SULFATIZED ESTERAMINES

Abstract

The present invention relates to sulfatized esteramines obtainable by a process comprising step a), wherein at least one alcohol containing at least two hydroxy groups (compound (A)) is reacted with at least one lactam (compound (B)) and with sulfuric acid (compound (C)). The present invention also relates to a process for preparing such sulfatized esteramines.

Claims

1.-17. (canceled)

18. A sulfatized esteramine obtained by a process comprising step a): a) reacting at least one alcohol containing at least two hydroxy groups (compound (A)) with at least one lactam (compound (B)) and with sulfuric acid (compound (C)).

19. The sulfatized esteramine according to claim 18, wherein within step a) i) at least a fraction of compound (A) is first mixed with at least a fraction of compound (B) followed by continuously adding at least a fraction of compound (C) over a specific period of time, and/or ii) compound (C) is added for a specific period of time and the specific period of time for continuously adding compound (C) is in the range of less than one hour, and/or iii) the reaction is carried out after all compounds (A) to (C) are admixed with each other at a temperature of 80 to 200° C. and/or water is removed from the reaction mixture.

20. The sulfatized esteramine according to claim 18, wherein compound (A) is at least one alcohol containing at least two hydroxy groups selected from diols, polyols, alkoxylated diols and alkoxylated polyols.

21. The sulfatized esteramine according to claim 18, wherein in case compound (A) comprises an alkoxylated alcohol containing at least two hydroxy groups, the alkoxylated fragment of the respective alcohol is based on at least one C.sub.2-C.sub.22 alkylene oxide.

22. The sulfatized esteramine according to claim 18, wherein the process comprises step b), which is carried out prior to step a): b) at least one alcohol containing at least two hydroxy groups and having a molecular weight M.sub.W of less than 500 g/mol is reacted with at least one alkylene oxide in order to obtain an alkoxylated alcohol as compound (A).

23. The sulfatized esteramine according to claim 22, wherein i) ethylene oxide and/or propylene oxide is employed, and/or ii) at least one alcohol containing at least two hydroxy groups and having a molecular weight M.sub.W of less than 500 g/mol is reacted with at least 1 mol of propylene oxide and/or with at least 1 mol of ethylene oxide, and/or iii) at least one alcohol containing at least two hydroxy groups and having a molecular weight M.sub.W of less than 500 g/mol is reacted batchwise with ethylene oxide and/or propylene oxide in order to obtain at least one block based on ethylene oxide and/or propylene oxide on the respective alkoxylated alcohol, and/or iv) at least one alcohol containing at least two hydroxy groups and having a molecular weight M.sub.W of less than 500 g/mol is reacted in at least one batch with 1 to 120 mol of propylene oxide followed by at least one batch of 1 to 150 mol ethylene oxide.

24. The sulfatized esteramine according to claim 18, wherein i) step a) is carried out in the presence of water, and/or ii) optionally carrying out a step c) by removing water and/or by removing excess alcohol according to compound (A).

25. The sulfatized esteramine according to claim 18, wherein in step a) the molar ratio of compound (C) to compound (B) is at least 100 mol-%.

26. The sulfatized esteramine according to claim 18, wherein in step a) the molar ratio of compound (C) to compound (B) is at least 90 mol-%.

27. The sulfatized esteramine according to claim 18, wherein in step a) the molar ratio of compound (B) to the hydroxy groups of compound (A) is in the range of 10 mol-% to 50 mol-%.

28. The sulfatized esteramine according to claim 18, wherein in step a) the molar ratio of compound (C) to the hydroxy groups of compound (A) is in the range of 10 mol-% to 62,5 mol-%.

29. The sulfatized esteramine according to claim 18, wherein in step a) at least 10% of all hydroxy groups of compound (A) are reacted with compound (B) in order to form ester groups within the respective sulfatized esteramine and/or at least 10% of all hydroxy groups of compound (A) are sulfatized in order to form OSO.sub.3 fragments within the respective sulfatized esteramine.

30. The sulfatized esteramine according to claim 29, wherein in step a) 20 to 50% of all hydroxy groups of compound (A) are reacted with compound (B) in order to form ester groups within the respective sulfatized esteramine, 20 to 50% of all hydroxy groups of compound (A) are sulfatized in order to form OSO.sub.3 fragments within the respective sulfatized esteramine, and 0 to 30% of all hydroxy groups of compound (A) remain in unreacted form within the respective sulfatized esteramine.

31. The sulfatized esteramine according to claim 18, wherein within step a) i) the reaction is carried out after all compounds (A) to (C) are admixed with each other at a temperature of 80 to 200° C. for a period of time of 1 to 30 hours, and/or ii) the reaction is carried out in a closed vessel under pressure from 1.0 up to 10 bar.

32. The sulfatized esteramine according to claim 18, wherein compound (B) is at least one ε-lactam.

33. A process for producing the sulfatized esteramine according to claim 18, wherein the process comprises step a): a) reacting at least one alcohol containing at least two hydroxy groups (compound (A)) with at least one lactam (compound (B)) and with sulfuric acid (compound (C)).

34. Sulfatized esteramines of Formula (I) and salts thereof, ##STR00003## wherein independently from each other n being an integer from 1 to 12, m being an integer for each repetition unit n independently selected from 0 to 12; p being an integer from 0 to 12, o being an integer for each repetition unit p independently selected from 0 to 12; r being an integer from 0 to 12, q being an integer for each repetition unit r independently selected from 0 to 12; s, t, u and v being an integer from 0 to 100; A.sub.1, A.sub.2, A.sub.3, and A.sub.4 are independently from each other and independently for each repetition unit s, t, u, or v, selected from the list consisting of alkyleneoxy group, such A-units stem from the reaction of one alcohol with at least two hydroxy groups with C2-C22 alkylene oxides, e.g. in case of ethoxylated alcohols with at least two hydroxy groups A is “—O—CH2—CH2—” wherein for s, t, u, and/or v equal to 1 the oxygen atom of the A.sub.1, A.sub.2, A.sub.3, and A.sub.4 group is bound to the B group and the following A.sub.1, A.sub.2, A.sub.3, and A.sub.4 groups are always bound via the oxygen atom to the previous A.sub.1, A.sub.2, A.sub.3, and A.sub.4 group. B.sub.1, B.sub.2, B.sub.3, and B.sub.4 are independently from each other selected from the group consisting of a bond, linear C.sub.1 to C.sub.12 alkanediyl groups, and branched C.sub.1 to C.sub.12 alkanediyl groups; such B-units are given by the molecular structure of one alcohol with at least two hydroxy groups, e.g. in case of example 2 (1,6-hexane diol, esterified with 1 mol caprolactam and esterified with 1 mole sulfuric acid) B1 and B2 are “—CH2—”, with p and r=0, n=1, m=2, t and u=0, R.sub.1, R.sub.2, R.sub.3 R.sub.4, R.sub.8, R.sub.9, and R.sub.12=H, Z1 and Z2=OSO3H, OH or Formula (II) with w=3, and R.sub.13, R.sub.14 R.sub.15, R.sub.16, R.sub.17, and R.sub.18=H, R.sub.1, R.sub.2, R.sub.3 R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 being independently for each repetition unit selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; such R-units are given by the molecular structure of one alcohol with at least two hydroxy groups, Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, independently for each repetition unit n, p, and r, are selected from the group consisting of OH, and OSO3—, and —OSO3H and a compound according to Formula (II), wherein said compound according to Formula (II) connects to the compound according to Formula (I) via the bond labeled with *, such Z-units stem from the reaction of one alcohol with at least two hydroxy groups with at least one lactam and with sulfuric acid, e.g. in case of reaction with C4 lactam and sulfuric acid, Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.4, are “—OC(O)—CH.sub.2—CH.sub.2—CH.sub.2—NH.sub.2 or SO.sub.3H or OH with the provisio that at least 10 mol % to 50 mol % of the substituents Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, are a compound according to Formula (II), and at least 10 mol % to 50 mol % of the substituents Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, are a group consisting OSO3—, or —OSO3H, and 0 mol % to 80 mol % of the substituents Z.sub.1, and/or Z.sub.2, and/or Z.sub.3, and/or Z.sub.4, are OH, ##STR00004## with independently from each other w being an integer from 0 to 12; R.sub.13, R.sub.14 R.sub.15, R.sub.16, R.sub.17, and R.sub.18 independently being selected from the group consisting of H, linear alkyl, branched alkyl, and cycloalkyl; such R-units stem from the lactam, e.g. in case of reaction with C4 lactam R.sub.13, R.sub.14 R.sub.15, R.sub.16, R.sub.17, and R.sub.18 are=H, w=1, and then Formula (II) is “—OC(O)—CH.sub.2—CH.sub.2—CH.sub.2—NH.sub.2”

Description

[0100] The following examples shall further illustrate the present invention without restricting the scope of the present invention.

Example 1: Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 2 Mole Caprolactam and Sulfatized with 2 Mole Sulfuric Acid

1a Sorbitol, Propoxylated with 18 Mole Propylene Oxide

[0101] In a 2 l autoclave 248.9 g sorbitol and 6.6 g potassium hydroxide (50% in water) are placed and the mixture is heated to 120° C. Vacuum is applied and the mixture is stirred for 2 hours under vacuum (<10 mbar). The vessel is filled with nitrogen and heated to 140° C. 1400.0 g propylene oxide is added in portions within 40 h. To complete the reaction, the mixture is allowed to post-react for additional 10 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 1635.0 g of a brown oil is obtained (hydroxy value: 262 mgKOH/g).

1b Sorbitol, Propoxylated with 96 Mole Propylene Oxide

[0102] In a 2 l autoclave 180.0 g sorbitol, propoxylated with 18 mole propylene oxide and 3.4 g potassium hydroxide (50% in water) are placed and the mixture is heated to 110° C. Vacuum is applied and the mixture is stirred for 2 hours under vacuum (<10 mbar). The vessel is filled with nitrogen and heated to 140° C. 665.9 g propylene oxide is added in portions within 6 h. To complete the reaction, the mixture is allowed to post-react for additional 6 h at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 836.0 g of a light brown oil is obtained (hydroxy value: 58.5 mgKOH/g).

1c Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide

[0103] In a 2 l autoclave 432.7 g sorbitol, propoxylated with 96 mole propylene oxide are placed and the mixture is heated to 60° C. The vessel is purged three times with nitrogen and heated to 140° C. 475.7 g ethylene oxide is added in portions within 4 hours. To complete the reaction, the mixture is allowed to post-react for additional 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 883.0 g of a viscous brown waxy solid is obtained (hydroxy value: 27.8 mgKOH/g).

1d Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 2 Mole Caprolactam and Sulfatized with 2 Mole Sulfuric Acid

[0104] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 157.3 g sorbitol, propoxylated with 96 mole propylene oxide and ethoxylated with 144 mole ethylene oxide (1 c), 3.7 g caprolactam (80% in water), and 1.8 g water are placed. To the mixture 2.7 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 10 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. 160.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 25% conversion of hydroxyl groups into 6-aminohexane acid ester and 33% conversion of hydroxyl groups into sulfuric acid ester.

Example 2: 1,6-Hexane Diol, Esterified with 1 Mole Caprolactam and Esterified with 1 Mole Sulfuric Acid

[0105] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 23.6 g 1,6-hexane diol, 28.3 g caprolactam (80% in water), and 12.3 g water are placed. To the mixture 20.8 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 50° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 3 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 2 hours. 60.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 45% conversion of hydroxyl groups into 6-aminohexane acid ester and 40% conversion of hydroxyl groups into sulfuric acid ester.

5 Example 3: 2-Butyl-2-ethyl-1,3-propane diol, Esterified with 1 Mole Caprolactam and Esterified with 1 Mole Sulfuric Acid

[0106] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 81.5 g molten 2-Butyl-2-ethyl-1,3-propane diol, 72.0 g caprolactam (80% in water), are placed at 30° C. To the mixture 52.4 g sulfuric acid (96%) is added within 10 minutes. Temperature rises up to 65° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 3 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 2 hours. 180.0 g of a light yellow highly viscous oil is obtained. .sup.1H-NMR in MeOD indicates 47% conversion of hydroxyl groups into 6-aminohexane acid ester and 35% conversion of hydroxyl groups into sulfuric acid ester.

Example 4: Polyethylene Glycol, Molecular Weight 4000 g/mol, Esterified with 1 Mole Caprolactam and Esterified with 1 Mole Sulfuric Acid

[0107] In a 250 ml glass pressure vessel with magnetic stir bar 103.61 g polyethylene glycol molecular weight 4000 g/mol, 3.53 g caprolactam (80% in water), and 7.25 g water are placed. To the mixture 2.60 g sulfuric acid (96%) is added within 10 minutes. Temperature rises up to 50° C. during sulfuric acid addition. The vessel is closed and heated to 148° C. bath temperature and stirred for 6 hours at this temperature. The reaction mixture is transferred to a 4-neck vessel with thermometer, nitrogen inlet, stirrer, and distillation head. Water is distilled off for 27 hours at 5 mbar and 130° C. bath temperature. 108.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 50% conversion of hydroxyl groups into 6-aminohexane acid ester and 50% conversion of hydroxyl groups into sulfuric acid ester.

Example 5: Polyethyleneglycol polypropyleneglycol Block Copolymer Pluronic PE 6400, Esterified with 1 Mole Caprolactam and Esterified with 1 Mole Sulfuric Acid

[0108] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 101.5 g polyethyleneglycol polypropyleneglycol block copolymer Pluronic PE 6400, 4.95 g caprolactam (80% in water), and 3.15 g water are placed. To the mixture 3.65 g sulfuric acid (96%) is added within 10 minutes. Temperature rises up to 50° C. during sulfuric acid addition. The reaction mixture is heated to 148° C. bath temperature and stirred for 6 hours at this temperature. The reflux condenser is replaced by a distillation head, and water is distilled off for 22 hours under vacuum up to 5 mbar. 107.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 45% conversion of hydroxyl groups into 6-aminohexane acid ester and 44% conversion of hydroxyl groups into sulfuric acid ester.

Example 6: Glycerol, Ethoxylated with 12 Mole Ethylene Oxide, Esterified with 1 Mole Caprolactam and Sulfatized with 1 Mole Sulfuric Acid

6a Glycerol, Ethoxylated with 12 Mole Ethylene Oxide

[0109] In a 2 l autoclave 110.5 g glycerol and 1.5 g potassium tert. butoxide are placed and the mixture is heated to 80° C. The vessel is purged three times with nitrogen and the mixture is heated to 140° C. 634.3 g ethylene oxide is added in portions within 11 hours. To complete the reaction, the mixture is allowed to post-react for additional 5 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 745.0 g of a brown oil is obtained (hydroxy value: 85.0 mgKOH/g).

6b Glycerol, Ethoxylated with 12 Mole Ethylene Oxide, Esterified with 1 Mole Caprolactam and Sulfatized with 1 Mole Sulfuric Acid

[0110] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 62.2 g glycerol, ethoxylated with 12 mole ethylene oxide 14.1 g caprolactam (80% in water), and 9.0 g water are placed. To the mixture 10.3 g sulfuric acid (96%) is added within 10 minutes. Temperature rises to 60° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and stirred for 6 hours at this temperature. The reflux condenser is removed and replaced by a distillation head. Water is distilled off for 5 hours under vacuum up to 5 mbar. 80.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 32% conversion of hydroxyl groups into 6-aminohexane acid ester and 31% conversion of hydroxyl groups into sulfuric acid ester.

Example 7: Pentaerythritol, Ethoxylated with 16 Mole Ethylene Oxide, Esterified with 1.3 Mole Caprolactam and Sulfatized with 1.3 Mole Sulfuric Acid

7a Pentaerythritol, Ethoxylated with 16 Mole Ethylene Oxide

[0111] In a 2 l autoclave 130.0 g pentaerythritol and 1.6 g potassium tert. butoxide and 300.0 ml xylene (mixture of isomers) are placed and the mixture is heated to 80° C. The vessel is purged three times with nitrogen and the mixture is heated to 140° C. 673.1 g ethylene oxide is added in portions within 6.5 hours. To complete the reaction, the mixture is allowed to post-react for additional 6 hours at 140° C. The reaction mixture is stripped with nitrogen and solvent xylene is removed in vacuo at 2 mbar at 120° C. After filtration 831.0 g of a yellow oil is obtained (hydroxy value: 271.0 mgKOH/g).

7b Pentaerythritol, Ethoxylated with 16 Mole Ethylene Oxide, Esterified with 1.3 Mole Caprolactam and Sulfatized with 1.3 Mole Sulfuric Acid

[0112] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 92.7 g pentaerythritol, ethoxylated with 16 mole ethylene oxide, 20.3 g caprolactam (80% in water), and 8.3 g water are placed. To the mixture 14.7 g sulfuric acid (96%) is added within 10 minutes. Temperature rises to 60° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and stirred for 7 hours at this temperature. The reflux condenser is removed and replaced by a distillation head. Water is distilled off for 8 hours at 135° C. bath temperature. Vacuum (5 mbar) is applied, and the mixture is stirred for 5 under vacuum and 135° C. bath temperature. 80.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 27% conversion of hydroxyl groups into 6-aminohexane acid ester and 32% conversion of hydroxyl groups into sulfuric acid ester.

Example 8: Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 3 Mole Caprolactam and Sulfatized with 3 Mole Sulfuric Acid

8a Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide

[0113] In a 3 l autoclave 140.0 g of a sorbitol propoxylate, propoxylated with 6.6 mole propylene oxide (Lupranol 3422, commercially available from BASF SE) and 5.0 g potassium butoxide are placed and the mixture is heated to 60° C. The vessel is purged three times with nitrogen and heated to 140° C. 1060.4 g propylene oxide is added in portions within 6 hours. To complete the reaction, the mixture is allowed to post-react for additional 6 hours at 140° C. 1295.3 g ethylene oxide is added within 6 hours at 140° C., followed by post-reaction time of 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 2490.0 g of a waxy brown solid is obtained (hydroxy value: 33.6 mgKOH/g).

8b Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 3 Mole Caprolactam and Sulfatized with 3 Mole Sulfuric Acid

[0114] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 122.5 g sorbitol, propoxylated with 96 mole propylene oxide and ethoxylated with 144 mole ethylene oxide (8 a), 4.24 g caprolactam (80% in water), and 1.8 g water are placed. To the mixture 3.11 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 7 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. The reaction mixture is stirred at 130° C. for 9 hours under vacuum (<25 mbar). 127.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 49% conversion of hydroxyl groups into 6-aminohexane acid ester and 47% conversion of hydroxyl groups into sulfuric acid ester.

Example 9: Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 1 Mole Caprolactam and Sulfatized with 1 Mole Sulfuric Acid

[0115] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 121.13 g sorbitol, propoxylated with 96 mole propylene oxide and ethoxylated with 144 mole ethylene oxide (1 c), 1.41 g caprolactam (80% in water), and 0.09 g water are placed. To the mixture 1.03 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 29 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. The reaction mixture is stirred at 130° C. for 6 hours under vacuum (<25 mbar). 120.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 15% conversion of hydroxyl groups into 6-aminohexane acid ester and 15% conversion of hydroxyl groups into sulfuric acid ester.

Example 10: Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 23.4 Mole Ethylene Oxide, Esterified with 3 Mole Caprolactam and Sulfatized with 3 Mole Sulfuric Acid

10a Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 23.4 Mole Ethylene Oxide

[0116] In a 2 l autoclave 354.0 g of a sorbitol propoxylate, (Sorbitol propoxylated with 6.6 mole propylene oxide (Lupranol 3422, commercially available from BASF SE)) and 1.8 g potassium butoxide are placed and the mixture is heated to 60° C. The vessel is purged three times with nitrogen and heated to 140° C. 532.3 g ethylene oxide is added in portions within 6 hours. To complete the reaction, the mixture is allowed to post-react for additional 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 110° C. After filtration 874.0 g of a brown oil is obtained (hydroxy value: 199.8 mgKOH/g).

10b Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 23.4 Mole Ethylene Oxide, Esterified with 3 Mole Caprolactam and Sulfatized with 3 Mole Sulfuric Acid

[0117] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 68.8 g sorbitol, propoxylated with 6.6 mole propylene oxide and ethoxylated with 23.4 mole ethylene oxide (10 a), 16.9 g caprolactam (80% in water), and 6.5 g water are placed. To the mixture 12.5 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 8 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. The reaction mixture is stirred at 130° C. for 8 hours under vacuum (<25 mbar). 90.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 33% conversion of hydroxyl groups into 6-aminohexane acid ester and 41% conversion of hydroxyl groups into sulfuric acid ester.

Example 11: Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 113.4 Mole Ethylene Oxide, Esterified with 1 Mole Caprolactam and Sulfatized with 1 Mole Sulfuric Acid

11a Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 113.4 Mole Ethylene Oxide

[0118] In a 2 l autoclave 300.0 g of a sorbitol alkoxylate (10 a) and 1.4 g potassium butoxide are placed and the mixture is heated to 60° C. The vessel is purged three times with nitrogen and heated to 140° C. 691.6 g ethylene oxide is added in portions within 6 hours. To complete the reaction, the mixture is allowed to post-react for additional 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. After filtration 990.0 g of a brown oil is obtained (hydroxy value: 64.7 mgKOH/g).

11b Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 113.4 Mole Ethylene Oxide, Esterified with 1 Mole Caprolactam and Sulfatized with 1 Mole Sulfuric Acid

[0119] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 85.4 g sorbitol, propoxylated with 6.6 mole propylene oxide and ethoxylated with 113.4 mole ethylene oxide (11 b), 2.1 g caprolactam (80% in water), and 0.9 g water are placed. To the mixture 1.6 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 6 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. The reaction mixture is stirred at 130° C. for 8 hours under vacuum (<25 mbar). 85.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 15% conversion of hydroxyl groups into 6-aminohexane acid ester and 15% conversion of hydroxyl groups into sulfuric acid ester.

Example 12: Sorbitol, Propoxylated with 6.6 Mole Propylene Oxide and Ethoxylated with 113.4 Mole Ethylene Oxide, Esterified with 3 Mole Caprolactam and Sulfatized with 3 Mole Sulfuric Acid

[0120] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 85.4 g sorbitol, propoxylated with 6.6 mole propylene oxide and ethoxylated with 113.4 mole ethylene oxide (11 a), 6.3 g caprolactam (80% in water), and 0.9 g water are placed. To the mixture 4.7 g sulfuric acid (96%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 55° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 8 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 3 hours. The reaction mixture is stirred at 130° C. for 7 hours under vacuum (<25 mbar). 89.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 40% conversion of hydroxyl groups into 6-aminohexane acid ester and 42% conversion of hydroxyl groups into sulfuric acid ester.

Comparative Example 1: Sorbitol, Propoxylated with 96 Mole Propylene Oxide and Ethoxylated with 144 Mole Ethylene Oxide, Esterified with 2 Mole Caprolactam as Methane Sulfonic Acid Salt

[0121] In a 4-neck vessel with thermometer, nitrogen inlet, dropping funnel, reflux condenser and stirrer 121.1 g sorbitol, propoxylated with 96 mole propylene oxide and ethoxylated with 144 mole ethylene oxide (1 c), 2.8 g caprolactam (80% in water), and 1.2 g water are placed. To the mixture 2.05 g methane sulfonic acid (99%) is added within 10 minutes under a constant stream of nitrogen. Temperature rises up to 40° C. during sulfuric acid addition. The reaction mixture is heated to 135° C. bath temperature and is stirred for 25 hours at 135° C. under reflux. The reflux condenser is removed and under a constant stream of nitrogen, water is distilled off for 7 hours. 120.0 g of a brown solid is obtained. .sup.1H-NMR in MeOD indicates 30% conversion of hydroxyl groups into 6-aminohexane acid ester as methane sulfonic acid salt.

Performance in Detergents

[0122] For the whiteness benefit test, the following laundry detergent composition is provided in table1:

TABLE-US-00001 TABLE 1 laundry detergent composition Ingredient % LAS 6.9 AE3S 11.3 Fatty Acid C1218 1 1,2 Propylene Glycol 6 Ethanol 2 Water balance

Test Preparation

[0123] The following fabrics are provided for the whiteness benefit test: [0124] Polyester 1: Polyester 854, available from Reichenbach Wirkstoffe (Germany) [0125] Polyester 2: PW19, available from Empirical Manufacturing Company (Cincinnati, OH, USA). [0126] Knitted Cotton 1: CW120, available from Empirical Manufacturing Company (Cincinnati, OH, USA).

[0127] “Washed and FE Treated” fabrics were prepared according to the following method: 400 g fabrics are washed in a WE Miniwasher (3.5 litre water) twice using the short program (45 minute wash cycle followed by three rinse cycles; total program is 90 minutes) at 60° C. with 18.6 g Ariel Compact powder detergent, twice using the short program, at 60° C. nil detergent, and then three times using the short program at 40° C. with 8.2 g Lenor Concentrate (a fabric enhancer) into each main wash. Fabrics are then dried in a tumble dryer on extra dry until dry.

[0128] “Washed” fabrics were prepared according to the following method: 400 g fabrics are washed in a WE Miniwasher (3.5 litre water) twice using the short program (45 minute wash cycle followed by three rinse cycles; total program is 90 minutes) at 60° C. with 18.6 g Ariel Compact powder detergent and twice using the short program, at 60° C. nil detergent. Fabrics are then dried in a tumble dryer on extra dry until dry.

Test Method

[0129] Four fabric samples are prepared: Polyester 1, washed and FE treated; Polyester 2, washed and FE treated; Knitted Cotton 1, washed and FE treated; Knitted Cotton 2, washed.

[0130] Each sample is run in a 96 well plate simulated washing system that uses magnetized bearings to simulate the agitation of a typical full scale washing machine according to the following conditions: 375 ppm detergent concentration, 150 μL water per well, 25° C., water hardness of 1.0 mM (2:1 Ca+2: Mg+2 molar ratio), wash pH of 8, 3000 ppm Arizona test dust (supplied PTI, Powder Technology Inc).

[0131] Each polymer (example 1 and comparative example 1) listed in table 2 is added at 100 ppm of the wash solution. Each fabric is washed for 60 minutes and dried in the dark under ambient conditions. For each wash condition, there are two 96 well plates, and eight internal replicates per 96 well plate, for a total of 16 replicates per wash condition. When the samples are dry, L*, a*, b* and CIE WI are measured on each 96 well plate spot using a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273). For each treatment, the average CIE WI is determined. Delta CIE WI, as reported in table 2 below, is the difference of the average CIE WI of the sample vs. the average CIE WI of a control sample without the tested polymer.

TABLE-US-00002 TABLE 2 Whiteness benefits of example 1 and comparative example 1 Delta CIE WI Polyester 1, Polyester 2, Knitted Cotton Knitted washed and washed and 1, washed and Cotton FE treated FE treated FE treated 1, washed Example 1 6.4 6.4 1.2 9.4 Comparative 2.6 3.8 −3.7 6.1 Example 1 LSD (95) 1.7 1.6 1.3 1.2