like polyether S.9 were obtained as a yellowish, highly viscous liquid.

Example 14: Synthesis of Star-Like Polyether S.10 by Acid Functionalization of Star-Like Polyether S.9

[0143] In a 250 ml reactor equipped with a heating system, a stirrer and a reflux condenser 47 g star-like polyether S.8 and 0.8 g of succinic acid anhydride (SAA) were charged at a temperature of 25° C. After purging with nitrogen the mixture was heated slowly to 100° C., afterwards the reaction mixture was reacted for further 4 hours at 120° C. Finally, 49 g of the acid functionalized star-like polyether S.10 were obtained as a yellowish, highly viscous liquid.

Example 15: Synthesis of Star-Like Polyether S.11 by Acid Functionalization of Star-Like Polyether S.9

[0144] In a 250 ml reactor equipped with a heating system, a stirrer and a reflux condenser 48 g star-like polyether S.8 and 1.6 g of succinic acid anhydride (SAA) were charged at a temperature of 25° C. After purging with nitrogen the mixture was heated slowly to 100° C., afterwards the reaction mixture was reacted for further 4 hours at 120° C. Finally, 49 g of the acid functionalized star-like polyether S.11 were obtained as a yellowish, highly viscous liquid.

Example 16: Synthesis of Star-Like Polyether S.12

[0145] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 40.0 g polyether core C.1 and 2.6 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 489 g ethylene oxide were added during a period of 12 hours. Upon completion of the addition, the reaction mixture was reacted for further 6 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 544 g of the star-like polyether S.12 were obtained as a yellowish solid.

Example 17: Synthesis of Star-Like Polyether S.13

[0146] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 50.0 g polyether core C.1 and 3.25 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 539 g propylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 6 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 615 g of the star-like polyether S.13 were obtained as a brown solid.

Example 18: Synthesis of Star-Like Polyether S.14

[0147] In a 2 L reactor equipped with a heating system, cooling coil, agitator and vacuum connection 40.0 g polyether core C.1 and 2.6 g potassium tert-butoxide were charged at a temperature of 80° C. After purging with nitrogen the mixture was heated to 130° C. and 430 g propylene oxide were added during a period of 12 hours. Subsequently 489 g ethylene oxide were added during a period of 6 hours. Upon completion of the addition, the reaction mixture was reacted for further 12 hours at 130° C. Thereafter, the reaction mixture was cooled down to 80° C. and all volatile by-products and residual monomers were removed in vacuo. Finally, 982 g of the star-like polyether S.14 were obtained as a orange, highly viscous liquid.

Characterization of Polymers

[0148] Molecular weights and molecular weight distribution were analyzed by gel permeation chromatography with a refractometer as a detector. The mobile phase used was hexafluoroisopropanol (HFIP), the standard used to determine the molecular weight was poly(methyl methacrylate) (PMMA). The OH number (mg KOH/g) was determined to DIN 53240, Part 2.

[0149] Analytical data of the polymers (star-like polyether according to the present invention and starting materials for their preparation) are summarized in table 1.

TABLE-US-00001 TABLE 1 Composition and physicochemical characterization of star-like polyether M.sub.n M.sub.w OH number Dendritic Chemistry (Dendritic (Dendritic (Dendritic Linear Linear End-group polyether dendritic core) core) core) inner outer funct. Polymer core core [g/mol] [g/mol] [mg KOH/g] block block [%] S.1 C.1 TEG/PE 1:1 630 5.490 650 24 EO 16 PO — S.2 C.1 TEG/PE 1:1 630 5.490 650 48 EO 32 PO — S.3 C.1 TEG/PE 1:1 630 5.490 650 36 EO 24 PO — S.4 C.1 TEG/PE 1:1 630 5.490 650 72 EO 48 PO — S.5 C.2 TEG/PE 1:1 900 11.300 563 24 EO 16 PO — S.6 C.2 TEG/PE 1:1 900 11.300 563 48 EO 32 PO — S.7 C.4 Polyglycerol 510 13110 806 24 EO 16 PO — S.8 C.3 TEG/PE 1:1 1000 23000 460 54 EO 36 PO — S.9 C.3 TEG/PE 1:1 1000 23000 460 48 EO 32 PO — S.10 C.3 TEG/PE 1:1 1000 23000 460 48 EO 32 PO SAA (40) S.11 C.3 TEG/PE 1:1 1000 23000 460 48 EO 32 PO SAA (80) S.12 C.1 TEG/PE 1:1 630 5.490 650 24 EO — — S.13 C.1 TEG/PE 1:1 630 5.490 650 16 PO — — S.14 C.1 TEG/PE 1:1 630 5.490 650 16 PO 24 EO — C.1 — TEG/PE 1:1 630 5.490 650 — — — C.2 — TEG/PE 1:1 900 11.300 563 — — — C.3 — TEG/PE 1:1 1000 23000 460 C.4 — Polyglycerol 510 13110 806 — — —

Application Experiments:

[0150] Use of star-like polymers according to the invention in detergents:

[0151] The secondary detergency of the star-like polymers according to the invention was determined. For the washing experiments, 2 liquid detergent formulations (F.1, F.2) were used, the composition of which is given in table 2. The washing conditions are listed in table 3.

TABLE-US-00002 TABLE 2 Composition of liquid detergent formulations F.1 F.2 [% [% Ingredients active] active] Alkylbenzene sulfonic acid (C10-C13) 7.5 5 Sodium lauryl ether sulfate, 2 moles ethylene oxide — 6 C13-C15 Oxoalcohol reacted with 7 moles of 7.5 5 ethylene oxide Potassium coconut soap 2.55 — Potassium hydroxide 1 — C12-C18 Fatty acid, sodium salt — 3 Sodium hydroxide — 2 Citric acid monohydrate 1 2 Diethylentriamine penta (methylene phosphonic acid) 0.2 0.2 Water to 100 to 100 pH value 8.5 8

TABLE-US-00003 TABLE 3 Washing conditions for evaluation of secondary detergency Washing conditions Device Launder-O-Meter+ from SDL Atlas, Rock Hill, USA Washing liquor 250 mL Washing time 20 minutes Washing temperature 40° C. Detergent concentration 5.0 g/L Water hardness 2.5 mmol/L; Ca:Mg:HCO3 4:1:8 Fabric to liquor ratio 1:10 Washing cycles* 3 Star-like polyether 3% by weight, based on the respective liquid addition detergent formulation Test fabric 3 different cotton test fabrics: 3.8 g WFK 12A (cotton terry cloth), 1.5 g WFK 80A (cotton knit) (fabrics from WFK Testgewebe GmbH, Brueggen, Germany), 2.0 g EMPA 221 (cotton fabric, cretonne, bleached, without optical brightener; EMPA Testmaterials, St. Gallen, Switzerland) Soiled fabric** 2.5 g EMPA 101 (carbon black/olive oil on cotton; EMPA Testmaterials, St. Gallen, Switzerland) + 2.5 g SBL 2004 (Soil Ballast Fabric ‘Formula 2004’ that simulates sebum grease stains; WFK Testgewebe GmbH, Brueggen, Germany) Ballast fabric 3 different synthetic test fabrics: 1.7 g WFK20A (polyester 65%, cotton 35%), 1.7 g WFK30A (polyester), 1.25 g EMPA 406 (poly- amide 6.6 spun, type 200, plain weave, ISO 105-F03); and 2 different cotton fabrics: 1.8 g WFK 10A (standard cotton), and 1.6 g T-Shirt (Kapart brand, Brantic, Steisslingen) *After the 3 cycles, test fabrics are rinsed in water, followed by drying at ambient room temperature overnight **New ballast soil is used for each cycle

[0152] To determine the secondary detergency, the greying of the 3 white cotton test fabrics was measured by determining the degree of whiteness (reflectance values) after washing using a sphere reflectance spectrometer (SF 500 type from Datacolor, USA, wavelength range 360-700 nm, optical geometry)d/8° with a UV cutoff filter at 460 nm.

[0153] The difference between the reflectance after wash (R1) with the respective inventive polymer and the reflectance after wash (R2) without polymer (delta reflectance) is summarized in table 4.

[0154] A value ΔR (=R1−R2)>0 shows a positive contribution of the polymer to the anti-greying performance of the formulation, and therefore a positive anti-greying effect. If ΔR is >2, the improved whiteness compared to the fabrics washed without additive, is clearly visible.

TABLE-US-00004 TABLE 4 Results from launder-O-meter washing tests Cotton Cotton Star-like WFK 12A WFK 80A EMPA221 polyether Delta Re- Delta Re- Delta Re- additive flectance flectance flectance Detergent (3% by weight) in % in % in % F.1 without star- 0 0 0 like polyether F.1 C.1 −1.1 0.5 0.2 F.1 S.1 5.3 5.3 5.6 F.1 S.2 13.8 9.9 11.9 F.1 S.3 9.6 8.3 9.2 F.1 S.4 7.6 9.8 9.6 F.1 S.12 0.9 −0.5 −3.5 F.1 S.13 n.d.* n.d.* n.d.* F.1 S.14 0.1 1.8 −2.6 F.1 C.2 1.1 −1.1 −0.5 F.1 S.5 8.5 7.8 8.6 F.1 S.6 9.2 9 9.5 F.1 C.3 −0.4 0.1 0.9 F.1 S.8 11.3 12.2 11.6 F.1 S.9 12.8 11.3 10.9 F.1 C.4 −0.4 −1.6 2.2 F.1 S.7 4.7 3.3 3.5 F.2 without star- 0 0 0 like polyether F.2 S.1 4.2 2.3 2.6 F.2 S.2 10.1 7.5 14.4 F.2 S.5 8.8 6.5 7 F.2 S.6 9.4 5.3 10.3 F.2 S.8 9.4 7.2 7.7 F.2 S.9 11.8 9.3 9.8 F.2 S.10 8.1 3.9 6.5 F.2 S.11 4.8 3.2 2.8 *n.d.: not determined due to insolubility of polymer in water

[0155] Liquid detergents comprising 2% by weight of the polyethers given in table 5, made by substituting 2% by weight of water in liquid detergent formulation F.2 by one of the polyethers, were used in a washing machine Miele® W 1714 (cotton wash program at 40° C., water with a hardness of 17° dH, standardized soil addition, 70 g of detergent per wash cycle) to treat unsoiled cotton textile samples (8 rectangular pieces with a sides of 20 cm and 40 cm), also given in table 5, in addition to clean fabrics to give washloads of 3.5 kg each. After 3 wash cycles the change of whiteness (Y) of the textile samples was compared to the change of whiteness of the textile samples washed 3 times under the same conditions with detergent F.2, comprising no star-like polyether. Table 5 gives the deltadeltaY-values in % thus obtained.

TABLE-US-00005 TABLE 5 Results from washing machine tests WFK WFK Terry Krefeld Double EMPA Polyether 10A 12A towel standard rib 221 S.2 3.8 6.1 2.6 5.2 6.5 5.1 S.6 4.0 3.2 2.7 5.1 5.3 4.0 S.9 2.6 6.4 1.9 4.4 6.3 5.2

[0156] To ascertain the stability of the copolymers in various liquid detergent formulations, in each case 1.5% by weight of star-like polyether was formulated into the liquid detergent, and a visual assessment with regard to phase separation, clouding, incompatibilities, etc. was undertaken.

[0157] The stability tests were carried out with liquid detergent formulation F.1 and F.2. Table 5 summarizes the visual assessments after storage for 2 weeks at 37° C. While a clear solution was obtained with the star-like polyether additive in both formulations, precipitation or phase-separation occurred in both F.1 and F.2 when adding CMC

TABLE-US-00006 TABLE 6 Stability tests. Additive Formulation Visual assesment Viscosity observation S.3 F1 1 A CMC* F1 3 C CMC* F2 3 C *CMC, Carboxymethylcellulose Dow Cellulosics (Walocel CRT2000PA) 1: clearly soluble 2: soluble, cloudy 3: soluble, but phase separation 4: partly soluble, insoluble parts 5: completely insoluble A: no effect on viscosity B: slight increase of viscosity C: strong increase of viscosity, gelation