BIODEGRADABLE GRAFT POLYMERS

Abstract

Disclosed herein are novel graft polymers including a block copolymer backbone (A) as a graft base having polymeric sidechains (B) grafted thereon. The polymeric sidechains (B) are obtainable by polymerization of a vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as optional further monomer (B2). Most preferably, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). Further disclosed herein is a process for obtaining such a graft polymer Further disclosed herein is a method of using such a graft polymer within, for example, fabric and home care products. Additionally disclosed herein are fabric and home care products containing such a graft polymer.

Claims

1. A graft polymer comprising: (A) a block copolymer backbone as a graft base, wherein said block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, wherein the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x is from 3 to 10, and (B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as optional further monomer (B2).

2. The graft polymer according to claim 1, comprising 20 to 95% by weight of the block copolymer backbone (A) and 5 to 80% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer).

3. The graft polymer according to claim 1, wherein the block copolymer backbone (A) is obtainable by polymerization of i) at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, and/or ii) one of the at least two monomers employed is ethylene oxide, and/or iii) the number (x) of individual blocks within the block copolymer backbone (A) is an integer, wherein x has a value from 3 to 5.

4. The graft polymer according to claim 1, wherein i) the graft polymer has a weight average molecular weight M.sub.w of from 1,000 to 100,000 g/mol, and/or ii) the graft polymer has a polydispersity M.sub.wM.sub.n of <3, (with M.sub.w=weight average molecular weight and M.sub.n=number average molecular weight [g/mol/g/mol]), and/or iii) the block copolymer backbone (A) is optionally capped at one or both endgroups, if the block copolymer backbone (A) is capped, the capping is done by C.sub.1-C.sub.25-alkyl groups, and/or iv) the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG).

5. The graft polymer according to claim 1, wherein the block copolymer backbone (A) has the structure according to formula (A1) or formula (A2) with formula (A1) is defined as follows: ##STR00005## with n is an integer in the range of 2 to 100, and m is an integer in the range of 2 to 100, or formula (A2) is defined as follows: ##STR00006## with o is an integer in the range of 2 to 100, and p is an integer in the range of 2 to 100.

6. The graft polymer according to claim 1, wherein the polymeric sidechains (B) are obtained by radical polymerization and the at least one vinyl ester monomer (B1) is vinyl acetate or vinyl propionate, and i) with optionally N-vinylpyrrolidone as further monomer (B2) being present, and ii) the polymeric sidechains (B) being fully or partially hydrolyzed after polymerization.

7. The graft polymer according to claim 1, wherein the polymeric sidechains (B) are obtained by radical polymerization of (B1) 25 to 100% by weight (in relation to the sum of (B1) and (B2)) of at least one vinyl ester monomer (B1), and (B2) 0 to 75% by weight (in relation to the sum of (B1) and (B2)) of N-vinylpyrrolidone as further monomer (B2).

8. The graft polymer according to claim 1, wherein the polymeric sidechains (B) are obtained by radical polymerization of 100% by weight (in relation to the total amount of monomers employed) of at least one vinyl ester monomer (B1).

9. The graft polymer according to claim 1, wherein the number average molecular weight M.sub.n of the tri-block copolymer backbone (A) is lower than 6000 g/mol, and the percentage by weight of vinyl acetate (monomer B) being grafted onto the backbone is in between 10 and 80 (in relation to the total weight of the graft polymer).

10. The graft polymer according to claim 1, wherein the number average molecular weight M.sub.n of the tri-block copolymer backbone (A) is lower than 6000 g/mol, and the backbone has the structure A2, and the percentage by weight of vinyl acetate (monomer B) being grafted onto the backbone is in between 10 and 80 (in relation to the total weight of the graft polymer).

11. A process for obtaining at least one graft polymer according to claim 1, wherein at least one monomer (B1) and optionally N-vinylpyrrolidone as optional further monomer (B2) are polymerized in the presence of at least one block copolymer backbone (A), wherein the polymeric sidechains (B) are obtained by radical polymerization.

12. The process according to claim 11, comprising the polymerization of at least one monomer (B1) selected from the group consisting of vinyl acetate and vinyl propionate and optionally at least one further monomer (B2) which is N-vinylpyrrolidone in order to obtain the polymer sidechains (B) in the presence of at least one block copolymer backbone (A), a free radical-forming initiator (C) and, if desired, up to 50% by weight, based on the sum of components (A), (B1), optionally (B2), and (C) of at least one organic solvent (D), at a mean polymerization temperature at which the initiator (C) has a decomposition half-life of from 40 to 500 min, in such a way that the fraction of unconverted graft monomers (B1) and optionally (B2) and initiator (C) in the reaction mixture is constantly kept in a quantitative deficiency relative to the block copolymer backbone (A).

13. A method of using the graft polymer according to claim 1, in laundry detergents, in cleaning compositions and/or in fabric and home care products.

14. A laundry detergent, a cleaning composition and/or a fabric and home care product containing at least one graft polymer according to claim 1.

15. The laundry detergent, the cleaning composition and/or the fabric and home care product according to claim 14, wherein the at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, in relation to the total weight of such composition or product.

16. A method of using a graft polymer in laundry detergents, in cleaning compositions and/or in fabric and home care products, wherein the graft polymer comprises (A) a block copolymer backbone as a graft base, wherein said block copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, and (B) polymeric sidechains grafted onto the block copolymer backbone, wherein said polymeric sidechains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) selected from the group consisting of vinyl acetate and vinyl propionate and optionally N-vinylpyrrolidone as optional further monomer (B2).

17. A laundry detergent, a cleaning composition and/or a fabric and home care product containing the at least one graft polymer as defined in claim 16.

18. The laundry detergent, the cleaning composition and/or the fabric and home care product according to claim 17, wherein the at least one graft polymer is present in an amount ranging from about 0.01% to about 20%, in relation to the total weight of such composition or product.

19. The graft polymer according to claim 1, comprising 40 to 85% by weight of the block copolymer backbone (A) and 15 to 60% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer).

20. The graft polymer according to claim 1, comprising 55 to 75% by weight of the block copolymer backbone (A) and 25 to 45% by weight of the polymeric sidechains (B) (in relation to the total weight of the graft polymer).

Description

EXAMPLES

[0236] Polymer Measurements

[0237] K-value measures the relative viscosity of dilute polymer solutions and is a relative measure of the average molecular weight. As the average molecular weight of the polymer increases for a particular polymer, the K-value tends to also increase. The K-value is determined in a 3% by weight NaCl solution at 23° C. and a polymer concentration of 1% polymer according to the method of H. Fikentscher in “Cellulosechemie”, 1932, 13, 58.

[0238] The number average molecular weight (M.sub.n), the weight average molecular weight (M.sub.w) and the polydispersity M.sub.w/M.sub.n of the inventive graft polymers were determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran comprising 0.035 mol/L diethanolamine. The concentration of graft polymer in tetrahydrofuran was 2.0 mg per mL. After filtration (pore size 0.2 μm), 100 μL of this solution were injected into the GPC system. Four different columns (heated to 60° C.) were used for separation (SDV precolumn, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL per min. A DRI Agilent 1100 was used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) having a molecular weight M.sub.n from 106 to 1 378 000 g/mol were used for the calibration.

[0239] The following (general) procedures were performed using the material and ratios and amounts as further indicated in table 1.

Procedure for Comparative Example 1

Graft Polymerization of Vinyl Acetate on Poly(Ethylene Glycol)—(Comp. Ex.1)

[0240] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 600 g of poly(ethylene glycol) under nitrogen atmosphere and melted at 90° C. Feed 1 containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.6 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90° C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95° C. and Feed 3 consisting of 3.16 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 15.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 ° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed.

[0241] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0242] General procedure for comparative polymers without grafting (Comparative examples 9-12)

[0243] 1098.90 g of triblock copolymer, 1.10 g vinyl acetate and 58.30 g of 1,2-propanediol were mixed in a polymerization vessel at 90° C. and stirred for 3 h.

[0244] General procedure 1 for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (60/40)—(Ex. 1, Ex. 3-Ex. 5, Ex. 7, Ex. 16, Ex. 18-Ex. 20; Comp. Ex. 2, Comp. Ex. 3, Comp. Ex. 6)

[0245] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 600 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.6 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed within 6:00 h at constant feed rate and 90° C. Upon completion of the Feeds 1 and 2, the temperature was increased to 95° C. and Feed 3 consisting of 3.16 g of tert-butyl peroxy ethylhexanoate, dissolved in 15.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 95 ° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed.

[0246] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar. The resulting graft polymer (Ex. 7) had a mean molecular weight M.sub.w of 5 190 g/mol and a polydispersity of 1.5.

[0247] General procedure 2 for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (40/60)

[0248] (Ex. 2, Ex. 6, Ex. 14, Comp. Ex. 7, Comp. Ex. 8)

[0249] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 440 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 35.09 g of 1,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (660 g of vinyl acetate) was started and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds, Feed 3 consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.21 g of 1,2-propanediol, were dosed within 56 min with constant flow rate at 90° C. The mixture was stirred for one hour at 90° C. upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0250] General procedure 3 for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (70 / 30)—(Ex. 8, Ex. 22, Comp. Ex. 4)

[0251] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 770 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 35.09 g of 1,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (330 g of vinyl acetate) was started and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds, Feed 3 consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.21 g of 1,2-propanediol, were dosed within 56 min with constant flow rate at 90° C. The mixture was stirred for one hour at 90° C. upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0252] Procedure for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (90 /10)—(Ex. 9)

[0253] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 990 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 7.97 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 35.09 g of 1,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (110 g of vinyl acetate) was started and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds, Feed 3 consisting of 5.28 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 23.21 g of 1,2-propanediol, were dosed within 56 min with constant flow rate at 90° C. The mixture was stirred for one hour at 90° C. upon complete addition of the feed.

[0254] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0255] Procedure for graft polymerization of vinyl acetate and vinyl pyrrolidone in tripropylene glycol—(Ex. 10)

[0256] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 300 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 6.92 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 58.5 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (180.00 g of vinyl acetate) and Feed 3 (120.00 g of vinyl pyrrolidone) were started simultaneously and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds the temperature was increased to 95° C. and Feed 4 consisting of 1.22 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 10.38 g of tripropylene glycol, was dosed within 56 min with constant flow rate at 95° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar. Water (512.40 g) was added.

[0257] Procedure for graft polymerization of vinyl acetate and vinyl pyrrolidone in 1,2-propanediol (Ex. 11)

[0258] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 376.3 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 7.12 g of tert-butyl perpivalate, dissolved in 17.01 g of 1,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (225.78 g of vinyl acetate) and Feed 3 (150.25 g of vinyl pyrrolidone) were started simultaneously and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. 3 h after the start of Feeds 2 and 3, Feed 4 (142.31 g 1,2-propanediol) was started and dosed to the reaction vessel in 3 h with constant feed rate. Upon completion of the feeds the temperature was increased to 95° C. and Feed 3 consisting of 4.72 g of tert- butyl perpivalate, dissolved in 11.25 g of 1,2-propanediol, was dosed within 56 min with constant flow rate at 95° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed.

[0259] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar. Water (76.84 g) was added.

[0260] Procedure for graft polymerization of vinyl acetate and vinyl pyrrolidone in tripropylene glycol followed by partial hydrolysis of (former) vinyl acetate (VAc) units after polymerization—(Ex. 12)

[0261] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 300 g of triblock copolymer under nitrogen atmosphere and melted at 90° C.

[0262] Feed 1 containing 6.92 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 58.5 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (180.00 g of vinyl acetate) and Feed 3 (120.00 g of vinyl pyrrolidone) were started simultaneously and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds the temperature was increased to 95° C. and Feed 4 consisting of 1.22 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 10.38 g of tripropylene glycol, was dosed within 56 min with constant flow rate at 95° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar. Water (512.40 g) was added and the temperature was reduced to 80° C. Sodium hydroxide solution (50%, 68.0 g) was added and the mixture was stirred at 80° C. for 60 min.

[0263] Procedure for graft polymerization of vinyl acetate and vinyl pyrrolidone in 1,2-propanediol followed by partial hydrolysis of (former) vinyl acetate (VAc) units after polymerization (Ex. 13)

[0264] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 376.3 g of triblock copolymer under nitrogen atmosphere and melted at 90° C.

[0265] Feed 1 containing 7.12 g of tert-butyl perpivalate, dissolved in 17.01 g of 1,2-propanediol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (225.78 g of vinyl acetate) and Feed 3 (150.25 g of vinyl pyrrolidone) were started simultaneously and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. 3 h after the start of Feeds 2 and 3, Feed 4 (142.31 g 1,2-propanediol) was started and dosed to the reaction vessel in 3 h with constant feed rate. Upon completion of the feeds the temperature was increased to 95° C. and Feed 3 consisting of 4.72 g of tert-butyl perpivalate, dissolved in 11.25 g of 1,2-propanediol, was dosed within 56 min with constant flow rate at 95° C. The mixture was stirred for one hour at 95° C. upon complete addition of the feed.

[0266] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar. Water (76.84 g) was added and the temperature was reduced to 80° C. Sodium hydroxide solution (50%, 67.0 g) was added and the mixture was stirred at 80° C. for 60 min.

[0267] Procedure for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide / VAc (50 / 50)—(Ex. 15, Comp. Ex. 5)

[0268] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 500 g of triblock copolymer under nitrogen atmosphere and melted at 90° C. Feed 1 containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 50.30 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds, Feed 3 consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 19.70 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 90° C.

[0269] The mixture was stirred for one hour at 90° C. upon complete addition of the feed. Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0270] Procedure for graft polymerization of vinyl acetate in a ratio of polyalkylene oxide/VAc (80/20)—(Ex. 17, Ex. 21, Ex. 23)

[0271] A polymerization vessel equipped with stirrer and reflux condenser was initially charged with 800 g of triblock copolymer under nitrogen atmosphere and melted at 90° C.

[0272] Feed 1 containing 10.20 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 47.61 g of tripropylene glycol, was dosed to the stirred vessel in 6:10 h, at 90° C. 5.56% of Feed 1 were dosed in the first 10 min and the rest was dosed with constant feed rate for 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and dosed to the reaction vessel within 6:00 h at constant feed rate and 90° C. Upon completion of the feeds, Feed 3 consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate, dissolved in 22.39 g of tripropylene glycol, were dosed within 56 min with constant flow rate at 90° C. The mixture was stirred for one hour at 90° C. upon complete addition of the feed.

[0273] Residual amounts of monomer were removed by vacuum distillation for 1 h at 95° C. and 500 mbar.

[0274] Biodegration Testing/Biodegradability

[0275] Biodegradation in waste water 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 (VVTVV). 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).

[0276] Performance evaluations of the graft polymers can be obtained by laundry- and cleaning-experiments. Laundry experiments can be performed in washing machines or alternatively in equipment to perform model laundry experiments like Launderometer or Tergotometer. For testing of anti-redeposition effects, white fabrics were washed together with soiled fabrics in presence of a detergent composition containing the graft polymer and the remission of the white fabric is determined before and after the wash. For testing soil removal effects, soiled fabrics were washed in presence of a detergent composition containing the graft polymer and the remission of the soiled fabric is determined before and after the wash. Dosage of the graft polymer was chosen at 0.5 to 5% per weight of the detergent composition. Dosage of detergents was chosen in the range of 1500-4500 ppm in the wash liquor. Water hardness (Ca.sup.2+ and Mg.sup.2+ concentration in the wash liquor) in the wash experiments was set between 1 and 3 mmol hardness. Wash temperature was chosen between 20° C. and 40° C.

TABLE-US-00001 TABLE 1 Graft polymers Back- Com- bone Back- Block- position Biodegra- Exam- M.sub.n bone copolymer Mono- BB/Monos dation ple [g/mol] % EO structure mers [Gew. %] [%], 28 d Comp. 6000 100 PEG VAc 40/60 28 Ex. 1 Comp. 5900 medium A1 VAc 60/40 12 Ex. 2 (40%) Comp. 4600 medium A1 VAc 60/40 14 Ex. 3 (40%) Comp. 5900 medium A1 VAc 70/30 14 Ex. 4 (40%) Comp. 3500 Low A1 Vac 50/50 15 Ex. 5 (10%) Comp. 6500 medium A1 VAc 60/40 16 Ex. 6 (50%) Comp. 8300 high A1 VAc 40/60 16 Ex. 7 (80%) Comp. 3650 Low A1 Vac 40/60 18 Ex. 8 (20%) Comp. 8300 high A1 VAc 99.9/0.1 80 Ex. 9 (80%) Comp. 2900 medium A1 VAc 99.9/0.1 83 Ex. 10 (40%) Comp. 2450 low A1 VAc 99.9/0.1 85 Ex. 11 (20%) Comp. 2000 low A1 VAc 99.9/0.1 102 Ex. 12 (10%) Ex.1 3500 low A1 VAc 60/40 45 (10%) Ex. 2 2000 low A1 VAc 40/60 35 (10%) Ex. 3 2000 low A1 VAc 60/40 74 (10%) Ex. 4 1000 low (10%) A1 VAc 60/40 70 Ex. 5 1750 medium A1 VAc 60/40 50 (40%) Ex. 6 2900 medium A1 VAc 40/60 32 (40%) Ex. 7 2900 medium A1 VAc 60/40 40 (40%) Ex. 8 8300 high A1 VAc 70/30 38 (80%) Ex. 9 8300 high A1 VAc 90/10 46 (80%) Ex. 10 2900 medium A1 VAc/VP 50/30/20 34 (40%) Ex. 11 2900 medium A1 VAc/VP 50/30/20 42 (40%) Ex.12 2900 medium A1 VAc/VP 50/30*/20 37 (40%) Ex.13 2900 medium A1 VAc/VP 50/30*/20 42 (40%) Ex.14 2650 medium A2 VAc 40/60 29 (40%) Ex. 15 2450 low A1 VAc 50/50 30 (20%) Ex. 16 2450 low A1 VAc 60/40 33 (20%) Ex. 17 2450 low A1 VAc 80/20 46 (20%) Ex. 18 3100 low A2 VAc 60/40 47 (20%) Ex. 19 2150 low A2 VAc 60/40 49 (20%) Ex. 20 2900 medium A1 VAc 80/20 50 (40%) Ex. 21 1950 low A2 VAc 70/30 52 (20%) Ex. 22 2650 medium A2 VAc 80/20 57 (40%) Ex. 23 2650 medium A2 VAc 60/40 59 (40%) Abbreviations used: Ex. = inventive example; Comp. Ex. = comparative example VAc = Vinyl acetate; VP = Vinyl pyrrolidone; * = 40 mol % of acetate units were hydrolyzed (by employing sodium hydroxide solution) to the respective alcohol

[0277] Viscosity Measurements

[0278] Viscosity of the samples was measured using a Brookfield Viscosimeter. For the measurements, the samples were diluted with tripropylene glycol to the solid content indicated in the table 2. The samples were heated to 60° C. and measured using spindle 31 at 30 rpm.

TABLE-US-00002 TABLE 2 Viscosities Example Solid content [%] Viscosity [mPas] Ex.23 85 632 Ex.23 80 550 Ex.23 75 360 Ex.23 70 322

[0279] Whiteness Performance in Detergents

[0280] The whiteness performances was tested using the following conditions: Clay dispersion/whiteness/3000 ppm clay/HDL 750 ppm/25° C./1mM hardness/15 ppm polymer.

[0281] The results are shown in table 3.

TABLE-US-00003 TABLE 3 Whiteness Delta whiteness index, Ingredients average over 4 fabrics nil 100 Comparative example 1 147 Example 15 138

[0282] For the whiteness benefit test, the following laundry detergent composition as listed in table 4 was used:

TABLE-US-00004 TABLE 4 Ingredient % Sodium dodecylbenzenesulfonate 6.9 Sodium laureth sulfate 11.3 Lutensol AO7 (C13C15-Oxo alcohol + 7 EO) 7 Fatty Acid C12-18 1 1,2-Propylene Glycol 6 Ethanol 2 Water balance

[0283] Test Preparation:

[0284] The following fabrics are provided for the whiteness benefit test: [0285] NA Polyester : PW19, available from Empirical Manufacturing Company (Cincinnati, Ohio, [0286] Knitted Cotton 1: Test fabrics, Inc 403 cotton interlock knit tubular CW120, available from Empirical Manufacturing Company (Cincinnati, Ohio, USA). Polycotton

[0287] “Washed and FE Treated” fabrics were prepared according to the following method: 400g fabrics are washed in a WE Miniwasher (3.5 litre water) twice using the short program (45 minute wash cycle followed by three rinse cycles; total program is 90 minutes) at 60° C. with 18.6g 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.

[0288] “Washed” fabrics were prepared according to the following method: 400 g fabrics are washed in a WE Miniwasher (3.5 litre water) twice using the short program (45 minute wash cycle followed by three rinse cycles; total program is 90 minutes) at 60° C. with 18.6 g Ariel™ Compact powder detergent and twice using the short program, at 60° C. nil detergent. Fabrics are then dried in a tumble dryer on extra dry until dry.

[0289] Test Method:

[0290] Four fabric samples are prepared: Polycotton, washed; Knitted Cotton, washed; NA Polyester washed and FE treated, Knitted washed and FE treated.

[0291] 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 μL 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).

[0292] Each polymer listed in table 5 is added at 15 ppm of the wash solution. Each fabric is washed for 60 minutes and dried in the dark under ambient conditions. For each wash condition, there are two 96 well plates, and eight internal replicates per 96 well plate, for a total of 16 replicates per wash condition.

[0293] 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.

[0294] The whiteness index (WI-index) as determined on several different fibre materials (see following table) was calculated as follow:

[0295] “Comparable scaling indicator” (for example listed) =(Sum (WI all fabric tested with technology A)×100) / Sum (all WI fabric tested with nil technology) with this comparison being set at “100” for the test using no graft polymer.

[0296] For the whiteness index, the CIE whiteness index formula was used and delta WI was calculated as follows: delta WI on a substrate=WI technology−WI nil .

TABLE-US-00005 TABLE 5 WI-Index as determined for several different fabric types Delta WI NA Polyester cotton washed washed Comparable Inventive Polycotton and FE and FE cotton scaling Examples washed treated treated washed indicator (without 0 0 0 0 100 graft polymer) nil Ex.1 6.3 6.4 7.5 4.1 133 Ex.2 6.6 5.5 8.6 5.2 135 Ex.4 3.2 3.1 6.0 1.4 118 Ex.5 3.9 3.1 5.1 1.4 118 Ex.6 4.1 5.0 7.4 3.8 127 Ex.14 7.5 6.9 8.7 4.6 137 Ex.15 6.8 6.4 9.4 5.6 138 Ex.16 5.6 5.2 8.9 4.2 132 Ex.17 4.7 3.4 6.7 5.3 127 Ex.18 6.4 5.6 7.0 4.1 131 Ex.19 4.9 4.6 6.8 4.4 128 Ex.20 4.2 3.3 5.8 2.6 121 Ex.21 6.9 4.5 8.3 4.3 131 Ex.22 5.4 4.2 6.1 2.7 124 Ex.23 7.8 5.8 7.7 5.7 135