Non-ionic associative thickeners containing cyclohexylol alkyls, formulations containing them and their uses

Abstract

The present invention concerns new associative thickeners of the HEUR type (Hydrophobically modified Ethylene oxide URethane) whose hydrophobic monomer is based on alkyl cyclohexylols. These are new polyurethanes that significantly thicken an aqueous formulation with a low, medium and high shear gradient. The invention also concerns the compositions containing them and their uses in different formulations such as aqueous paints.

Claims

1. A water soluble polyurethane consisting of polymerized units resulting from the condensation of: a monomer of formula (I) ##STR00006## where R designates an alkyl group with 9 carbon atoms, a polyalkylene glycol, and a polyisocyanate.

2. The polyurethane according to claim 1, consisting of polymerized units resulting from the condensation of: a) 1% to 29% by weight of said monomer of formula (I), b) 70% to 98% by weight of said polyalkylene glycol, and c) 1% to 29% by weight of said polyisocyanate where the sum of these mass percentages is equal to 100%.

3. The polyurethane according to claim 1, consisting of polymerized units resulting from the condensation of a) 3% to 7% by weight of said monomer of formula (I), b) 86% to 94% by weight of said polyalkylene glycol, and c) 3% to 7% by weight of said polyisocyanate where the sum of these mass percentages is equal to 100%.

4. The polyurethane according to claim 1, where the polyalkylene glycol is polyethylene glycol the molecular mass by weight of which is 2,000 g/mol-20,000 g/mol.

5. The polyurethane according to claim 1, where the polyisocyanate is chosen from the group consisting of toluene diisocyanate, the toluene diisocyanate dimers, the toluene diisocyanate trimers, 1,4-butane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4diisocyanatodicyclohexylmethane, 1-methyl-2,4-diisocyanatocyclohexane, a blend of 1-methyl-2,4-diisocyanatocyclohexane and 1-methyl-2,6-diisocyanatocyclohexane, the biuret of hexamethylene diisocyanate, the dimers of the biuret of hexamethylene diisocyanate, the trimers of biuret of hexamethylene diisocyanate, and mixtures thereof.

6. An aqueous composition comprising water and a polyurethane according to claim 1.

7. An aqueous composition according to claim 6, further comprising a surfactant.

8. An aqueous composition according to claim 6, further comprising an additive selected from the group consisting of a biocide, a solvent, an anti-foaming agent, a pH regulator, a coalescent agent and mixtures thereof.

9. An aqueous composition according to claim 6, comprising: 5% to 45% by weight of said polyurethane, 5% to 30% by weight of a surfactant, 25% to 75% by weight of water, and 0 to 5% by weight of an additive selected from the group consisting of a biocide, a solvent, an anti-foaming agent, a pH regulator, a coalescent agent, and mixtures thereof, where the sum of these mass percentages is equal to 100%.

10. The polyurethane according to claim 1, wherein the monomer of formula (I) is a compound of the following formula (II): ##STR00007## where R designates an alkyl group having 9 carbon atoms.

11. An aqueous composition according to claim 6, wherein the monomer of formula (I) is a compound of the following formula (II): ##STR00008## where R designates an alkyl group having 9 carbon atoms.

12. The polyurethane according to claim 1, consisting of polymerized units resulting from the condensation of a) 3% to 7% by weight of said monomer of formula (I), b) 86% to 94% by weight of said polyalkylene glycol, and c) 3% to 7% by weight of said polyisocyanate where the sum of these mass percentages is equal to 100%, the polyalkylene glycol is polyethylene glycol the molecular mass by weight of which is 2,000 g/mol-20,000 g/mol, and the polyisocyanate is chosen from the group consisting of toluene diisocyanate, the toluene diisocyanate dimers, the toluene diisocyanate trimers, 1,4-butane diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4diisocyanatodicyclohexylmethane, 1-methyl-2,4-diisocyanatocyclohexane, a blend of 1-methyl-2,4-diisocyanatocyclohexane and 1-methyl-2,6-diisocyanatocyclohexane, the biuret of hexamethylene diisocyanate, the dimers of the biuret of hexamethylene diisocyanate, the trimers of biuret of hexamethylene diisocyanate, and mixtures thereof.

Description

EXAMPLES

Example 1

(1) This example describes a polyurethane according to the invention that uses a compound of formula (I) where R designates the linear alkyl group with 9 carbon atoms. Thus, we have here a hydrophobic monomer with the formula (I) with 15 carbon atoms.

(2) At the same time, this example also illustrates 4 polyurethanes according to the prior art that use linear fatty alcohols with 12, 14, 16 and 18 carbon atoms.

(3) This example describes a polyurethane apart from the invention that uses a compound of formula (I) where R designates the linear alkyl group with 12 carbon atoms. Thus, we have here a hydrophobic monomer with the formula (I) with 18 carbon atoms.

(4) All the polyurethanes are products that are the result of the condensation, expressed in % by weight of each of the constituents, of 90% polyethylene glycol with a molecular mass by weight equal to 10,000 g/mol, of 5% of a monomer terminated by a hydrophobic group, the nature of which will be specified later, and of 5% of isophorone diisocyanate.

(5) Finally, all these polyurethanes are formulated in water in the presence of a non-ionic surfactant (in this instance, a blend of commercially available branched alcoxylated C8 and C10 compounds) (ratio by weight: 30% polyurethane, 20% surfactant, 50% water).

(6) An aqueous composition is obtained in this manner.

(7) Test No. 1

(8) This test illustrates a domain outside of the invention and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer has the formula (I), where R designates the linear alkyl group with 12 carbon atoms.

(9) Test No. 2

(10) This test illustrates the invention and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer has the formula (I), where R designates the linear alkyl group with 9 carbon atoms.

(11) Test No. 3

(12) This test illustrates the prior art and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer is a linear alcohol with 12 carbon atoms marketed under the name Nacol 12-96 by the SASOL company.

(13) Test No. 4

(14) This test illustrates the prior art and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer is a linear alcohol with 14 carbon atoms marketed under the name Nacol 14-98 by the SASOL company.

(15) Test No. 5

(16) This test illustrates the prior art and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer is a linear alcohol with 16 carbon atoms marketed under the name Nacol 16-95 by the SASOL company.

(17) Test No. 6

(18) This test illustrates the prior art and corresponds to a formulation in water at 30% by dry weight of a polyurethane with a molecular mass by weight equal to approximately 11,000 g/mol where the hydrophobic monomer is a linear alcohol with 18 carbon atoms marketed under the name Nacol 18-98 by the SASOL company.

(19) Test No. 7

(20) This test illustrates the prior art and uses Acrysol RM 8 W marketed by the DOW company.

Example 2

(21) This example illustrates the use of polyurethanes of example 1 as thickening agents for a flat paint.

(22) The composition of the said paint is indicated in table 1, the mass of each constituent being indicated in grams.

(23) The paint is formulated according to methods well known to the person skilled in the art.

(24) In each test, 0.2% by dry weight of the polymer according to the invention is used in relation to the total weight of the paint formulation, i.e. approximately for 1 kg of formulation as defined below, 6.67 g of an aqueous composition as mentioned above.

(25) TABLE-US-00001 TABLE 1 Constituents Mass (g) Water 190 Ecodis P50 (Coatex) 4 Acticide MBS (Thor) 2 Tego 810 (Tego) 1 NaOH (20%) 1 Tiona 568 (Millenium) 80 Durcal 2 (Omya) 300 Omyacoat 850 OG (Omya) 220 Acronal 290 D (BASF) 130 Monopropylene glycol 10 Texanol (Eastman) 10 Water QS 1,000

(26) The resulting viscosities are then determined at T=24 hours at 25 C., at low shear rate, Brookfield viscosity at 10 RPM, designated .sub.Bk10 (mPa.Math.s), at medium shear rate, Stormer viscosity, designated .sub.S (KU), and at high shear rate, ICI viscosity, designated .sub.ICI (Poise or P).

(27) The results are shown in table 2.

(28) TABLE-US-00002 TABLE 2 Test No. 1 2 3 4 5 6 7 PA/IN OI IN PA PA PA PA PA associative C18 C15 C12 C14 C16 C18 Acrysol monomer RM8W .sub.ICI (P) 0.95 1.2 1.2 0.95 0.95 0.85 1.0 .sub.S (KU) 128 102 96 106 125 116 103 .sub.Bk10 (mPa .Math. s) 18,000 3,800 3,160 12,000 20,300 23,900 3,800

(29) If the results obtained with the linear structures of the prior art are analysed, it will be apparent that the associativity of polymers disappears or decreases very significantly for more than 12 carbon atoms. At the same time, the Brookfield viscosity increases very significantly for 14 carbon atoms and more.

(30) The polymers of the prior art of which the hydrophobic monomer is a linear C14, C16 or C18 are therefore not efficient enough in terms of ICI viscosity. As to the C12 polymer, it does not develop a sufficient Brookfield and Stormer viscosity.

(31) However, surprisingly, the polymer according to the invention develops a totally unique rheology: it enables an equaling of the ICI viscosity obtained with the C12 polymer while exceeding its Brookfield and Stormer viscosity levels.

(32) It can even improve the performances obtained with the commercial polymer according to test No. 7, which produces a significant deficit in ICI viscosity.

(33) Finally, test No. 1 demonstrates the importance of limiting the number of carbons in the hydrophobic monomer according to the invention. With 18 carbon atoms, the polymer in test No. 1 is not effective enough at a high shear gradient (ICI viscosity).

Example 3

(34) This example illustrates the use of the polyurethanes of example 1 as thickening agents for another flat paint.

(35) The composition of the said paint is indicated in table 3, the mass of each constituent being indicated in grams.

(36) The paint is formulated according to methods well known to the person skilled in the art.

(37) In each test, 0.36% by dry weight of the polymer according to the invention is used in relation to the total weight of the paint formulation.

(38) TABLE-US-00003 TABLE 3 Constituents Mass (g) Water 277 Ecodis P50 (Coatex) 4 Acticide MBS (Thor) 2 Tego Airex 901 W (Tego) 1 NaOH (20%) 0.9 Tiona 568 (Millenium) 81 Durcal 2 (Omya) 300.1 Omyacoat 850 OG (Omya) 133 Mowilith LDM 1871 (Celanese) 150 Tego 825 (Tego) 10 Water QS 1,000

(39) The resulting viscosities are then determined at T=24 hours at 25 C., at low shear rate, Brookfield viscosity at 10 RPM, designated .sub.Bk10 (mPa.Math.s), at medium shear rate,

(40) Stormer viscosity, designated .sub.S (KU), and at high shear rate, ICI viscosity, designated .sub.ICI (Poise or P).

(41) The results are shown in table 4.

(42) TABLE-US-00004 TABLE 4 Test No. 1 2 3 4 5 6 7 PA/IN OI IN PA PA PA PA PA associative C18 C15 C12 C14 C16 C18 Acrysol monomer linear linear linear linear RM8W .sub.ICI (P) 0.7 1.1 1.1 0.75 0.65 0.6 0.75 .sub.S (KU) 137 104 100 110 135 121 93 .sub.Bk10 (mPa .Math. s) 25,000 10,200 8,800 20,000 36,000 45,000 9,700

(43) The same conclusions are drawn from this table as those of the previous example.