NEW CATIONIC POLYMERS, PROCESS FOR PRODUCING THE SAME FROM MONOUREA DIAMINE CONDENSATES AND ETHER DERIVATIVES, AND USES THEREOF

Abstract

The present invention relates to new cationic polymers, a synthesis process for preparing them from monourea diamine condensates and bifunctional ether derivatives, notably dihalogeno ether derivatives, and to the use of said new cationic polymers for surface treatment applications including, but not limited to, home and personal care applications as well as industrial and institutional cleaning applications.

Claims

1. A polymer comprising the following repeating unit I: ##STR00011## wherein: R.sub.1 are each independently a hydrogen atom, a C.sub.1 to C.sub.4 alkyl or hydroxyalkyl group, or a C.sub.2 to C.sub.4 alkenyl group; R.sub.2 are each independently a C.sub.2 to C.sub.10 alkylene group; R.sub.3 are each independently a hydrogen atom, a C.sub.1 to C.sub.4 alkyl or hydroxyalkyl group, or a C.sub.2 to C.sub.4 alkenyl group; R.sub.4 represents an oxyalkylene group of formula A:
(CHR.sub.5CH.sub.2).sub.a-(OCH.sub.2CHR.sub.6).sub.b-(OCH.sub.2CHR.sub.7).sub.c-(OCH.sub.2CHR.sub.8).sub.d (A) wherein a represents 1; b represents an integer of 1 or more; c and d represent independently from one another an integer of 0 or more; and R.sub.5, R.sub.6, R.sub.7 and R.sub.8 represent independently from one another a hydrogen atom or a C.sub.1 to C.sub.4 alkyl group; Y represents an oxygen atom, NR.sub.9- or N.sup.+R.sub.10R.sub.11- wherein R.sub.9 represents a hydrogen atom or a radical deriving from any electrophilic compound present in the reaction mixture during the synthesis process of the polymer and that reacted by alkylation reaction with a secondary amine (Y=NH) present on the polymer during its synthesis; and R.sub.10 and R.sub.11 represent radicals deriving from any electrophilic compounds present in the reaction mixture during the synthesis process of the polymer and that are reacted by successive alkylation reactions with a secondary amine (Y=NH) and then a tertiary amine (e.g. Y=NR.sub.10-) present on the polymer during its synthesis; Z represents a positive integer from 2 to 4; n represents a positive integer from 1 to 50 m represents a positive integer from 1 to 3; and X represents an electrophilic group.

2. The polymer according to claim 1, wherein in formula I: R.sub.1 are C.sub.1 alkyl groups; R.sub.2 are C.sub.2 or C.sub.3 alkylene group; R.sub.3 are hydrogen atoms.

3. The polymer according to claim 1, wherein in formula I: R.sub.4 represents an oxyalkylene group of formula A:
(CHR.sub.5CH.sub.2).sub.a-(OCH.sub.2CHR.sub.6).sub.b-(OCH.sub.2CHR.sub.7).sub.c-(OCH.sub.2CHR.sub.8).sub.d (A) wherein a represents 1; b represents an integer of 1 or more; c and d represent independently from one another an integer of 0 or more; and R.sub.5 is methyl or hydrogen, R.sub.6 is hydrogen, R.sub.7 is hydrogen or methyl and R.sub.8 is methyl group; and Y represents an oxygen atom.

4. The polymer according to claim 1, wherein in formula I: n represents a positive integer from 1 to 50; m is 1 and X is Cl.

5. The polymer according to claim 1, having a weight average molecular weight ranging from 1 to 100 kg/mol.

6. The polymer according to claim 1, having a cationic charge density ranging from 0.1 to 4.25 mmol/g.

7. A [[P]] process for preparing a polymer according to claim 1, comprising a step (i) of reacting a compound of formula II: ##STR00012## wherein R.sub.1 are each independently a hydrogen atom, a C.sub.1 to C.sub.4 alkyl or hydroxyalkyl group, or a C.sub.2 to C.sub.4 alkenyl group; R.sub.2 are each independently a C.sub.2 to C.sub.10 alkylene group; R.sub.3 are each independently a hydrogen atom, a C.sub.1 to C.sub.4 alkyl or hydroxyalkyl group, or a C.sub.2 to C.sub.4 alkenyl group; with a compound of formula III: ##STR00013## wherein R.sub.4 represents an oxyalkylene group of formula A:
(CHR.sub.5CH.sub.2).sub.a-(OCH.sub.2CHR.sub.6).sub.b-(OCH.sub.2CHR.sub.7).sub.c-(OCH.sub.2CHR.sub.8).sub.d (A) wherein a represents 1; b represents an integer of 1 or more; c and d represent independently from one another an integer of 0 or more; and R.sub.5, R.sub.6, R.sub.7 and R.sub.8 represent independently from one another a hydrogen atom or a C.sub.1 to C.sub.4 alkyl group; Y represents an oxygen atom, NR.sub.9- or N.sup.+R.sub.10R.sub.11- wherein R.sub.9 represents a hydrogen atom or a radical deriving from any electrophilic compound present in the reaction mixture during the synthesis process of the polymer and that reacted by alkylation reaction with a secondary amine (Y=NH) present on the polymer during its synthesis; and R.sub.10 and Ru represent radicals deriving from any electrophilic compounds present in the reaction mixture during the synthesis process of the polymer and that reacted by successive alkylation reactions with a secondary amine (Y=NH) and then a tertiary amine (e.g. Y=NR.sub.10-) present on the polymer during its synthesis; and X represents an electrophilic group, preferably selected from halogens or sulfates.

8. The process according to claim 7, wherein the molar ratio between the compound of formula II and the compound of formula III is ranging from 0.75 to 1.25.

9. The process according to claim 7, wherein the compound of formula II is prepared by reaction of a diamine of formula IV: ##STR00014## with urea of formula V NH.sub.2CONH.sub.2 (V), in a molar ratio IV:V of at least 1.5 mol of the compound IV to 1 mol of compound V.

10. The process according to claim 7, wherein the compound of formula III is prepared by reaction of a bifunctional compound of formula VI:
HYR.sub.4YH (VI) with on oxirane containing compound of formula VII:
XCH.sub.2CH(CH.sub.2O) (VII), in presence of an acid catalyst and in a molar ratio VII:VI ranging from 1.8 to 2.1 of the molecule VII to 1 mol of molecule VI.

11. The process according to claim 7, wherein R.sub.4 represents an oxyalkylene group of formula A:
(CHR.sub.5CH.sub.2).sub.a-(OCH.sub.2CHR.sub.6).sub.b-(OCH.sub.2CHR.sub.7).sub.c-(OCH.sub.2CHR.sub.8).sub.d (A) wherein a represents 1; b represents an integer of 1 or more and preferably up to 70; c and d represent independently from one another an integer of 0 or more; and R.sub.5 is methyl or hydrogen, R.sub.6 is hydrogen, R.sub.7 is hydrogen or methyl and R.sub.8 is methyl group; and Y represents an oxygen atom.

12. A method comprising improving biodegradability for home and personal care applications with the polymer according to claim 1.

13. A method comprising improving biodegradability for industrial and institutional cleaning applications with the polymer according to claim 1.

14. A method comprising killing or inhibiting the growth of microorganisms with the polymer according to claim 1, in i. laundry compositions; ii. hard surface cleaning compositions; iii. dish wash cleaning compositions; or iv. hair care compositions.

15. A method comprising incorporating the polymer according to claim 1, as dye fixing agent or transfer inhibitor agent or soil anti-redeposition agent or soil release agent or laundry additives deposition agent in laundry compositions.

16. A method comprising incorporating the polymer according to claim 1, as soil anti-redeposition agent or soil release agent or shining agent in dish wash compositions.

17. A formulation comprising: the polymer as defined in claim 1; and an adjuvant selected from a surfactant and/or a thickening agent.

Description

EXAMPLES

A. Raw Materials

[0171] Table 1 below shows the reagents used in the examples and its abbreviations. All reagents used were purchased from Sigma Aldrich.

TABLE-US-00001 TABLE 1 Raw materials used in the experimental part. Product Abbreviation CAS Urea 57-13-6 Dimethylaminopropylamine DMAPA 109-55-7 Polyethylene glycol of Mn around PEG 200, 600, 1500 25322-68-3 200 and 600, and 1500 g/mol Jeffamine ED-600, ED-900, D-400 JFA ED-600, ED-900, 83713-18-5 D-400 Bis(chloroethyl) ether DCE1 111-44-4 Epichlorohydrin EPI 106-89-8 Triflic acid TA 1493-13-6 Polyquaternium-2 polymer PQ-2 68555-36-5

B. Di-Chloro Compounds Synthesis

Di-Chloro Compounds from PEG and EPI

##STR00009##

[0172] All di-chloro compounds were synthetized according to the same process. The whole synthesis is conducted in a reactor equipped with temperature control heating system, a lid containing multiple entries with installed a reflux system, a mechanical stirring system, a nitrogen purge line and a raw materials feed line. To ensure a total conversion of the reagents at reasonable times the TA catalyst was used

[0173] Adequate PEG was weighed and transferred to the purged with nitrogen reactor. The catalyst was then added to the reactor in a one shot manner. The reaction mixture was heated to 40 C. (or to 50 C. in case of the PEG1500) and stirred for 12 hours. During the first two hours of the heating the epichlorohydrine was added semi-continuously using a syringe type pump. The temperature was controlled by cryothermostat type bath.

[0174] The reaction completion was followed with 13C NMR analyses which indicated that the EPI and PEG were converted into target di-chloro compounds.

[0175] The quantities of the reagents used for the particular examples are provided in Table 2 below and the conversion results of the reaction is provided in Table 3 below.

TABLE-US-00002 TABLE 2 Reagents quantities used for PEG and EPI based di-chloro compounds synthesis. Catalyst Reagent 1 Reagent 2 (Triflic acid, TA) Example Type grams Type grams grams Example 1 PEG 200 67.3 EPI 62.2 0.50 Example 2 PEG 1500 115.6 EPI 14.3 0.15 Example 3 PEG 600 98.5 EPI 30.5 0.50

TABLE-US-00003 TABLE 3 Conversion results for the PEG/EPI di-chloro compounds synthesis. Conversion of Example Catalyst T C. EPI (.sup.1H NMR) Comment Example 1 Triflic 40 100% Desired product obtained, acid reaction mixture transparent and nearly colorless Example 2 Triflic 50 100% Desired product obtained, acid 50 C. due to solid form of PEG1500 at 40 C.; reaction mixture transparent and nearly colorless Example 3 Triflic 40 100% Desired product obtained, acid reaction mixture transparent and nearly colorless Conclusion: a total conversion of the EPI was obtained.
Di-Chloro Compounds from JFA and EPI

##STR00010##

[0176] All di-chloro compounds were synthetized according to the same process. The whole synthesis is conducted in a reactor equipped with temperature control heating system, a lid containing multiple entries with installed a reflux system, a mechanical stirring system, a nitrogen purge line and a raw materials feed line. None catalyst addition was needed to convert the EPI and Jeffamine into desired di-chloro compounds.

[0177] Adequate JFA was weighed and transferred to the purged with nitrogen reactor. The reaction mixture was heated to 40 C. and stirred for 6 hours. During the first two hours of the heating the epichlorohydrine was added semi-continuously using a syringe type pump. The exothermic effect was controlled by cryothermostat type bath.

[0178] The reaction completion was followed with 13C NMR analyses. The EPI and JFA were converted into target di-chloro compounds. The branching alkylation reaction of the resulted secondary amine with the chloro compounds present in the reaction mixture was also stated with 13C NMR analyses. The branching reaction continued during product storage up to very viscous product of gel-like form after few weeks of storage at room temperature.

[0179] The quantities of the reagents used for the particular examples are provided in the Table 4 below and the conversion results of the reaction is provided in Table 5 below.

TABLE-US-00004 TABLE 4 Reagents quantities used for JFA and EPI based di-chloro compounds synthesis. Reagent 1 Reagent 2 Example Type grams Type grams Example 4 JFA ED600 99.4 EPI 30.6 Example 5 JFA ED900 107.8 EPI 22.2 Example 6 JFA D400 90.9 EPI 39.1

TABLE-US-00005 TABLE 5 Conversion results for the Jeffamine/EPI di-chloro compounds synthesis. Conversion of EPI Example T C. (.sup.1H NMR) Jeffamine Comment Example 4 40 100% ED-600 Desired product obtained, branching visible on NMR spectra; reaction mixture transparent and yellowish Example 5 40 100% ED-900 Desired product obtained, branching visible on NMR spectra; reaction mixture transparent and yellowish Example 6 40 100% D-400 Desired product obtained, branching visible on NMR spectra; reaction mixture transparent and yellowish Conclusion: a total conversion of the EPI was obtained.

C. Mono Urea Di-Amine Compounds Synthesis

[0180] The Mono urea di-amine compounds were synthetized according to the same process. The whole synthesis is conducted in a reactor equipped with temperature control heating system, a lid containing multiple entries with installed a reflux system prolonged with the ammonia recovery line, a mechanical stirring system, a nitrogen purge line and a raw materials feed line. The ammonia recovery line is composed of two flasks where ammonia is trapped thanks to purging through the water. The water quantity applied corresponds to 10% wt. of ammonia concentration based on total consumption of the urea during the reaction. Another, empty recovery flask was placed between a reflux column at the outlet of the reactor and the water flask to collect eventual amine condensates carried away with ammonia gas.

[0181] To synthetize the mono urea di-amine compound the primary/tertiary amine used is DMAPA.

[0182] The molar ratios of the reagents are provided in Table 6 below and the quantities of the reagents are provided in Table 7 below.

[0183] The applied ratio of urea to amine compounds was equal to one. This ratio concerns the reacting functionalities of the urea with particular amines compounds. Thus, the molar ratio between urea and DMAPA noted respectively as x:z was kept to respect the equation x=z/2.

TABLE-US-00006 TABLE 6 Molar ratio of reagents used for mono urea di-amine compounds synthesis Mono urea di- Urea DMAPA amine compound x z Example 7 1 2

TABLE-US-00007 TABLE 7 Reagents quantities used for mono urea di-amine compounds synthesis Mono urea and polyurea di-amine compound Urea, grams DMAPA, grams Example 7 25.25 85.6

[0184] The general synthesis protocol of the mono urea di-amine compounds was as following:

[0185] A stream of nitrogen was introduced into the reactor to prevent the oxidation of the reaction mixture and its discoloration. The appropriate weighted quantities of the Urea and primary/tertiary amine are introduced into the reactor.

[0186] Stirring and heating are maintained for around 11 hours. The reaction is done at 2 temperatures, at the begging during first 7 hours the temperature is maintained at around 120 C., than during next 4 hours at around 145 C.-150 C. During all heating time the ammonia purge is observed at trapping water flasks.

[0187] After 11 hours of the reaction at atmospheric pressure, the assembly is placed under vacuum at around 450 mmHg at 145-150 C. for 2 hours to recover the remaining in the reactor ammonia and not reacted di-amine raw materials. The vacuum is then broken and the assembly is cooled to ambient temperature. The obtained product had a liquid form at room temperature.

[0188] Finally, the contents of the ammonia trapping flasks, of the di-amine recovery flask and of the reactor are collected separately in order to be analyzed.

[0189] The reaction yield, which is provided in Table 8 below, was calculated from water ammonia solutions amine number titration data (solutions recovered from ammonia trapping flasks). The Amine number (AN) titration is done by diluting of 0.2 to 0.3 gram of sample in 50 mL of acetic acid and titrating it against 0.1 M perchloric acid. The number of moles of perchloric acid needed to achieve the equivalency point corresponds to number of moles of the ammonia in the test sample. To calculate the reaction yield, the titrated formed during reaction ammonia is compared to overall theoretical ammonia quantity possible to be formed from applied for reaction urea quantity.

TABLE-US-00008 TABLE 8 Reaction yield data and product appearance for particular synthesis examples. Formed NH.sub.3, Reaction Product Mono urea di- grams - based on yield based form at amine titration on NH.sub.3 room compound analysis titration data, % temperature Example 7 13.7 96% Yellowish viscous liquid

[0190] The Equivalent Molecular Weight (EMW) of the obtained mono urea compound was calculated from Amine number titration data of the final reaction mixture according to equation 1.

EMW=56100 (mg KOH/mol)/AN1 (mg KOH/g). (1)

[0191] The Amine number (AN1) titration is done as above described. The number of moles of perchloric acid needed to achieve the equivalency point corresponds to number of moles of the amine functionalities in the test sample. The Amine number is expressed in mg KOH/g of sample. Table 9 regroups the obtained data for the example 7.

TABLE-US-00009 TABLE 9 Amine number (AN1) and Equivalent Molecular Weight (EMW) data obtained. Example AN1 (mg KOH/g) EMW (g/mol) Example 7 490.4 114.4

D. Cationic Polymers Synthesis

[0192] All cationic polymers based on di-chloro compounds were synthetized according to the same process. The whole synthesis is conducted in a reactor equipped with temperature control heating system, a lid containing multiple entries with installed a reflux system, a mechanical stirring system, a nitrogen purge line and a raw materials feed line.

[0193] A stream of nitrogen was introduced into the reactor to prevent the oxidation of the reaction mixture and its discoloration.

[0194] The weighted then diluted with water to about 35%-50% concentration mono urea di-amine compound was placed into the reactor. Adequate chlorinated alkylating agent (di-chloro compound) was weighted and transferred to syringe type feeding pump. The initial reactor content was heated to 100 C. and reaction mixture was stirred during all the synthesis process. During the first 4 hours of the heating the chlorinated alkylating agent was added semi-continuously using a syringe type pump. The exothermic effect was controlled by cryothermostat type bath. After 8 hours of heating at 100 C. the reaction mixture was cooled down to room temperature and the product was analyzed by .sup.1H NMR and .sup.13C NMR to determine residual di-chloro compounds residual mono urea compounds, as well as Solid Content, pH, Brookfield viscosity and amine number (AN1).

[0195] For comparison aspects the Polyquaternium-2 (PQ-2) polymer can be obtained from Aldrich being the cationic polymer of the Monourea di-amine compound with DCE1 di-halogen alkylating agent.

[0196] The molar ratio of the reagents and quantities of the reagents (calculations according to EMW which takes into account the number of reactive groups in the particular reagent) used for the particular cationic polymers synthesis examples based on mono urea di-amine compounds with various di-chloro compounds are provided in Tables 10 and 11 respectively below. The obtained products analysis characteristics are provided in Table 12 below.

TABLE-US-00010 TABLE 10 Molar ratio of the reagents used for cationic polymers synthesis based on mono urea di-amine with various di-chloro compounds and the corresponding theoretical cationic charge densities of the cationic polymers. Reagent 1 Reagent 2 Cationic charge Cationic polymer Type Mol ratio Type Mol ratio density, mmol/g Comparative Mono urea di- 1 DCE1 1 5.4 Example 11 amine (Polyquaternium-2) Example 12 Mono urea di- 1 DCE1 and 0.5 2.9 amine Example 4 0.5 (Example 7) JFA ED600/EPI Example 13 Mono urea di- 1 Example 4 1 2.0 amine JFA ED600/EPI (Example 7) Example 14 Mono urea di- 1 Example 5 1 1.5 amine JFA ED900/EPI (Example 7) Example 15 Mono urea di- 1 Example 6 1.2 2.15 amine JFA D400/EPI (Example 7) Example 16 Mono urea di- 1 Example 1 1 3.25 amine PEG200/EPI (Example 7) Example 17 Mono urea di- 1 Example 3 1 2.9 amine PEG600/EPI (Example 7) Example 18 Mono urea di- 1 Example 2 1 1.0 amine PEG1500/EPI (Example 7)

TABLE-US-00011 TABLE 11 Quantities of the reagents used for cationic polymers synthesis based on mono urea di-amine with various di-chloro compounds. Water, Cationic polymer Reagent 1, grams Reagent 2, grams grams Comparative Mono urea di-amine DCE1 = 22.25 38.5 Example 11 (Example 7) = 35.8 (PQ-2) Example 12 Mono urea di-amine DEC1 = 30.4 200 (Example 7) = 98.9 JFA ED600/EPI Example 4 = 170.6 Example 13 Mono urea di-amine JFA ED600/EPI Example 4 = 40.0 (Example 7) = 13.7 46.3 Example 14 Mono urea di-amine JFA ED900/EPI Example 5 = 40.0 (Example 7) = 9.36 50.6 Example 15 Mono urea di-amine JFA D400/EPI Example 6 = 40.0 (Example 7) = 14.4 53.4 Example 16 Mono urea di-amine PEG200/EPI Example 1 = 40.0 (Example 7) = 21.95 36.35 Example 17 Mono urea di-amine PEG600/EPI Example 3 = 40.0 (Example 7) = 13.8 46.2 Example 18 Mono urea di-amine PEG1500/EPI 40.0 (Example 7) = 7.3 Example 2 = 52.7

TABLE-US-00012 TABLE 12 Characteristics of the final cationic polymers based on mono urea di-amine with various di-chloro compounds. Residual Solid Residual di- Mono urea Amine Content, % Viscosity chloro di-amine Number (Gravimetric, cP compound compound AN, 1 gram, 20 C., pH Cationic (GC or .sup.13C (.sup.1H NMR or mgKOH/g 1 hour, 30 rpm, (solution polymer NMR) HPLC) (titration) 115 C.) RV#3 as is) Comparative 62 8.2 Example 11 (PQ-2) Example 12 0.04%.sup. 0.7% 56.6 67.0 3700 9.3 Example 13 <1% 2.3% 74.5 59.6 380 9.3 Example 14 <1% <1% 47.5 60.3 490 8.7 Example 15 <1% 2.2% 87.4 66.4 4300 8.7 Example 16 <1% 0.6% 17.2 60.1 200 10.0 Example 17 <1% 0.3% 2.0 56.8 720 8.4 Example 18 <1% 1.3% 11.9 58.7 220 9.8

[0197] The obtained products measured molecular weight analysis results are provided in Table 13 below.

TABLE-US-00013 TABLE 13 Measured molecular weight data for the final cationic polymers based on mono urea di-amine with various di-chloro compounds. Cationic Mn, Mw Polydispersity polymer g/mol g/mol index (Ip) Comparative Example 11 4.0 8.0 2.0 (PQ-2) Example 12 Example 13 3.1 12.0 3.9 Example 14 2.7 14.2 5.3 Example 15 Example 16 1.4 2.7 1.9 Example 17 Example 18

E. Soil Release Performance Test in Laundry Composition.

[0198] The soil release performance was evaluated using dirty motor oil. The polymers comprising the repeating unit of formula I were formulated in concentrated liquid detergent compositions given in Table 14.

TABLE-US-00014 TABLE 14 Concentrated liquid detergent compositions. Comp Comp Example 19 Example 20 Example 21 Example 22 Example 23 Concentrated liquid Part by Part by Part by Part by Part by laundry composition weight weight weight weight weight Linear alkyl benzene 10.0 10.0 10.0 10.0 10.0 sulphonate, sodium salt Ethoxylated fatty 10.0 10.0 10.0 10.0 10.0 alcohol C.sub.12-18 (7 EO units) Sodium fatty acid soap 5.5 5.5 5.5 5.5 5.5 (C.sub.10-18) Sodium laureth 5.0 5.0 5.0 5.0 5.0 sulphate (2 EO units) Propylene glycol 6.5 6.5 6.5 6.5 6.5 Comparative 1.0 example 11 Example 12 1.0 Example 14 1.0 Example 17 1.0 Water To 100 To 100 To 100 To 100 To 100

[0199] The soil release performance is carried out on the following test fabrics: [0200] Test fabric 1: 100% polyester, Style #777 from Testfabrics [0201] Test fabric 2: 50%/50% polyester-cotton blend, Style #7422 from Testfabrics [0202] Test fabric 3: 100% polyester, W-30A from WFK [0203] Test fabric 4: 65%/35% polyester-cotton blend, W-20A from WFK. [0204] Test fabric 5: 100% Cotton from, W-10A from WFK. [0205] Test fabric 6: 100% Bleached Cotton, Interlock Knit, T-460 from Testfabrics

Prewashing:

[0206] The test fabrics were cut into squares 7 cm7 cm in size in three replicates and were prewashed in a Tergotometer for 20 minutes at 40 C. with the laundry detergent compositions shown in Table 14. The water employed had a hardness of 25 FH (with Ca:Mg molar ratio=2.4:1) and the quantity of the laundry detergent compositions used was 2.5 grams per liter of water. The Tergotometer speed was set at 120 oscillations per minute.

[0207] The test fabric squares were then rinsed 3 times for 5 minutes with cold water (20 C.) and then dried.

Soiling:

[0208] After the test fabric squares were completely dried, they were soiled using three drops of dirty motor oil (DMO) added from a 3 ml disposable pipette. The soiled test fabric squares were left overnight before washing. To allow good reproducibility of the results the soiled test fabrics squares were washed within 24 hours.

[0209] Washing:

[0210] The washing was performed in the same conditions as the prewashing in a Tergotometer for 20 minutes at 40 C. with the laundry detergent compositions shown in Table 14. The water employed had a hardness of 25 FH (with Ca:Mg molar ratio=2.4:1) and the quantity of the laundry detergent compositions used was 2.5 grams per liter of water. The Tergotometer speed was set at 120 oscillations per minute.

[0211] The test fabric squares were then rinsed 3 times for 5 minutes with cold water (20 C.) and then dried.

Evaluation:

[0212] The test fabric squares before soiling (referred to as white), after soiling (referred to as soil) and after washing (referred to as wash) were analyzed with the ColorQuest XE reflectance colorimeter from HunterLab to measure their CIEALAB color space (L*, a*, b*).

[0213] The soil release performance of the laundry detergent compositions with the polymers comprising the repeating unit of formula I according to the present invention and of the laundry detergent composition without polymer is assessed based on the following formula:

[00001]$\mathrm{Soil}\mathrm{Removal}\mathrm{in}\%=\frac{\sqrt{L^2+a^2+b^2}}{\sqrt{L^2+a^2+b^2}}$$\mathrm{Where}:$$L=L^{*}\left(\mathrm{wash}\right)-L^{*}\left(\mathrm{stain}\right)$$a=a^{*}\left(\mathrm{wash}\right)-a^{*}\left(\mathrm{stain}\right)$$b=b^{*}\left(\mathrm{wash}\right)-b^{*}\left(\mathrm{stain}\right)$$L^{}=L^{*}\left(\mathrm{white}\right)-L^{*}\left(\mathrm{stain}\right)$$a^{}=a^{*}\left(\mathrm{white}\right)-a^{*}\left(\mathrm{stain}\right)$$b^{}=b^{*}\left(\mathrm{white}\right)-b^{*}\left(\mathrm{stain}\right)$

[0214] The effectiveness of the soil release performance of the laundry detergent compositions with the polymers comprising the repeating unit of formula I according to the present invention is compared to the laundry detergent composition without polymer based on the following formula:

Soil Removal With Polymer in %-Soil Removal Without Polymer in %

[0215] The effectiveness of the soil release performance of the laundry detergent compositions with the polymers comprising the repeating unit of formula I is given in Table 15 below.

TABLE-US-00015 TABLE 15 The effectiveness of the soil release performance of the laundry detergent compositions with the polymers comprising the repeating unit of formula I Liquid Laundry Composition/ Comp Comp Example Example Example Test fabrics Example 19 Example 20 21 22 23 Test fabric 1 0.2 2.47 7.37 2.9 Test fabric 2 4.1 4.85 12.51 7.78 Test fabric 3 0.65 2.95 4.38 3.38 Test fabric 4 0.88 2.33 5.82 5.12 Test fabric 5 1.87 0.99 0.54 2.34 Test fabric 6 4.01 0.79 0.21 2.36 Total 9.55 14.38 30.83 23.88

[0216] As shown by the results in Table 15, the presence of the polymers comprising the repeating unit of formula I of the present invention in the laundry detergent compositions improves the soil releasing performance across different type of test fabrics.

F. Example 24Antimicrobial Performance

[0217] Standard cotton fabric W-10A from WFK was treated with a 65 ppm of aqueous solution of Example 16 prepared by diluting the polymer of Example 16 in Singapore tap water which has maximum water hardness of 150 ppm.

[0218] The treatment of the test fabric was done using LaunderOmeter (SDLATLAS). The volume of the 65 ppm aqueous solution of Example 16 is 500 ml. The fabric to treatment liquor ratio (wt/wt) is 1 to 10. The treatment was done at temperature of 40 degree centigrade for 30 minutes. Fifty pieces of steel balls was added to the LaunderOmeter pot. After the treatment, the fabrics were rinse twice with Singapore tab water for 1 minute each. Finally, the fabrics were line-dried at temperature 22 degree centigrade with humidity of 60%.

[0219] The treated and dried fabrics were cut into square swatches with size of 3.83.8+0.1 cm. The number of swatches needed for the test is equal to 1.0+0.1 gram. Bacteria strain Klebsiella pneumonia (ATCC 4352) was used for the test. The detail test was done according to the protocol AATCC TM 100-2019 which is available online via https://members.aatcc.org/store/tm100/513/.

[0220] The test results were shown in the Table 16 below.

TABLE-US-00016 TABLE 16 Count of test microorganism recovered from the inoculated fabric. Untreated Fabric treated with cotton fabric Polymer example 16 Bacteria count at 0 hours, 270000 230000 CFU Bacteria count at 24 hours, 32000000 37000 CFU

[0221] The bacteria inoculated on the untreated cotton fabric grew from 270000 CFU to 32000000 CFU over 24 hours incubation whereas the bacteria inoculated on the cotton fabric treated with Polymer of example 16 reduced from 230000 CFU to 37000 CFU which showed that the Polymer of example 16 is capable of inhibiting the growth of the test bacteria.