Amphiphilic alkoxylated polyamines and their uses

Abstract

A novel alkoxylated polyamines obtainable by a process including the steps a) to d) and having amphiphilic properties. According to step a), a polyamine containing up to 10 amine-groups as such is reacted with a first alkylene oxide (AO1) in order to obtain a first intermediate (I1). Said first intermediate (I1) is reacted with a lactone and/or a hydroxy carbon acid in step b) in order to obtain a second intermediate (I2) followed by step c), wherein said second intermediate (I2) is reacted optionally with alkylene oxide in order to obtain a third intermediate (I3). Afterwards, said third intermediate (I3) is reacted in optional step d) with a second alkylene oxide (AO2) in order to obtain the novel alkoxylated polyamines. The alkoxylated polyamines may also be included in cleaning compositions and/or in fabric and home care products, and the compositions or products as such.

Claims

1. A cleaning composition comprising: a) an alkoxylated polyamine comprising a structural unit derived from a polyamine according to general formula (I) ##STR00008## 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): ##STR00009## 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 about 0 to about 50 or iii) C.sub.5-C.sub.10 cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3 alkyl; y is an integer having a value in the range of about 0 to about 8; wherein the alkoxylated polyamine comprises at least one residue according to general formula (IIa) ##STR00010## 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 about 1 and up to about 10; n is an integer having a value of at least about 1 and up to about 25; o is an integer having a value of from 0 and up to 25; p is an integer having a value of at least about 1 and up to about 5; with the proviso that the sum of n+0+p is at most about 25, wherein at least about 50 weight percent of the total amount of moieties the residues R.sup.1, R.sup.4 in the alkoxylated polyamine originates from C.sub.3 and/or C.sub.4-alkylene oxides, andwhen o is not zerothen R.sup.1 and R.sup.5 are selected such that the moieties containing R.sup.1 and R.sup.5 are of different chemical composition and/or different chemical structure such that there are different arrangements of the alkylene oxides if more than one alkylene oxide is selected for R.sup.1 and R.sup.5 and the selected alkylene oxides are the same for both R.sup.1 and R.sup.5; and b) a surfactant.

2. The cleaning composition of claim 1, containing at least one residue according to general formula (IIb) ##STR00011## 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 about 1 up to about 10; n is an integer having a value of about 1 and up to about 25; o is an integer having a value of from 0 and up to 25; wherein at least about 50 weight percent of the total amount of moieties in residues R.sup.1 andwhen residues of the formula (IIa) are also presentalso R.sup.4, in the alkoxylated polyamine originates from C.sub.3 and/or C.sub.4-alkylene oxides, wherein R.sup.1 and R.sup.5 are selected such that the moieties containing R.sup.1 and R.sup.5 are of different chemical composition and/or different chemical structure such that there are different arrangements of the alkylene oxides if more than one alkylene oxide is selected for R.sup.1 and R.sup.5 and the selected alkylene oxides are the same for both R.sup.1 and R.sup.5, with the proviso that the sum of n+o is at most about 25.

3. The cleaning composition of claim 2, wherein the sum of n+o is at most about 15.

4. The cleaning composition of claim 1, wherein the alkoxylated polyamine comprises at least one residue according to general formula (IIc) ##STR00012## 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 about 5 and up to about 100; o is an integer having a value of from 0 and up to 100; wherein at least about 50 weight percent of the total amount of moieties in the alkoxylated polyamine stemming from alkylene oxides such that the residues R1 andwhen residues of the formula IIa are also presentalso R4 originates from C3 and/or C4-alkylene oxides, with the proviso that the sum of n+o is at most about 25.

5. The cleaning composition of claim 4, wherein n is an integer of up to about 15.

6. The cleaning composition of claim 1, wherein 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 about 1 to about 10, and R.sup.10, R.sup.11, R.sup.12 are independently selected from linear or branched C.sub.3 to C.sub.4 alkylene radicals.

7. The cleaning composition of claim 1, wherein the alkoxylated polyamine comprises at least one residue according to general formula (IIb) ##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.5 represents 1,2-ethylene; m is an integer having a value of about 1 up to about 10; n is an integer having a value of about 1 and up to about 25; o is an integer having a value of from 0 and up to 25; wherein at least about 50 weight percent of the total amount of moieties in residues R1 andwhen residues of the formula (IIa) are also presentalso R.sup.4, in the alkoxylated polyamine originates from C3 and/or C4-alkylene oxides, wherein R.sup.1 and R.sup.5 are selected such that the moieties containing R.sup.1 and R.sup.5 are of different chemical composition and/or different chemical structure such that there are different arrangements of the alkylene oxides if more than one alkylene oxide is selected for R.sup.1 and R.sup.5 and the selected alkylene oxides are the same for both R.sup.1 and R.sup.5, with the proviso that the sum of n+o is at most about 25; wherein the alkoxylated polyamine further contains at least one residue according to general formula (IIc) ##STR00014## 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 about 5 and up to about 100; o is an integer having a value of from 0 and up to 100; wherein at least about 50 weight percent of the total amount of moieties in the alkoxylated polyamine stemming from alkylene oxides such that the residues R1 andwhen residues of the formula IIa are also presentalso R4 originates from C3 and/or C4-alkylene oxides, with the proviso that the sum of n+o is at most about 25; and wherein the residue (IIa) accounts for at least about 80 weight percent of all residues (IIa), (IIb) and (IIc) attached to the amino-groups of the polyamine.

8. The cleaning composition of claim 7, wherein residue (IIa) accounts for about 95 weight percent or more of all residues (IIa), (IIb) and (IIc) attached to the amino-groups of the polyamine.

9. The cleaning composition of claim 1, wherein y is up to about 6.

10. The cleaning composition of claim 1, wherein y is up to about 2.

11. The cleaning composition of claim 1, wherein R represents identical or different: ia) C.sub.2-C.sub.6-alkylene radicals being selected from ethylene, propylene and hexamethylene; or iib) C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl.

12. The cleaning composition of claim 1, wherein o is 0.

13. A cleaning composition comprising an alkoxylated polyamine comprising a structural unit according to general formula (I) ##STR00015## 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): ##STR00016## 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 about 0 to about 50 or iii) C.sub.5-C.sub.10 cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3 alkyl; y is an integer having a value in the range of about 0 to about 8; wherein the alkoxylated polyamine comprises at least one residue according to general formula (IIa) ##STR00017## 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 about 1 and up to about 10; n is an integer having a value of at least about 1 and up to about 25; o is an integer having a value of from 0 and up to 25; p is an integer having a value of at least about 1 and up to about 5; with the proviso that the sum of n+o+p is at most about 25, wherein at least about 50 weight percent of the total amount of moieties the residues R.sup.1, R.sup.4 in the alkoxylated polyamine originates from C3 and/or C4-alkylene oxides, andwhen o is not zerothen R.sup.1 and R.sup.5 are selected such that the moieties containing R1 and R.sup.5 are of different chemical composition and/or different chemical structure such that there are different arrangements of the alkylene oxides if more than one alkylene oxide is selected for R.sup.1 and R.sup.5 and the selected alkylene oxides are the same for both R.sup.1 and R.sup.5.

14. The cleaning composition of claim 13, wherein y is an integer having a value in the range of about 0 to about 4.

15. The cleaning composition of claim 13, wherein R represents identical or different, ia) C.sub.2-C.sub.6-alkylene radicals being selected from ethylene, propylene and hexamethylene, or iib) C.sub.5-C.sub.10-cycloalkylene radicals optionally substituted with at least one C.sub.1-C.sub.3-alkyl.

16. The cleaning composition of claim 15, wherein iib) is at least one C.sub.6-C.sub.7-cycloalkylene radical substituted with at least one methyl or ethyl.

17. The cleaning composition of claim 15, wherein R is selected only from group ia).

18. The cleaning composition of claim 13, wherein n+o+p is at most about 15.

19. The cleaning composition of claim 13, wherein n is an integer of up to about 15.

20. The cleaning composition of claim 13, wherein o is 0.

Description

EXAMPLES

Synthesis Examples

(1) The following examples have been performed with the shown results obtained (also see Table 5), following the described procedures:

Example 1

(2) HMDA+1 PO per mol of NH functionality+0.25 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality

(3) (HMDA+1 PO/NH+0.25 Caprolacton/NH+8 PO/NH)

(4) Example 1 a: HMDA+1 PO per mol of NH Functionality

(5) A 2 I autoclave was charged with 245.0 g hexamethylene diamine and 12.3 g water. The reactor was purged three times with nitrogen and heated to 110 C. 489.8 g propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110 C. Volatile compounds were removed in vacuo at 90 C. A viscous yellow oil (730.0 g) was obtained. .sup.1H-NMR in CDCl.sub.3 indicated complete conversion.

(6) Example 1 b: HMDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality

(7) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 278.8 g hexamethylene diamine+1 PO per mol of NH functionality (example 1 a) were placed and heated to 110 C. 91.3 g caprolactone was added within 10 minutes. The reaction mixture was heated to 160 C. and was stirred for 8 hours at 160 C. 370.0 g of a brown viscous oil was obtained. .sup.1H-NMR in MeOD indicated complete conversion of caprolactone.

(8) Example 1 c: HMDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(9) In a 2 I autoclave 185.1 g hexamethylene diamine+1 PO per mol of NH functionality+0.25 caprolactone per mol of NH functionality (example 1 b) and 1.9 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 743.4 g propylene oxide was added in portions within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds are removed in vacuo at 90 C. for 2 hours. 927.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 2

(10) HMDA+1 PO per mol of NH functionality+0.5 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(11) (HMDA+1 PO/NH+0.5 Caprolacton/NH+8 PO/NH)

(12) Example 2 a: HMDA+1 PO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality

(13) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 139.4 g hexamethylene diamine +1 PO per mol of NH functionality (example 1 a) were placed and heated to 70 C. 91.3 g caprolactone was added within 15 minutes. The reaction mixture was heated to 160 C. and was stirred for 8 hours at 160 C. 223.0 g of an orange viscous oil is obtained. .sup.1H-NMR in Me0D indicated complete conversion of caprolactone.

(14) Example 2 b: HMDA+1 PO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(15) In a 2 I autoclave 115.4 g hexamethylene diamine+1 PO per mol of NH functionality+0.5 caprolactone per mol of NH functionality (example 2a) and 1.0 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 371.7 g propylene oxide was added in portions within 6 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds are removed in vacuo at 90 C. for 2 hours. 490.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 3

(16) EDA+1 PO per mol of NH functionality+0.25 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(17) (EDA+1 PO/NH+0.25 Caprolacton/NH+8 PO/NH)

(18) Example 3 a: EDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality

(19) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 146.2 g ethylene diamine+1 PO per mol of NH functionality (Quadrol L, purchased from BASF) were placed and heated to 40 C. 57.1 g caprolactone was added within 5 minutes. The reaction mixture was heated to 160 C. and was stirred for 8 hours at 160 C. 202.0 g of an orange viscous oil was obtained. .sup.1H-NMR in MeOD indicated 98.5% conversion of caprolactone.

(20) Example 3 b: EDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(21) In a 2 I autoclave 101.6 g ethylene diamine+1 PO per mol of NH functionality+0.25 caprolactone per mol of NH functionality (example 3 a) and 1.1 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 464.6 g propylene oxide was added in portions within 8 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 570.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 4

(22) HMDA+1 EO per mol of NH functionality+0.25 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(23) (HMDA+1 EO/NH+0.25 Caprolacton/NH+8 PO/NH)

(24) Example 4 a: HMDA+1 EO per mol of NH Functionality

(25) A 2 I autoclave was charged with 348.6 g hexamethylene diamine and 17.4 g water. The reactor was purged three times with nitrogen and heated to 90 C. 528.6 g ethylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 90 C. Volatile compounds were removed in vacuo at 90 C. A beige wax (875.0 g) was obtained. .sup.1H-NMR in CDCl.sub.3 indicated complete conversion.

(26) Example 4 b: HMDA+1 EO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality

(27) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel and reflux cooler 263.2 g hexamethylene diamine+1 EO per mol of NH functionality (example 4 a) were placed and heated to 80 C. 102.7 g caprolactone were added in one portion at 80 C. The reaction mixture was heated to 160 C. and was stirred for 13 hours at 160 C. 360.0 g of a brown oil was obtained. 1H-NMR in MeOD indicated 93% conversion of caprolactone.

(28) Example 4 c: HMDA+1 EO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(29) In a 2 I autoclave 162.6 g hexamethylene diamine+1 EO per mol of NH functionality+0.25 caprolactone per mol of NH functionality (example 4 b) and 1.9 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 743.4 g propylene oxide was added in portions within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 895.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 5

(30) HMDA+1 EO per mol of NH functionality+0.5 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(31) (HMDA+1 EO/NH+0.5 Caprolacton/NH+8 PO/NH)

(32) Example 5 a: HMDA+1 EO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality

(33) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel and reflux cooler 131.6 g hexamethylene diamine+1 EO per mol of NH functionality (example 4 a) were placed and heated to 70 C. 102.7 g caprolactone were added within 5 minutes. The reaction mixture was heated to 160 C. and was stirred for 8 hours at 160 C. 227.6 g of a dark brown oil was obtained. .sup.1H-NMR in MeOD indicated 94% conversion of caprolactone.

(34) Example 5 b: HMDA+1 EO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(35) In a 2 I autoclave 134.0 g hexamethylene diamine+1 EO per mol of NH functionality +0.5 caprolactone per mol of NH functionality (example 5 a) and 1.2 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 478.3 g propylene oxide was added in portions within 8 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 610.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 6

(36) PDA+1 PO per mol of NH functionality+0.25 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(37) (PDA+1 PO/NH+0.25 Caprolacton/NH+8 PO/NH)

(38) Example 6 a: PDA+1 PO per mol of NH Functionality

(39) A 2 I autoclave was charged with 222.4 g 1,3-propane diamine and 11.2 g water. The reactor was purged three times with nitrogen and heated to 110 C. 697.0 g propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110 C. Volatile compounds were removed in vacuo at 90 C. A viscous light brown oil (919.0 g) was obtained. .sup.1H-NMR in CDCl.sub.3 indicated complete conversion.

(40) Example 6 b: PDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality

(41) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 306.4 g 1,3-propane diamine+1 PO per mol of NH functionality (example 6 a) were placed and heated to 50 C. 114.1 g caprolactone was added within 50 minutes. The reaction mixture was heated to 160 C. and was stirred for 4 hours at 160 C. 420 g of a brown viscous oil was obtained. .sup.1H-NMR in MeOD indicated complete conversion of caprolactone.

(42) Example 6 c: PDA+1 PO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(43) In a 2 I autoclave 168.2 g 1,3-propane diamine+1 PO per mol of NH functionality+0.25 caprolactone per mol of NH functionality (example 6 b) and 1.8 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 743.4 g propylene oxide was added in portions within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 915.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 7

(44) N4 amine+1 PO per mol of NH functionality+0.33 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(45) (N4 amine+1 PO/NH+0.33 Caprolacton/NH+10.7 PO/NH)

(46) Example 7 a: N4 Amine+1 PO per mol of NH Functionality

(47) A 2 I autoclave was charged with 261.4 g N4 amine (N,N-bis(3-aminopropyl) ethylene diamine) and 13.0 g water. The reactor was purged three times with nitrogen and heated to 110 C. 522.7 g propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110 C. Volatile compounds were removed in vacuo at 90 C. A viscous light brown oil (784.0 g) was obtained. .sup.1H-NMR in CDCl.sub.3indicated complete conversion.

(48) Example 7 b: N4 Amine+1 PO per mol of NH Functionality+0.33 Caprolactone per mol of NH Functionality

(49) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 200.0 g N4 amine+1 PO per mol of NH functionality (example 7 a) were placed and heated to 50 C. 87.4 g caprolactone was added within 50 minutes. The reaction mixture was heated to 160 C. and was stirred for 5 hours at 160 C. 420 g of a brown viscous oil was obtained. .sup.1H-NMR in MeOD indicated 96% conversion of caprolactone.

(50) Example 7 c: N4 Amine+1 PO per mol of NH Functionality+0.33 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(51) In a 2 I autoclave 150.2 g N4 amine+1 PO per mol of NH functionality+0.33 caprolactone per mol of NH functionality (example 7 b) and 1.0 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 743.4 g propylene oxide was added in portions within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 900.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 8

(52) EDA+1 EO per mol of NH functionality+0.25 Caprolactone per mol of NH functionality+8 PO per mol of NH functionality.

(53) (EDA+1 EO/NH+0.25 Caprolacton/NH+8 PO/NH)

(54) Example 8 a: EDA+1 EO per mol of NH Functionality

(55) A 2 I autoclave was charged with 199.0 g ethylene diamine and 9.9 g water. The reactor was purged three times with nitrogen and heated to 110 C. 583.4 g ethylene oxide was added within 12 hours. To complete the reaction, the reaction mixture was allowed to post-react for 5 hours at 110 C. Volatile compounds were removed in vacuo at 90 C. A light viscous oil (780.0 g) was obtained. .sup.1H-NMR in CDCl.sub.3 indicated complete conversion.

(56) Example 8 b: EDA+1 EO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality

(57) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel and reflux cooler 141.8 g ethylene diamine+1 EO per mol of NH functionality (example 8 a) were placed and heated to 80 C. 68.4 g caprolactone were added in one portion at 80 C. The reaction mixture was heated to 160 C. and was stirred for 8 hours at 160 C. 210.0 g of a orange oil was obtained. 1H-NMR in MeOD indicated 99% conversion of caprolactone.

(58) Example 8 c: EDA+1 EO per mol of NH Functionality+0.25 Caprolactone per mol of NH Functionality+8 PO per mol of NH Functionality

(59) In a 2 I autoclave 106.9 g ethylene diamine+1 EO per mol of NH functionality+0.25 caprolactone per mol of NH functionality (example 8 b) and 1.4 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 567.4 g propylene oxide was added in portions within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 670.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 9

(60) HMDA+1 PO per mol of NH functionality+0.5 Caprolactone per mol of NH functionality+2 EO per mol of NH functionality+8 PO per mol of NH functionality.

(61) (HMDA+1 PO/NH+0.5 Caprolactone/NH+2 EO/NH+8 PO/OH)

(62) In a 2 I autoclave 151.0 g hexamethylene diamine+1 PO per mol of NH functionality+0.5 caprolactone per mol of NH functionality (example 2a) and 1.5 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 92.2 g ethylene oxide was added within 2 hours. The reaction mixture was stirred for 2 hours at 140 C., then 486.6 g propylene oxide was added within 10 hours. To complete the reaction, the mixture was allowed to post-react for additional 5 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds are removed in vacuo at 90 C. for 2 hours. 720.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

Example 10

(63) EDA+1 PO per mol of NH functionality+0.5 Caprolactone per mol of NH functionality+2 EOper mol NH functionality+8 PO per mol of NH functionality. ( )

(64) (EDA+1 PO/NH+0.5 Caprolactone/NH+2 EO/NH+8 PO/NH)

(65) Example 10 a: EDA+1 PO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality

(66) In a 3-neck reaction vessel with stirrer, thermometer, dropping funnel, and reflux cooler 251.4 g ethylene diamine+1 PO per mol of NH functionality (Quadrol L, purchased from BASF) and 0.45 g tin(II) 2-ethylhexanoate were placed and heated to 100 C. 196.3 g caprolactone was added within 5 minutes. The reaction mixture was heated to 160 C. and was stirred for 4 hours at 160 C. 377.0 g of an orange viscous oil was obtained. .sup.1H-NMR in MeOD indicated 97.5% conversion of caprolactone.

(67) Example 10 b: EDA+1 PO per mol of NH Functionality+0.5 Caprolactone per mol of NH Functionality+2 EO per mol NH Functionality+8 PO per mol of NH Functionality

(68) In a 2 I autoclave 156.2 g ethylene diamine+1 PO per mol of NH functionality+0.5 caprolactone per mol of NH functionality (example 10 a) and 1.6 g potassium tert. butoxide were placed and the mixture was heated to 140 C. The vessel was purged three times with nitrogen. 105.7 g ethylene oxide was added within 1.5 hours. The reaction mixture was stirred for 2 hours at 140 C., then 557.6 g propylene oxide was added within 12 hours. To complete the reaction, the mixture was allowed to post-react for additional 10 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 90 C. for 2 hours. 821.0 g of a light brown oil was obtained. Identity was confirmed by .sup.1H-NMR in CDCl.sub.3.

(69) The following comparative examples have been performed with the shown results obtained (also see Table 5), following the described procedures:

Comparative Example 1

(70) Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 20 mole ethylene oxide per mole of NH-functionality

(71) (PEI800+20 EO/NH), Synthesized as described in WO9532272

Comparative Example 1a

(72) Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 1 mole ethylene oxide per mole of NH-functionality

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

Comparative Example 1b

(74) Polyethylene imine, molecular weight 800 g/mole, ethoxylated with 20 mole ethylene oxide per mole of NH-functionality

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

Comparative Example 2

(76) HMDA+8 PO per mol of NH functionality

(77) (HMDA+8 PO/NH)

(78) In a 5 I autoclave 672.9 g hexamethylene diamine+1 PO per mol of NH functionality (prepared similar to example 1 a) and 16.0 g potassium hydroxide (50% in water) were placed. The vessel was purged three times with nitrogen and heated to 120 C. Vacuum was applied and the mixture was dewatered for 2 hours at 120 C. and <20 mbar. Vacuum was removed with nitrogen and temperature was increased to 140 C. 3089.9 g propylene oxide was added within 35 hours. To complete the reaction, the mixture was allowed to post-react for additional 10 hours at 140 C. The reaction mixture was stripped with nitrogen and volatile compounds are removed in vacuo at 90 C. for 2 hours. 3370.0 g of a light brown oil was obtained. Identity was confirmed by 1H-NMR in CDCl3.

(79) TABLE-US-00005 TABLE 5 Polymer amine/ example imine step a) step b) step c) step d) Polymer structure information 1 HMDA 1 PO 0.25 8 PO HMDA + 1 PO/NH + 0.25 Caprolactone Caprolacton/NH + 8 PO/NH 2 HMDA 1 PO 0.50 8 PO HMDA + 1 PO/NH + 0.5 Caprolactone Caprolacton/NH + 8 PO/NH 3 EDA 1 PO 0.25 8 PO EDA + 1 PO/NH + 0.25 Caprolactone Caprolacton/NH + 8 PO/NH 4 HMDA 1 EO 0.25 8 PO HMDA + 1 EO/NH + 0.25 Caprolactone Caprolacton/NH + 8 PO/NH 5 HMDA 1 EO 0.50 8 PO HMDA + 1 EO/NH + 0.5 Caprolactone Caprolacton/NH + 8 PO/NH 6 PDA 1 PO 0.25 8 PO PDA + 1 PO/NH + 0.25 Caprolactone Caprolacton/NH + 8 PO/NH 7 N4 amine 1 PO 0.33 10.7 PO N4 amine + 1 PO/NH + 0.33 Caprolactone Caprolacton/NH + 10.7 PO/NH 8 EDA 1 EO 0.25 8 PO EDA + 1 EO/NH + 0.25 Caprolactone Caprolacton/NH + 8 PO/NH 9 HMDA 1 PO 0.25 2 EO 8 PO HMDA + 1 PO/NH + 0.5 Caprolactone Caprolactone/NH + 2 EO/NH + 8 PO/OH 10 EDA 1 PO 0.5 2 EO 8 PO EDA + 1 PO/NH + 0.5 Caprolactone Caprolactone/NH + 2 EO/NH + 8 PO/NH Comp. PEI(800) 20 EO PEI800 + 20 EO/NH Ex 1 Comp. HMDA 8 PO HMDA + 8 PO/NH Ex 2 Comp. Ex. = Comparative Example

(80) In the following examples showing application and other test results of certain inventive polymers, whenever Polymer example(s) and a number is mentioned, it is meant that the final product, i.e. the alkoxylated polyamine resulting is employed.

(81) Polymer Biodegradability

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

(83) The biodegradation data of inventive polymers at 28 day of the OECD 301F test is summarized in Table 6.

(84) TABLE-US-00006 TABLE 6 Polymer biodegradability Bio- polymer Amine/ step Step step degradation example imine a) b) c) % (28 d) 1 HMDA 1 PO 0.25 Caprolactone 8 PO 59 3 EDA 1 PO 0.25 Caprolactone 8 PO 66 4 HMDA 1 EO 0.25 Caprolactone 8 PO 64 Comparative PEI800 20 EO <20 example 1 Comparative HMDA 8 PO 45 example 2
Polymer Anti-Redeposition Performance in Laundry Detergents

(85) The following liquid laundry detergent composition (Table 7) was used as base detergent to test polymer anti-redeposition performance. Polymer anti-redeposition performance were tested using the following conditions: 3000 ppm clay, 688 ppm base detergent/25 C./1 mM hardness/19.6 ppm polymer.

(86) TABLE-US-00007 TABLE 7 Liquid laundry base detergent for polymer anti-redeposition and cleaning test. Comp (% wt) Linear alkylbenzene sulfonate LAS 8.9 C.sub.10-C.sub.16 Alkyl Sulfate SLS 7.7 NI 7.8 Amine oxide 0.6 Inventive Polymer 1 Citric acid 1.8 Enzymes (combined) 0.079 Sodium tetraborate 1.5 Calcium/sodium formate 0.13 DTPA 0.5 Brightener 0.08 Ethanol 1.7 Propylene glycol 2.3 Monoethanolamine 2.65 DETA 0.05 Sodium cumene sulfonate (NaCS) 1.3 Aesthetic dye 0.01 Perfume 0.6 Antifoam 0.21 Hueing dye 0.026 Water & minors balance .sup.a Fluorescent Brightener is disodium 4,4-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2-stilbenedisulfonate or 2,2-([1,1-Biphenyl]-4,4-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt. .sup.b 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5] .sup.c Dow Corning supplied antifoam blend 80-92% ethylmethyl, methyl(2-phenyl propyl)siloxane; 5-14% MQ Resin in octyl stearate a 3-7% modified silica.
Test Preparation

(87) The following fabrics are provided for the whiteness benefit test: NA Polyester: PW19, available from Empirical Manufacturing Company (Cincinnati, OH, Knitted Cotton 1: Test fabrics, Inc 403 cotton interlock knit tubular CW120, available from Empirical Manufacturing Company (Cincinnati, OH, USA). Polycotton

(88) Washed and FE Treated fabrics were prepared according to the following method: 400 g fabrics are washed in a WE Miniwasher Electrolux EWC1350 (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.

(89) Washed fabrics were prepared according to the following method: 400 g fabrics are washed in a WE Miniwasher Electrolux EWC 1350 (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.

(90) Test Method

(91) Four fabric samples are prepared: Polycotton, washed; Knitted Cotton, washed; NA Polyester washed and FE treated, Knitted cotton washed and FE treated. 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: 750 ppm detergent concentration, 150 L water per well, 25 C., water hardness of 1.0 mM (2:1 Ca+2:Mg+2 molar ratio), wash pH of 8.3, 3000 ppm Arizona test dust (supplied by PTI, Powder Technology Inc).

(92) 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 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.

(93) For the whiteness index, the CIE whiteness index formula was used and delta WI was calculated as follows: delta WI on a substrate=WI technologyWI nil.

(94) The results are shown in Table 8, inventive polymers can deliver clear anti-redeposition performance.

(95) TABLE-US-00008 TABLE 8 Polymer anti-redeposition performance Delta CIE WI vs nil polymer NA Polyester cotton Polymer Add. Polycotton washed and washed and cotton Example ppm washed FE treated FE treated washed Average Nil polymer ref ref ref ref ref 1 19.6 7.7 5.1 9.0 5.6 6.9 2 19.6 7.9 6.3 10.5 7.0 7.9 3 19.6 7.2 6.2 11.6 6.1 7.8 4 19.6 10.0 6.7 11.0 7.9 8.9 5 19.6 6.4 5.8 9.6 6.5 7.1 6 19.6 6.8 5.2 9.6 5.4 6.8 7 19.6 10.3 5.6 12.3 6.7 8.7
Polymer Cleaning Performance in Laundry Detergent

(96) Polymer cleaning performance in laundry detergent were carried out with the formulation stated Table 7 and the washing conditions for single wash cycle performance may be summarized as follows: Machine: Launder-o-meter Washing liquor 500 mL Washing time 30 minutes Washing temperature 25 C. Detergent concentration 0.688 g/L Water hardness 1 mmol/L; (Ca:Mg):HCO3 (4:1):8 Ballast: white cotton fabric (Cotton interlock knit tubula from CFT) 721 cm

(97) Soiled fabrics: PC-S 94, WFK 20D, PC-S 132 from CFT

(98) After the one cycle, soiled fabrics were twice rinsed with water, followed by shortly spin-drying and drying at room temperature over a period of 12 hours.

(99) To evaluate the primary detergency of different stains, different soiled fabrics were determined before and after washing using soil removal index (SRI) formula from ASTM D4265. For obtaining the reflectance values for the respective fabric both before and after washing using a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273), an average of 6 different measuring points were taken each before and after washing. Higher delta reflectance values demonstrate a better primary detergency.

(100) ASTM D4265-14: Evaluation of Stain Removal Performance in Home Laundry Stain Removal Index=SRI SRI=100(((delta E*(before washunstained)delta E*(after washunstained)/delta E*(before washunstained))) delta E*=((delat L*).sup.2+(delta a*).sup.2+(delta b*).sup.2).sup.1/2

(101) Average delta SRI=(sum delta SRI all stains)/number of stains

(102) The cleaning performance of inventive polymers is summarized in Table 9. Inventive polymers can deliver clear improvement on stain removal, especially on stains that contain sebum (PCS94, WFK 20D and PCS132).

(103) TABLE-US-00009 TABLE 9 Polymer cleaning performance. Polymer Example used as Additive Delta SRI Average additive ppm PCS 94 WFK20D PCS132 delta SRI 1 19.6 7.0 6.3 4.0 5.8 2 19.6 5.1 3.6 4.9 4.5 3 19.6 6.1 7.7 2.3 5.3 4 19.6 7.3 6.3 5.9 6.5 5 19.6 6.0 5.6 4.6 5.4 6 19.6 6.9 6.7 4.3 6.0 7 19.6 6.2 7.2 3.6 5.7
Polymer Whiteness Performance

(104) Whiteness maintenance, also referred to as whiteness preservation, is the ability of a detergent to keep white items from whiteness loss when they are washed in the presence of soils. White garments can become dirty/dingy looking over time when soils are removed from dirty clothes and suspended in the wash water, then these soils can re-deposit onto clothing, making the clothing less white each time they are washed.

(105) The whiteness benefit of polymers of the present disclosure is evaluated using automatic Tergotometer with 10 pots for laundry formulation testing.

(106) SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used to simulate consumer soil levels (mix of body soil, food, dirt etc.). On average, every 1 SBL2004 strip is loaded with 8 g soil. The SBL2004 test soil strips were cut into 55 cm squares for use in the test.

(107) Additionally Black Todd clay is used to stress the system further. The clay is added at 0.25 g per 1 L wash solution. The soil is supplied by Warwick Equest Ltd.

(108) White Fabric swatches of Table 10 below purchased from WFK Testgewebe GmbH are used as whiteness tracers.

(109) TABLE-US-00010 TABLE 10 % Fiber Fabric Code Fiber Content Content Construction Size WFK Code CK Cotton 100 Weft Knit (5 5 cm) 19502_5 5_stamped PC Polyester/cotton 65/35 Weave (5 5 cm) 19503_5 5_stamped PE Polyester 100 Weft Knit (5 5 cm) 19508_5 5_stamped PS Polyester/Spandex 95/5 Weft Knit (5 5 cm) 19507_5 5_stamped

(110) Additional ballast (background fabric swatches) is also used to simulate a fabric load and provide mechanical energy during the real laundry process. Ballast loads are comprised of cotton and polycotton knit swatches at 55 cm size.

(111) 4 cycles of wash are needed to complete the test: Cycle 1: Desired amount of detergent is fully dissolved by mixing with 1 L water (at defined hardness) in each tergotometer port. Also, at this point 0.25 g of Black Todd clay is added. 60 grams of fabrics, including whiteness tracers (4 types, each with 4 replicates), 10 pieces 55 cm SBL2004 and ballast are washed and rinsed in the tergotometer pot under defined conditions.

(112) In the test of water-soluble unit dose composition, wash concentration is 2000 ppm. The wash temperature is 30 C., water hardness is 7 gpg. Cycle 2: The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (55 cm, 10 pieces) follow the process of cycle 1. All other conditions remain same as cycle 1. Cycle 3: The whiteness tracers and ballast from each pot are then washed and rinsed again together with a new set of SBL2004 (55 cm, 10 pieces) follow the process of cycle 1. All other conditions remain same as cycle 1. Cycle 4: The whiteness tracers and ballast from each port are then washed and rinsed again together with a new set of SBL2004 (55 cm, 10 pieces) follow the process of cycle 1. All other conditions remain same as cycle 1.

(113) After Cycle 4, all whiteness tracers & ballast are flat dried until dry, the tracers are then measured using Konica Minolta CM-3610D spectrophotometer. The Whiteness Index (WI(CIE)) is part of the Konica Minolta report.

(114) Liquid detergent composition E and F below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients (Table 11).

(115) The whiteness maintenance of the inventive and comparative polymers is evaluated according to the method for evaluating whiteness performance of polymers by directly comparing the whiteness performance of reference composition E and test composition F. WI(CIE) of composition F vs composition E is reported in bottom Table 11 as an indication of polymer whiteness performance benefit. Inventive polymer can deliver strong whiteness benefit.

(116) TABLE-US-00011 TABLE 11 Comp. E Comp. F % wt % wt Linear alkylbenzene sulfonate LAS 8.9 8.9 C.sub.10-C.sub.16 Alkyl Sulfate SLS 7.7 7.7 NI 7.8 7.8 Amine oxide 0.6 0.6 Inventive Polymer 0 2.86 Citric acid 1.8 1.8 Enzymes (combined) 0.079 0.079 Sodium tetraborate 1.5 1.5 Calcium/sodium formate 0.13 0.13 DTPA 0.5 0.5 Brightener 0.08 0.08 Ethanol 1.7 1.7 Propylene glycol 2.3 2.3 Monoethanolamine 2.65 2.65 DETA 0.05 0.05 Sodium cumene sulfonate (NaCS) 1.3 1.3 Aesthetic dye 0.01 0.01 Perfume 0.6 0.6 Antifoam 0.21 0.21 Hueing dye 0.026 0.026 Water & minors balance balance

(117) TABLE-US-00012 TABLE 12 Whiteness maintenance performance of novel polymers and non-inventive polymer. WI(CIE) vs Reference WI(CIE) vs Reference Inventive Polymer (PC: 65:35 polycotton) (PE) 1 1.37 3.18 2 0.91 1.65 3 1.06 2.18 4 4.49 2.87 5 3.88 4.24
Polymer Suds Mileage Performance in Hand Dish Detergent

(118) Polymer suds mileage performance were evaluated using the following method for evaluating suds mileage of hand dish composition:

(119) The objective of the Suds Mileage Index test is to compare the evolution over time of suds volume generated for different test formulations at specified water hardness, solution temperatures and formulation concentrations, while under the influence of periodic soil injections. Data are compared and expressed versus a reference composition as a suds mileage index (reference composition has suds mileage index of 100). The steps of the method are as follows: 1) A defined amount of a test composition, depending on the targeted composition concentration (0.12 wt %), is dispensed through a plastic pipette at a flow rate of 0.67 mL/sec at a height of 37 cm above the bottom surface of a sink (dimension: 300 mm diameter and 288 mm height) into a water stream (water hardness: 2 gpg, water temperature:35 C.) that is filling up the sink to 4 L with a constant pressure of 4 bar. 2) An initial suds volume generated (measured as average foam height X sink surface area and expressed in cm.sup.3) is recorded immediately after end of filling. 3) A fixed amount (6 mL) of soil is immediately injected into the middle of the sink. 4) The resultant solution is mixed with a metal blade (10 cm5 cm) positioned in the middle of the sink at the air liquid interface under an angle of 45 degrees rotating at 85 RPM for 20 revolutions. 5) Another measurement of the total suds volume is recorded immediately after end of blade rotation. 6) Steps 3-5 are repeated until the measured total suds volume reaches a minimum level of 400 cm.sup.3. The amount of added soil that is needed to get to the 400 cm.sup.3 level is considered as the suds mileage for the test composition. 7) Each test composition is tested 4 times per testing condition (i.e., water temperature, composition concentration, water hardness, soil type). 8) The average suds mileage is calculated as the average of the 4 replicates for each sample. 9) Calculate a Suds Mileage Index by comparing the average mileage of a test composition sample versus a reference composition sample. The calculation is as follows:

(120) $\mathrm{Suds}\mathrm{Mileage}\mathrm{Index}=\frac{\mathrm{Average}\mathrm{number}\mathrm{of}\mathrm{soil}\mathrm{additioin}\mathrm{of}\mathrm{test}\mathrm{composition}}{\mathrm{Average}\mathrm{number}\mathrm{of}\mathrm{soil}\mathrm{addition}\mathrm{of}\mathrm{reference}\mathrm{composition}}100$

(121) Soil composition is produced through standard mixing of the components described in Table 13.

(122) TABLE-US-00013 TABLE 13 Greasy Soil Ingredient Weight % Crisco Oil 12.730 Crisco shortening 27.752 Lard 7.638 Refined Rendered Edible Beef Tallow 51.684 Oleic Acid, 90% (Techn) 0.139 Palmitic Acid, 99+% 0.036 Stearic Acid, 99+% 0.021
Polymer Performance in Hand Dish Detergent

(123) Hand dish detergent composition below are prepared by traditional means known to those of ordinary skill in the art by mixing the listed ingredients. The impact of inventive polymers on suds mileage are evaluated by comparing the suds mileage of formulation A (Reference) and B (Reference with inventive polymers) in Table 14. The suds mileage performance is evaluated using method for evaluating suds mileage of hand dish compositions described herein, and Suds Mileage Index is reported in Table 15.

(124) TABLE-US-00014 TABLE 14 B A (Test composition: (Reference Reference with composition) inventive polymers) Ingredient % by weight of the composition NaCl 0.9 0.9 Polypropylene glycol (mw 2000) 0.809 0.809 Ethanol 1.7 1.7 mixture of 2-methylcyclohexane- 0.23% 0.23% 1,3-diamine, 4-methylcyclohexane- 1,3-diamine Magnesium sulfate heptahydrate 0.04286 0.04286 C12-13 AE0.6S anionic surfactant 18.61 18.61 C12-14 dimethyl amine oxide 6.65 6.65 BIT 0.0045 0.0045 Phenoxyethanol 0.08 0.08 Perfume 0.195 0.195 Yellow Dye 0.004 0.004 Blue Dye 0.00165 0.00165 Inventive Polymer 0 2 Water Balance Balance NaOH trim to pH 9.0* trim to pH 9.0* *measured as a 10 w/w % product dilution in demineralized water at 22 C.

(125) As indicated in Table 15, inventive polymers can deliver clear suds mileage benefit.

(126) TABLE-US-00015 TABLE 15 Polymer performance in hand dish detergent Inventive Polymer Suds mileage index vs A (Ref) 1 110 4 120

(127) The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as 40 mm is intended to mean about 40 mm.

(128) Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

(129) While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.