COMPOSITIONS COMPRISING POLYMERS, POLYMERS, AND THEIR USE

Abstract

Described herein is a composition including (A) at least one polymer comprising including (a) a backbone that bears one to forty -aminoalcohol groups or -amino-(alkylenoxide) groups, (b) where some -aminoalcohol groups or -amino-(alkylenoxide) groups are esterified with a mono- or diacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, or with the monomethyl ether of a monoacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, and, optionally, (c) of which some -aminoalcohol groups or -amino-(alkylenoxide) groups are esterified with aliphatic C.sub.4-C.sub.10-di- or tricarboxylic acid.

Claims

1. A composition comprising (A) at least one polymer comprising (a) at least one backbone that bears one to forty -aminoalcohol groups or -amino-(alkylenoxide) groups, (b) wherein some -aminoalcohol groups or -amino-(alkylenoxide) groups are esterified with a mono- or diacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, or with the monomethyl ether of a monoacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, and, optionally, (c) wherein some -aminoalcohol groups or -amino-(alkylenoxide) groups are esterified with aliphatic C.sub.4-C.sub.10-di- or tricarboxylic acid.

2. The composition according to claim 1 wherein said -aminoalcohol groups are selected from the group consisting of NCH.sub.2CH.sub.2OH-groups, N(CH.sub.2CH.sub.2O).sub.2H-groups, NCH.sub.2CH(CH.sub.3)OH-groups, N(CH.sub.2CH(CH.sub.3)O).sub.2H-groups, and combinations of at least two of the aforementioned.

3. The composition according to claim 1 wherein said aliphatic C.sub.4-C.sub.6-di- or tricarboxylic acid is selected from the group consisting of succinic acid, malonic acid, sebacic acid, adipic acid and citric acid.

4. The composition according to claim 1 wherein polymer (A) has an average molecular weight M.sub.n in the range of from 1,500 to 20,000 g/mol.

5. The composition according to claim 1 wherein the backbone of polymer (A) is selected from the group consisting of alkoxylated triethanolamine, alkoxylated N,N-bis-(3-aminopropyl)-ethylenediamine, alkoxylated polyethylenimine, alkoxylated N,N-bis(2-aminoethyl)-1,2-ethanediamine 1,1-bis(2-hydroxyethyl)-ethanolamine and alkoxylated compounds of methyldiaminocyclohexane, ##STR00009##

6. The composition according to claim 1 wherein said composition additionally comprises (B) at least one hydrolase.

7. The composition according to claim 6 wherein said hydrolyse (B) is a lipase (B) that is selected from the group consisting of triacylglycerol lipases (EC 3.1.1.3).

8. A method of using the composition according to claim 1, the method comprising using the composition for laundry care.

9. A polymer comprising as building blocks (a) at least one backbone that bears one to forty -aminoalcohol groups or -amino-(alkylenoxide) groups that are at least partially esterified with (b) mono- or diacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, or with the monomethyl ether of a monoacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, and, optionally, (c) with an aliphatic C.sub.4-C.sub.6-di- or tricarboxylic acid.

10. The polymer according to claim 9 having an average molecular weight Mn in the range of from 1,500 to 20,000 g/mol.

11. The polymer according to claim 9 wherein said -aminoalcohol groups are selected from the group consisting of NCH.sub.2CH.sub.2OH-groups, N(CH.sub.2CH.sub.2O).sub.2H-groups, NCH.sub.2CH(CH.sub.3)OH-groups, N(CH.sub.2CH(CH.sub.3)O).sub.2H-groups, and combinations of at least two of the aforementioned groups.

12. The polymer according to claim 9 wherein the backbone of polymer (A) is selected from the group consisting of alkoxylated triethanolamine, alkoxylated N,N-bis-(3-aminopropyl)-ethylenediamine, alkoxylated polyethylenimine, alkoxylated N,N-bis(2-aminoethyl)-1,2-ethanediamine 1,1-bis(2-hydroxyethyl)-ethanolamine and alkoxylated compounds of methyldiaminocyclohexane, ##STR00010##

13. A process for making polymers according to claim 9, comprising the steps of () providing a backbone molecule that bears one to forty -aminoalcohol groups or -amino-(alkylenoxide) groups, () reacting said backbone molecule with monoacid or diacid of polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, or with the monomethyl ether of a monoacid of a polyalkylene oxide of which at least 50 mol-% of the alkylene oxide groups are ethylene oxide groups, () and, optionally, with at least one dicarboxylic or tricarboxylic acid, or, in each case, with their respective anhydrides or C.sub.1-C.sub.4-alkylesters, in a molar ratio of carboxyl groups to hydroxyl groups in the range of from 0.9:1 to 1.1:1, thereby obtaining an ester.

14. The process according to claim 13 wherein, in step (), said backbone molecule is reacted with the di-C.sub.1-C.sub.2-alkyl ester of succinic acid, malonic acid or adipic acid and, optionally, with the triethyl ester of citric acid.

15. A method of improving the cleaning performance of a liquid detergent composition, comprising adding the polymer (A) according to claim 9 to a detergent composition that comprises at least one lipase and/or at least one protease.

16. A method of preserving a composition according to claim 1 against microbial contamination or microbial growth, the method comprising adding 2-phenoxyethanol to the composition.

17. A method of providing an antimicrobial effect on textiles, the method comprising treating the textiles with a composition according to claim 1, wherein the composition comprises 4,4-dichloro 2-hydroxydiphenyl ether.

Description

I. SYNTHESES OF INVENTIVE POLYMERS (A)

[0258] Synthesis data and analytical data of exemplified inventive polymers (A) are summarized in Table 3. Some exemplified syntheses are disclosed below.

I.1 Syntheses of Selected Backbone Molecules (a)

Step (.4)

[0259] A 3.5-liter steel autoclave was charged with 896 g methylcyclohexyldiamine (MCDA, 7 mol) as 4:1 mixture of 2,4-diamines and 2,6-diamines, and 450 g water and then heated to 100 C. Then, 250 g of ethylene oxide were dosed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 982 g of ethylene oxide (EO) were dosed into the autoclave within 6 hours, total amount of EO: 28 mol. The system was kept at 100 C. for further 6 hours. After hat, the mixture is removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 C. for two hours. 2.35 kg of backbone molecule (a.4) were obtained as a yellow viscous liquid.

Step (.5)

[0260] A 3.5-liter steel autoclave was charged with 1.28 kg methylcyclohexyldiamine (MCDA, 10 mol) as 4:1 mixture of 2,4-diamines and 2,6-diamines, and 340 g water and then heated to 100 C. Then, 240 g of propylene oxide were dosed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 880 g of PO were dosed into the autoclave within 6 hours, total amount of PO: 16 mol. The reaction mixture was kept at 100 C. for further 6 hours. After that, the mixture was removed from the autoclave and residual PO and water were stripped under reduced pressure (20 mbar) at 80 C. for two hours. 2.56 kg of backbone molecule (a.5) were obtained as a yellow viscous liquid.

Step (.6)

[0261] The protocol of step (.4) was followed but with addition of 475 g instead of 1.051 kg of PO. An amount of 1.95 kg of backbone (a.6) were obtained as a yellow viscous liquid.

I.2 Combined Steps () and ()

I.2.1 Synthesis of Inventive Polymer (A.6.1)Steps (.2) and (.2)

[0262] A 250-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with 136 g of backbone (a.6) (0.63 mol), citric acid (8.1 g, 4.22 mmol), sebacic acid (91 g, 0.45 mol). Methanesulfonic acid was added in accordance with Table 3. The reaction mixture was then heated to 160 C. (inside temperature). Water distilled off. Stirring at 160 C. was continued under nitrogen for 4.8 hours. Then, 58 g (b.1) was added and heating and water removal were continued for 1.5 hours. The resultant polymer (A.6.1) was collected as a solid material (276 g).

[0263] GPC in HFIP: M.sub.n 4800 g/mol, M.sub.w 21,500 g/mol

[0264] Acid number: 165 mg KOH/g

I.2.2 Synthesis of Inventive Polymer (A.6.8)Steps (.1) and (.1)

[0265] A 250-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with 150 g of backbone molecule (a.6) (0.69 mol) and succinic acid (64.9 g, 0.55 mol). Methanesulfonic acid was added in accordance with Table 3. The reaction mixture was then heated to 160 C. (inside temperature). Water was distilled off. Stirring at 160 C. was continued under nitrogen for 4.8 hours. Then, 63.2 g (b.8) was added and heating and water removal were continued for 1.5 hours. The resultant polymer (A.6.8) was collected as a solid material (358 g).

[0266] GPC in HFIP: M.sub.n 3116 g/mol, M.sub.w 17,600 g/mol

[0267] Acid number: 116 mg KOH/g

I.2.3 Synthesis of Inventive Polymer (A.17.8)Steps (.3) and (.3)

[0268] GPC in HFIP: M.sub.n 788 g/mol, M.sub.w 33,000 g/mol

[0269] Acid number: 165 mg KOH/g

[0270] A 250 ml flask with temperature control, nitrogen inlet, Dean-Stark apparatus, and overhead stirrer was charged with 95.8 g backbone (a.17). Then 227 g (b.8) were added and the resultant mixture was heated to 140 under nitrogen atmosphere and stirred for 8 hours while water was distilled off. Subsequently, the resultant polymer (A. 17.8) was cooled to ambient temperature and obtained as a brownish material, 314 g.

TABLE-US-00003 TABLE 3 Syntheses and properties of inventive polymers Polymer acid molar ratio Catalyst, rt state at M.sub.n M.sub.w (A) (a) (b) (c) (a)/(b)/(c) % [h] 20 C. [g/mol] [g/mol] (A.1.5) (a.1) (b.5), 1/0.4/1.5 cat. 1, 6 paste 2900 12350 (b.8) 0.3 (A.2.3) (a.2) (b.3), 1/0.7/0.7 cat. 2, 5.5 paste 3710 18700 (b.8) 0.2 (A.3.9) (a.3) (b.9) (c.1) 1/1.5/0.3 cat. 3, 6.5 liquid 4300 21100 0.15 (A.4.1) (a.4) (b.1) (c.2) 1/0.65/0.35 cat. 1, 5.5 paste 2370 7690 0.3 (A.5.2) (a.5) (b.2) (c.1) 1/0.7/0.1 cat. 1, 6.5 paste 3,500 9150 0.3 (A.6.1) (a.6) (b.1) (c.1) 1/0.8/0.1 cat. 1, 6.3 solid 4800 21500 0.25 (A.6.8) (a.6) (b.8) (c.3) 6.3 3116 17,600 (A.7.5) (a.7) (b.5) 1/0.8 cat. 1, 5.5 solid 3740 17600 0.3 (A.8.7) (a.8) (b.7) 1/0.85 cat. 2, 7 paste 4150 14800 0.2 (A.10.1) (a.10) (b.1) (c.1) 1/0.65/0.15 cat. 2, 5.5 solid 5600 21600 0.15 (A.11.9) (a.11) (b.9) 1/0.85 cat. 3, 5 liquid 1800 3600 0.2 (A.12.10) (a.12) (b.10) (c.1) 1/0.65/0.1 cat. 2, 4.5 solid 4400 14100 0.2 (A.13.9) (a.13) (b.9) 1/1 cat. 2, 4.5 paste 5300 14160 0.2 (A.14.9) (a.14) (b.9) 1/1.05 cat. 1, 3.5 solid 5870 17650 0.3 (A.15.10) (a.15) (b.10) 1/0.95 cat. 1, 3.5 paste 6370 15040 0.3 (A.16.10) (a.16) (b.10) 1/1 cat. 1, 4 paste 7890 22100 0.3 Percentages of catalysts refer to the sum of reactants. rt: reaction time in hours of combined steps () and (), if applicable, otherwise: step () cat. 1: methanesulfonic acid (MSA) cat. 2: Ti(IV) tetra-isobutylate cat. 3: Zn octoate citric acid: (c.1), sebacic acid: (c.2), succinic acid (c.3)

[0271] II. Washing performance (

[0272] II.1 Laundry cleaning

[0273] The primary wash performance of inventive polymers was tested in the washing machine preparing wash solutions using water of 14 dH hardness (2.5 mmol/L; Ca: Mg: HCO.sub.3 4:1:8) containing 3.0 g/L of the liquid test detergent L. 1, see composition in Table 4.1 or 4.2, and 2.0% of an inventive polymer (A) according to Table 3.

TABLE-US-00004 TABLE 4.1 Ingredients of base mixture L.1 for a liquid detergent formulation ingredient % by weight Alkylbenzene sulfonic acid (C.sub.10-C.sub.13), Na salt 5.5 C.sub.13/C.sub.15-Oxoalkohol reacted with 7 moles of EO 5.4 1,2 propylene glycol 6 ethanol 2 potassium coconut soap 2.4 Monoethanolamine 2.5 lauryl ether sulphate (C.1) 5.4 Sodium citrate 3 (D.1) - structure see below 2 Polymer (A) 2 Water to 100

TABLE-US-00005 TABLE 4.2 Ingredients of base mixture L.2 for a liquid detergent formulation ingredient % by weight MGDA-Na.sub.3 5.5 Branched C.sub.13-Polyglucoside 3.5 1,2 propylene glycol 6 ethanol 2 potassium coconut soap 4.4 NaOH 2.2 lauryl ether sulphate (C.1) 9.5 Sodium citrate 3 Polymer (A) 2 Water to 100

##STR00008##

[0274] Anti greying tests were also executed in a launderometer with 1I beakers (LP2 type from SDL Atlas, Inc.). One wash cycle (60 min.) was run at 25 C. containing the wash-solution (0.25 L) together with multi-stain monitors (MSM1 and MSM2, one each) and a cotton ballast fabric of 2.5 g (fabric to liquor ratio of 1:10). After the 1 cycle, the multi stain monitors were rinsed in water, followed by drying at ambient room temperature overnight. The multi-stain monitors MSM1 and MSM2 (Table 5) contain respectively 8 and 4 standardized soiled fabrics, of respectively 5.05.0 cm and 4.54.5 cm size and stitched on two sides to a polyester carrier.

TABLE-US-00006 TABLE 5 Multi-stain monitors for the washing machine tests MSM1 (circular stains, 5 cm diameter): CFT C-S-10: butterfat with colorant on cotton CFT C-S-62: lard, colored on cotton CFT C-S-78: soybean oil with pigment on cotton EMPA 112: cocoa on cotton EMPA 141/1: lipstick on cotton EMPA 125: soiling on cotton fabric, sensitive to surfactants as well as to lipases wfk20D: pigment and sebum-type fat on polyester/cotton mixed fabric CFT C-S-70: chocolate/mousse cream on cotton MSM2: CFT C-S-10: butterfat with colorant on cotton CFT C-S-62: lard, colored on cotton CFT C-S-61: beef fat, colored on cotton CFT PC-S-04: Saturated with colored olive oil on Polyester/Cotton (65/35).

[0275] The total level of cleaning was evaluated using color measurements. Reflectance values of the stains on the monitors were measured using a sphere reflectance spectrometer (SF 500 type from Datacolor, USA, wavelength range 360-700 nm, optical geometry d/8) with a UV cutoff filter at 460 nm. In this case, with the aid of the CIE-Lab color space classification, the brightness L *, the value a * on the red-green color axis and the b * value on the yellow-blue color axis, were measured before and after washing and averaged for the respective stains of the monitor. The change of the color value (Delta E, E) value, defined and calculated automatically by the evaluation color tools on the following formula,

[00002]$E_{\mathrm{ab}}^{*}=\sqrt{L^{*2}+a^{*2}+b^{*2}}$

is a measure of the achieved cleaning effect. All experiments were repeated three times to provide a representative average number.

[0276] Higher Delta E values show better cleaning. For each stain, a difference of 1 unit can be detected visually by a skilled person. A non-expert can visually detect 2 units easily. The E values of the formulations for the 4, 8 and 11 stains of correspondingly MSM1 and MSM2 and for some selected single stains are shown in Tables 6.1 and 6.2.

TABLE-US-00007 TABLE 6.1 Results of launder-O-meter test fabric monitor cleaning performance Anti-greying Formulation EMPA/SBL Clay Slurry LD.1 Total E E E Cotton Polyester Sum Cotton Polyester Sum (A) E (CFT C-S-62) (wfk20D) (EMPA141/1) (BW) (PES) BW + PES (BW) (PES) BW + PES 136 31.0 10.8 11.9 22.3 21.8 44.1 22.1 20.1 42.2 (A.1.5) 143 32.4 12.0 13.7 24.4 23.2 47.6 24.0 22.6 46.6 (A.2.3) 142 32.6 11.6 13.1 24.0 22.9 46.9 23.5 22.5 44.0 (A.17.8) 145 33.0 12.8 13.9 23.1 24.0 47.1 19.5 27.1 46.6 (A.5.2) 147 35.2 13.7 15.6 25.2 24.5 49.7 22.7 26.6 49.3 (A.6.1) 154 38.2 16.5 17.0 26.0 25.6 51.6 25.4 26.3 51.7 (A.7.5) 153 36.7 16.0 15.5 25.4 25.6 51.0 25.8 25.7 51.5 (A.8.7) 148 34.2 14.3 15.0 23.7 27.0 50.7 24.0 24.8 48.8 (A.10.1) 148 34.7 14.6 14.3 25.0 26.1 51.1 23.9 25.2 49.1 (A.11.9) 149 33.9 14.5 14.9 23.0 26.7 49.7 25.9 23.4 49.3 (A.12.10) 150 35.0 15.0 14.3 25.1 26.0 51.1 24.7 25.6 50.3 (A.13.9) 147 34.0 14.0 13.6 25.9 26.3 52.2 26.7 25.5 52.2 (A.14.9) 145 35.0 14.5 14.2 26.1 24.7 50.8 27.2 25.9 53.1 (A.15.10) 146 33.9 13.2 14.0 26.9 25.4 52.3 28.2 24.9 53.1 (A.16.10) 145 33.4 14.0 14.1 26.5 24.9 51.4 29.0 24.3 53.3

TABLE-US-00008 TABLE 6.2 Results of launder-O-meter test fabric monitor cleaning performance Anti-greying Formulation EMPA/SBL Clay Slurry LD.2 Total E E E Cotton Polyester Sum Cotton Polyester Sum (A) E (CFT C-S-62) (wfk20D) (EMPA141/1) (BW) (PES) BW + PES (BW) (PES) BW + PES 132 28.5 10.0 11.5 20.1 20.8 40.9 22.1 20.1 42.2 (A.1.5) 140 31.2 11.7 13.0 23.5 22.8 46.3 23.0 22.1 46.1 (A.2.3) 138 30.8 11.2 12.5 23.0 22.4 45.4 23.1 21.7 44.8 (A.17.8) 142 31.4 12.1 13.3 23.0 23.6 46.6 19.5 27.1 46.6 (A.5.2) 144 32.2 13.0 14.5 24.2 24.2 48.4 21.7 25.2 46.9 (A.6.1) 148 34.1 14.2 15.2 25.0 24.9 49.9 23.4 25.1 48.5 (A.7.5) 147 34.7 14.0 15.1 24.4 25.0 49.4 24.5 24.5 49.0 (A.8.7) 147 34.0 13.8 14.5 23.3 26.0 49.3 24.1 23.8 47.9 (A.10.1) 148 34.1 14.1 14.3 26.0 25.4 51.4 23.7 24.8 48.5 (A.11.9) 147 33.9 13.8 13.9 23.8 25.4 49.2 25.4 24.4 49.8 (A.12.10) 148 34.2 14.3 14.0 25.1 26.4 51.5 23.7 24.3 48.3 (A.13.9) 147 33.0 13.2 13.1 25.1 24.9 50.0 26.5 25.1 51.6 (A.14.9) 148 33.9 14.0 13.7 25.6 24.2 49.8 26.2 25.3 51.5 (A.15.10) 148 33.3 13.4 14.0 26.0 24.4 50.4 27.1 23.9 51.0 (A.16.10) 147 33.6 13.1 13.8 26.1 24.5 50.6 28.0 24.0 52.0

III. BIODEGRADATION TESTS

[0277] General: the tests were carried out in accordance with the OECD Guidelines. According to the OECD guidelines a test is valid if: [0278] 1. The reference reaches 60% within 14 days. [0279] 2. The difference of the extremes of the test replicates by the end of the test is less than 20%. [0280] 3. Oxygen uptake of inoculum blank is 20 to 30 mg O.sub.2/I and must not be greater than 60 mg O.sub.2/l. [0281] 4. The pH value measured at the end of the test must be between 6 and 8.5.

Description of the Test Method Used in the Context of the Present Invention

[0282] Biodegradation in sewage was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures biodegradation of a sewage sample by measuring the consumption of oxygen. To a measured volume of sewage, 100 mg/L test substance, which is the nominal sole source of carbon, was added along with the inoculum (aerated sludge taken from the municipal sewage treatment plant, Mannheim, Germany). This sludge was stirred in a closed flask at a constant temperature (25 C.) for 28 days. The consumption of oxygen is determined by measuring the change in pressure in the closed flask using an Oxi TopC. Carbon dioxide evolved was absorbed in a solution of sodium hydroxide. Nitrification inhibitors were added to the flask to prevent consumption of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control glucose/glutamic acid is run along with the test samples for each cabinet as reference.

[0283] Calculations: Theoretical oxygen demand: Amount of O.sub.2 required to oxidize a compound to its final oxidation products. This amount is calculated using the elemental analysis data. % Biodegradation

[00003]$\mathrm{Experimental}{O}_2\mathrm{uptake}100\mathrm{and}\mathrm{divided}\mathrm{by}\mathrm{the}\mathrm{theoretical}\mathrm{oxygen}\mathrm{demand}$

[0284] The results of biodegradability tests are summarized in Table 7.

TABLE-US-00009 TABLE 7 summary of biodegradation tests sample Biodegradation [%] (A.1.5) 76.5 (A.2.3) 79 (A.3.9) 72.6 (A.4.1) 72.6 (A.5.2) 74.5 (A.6.1) 75.9 (A.7.5) 72 (A.8.7) 69 (A.10.1) 73.5 (A.11.9) 74 (A.12.10) 72 (A.13.9) 74 (A.14.9) 72 (A.15.10) 67 (A.16.10) 63 In each test, the reference had a biodegradability of more than 60%.