POLYMER SUITABLE AS A THICKENER

Abstract

The invention relates to polymer comprising structural units according to formula (I), R.sup.1X(CO)NHR.sup.2NH(CO)OPOA-R.sup.3(OPOA-R.sup.4).sub.n wherein R.sup.1 represents an organic group terminated by a hydrocarbyl group having 6 to 50 carbon atoms, X represents O or NR.sup.5, wherein R.sup.5 represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms, R.sup.2 represents a hydrocarbyl group comprising an aromatic group and having 6 to 40 carbon atoms, POA represents a polyoxyalkylene group, R.sup.3 represents an organic group having 2 to 40 carbon atoms, n is an integer from 1 to 6, R.sup.4 is independently selected from (CO)NHR.sup.2NH(CO)NHR.sup.1, R.sup.6, wherein R.sup.6 represents a hydrogen atom or an aliphatic or aromatic group having 1 to 24 carbon atoms, and wherein the polymer has an average of at least 1.8 end groups R.sup.1 per molecule, a number average molecular weight in the range of 2000 to 100000 Daltons, and a polydispersity in the range of 1.0 to 5.0, wherein the quotient of the polydispersity divided by (n+1) is less than 1.0.

Claims

1. A polymer comprising structural units according to formula (I),
R.sup.1X(CO)NHR.sup.2NH(CO)OPOA-R.sup.3(OPOA-R.sup.4).sub.n wherein R.sup.1 represents an organic group terminated by a hydrocarbyl group having 6 to 50 carbon atoms, X represents O or NR.sup.5, wherein R.sup.5 represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms, R.sup.2 represents a hydrocarbyl group comprising an aromatic group and having 6 to 40 carbon atoms, POA represents a polyoxyalkylene group, R.sup.3 represents an organic group having 2 to 40 carbon atoms, n is an integer from 1 to 6, R.sup.4 is independently selected from (CO)NHR.sup.2NH(CO)XR.sup.1, (CO)NHR.sup.1, R.sup.6, wherein R.sup.6 represents a hydrogen atom or an aliphatic or aromatic group having 1 to 24 carbon atoms, and wherein the polymer has an average of at least 1.8 end groups R.sup.1 per molecule, a number average molecular weight in the range of 2000 to 100000 g/mol (Daltons), and a polydispersity in the range of 1.0 to 5.0, wherein the quotient of the polydispersity divided by (n+1) is less than 1.0.

2. The polymer according to claim 1, wherein X is O.

3. The polymer according to claim 1, wherein at least one R.sup.1 represents a polyoxyalkylene group terminated by a hydrocarbyl group having 6 to 50 carbon atoms.

4. The polymer according to claim 1, wherein at least one R.sup.1 represents a hydrocarbyl group having 6 to 30 carbon atoms.

5. The polymer according to claim 1, wherein the polyoxyalkylene group comprises repeating units selected from [C.sub.2H.sub.4O] and [C.sub.3H.sub.6O].

6. The polymer according to claim 1, having a content of the structural units according to formula (I) of at least 70% by weight, calculated on the total mass of the polymer.

7. A process for preparing a polymer, comprising reacting a compound of formula
R.sup.1X(CO)NHR.sup.2NCO(II)
and a compound of formula
HOPOA-R.sup.3(OPOA-R.sup.4).sub.n(III), wherein R.sup.1 to R.sup.4, POA, X, and n are as defined above.

8. The process according to claim 7, wherein the compound of formula (II) is obtained by reacting a diisocyanate of formula OCNR.sup.2NCO (IV) and a compound of formula R.sup.1XH (V).

9. The process according to claim 8, wherein the isocyanate groups of the diisocyanate of formula (IV) differ in reactivity towards the compound of formula (V).

10. (canceled)

11. A composition comprising a) a continuous aqueous liquid phase, b) the polymer according to claim 1 dissolved in the continuous aqueous liquid phase, and c) a hydrophobic component dispersed in the continuous aqueous liquid phase.

12. The composition according to claim 11, wherein the hydrophobic component is an organic film-forming binder.

13. The composition according to claim 11, further comprising solid particles.

14. The composition according to claim 13, wherein the solid particles are selected from pigments, fillers, and combinations thereof.

15. An additive composition comprising a) 10.0 to 60.0% by weight of the polymer according to claim 1, b) 40.0 to 90.0% by weight of water, c) 0.0 to 1.0% by weight of a biocide, and d) 0.0 to 75.0% by weight of a viscosity depressant.

Description

EXAMPLES

[0078] Preparation of starting materials, polymers according to the invention, and comparative polymers

[0079] Molecular weights and molecular weight distributions were determined using gel permeation chromatography (GPC) according to DIN 55672 part 1 (2016-03). Tetrahydrofuran (THF) was used as the eluent. The calibration was achieved using narrowly distributed linear polyethylene glycol standards of molecular weights between 44,000 and 238 g/mol. The temperature of the column system was 40 C.

[0080] Description of raw materials used

TABLE-US-00001 Trade designation Chemical Description Supplier Desmodur 2,4-toluylene diisocyanate COVESTRO T 100 benzoyl chloride SIGMA-ALDRICH octadecyl alcohol SIGMA-ALDRICH 2-ethylhexanol SIGMA-ALDRICH 3,5,5-trimethyl hexanol SIGMA-ALDRICH Isalchem 125 C12-C15 isomeric alcohols SASOL Polyether X alkoxylated pentaerythritol with a 80/20 weight ratio of ethylene oxide and propylene oxide repeating units and a hydroxyl value of 16 mg KOH/g Polyglykol Polyglykol 12000 S-a polyethylene Clariant 12000 glycol with a mean molecular (PEG-12) weight of 12000 Polyglykol Polyglykol 20000 S-a polyethylene Clariant 20000 glycol with a mean molecular (PEG-20) weight of 20000 Polyglykol Polyglykol 35000 S-a polyethylene Clariant 35000 glycol with a mean molecular (PEG-35) weight of 35000 K-KAT 348 Bismuth carboxylate catalyst KING Industries

List of Abbreviations Used

[0081] TDI: 2,4-toluylene diisocyanate
PEG: polyethylene glycol
PDI: polydispersity index
Mn: number average molecular weight
Mw: weight average molecular weight
TMH: 3,5,5-trimethylhexanol
VS: volume solid

[0082] Preparation of mono-adducts of diisocyanates and monoalcohols

[0083] Alcohols were reacted with a diisocyanate to form a mono-adduct according to the procedure described in EP 1188779. All mono-adducts were prepared in two steps comprising the synthesis and removal of excess diisocyanate by thin film evaporation

[0084] TDI and benzoyl chloride were heated to 50-70 C. and the alcohol was added dropwise. The reaction mixture was stirred for 3-6 hours and the reaction conversion was controlled by the measurement of the isocyanate value.

[0085] Afterwards, the distillation of excess TDI was done via a thin-film evaporator at a temperature between 100 C. and 150 C. After this step, the mono-adducts contained less than 0.2% by weight of residual diisocyanate.

TABLE-US-00002 TABLE 1 Overview of mono-adducts Monoadduct no. alcohol isocyanate MA-1 octadecyl alcohol TDI MA-2 2-ethylhexanol TDI MA-3 3,5,5-trimethyl hexanol TDI MA-4 C12-C15 isomeric alcohols TDI

[0086] Preparation of polymers according to the invention and comparative polymers

Examples According to the Invention

[0087] Urethane UR-1

[0088] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 99.92 g (7.1 mmol) of the polyether X were heated to 80 C. 13.00 g (0.0285 mol) of MA-1 were added. After 2.5 h at 80 C., 500 ppm of the bismuth carboxylate catalyst were added to the reaction mixture which was then reacted for another 2.5 h at 80 C. The reaction product is a highly viscous slightly brownish product.

[0089] Urethane UR-2

[0090] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 126.23 g (9 mmol) of the polyether X were heated to 80 C. 8.29 g (27 mmol) of MA-2 were added. The reaction mixture was reacted for 3 h at 80 C. The reaction product is a highly viscous yellowish product.

[0091] Urethane UR-3

[0092] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 121.32 g (8.7 mmol) of the polyether X were heated to 80 C. 5.77 g (17.3 mmol) of MA-3 were added. The reaction mixture was reacted for 3 h at 80 C. The reaction product is a highly viscous yellowish product.

[0093] Urethane UR-4

[0094] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 124.82 g (8.9 mmol) of the polyether X were heated to 80 C. 5.48 g (17.8 mmol) of MA-2 were added. The reaction mixture was reacted for 3 h at 80 C. The reaction product is a highly viscous yellowish product.

Comparative Example CE-1

[0095] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 98.18 g (7 mmol) of the polyether X and 7.57 g (0.028 mol) of octadecyl alcohol were heated to 80 C. Following this, 4.87 g (0.028 mol) of TDI were added slowly to the reaction mixture. During the course of the isocyanate addition, an increase of temperature and viscosity could be observed. Finally, the reaction was discontinued, since the stirring of the reaction product turned out to be impossible.

Comparative Example CE-2

[0096] In analogy to example CE-1, a conventional urethane thickener was prepared by reaction of polyether X and 1-isocyanatooctadecane.

Comparative Example CE-3

[0097] In a four-neck round bottom flask equipped with stirrer, reflux condenser and nitrogen inlet, 105.19 g (7.5 mmol) of polyether X were heated to 80 C. 2.16 g (15 mmol) of 3,5,5-trimethyl hexanol were added. After homogenization of this mixture, 2.61 g (15 mmol) of TDI were added and the reaction mixture was reacted for 3 h at 80 C. The reaction product is a highly viscous yellowish product.

Comparative Example CE-4

[0098] In analogy to example CE-3, a conventional urethane thickener was prepared by reaction of ethoxylated decanol and an aliphatic triisocyanate.

TABLE-US-00003 TABLE 2 Overview of polymers prepared Mn Mw PDI/ Example Monoadduct Polyether Alcohol [g/mol] [g/mol] PDI (n + 1) Polyether X 6592 14924 2.26 UR-1 octadecyl alcohol Polyether X 5997 23764 3.96 0.99 UR-2 2-ethylhexanol Polyether X 5418 17258 3.19 0.79 UR-3 3,5,5- Polyether X 7142 21177 2.97 0.74 trimethylhexanol UR-4 2-ethylhexanol Polyether X 6163 18699 3.03 0.76 CE-3 Polyether X TMH 7765 45465 5.86 1.47

Preparation of Further Polymers According to the Invention

Example X.1

[0099] A four-necked round-bottom flask equipped with stirrer, temperature probe, and reflux condenser was charged with 0.0503 moles (350.00 g) Polyglykol 12000 S and heated to 120 C. under vacuum with constant stirring. After three hours of drying time, the round-bottom flask was cooled to 70 C. and put under nitrogen. A solution of 0.0503 moles (16.75 grams) of MA-3 dissolved in toluene was added to the round-bottom flask. The reaction is exothermic and the solution was added slowly so that the temperature of the flask does not exceed 80 C. After the complete addition of the monoadduct the mixture was stirred for 3 hours at 70 C. under nitrogen. The finished product was poured onto a pan to allow the solvent to evaporate. The final product was broken into opaque white flakes which were subsequently dissolved into water for testing.

[0100] The same basic procedure was followed for examples X.2-X.9 with a 2:1 molar ratio of TDI-monoadduct and polyethylene glycol (PEG).

TABLE-US-00004 TABLE 3 List of polyethylene glycol (PEG) starting material and inventive polymers. The PEG is listed as an abbreviated form of the tradename: Polyglykol 12000 S (PEG-12), Polyglykol 20000 S (PEG-20) and Polyglykol 35000 S (PEG-35) available from Clariant. The molecular weights and polydispersity index (PDI) have been measured by GPC as described above. TDI- Polyethylene TDI- monoadduct Polyethylene glycol Mn Mw PDI/ Example monoadduct (mass) glycol (mass) (g/mol) (g/mol) PDI (n + 1) PEG-12 13832 16267 1.18 PEG-20 19463 23322 1.20 PEG-35 30242 40909 1.35 X. 1 MA-3 16.75 g PEG-12 350.00 g 10630 16712 1.57 0.79 X. 2 MA-3 12.14 g PEG-20 350.00 g 19610 26221 1.33 0.67 X. 3 MA-3 6.66 g PEG-35 350.00 g 31863 45712 1.43 0.72 X. 4 MA-2 15.54 g PEG-12 350.00 g 13460 16876 1.25 0.63 X. 5 MA-2 11.27 g PEG-20 350.00 g 20796 27805 1.34 0.67 X. 6 MA-2 6.18 g PEG-35 350.00 g 30872 43385 1.41 0.71 X. 7 MA-4 19.92 g PEG-12 350.00 g 13131 16578 1.26 0.63 X. 8 MA-4 14.44 g PEG-20 350.00 g 20021 25643 1.28 0.64 X. 9 MA-4 7.92 g PEG-35 350.00 g 29347 41676 1.42 0.71

[0101] Preparation of Further Comparative Polymers

Comparative Example C.1

[0102] A four-necked round-bottom flask equipped with stirrer, temperature probe, and reflux condenser was charged with 0.0250 moles (500.00 g) Polyglykol 20000 S and heated to 120 C. under vacuum with constant stirring. After three hours of drying time, the round-bottom flask was cooled to 70 C. and put under nitrogen. A combination of 0.500 moles of toluene diisocyanate (8.71 grams), 0.500 moles of 3,5,5-trimethylhexanol (7.21 g) and 0.67 grams of a bismuth carboxylate catalyst was added to the round-bottom flask. The reaction is exothermic and the solution was added slowly so that the temperature of the flask did not exceed 80 C. After the complete addition of the reactants the mixture was stirred for 1.5 hours at 70 C. under nitrogen. The finished product was poured onto a pan to allow any solvent to evaporate. The following data were determined: Mn 25550, Mw 54230, PDI 2.12, PDI/(n+1) 1.06. The final product was broken into opaque white flakes which were subsequently dissolved into water for further testing.

Comparative Example C.2

[0103] A four-necked round-bottom flask equipped with stirrer, temperature probe, and reflux condenser was charged with 0.0143 moles (500.00 g) Polyglykol 35000 S and heated to 120 C. under vacuum with constant stirring. After three hours of drying time, the round-bottom flask was cooled to 70 C. and put under nitrogen. A combination of 0.286 moles of toluene diisocyanate (4.98 grams), 0.286 moles of 3,5,5-trimethylhexanol (4.12 g) and 0.66 grams of a bismuth carboxylate catalyst was added to the round-bottom flask. The reaction is exothermic and the solution was added slowly so that the temperature of the flask does not exceed 80 C. After the complete addition of the reactants the mixture was stirred for 1.5 hours at 70 C. under nitrogen. The finished product was poured onto a pan to allow any solvent to evaporate. The following data were determined: Mn 36160, Mw 87540, PDI 2.42, PDI/(n+1) 1.21. The final product was broken into opaque white flakes which were subsequently dissolved into water for further testing.

Comparative Example C.3

[0104] A conventional urethane thickener was prepared by reaction of polyethylene glycol, diisocyanate and branched mono-functional alcohols. The following data were determined: Mn 24350, Mw 66830, PDI 2.74, PDI/(n+1) 1.37.

Preparation of an Additive Composition

[0105] The polyurethanes UR-1 and CE-2 were dissolved in the following formulations to form an aqueous additive compositions.

TABLE-US-00005 Component Description concentration [wt. %] UR-1/CE-2 polyurethane 20.00 Viscosity depressant 1 nonionic surfactant based 12.75 on block copolymer of propylene oxide and ethylene oxide with 30% ethylene oxide Viscosity depressant 2 C8C14- 7.50 alkylpolyglucoside Water 59.45 Acticide MBS (Biocide) 1,2-benzisothiazolin-3- 0.30 one & 2-methyl-4-isothiazolin-3- one

[0106] Preparation of a Paint Formulation

[0107] A high gloss acrylic emulsion paint was prepared from the following components using a Dispermat CV (VMA Getzmann):

TABLE-US-00006 Raw Materials wt. % Water 4.00 Acticide MBS THOR GmbH, Speyer, Germany 0.20 DISPERBYK-199 BYK Additives, Wesel, Germany 1.10 BYK-1640 BYK Additives, Wesel, Germany 0.30 Kronos 2190 KRONOS Titan GmbH, Leverkusen, 22.50 Germany Water 0.50 BYK-7420 ES BYK Additives, Wesel, Germany 0.30 Water 5.00 Dispersing with Dispermat CV for 20 minutes at 12 m/s Acronal DS 6262 BASF SE, Ludwigshafen, Germany 57.00 Texanol Eastman Chemical Company, 1.50 Kingsport, USA BYK-093 BYK Additives, Wesel, Germany 0.30 Additive Additive compositions of 0.75 composition polymers UR-1 or CE-2 post add Water 6.55 Total 100.00

TABLE-US-00007 Technical Component Function Description Source Acronal DS Binder Acrylic BASF SE 6262 Polymer Ludwigshafen, Germany Kronos 2190 Pigment Titanium KRONOS Titan GmbH Dioxide Leverkusen, Germany Texanol Coalescent Ester Alcohol Eastman Chemical Company Kingsport, Tennessee, USA DISPERBYK- Dispersant Solution of a BYK Additives & 199 copolymer with Instruments pigment Wesel, Germany affinic groups BYK-1640 Defoamer Defoamer BYK Additives & formulation Instruments made Wesel, Germany of polyamide particles & highly branched polymers BYK-093 Defoamer Mixture of BYK Additives & foam-destroying Instruments polysiloxanes Wesel, Germany and hydrophobic solids in polyglycol BYK-7420 Rheology solution of BYK Additives & ES Modifier a modified Instruments urea Wesel, Germany Acticide biocide and 1,2- THOR GmbH MBS algicide & benzisothiazolin- Speyer, Germany fungicide 3-one & 2-methyl-4- isothiazolin- 3-one

[0108] Incorporation of Additive Compositions:

[0109] The additive compositions are post added under stirring and well incorporated for 5 minutes.

[0110] Evaluation of Application Properties:

[0111] Color acceptance: 97 wt. % of the paint sample and 3 wt. % of a blue pigment concentrate are mixed by hand. A 150 m drawdown is carried out directly after mixing and after 1-5 days on BYK-Gardener contrast Chart 2811 (each series same day), rub-out is done after approx. 12 minutes.

[0112] The L*, a*, b* and E values are measured by BYK-Gardner Color Guide sphere.

[0113] The target of the E value is to be low.

Conclusion

[0114] The results in the table below show improved E values with the inventive chemistry in comparison to CE-2 without negative influence on other properties, such as gloss and visual appearance.

TABLE-US-00008 Sample E value CE-2 5.4 comparison UR-1 1.5 inventive polymer

[0115] Preparation of Further Additive Compositions

[0116] The polyurethanes UR-2 to UR-4, CE-3 and CE-4 were dissolved in the following formulation to form aqueous solutions.

TABLE-US-00009 concentration Component Description [wt. %] UR-2/UR-3/UR-4/ polyurethane 25 CE-3/CE-4 Viscosity depressant 3 isotridecyl 40 ethoxylate alcohol Viscosity depressant 4 bisphenol-A- 10 Water ethoxylate 25

[0117] Preparation of a Paint Formulation

[0118] A high gloss acrylic emulsion paint was prepared from the following components:

TABLE-US-00010 Raw Materials wt. % Grind Water 4.00 Acticide MBS THOR GmbH, Speyer, Germany 0.20 BYK-1640 BYK Additives, Wesel, Germany 0.20 DISPERBYK-199 BYK Additives, Wesel, Germany 0.90 Kronos 2310 KRONOS Titan GmbH, Leverkusen, 18.75 Germany Water 0.50 BYK-7420 ES BYK Additives, Wesel, Germany 0.25 Water 3.45 Dispersing with Dispermat CV for 20 minutes at 12 m/s Letdown Alberdingk AC 2025 Alberdingk Boley Inc., 59.00 Propylene Glycol Greensboro, USA 3.00 Water 3.65 Aquacer 539 BYK Additives, Wesel, Germany 4.00 Additive composition Aqueous solutions of UR-2/UR-3/UR- 1.50 post add 4/CE-3/CE-4 BYK-093 BYK Additives, Wesel, Germany 0.30 BYK-349 BYK Additives, Wesel, Germany 0.30 Total 100.00

TABLE-US-00011 Component Function Technical Description Source AC 2025 Binder Acrylic Polymer Alberdingk Boley Greensboro, USA Kronos 2310 Pigment Titanium Dioxide KRONOS Titan GmbH Leverkusen, Germany AQUACER- Wax Non-ionic emulsion of BYK Additives & 539 modified Instruments paraffin wax Wesel, Germany DISPERBYK- Dispersant Solution of a copolymer BYK Additives & 199 with Instruments pigment affinic groups Wesel, Germany BYK-1640 Defoamer Defoamer formulation BYK Additives & made Instruments of polyamide particles Wesel, Germany & highly branched polymers BYK-093 Defoamer Mixture of foam- BYK Additives & destroying Instruments polysiloxanes and Wesel, Germany hydrophobic solids in polyglycol BYK-349 Silicone Polyether-modified BYK Additives & surfactant siloxane Instruments Wesel, Germany BYK-7420 Rheology solution of a modified BYK Additives & ES Modifier urea Instruments Wesel, Germany Acticide Microbiocide 1,2-benzisothiazolin- THOR GmbH MBS and 3-one & Speyer, Germany algicide & 2-methyl-4- fungicide isothiazolin-3- one

[0119] Incorporation of Additive Compositions:

[0120] The additive compositions were post added under stirring and well incorporated for 5 minutes using a Dispermat CV.

[0121] Evaluation:

[0122] Leveling bar: The leveling test blade is designed to comply with ASTM method D 4062 to measure the leveling properties of water and solvent based architectural coatings. The leveling blade creates parallel ridges to simulate brush marks. After the coating dries, the drawdown is evaluated by rating scale.

[0123] The leveling test bar is a cylinder rod with alternating gap clearances of 100 and 300 microns. Plastic side arms are a guide to maintain a straight blade movement.

[0124] The paint samples are applied by a Leneta leveling bar on BYK-Gardener contrast Chart 2811. For all paint samples, this application is carried out by the same speed and same person and therefore, all samples having the same film thickness, independent of the rheology of the sample.

[0125] Evaluation is done visually after drying.

[0126] Evaluation by rating scale: 1-5; 1=perfect leveling; 5=no leveling.

[0127] Brush ability: The samples are applied by brush (Wistoba 2040 06) on BYK-Gardener contrast Chart 2803 in an upright position (in consideration of film thickness differences between the paint samples due to the different rheology of the samples).

[0128] The visual evaluation of the ability to brush the samples (in terms of brush resistance and a similar feeling like a solvent borne alkyd paint) is done during the application.

[0129] Evaluation by rating scale: 1-5; 1=best; 5=worst.

[0130] Leveling brush application: Due to differences in film thickness, the leveling of the brush application needs to be evaluated (in comparison to leveling bar application where all samples are applied with the same film thickness). Evaluation is done visually after drying.

[0131] Evaluation by rating scale: 1-5; 1=perfect leveling; 5=no leveling.

Conclusion

[0132] The results in the table below show an improved leveling and brush ability with the inventive polymers in comparison to CE-4 without negative influence on other properties, such as gloss and visual appearance. In comparison to CE-3, an improved brush ability is achieved by using the inventive polymers.

TABLE-US-00012 Leveling Leveling Brush Sample bar brush application ability CE-4 5 4.5 3 comparison UR-2 2.25 1.5 2 inventive polymer UR-3 1 1.5 1.75 inventive polymer UR-4 1 1.75 2.75 inventive polymer CE-3 1 3 3 comparison

[0133] Evaluation by rating scale: 1-5; 1=best; 5=worst.

[0134] Raw materials for preparation of further paint systems

TABLE-US-00013 TABLE 4 A list of materials in the SNAP 720 and SG-10AF paint systems. Component Function Technical Description Manufacturer SNAP 720 Binder Acrylic polymer. Arkema Coating Resins; Colombes, France Rhoplex SG- Binder Acrylic polymer. The DOW Chemical Company; 10AF Midland, Michigan, United States Ti Pure R-900 Pigment Titanium dioxide. The Chemours Company; Wilmington, Delaware, United States Ropaque Ultra Pigment Ultra opaque polymer. The DOW Chemical Company; Midland, Michigan, United States Disperbyk 199 Dispersant A solution of a BYK Additives & Instruments; copolymer with pigment Wesel, Germany affinic groups. Tamol 731A Dispersant Hydrophobic copolymer The DOW Chemical Company; polyelectrolyte. Midland, Michigan, United States BYK 038 Defoamer Mixture of paraffinic BYK Additives & Instruments; mineral oils and Wesel, Germany hydrophobic components. Kathon LX Microbicide Aqueous solution of 5- The DOW Chemical Company; chloro-2-methyl- Midland, Michigan, United States 4isothiazolin-3-one and 2-methyl-4-isothiazolin- 3-one. Texanol Coalescent Ester Alcohol. Eastman Chemical Company; Kingsport, Tennessee, United States

[0135] SNAP 720 Latex Paint

TABLE-US-00014 TABLE 5 Recipe for the 40% volume solid (VS) paint based on SNAP 720. The amount of associative thickener and water in the final step is dependent on the desired wet level of the associative thickener. Component 40% VS SNAP 720 system Water 2.92 wt % Propylene glycol 6.15 wt % Disperbyk 199 1.22 wt % BYK 038 0.19 wt % Kathon LX 0.17 wt % Ti Pure R-900 23.93 wt % Grind at 1,500 RPM for 30 minutes SNAP 720 52.22 wt % Ropaque Ultra 2.64 wt % Texanol 2.30 wt % Mix at low speed for 30 minutes BYK 038 0.19 wt % Water variable wt % Polymer of inventive and comparative examples variable wt % Mix at low speed for 30 minutes

TABLE-US-00015 TABLE 6 Application results of the X.2 and X.3 inventive polymers compared to comparative examples in a 40% volume solids SNAP 720 acrylic latex system (see Table 5 for recipe). The shear viscosities were measured 24 hours after the incorporation of the associative thickener. Concentration [g/L] of inventive and comparative additive Brookfield Stormer Sag Sample examples [cP] [KU] ICI [P] [microns] C.1 3.00 7,200 94.1 2.43 381 C.1 4.19 13,000 104.2 3.27 483 C.1 5.39 27,800 115.8 4.02 660 C.2 3.00 5,800 83.8 2.05 274 C.2 4.19 10,260 93.5 2.44 361 C.2 5.39 20,000 102.6 2.50 483 C.3 3.00 7,000 101.3 2.68 274 C.3 4.19 10,600 109.2 3.10 351 C.3 5.39 14,800 118.4 3.40 406 X.2 3.00 11,600 104.7 2.53 381 X.2 4.19 23,800 119.0 3.36 635 X.2 5.39 50,200 131.7 3.99 889 X.3 3.00 7,400 87.4 2.01 330 X.3 4.19 21,400 102.6 2.60 533 X.3 5.39 43,800 111.7 2.88 635

[0136] Acrysol SG-10AF Latex Paints

TABLE-US-00016 TABLE 7 Recipe for the 36% volume solid (VS) paint based on Rhoplex SG-10AF. The amount of associative thickener and water in the final step is dependent on the desired wet level of the associative thickener. Percent for 36% VS SG-10AF Component system Water 6.64 wt % Propylene glycol 6.17 wt % Tamol 731 1.22 wt % BYK 038 0.09 wt % Kathon LX 0.17 wt % Ti Pure R-900 24.00 wt % Grind at 1,500 RPM for 30 minutes Water 0.76 wt % Rhoplex SG-10AF 47.54 wt % Ropaque Ultra 2.65 wt % Texanol 2.31 wt % Mix at low speed for 30 minutes BYK 038 0.09 wt % Water variable wt % Polymer of inventive and comparative variable wt % examples Mix at low speed for 30 minutes

TABLE-US-00017 TABLE 8 Application results of the inventive polymer X.3 compared to comparative examples in a 36% volume solids SG-10AF acrylic latex system (see Table 7 for recipe). The samples were rolled out and the color difference (Delta-E) was measured as detailed above. Concentration [g/L] of inventive and comparative Brookfield Stormer Delta- Sample examples [cP] [KU] ICI [P] E [avg] C.1 3.00 4,200 71.6 1.804 3.6 C.1 4.20 4,600 76.4 2.567 3.3 C.1 5.40 6,400 81.8 2.852 3.0 C.2 3.00 6,200 67.2 1.308 3.8 C.2 4.20 14,400 75.8 1.887 3.5 C.2 5.40 23,660 85.0 2.533 3.5 C.3 3.00 15,400 80.3 1.367 4.5 C.3 4.20 10,200 85.6 1.725 4.2 C.3 5.40 7,600 89.4 2.308 4.4 X.2 3.00 57,000 94.8 2.333 2.7 X.2 4.20 50,400 100.2 3.062 2.4 X.2 5.40 58,200 100.5 3.875 2.3 X.3 3.00 4,580 67.0 1.137 3.1 X.3 4.20 6,620 75.4 1.442 2.7 X.3 5.40 9,200 81.8 2.217 2.6

[0137] Methods

[0138] Measurement of Rheology Properties in a Latex Paint

[0139] The shear viscosity of the latex paint was measured with ASTM International methodology. The Brookfield reported values were measured with a Brookfield DV-E Viscometer (BYK Additives & Instruments; Wesel, Germany) according to ASTM D2196-86 standard test method. The Stormer reported values were measured with a KU-1+ Viscometer (BYK Additives & Instruments; Wesel, Germany) according to the ASTM D562-81 standard test method. The ICI Cone/Plate CAP-1000+ Viscometer (Brookfield Engineering; Middleboro, Mass., United States) according to the ASTM D4287-83 standard test method. The dynamic viscosity units of poise (P) and centipoise (cP) convert to 0.1 and 0.001 Pascal-seconds.

[0140] Measurement of Sag Resistance

[0141] The sag resistance was measured according to ASTM D440-84. This standard test method utilizes a drawdown blade with a series of notches of successively higher clearance. The coating is applied to a test chart with the multinotch applicator. The charts are immediately hung vertically with the drawdown strips horizontal. The sag is measured from the drawdown after the film has dried completely.

[0142] Rollout Procedure to Measure Color Difference/Hiding

[0143] The drywall was prepared with commercial white primer applied with a quarter inch nap roller. Afterwards, a 9 inch stripe of commercial paint tinted with 12 oz of black colorant per gallon was applied with a quarter inch nap roller in the middle of the drywall. The final test region was approximately 1 by 2 feet in an area including the black and white primer. The samples were applied with a wet roller in a cycle consisting of down and up across 2 feet of dry wall. A total of five cycles were applied and the paint was allowed to dry for a minimum of 24 hours. The color difference was measured with a BYK spectro-guide 45/0 instrument. The recorded differences (Delta-E) are of the dried paint samples on black primer all relative to the same control of white primer alone. Eight color difference measurements, each a further inch down from the center of the rollout on black primer, were combined into one average.

[0144] SNAP 720 Latex

Conclusion: Increased Low Shear Efficiency and Sag Resistance with Inventive Polymers

[0145] The inventive polymers X.2 and X.3 have been compared in latex paint to polymers made in a random polymerization as described for comparative examples C.1, C.2 and C.3. As can be seen in Table 6, the inventive polymers are superior to the non-inventive comparative examples with respect to low shear efficiency and sag resistance. In each case the polymers were added to the paint at three different levels to a 40% VS paint based on SNAP 720. The inventive and comparative polymers impart equivalent high shear viscosity as witnessed by the ICI viscosity readings. However, compared to paints containing comparative examples the paints with the inventive polymers show improved low and medium shear viscosity. The advantage of this low shear impact is evident in the improved sag resistance imparted by the inventive polymers. Sag resistance is essential for both producers and consumers as coatings on slanted or vertical surfaces tend to sag when first applied. When the sag resistance of a latex paint is insufficient, the formulator will have to add additional thickener that is designed to increase low shear viscosity. This additional thickener increases the cost of the formulation and often leads to the degradation of the physical properties such as block resistance, stain resistance, scrub resistance, and others.

[0146] SG-10AF Latex

Conclusion: Improved Hiding Power with Inventive Polymers

[0147] The inventive polymers X.2 and X.3 have been compared in latex paint to polymers made in a random polymerization as described for comparative examples C.1, C.2 and C.3. As can be seen in Table 8, the inventive polymers are superior to the non-inventive comparative examples with respect to hiding power on application. In each case the polymers were added to the paint at three different levels to a 40% VS paint based on Rhoplex SG-10AF. The samples incorporated in the white pigmented paint were applied onto drywall with a roller applicator across a black primed surface. The inventive examples had improved hiding relative to comparative examples and to quantitate this improvement the color difference was measured (see method for rollout and color difference measurement procedure). The color difference between the painted black primed surface and unpainted white primed surface was significantly less for the inventive examples. A principal limitation of latex paints is the difficulty of achieving adequate hiding in a minimal number of coats. The high hiding power of the inventive examples decreases the number of coats needed by the consumer. A higher concentration of titanium dioxide in the paint may even lead to one coat hide with these inventive examples.