RHEOLOGY-MODIFYING DIURETHANE COMPOUND

Abstract

A diurethane compound T prepared by reacting one molar equivalent of at least one diisocyanate compound (a) and two molar equivalents of a polyalkoxylated compound (b) selected from the group consisting of monoaromatic monoalcohols (b1) comprising from 6 to 30 polyalkoxylated carbon atoms and comprising from 80 to 500 alkoxy groups, and polyaromatic monoalcohols (b2) comprising from 10 to 80 polyalkoxylated carbon atoms and comprising more than 100 and up to 500 alkoxy groups.

Claims

1. A diurethane compound T prepared by reacting: a. one molar equivalent of at least one diisocyanate compound (a) and b. two molar equivalents of a polyalkoxylated compound (b) selected from the group consisting of monoaromatic monoalcohols (b1) comprising from 6 to 30 polyalkoxylated carbon atoms and comprising from 80 to 500 alkoxy groups, and polyaromatic monoalcohols (b2) comprising from 10 to 80 polyalkoxylated carbon atoms and comprising more than 100 and up to 500 alkoxy groups.

2. The diurethane compound T according to claim 1, comprising a single compound (a) or two or three different compounds (a).

3. The diurethane compound T according to claim 1 wherein the compound (a) is selected from the group consisting of symmetric aromatic diisocyanate compounds, symmetric alicyclic diisocyanate compounds, symmetric aliphatic diisocyanate compounds, asymmetric aromatic diisocyanate compounds, and asymmetric alicyclic diisocyanate compounds.

4. The diurethane compound T according to claim 1, wherein the compound (a) is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), methylene bis(4-cyclohexylisocyanate) (H.sub.12MDI), and combinations thereof.

5. The diurethane compound T according to claim 1 wherein a degree of polyalkoxylation is between 80 and 500, wherein the polyalkoxylated compound (b) comprises from 100 to 500 alkoxy groups wherein the alkoxy groups are selected from the group consisting of oxyethylene (—CH.sub.2CH.sub.2O—), oxypropylene (—CH.sub.2CH(CH.sub.3)O— or —CH(CH.sub.3)CH.sub.2O—), oxybutylene (—CH(CH.sub.2CH.sub.3)CH.sub.2O— or —CH.sub.2CH(CH.sub.2CH.sub.3)O—) and combinations thereof.

6. The diurethane compound T according to claim 1, wherein the polyalkoxylated compound (b) is selected from the group consisting of a monoaromatic monoalcohol (b1) wherein a hydrocarbon chain of the monoaromatic monoalcohol (b1) comprises from 12 to 30 carbon atoms and a polyaromatic monoalcohol (b2) wherein a hydrocarbon chain of the polyaromatic monoalcohol (b2) comprises from 10 to 60 carbon atoms.

7. A method for preparing a diurethane compound T, comprising reacting: a. one molar equivalent of at least one diisocyanate compound (a) and b. two molar equivalents of a polyalkoxylated compound (b) selected from the group consisting of monoaromatic monoalcohols (b1) comprising from 6 to 30 polyalkoxylated carbon atoms and comprising from 80 to 500 alkoxy groups, and polyaromatic monoalcohols (b2) comprising from 10 to 80 polyalkoxylated carbon atoms and comprising more than 100 and up to 500 alkoxy groups.

8. The method according to claim 7 for the preparation of the diurethane compound T comprising a single compound (a) or two or three different compounds (a).

9. An aqueous composition comprising: the diurethane compound T according to claim 1; and at least one additive selected from the group consisting of an amphiphilic compound, a polysaccharide derivative, a solvent, an anti-foaming agent, and a biocide agent.

10. An aqueous formulation comprising: at least one aqueous composition according to claim 9; at least one organic or mineral pigment or organic, organo-metallic or mineral particles, and at least one agent selected from the group consisting of a particle-spacer agent, a dispersing agent, a stabilising steric agent, an electrostatic stabiliser, an opacifying agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative agent, a biocide agent, a spreading agent, a thickening agent, a film-forming copolymer, and mixtures thereof.

11. The aqueous formulation according to claim 10, wherein the aqueous formulation is an ink formulation, a varnish formulation, a binder formulation, or a paint formulation.

12. A concentrated water-based pigment pulp comprising at least one diurethane compound T according to claim 1.

13. A method for controlling a viscosity of an aqueous composition comprising adding at least one diurethane compound T according to claim 1.

14. A method for controlling a viscosity of the aqueous composition according to claim 9 comprising adding at least one diurethane compound T.

Description

EXAMPLE 1

Preparation of Diurethane Compounds According to the Invention

Example 1-1: Preparation of a Compound T1 According to the Invention

[0064] In a 3 L glass reactor equipped with mechanical stirring rod, a vacuum pump, and a nitrogen inlet and heated by means of a double jacket in which oil circulates, 450.9 g of ethoxylated tristyrylphenol is introduced with 130 mol of ethylene oxide (MM=6,120 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0065] Under stirring and in an inert atmosphere, 6.20 g of HDI (MM=168.2 g/mol) are then added in one hour in the presence of 200 ppm of bismuth carboxylate catalyst. When the addition is complete, the reaction mixture is left to stir for 60 minutes at 90° C.±1° C. Then, the absence of isocyanate is checked by back titration. 1 g is collected from the reaction medium to which an excess of dibutylamine (1 mol, for example) is added, which reacts with any isocyanate groups that may be present in the medium.

[0066] Any unreacted dibutylamine is then assayed with hydrochloric acid (1 N, for example). The number of isocyanate groups present in the reaction medium can then be deduced. If this number is not zero, the reaction is continued for 15-minute periods until the reaction is completed. When the level reaches zero, the compound T1 obtained is formulated in water to which is added 1,000 ppm of a biocide agent (Biopol SMV Chemipol) and 1,000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 1 is obtained consisting of 20% by mass of compound T1 according to the invention and 80% by mass of water.

Example 1-2: Preparation of a Compound T2 According to the Invention

[0067] In a 3 L glass reactor equipped with mechanical stirring rod, a vacuum pump, and a nitrogen inlet and heated by means of a double jacket in which oil circulates, 448.1 g of ethoxylated tristyrylphenol is introduced with 130 mol of ethylene oxide (MM=6,120 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0068] Under stirring and in an inert atmosphere, 8.14 g of IPDI (MM=222.3 g/mol) are then added in one hour in the presence of 200 ppm of bismuth carboxylate catalyst. When the addition is complete, the reaction mixture is left to stir for 60 minutes at 90° C.±1° C. Then, the absence of isocyanate is checked by back titration. If this number is not zero, the reaction is continued for 15-minute periods until the reaction is completed. When the level reaches zero, the compound T2 obtained is formulated in water to which is added 1,000 ppm of a biocide agent (Biopol SMV Chemipol) and 1,000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 2 is obtained consisting of 20% by mass of compound T2 according to the invention and 80% by mass of water.

EXAMPLE 2

Preparation of Paint Formulations According to the Invention

[0069] Paint formulations F1 and F2 according to the invention are prepared respectively from aqueous compositions 1 and 2 of diurethane compounds T1 and T2 according to the invention.

[0070] All of the ingredients and proportions (% by mass) used are listed in Table 1.

TABLE-US-00001 TABLE 1 Ingredients: Amount (g): water 99.7 dispersing agent (Coadis BR3 Coatex) 3.9 biocide agent (Acticide MBS Thor) 1.3 anti-foaming agent (Airex 901W Evonik) 1.31 NH.sub.4OH (28%) 0.6 TiO.sub.2 pigment (RHD2 Huntsman) 122.2 CaCO.sub.3pigment (Omyacoat 850 OG Omya) 84.6 binding agent (Acronal S790 Basf) 270.7 monopropylene glycol 6.5 solvent (Texanol Eastman) 6.5 anti-foaming agent (Tego 825 Evonik) 1.0 aqueous composition 1 according to the invention 28.7 added water q.s.p 650 g total

EXAMPLE 3

Characterisation of Paint Formulations According to the Invention

[0071] For the paint formulations according to the invention, the Brookfield viscosity, measured at 25° C. and at 10 rpm and 100 rpm (μ.sub.Bk10 and μ.sub.Bk100 in mPa.$) was determined 24 hours after their preparation using a Brookfield DV-1 viscometer with RVT spindles.

TABLE-US-00002 TABLE 2 The properties of the paint formulations are listed in Table 2. Formulation Compound μ.sub.Bk10 μ.sub.Bk100 F1 T1 5050 4025 F2 T2 5500 4335

[0072] The diurethane compounds according to the invention are highly effective in obtaining excellent low and medium shear gradient viscosities for paint compositions.

EXAMPLE 4

Characterisation of Paint Formulations According to the Invention

[0073] For the paint formulations according to the invention, the Cone Plan viscosity or ICI viscosity, measured at high shear gradient (μI in mPa.Math.s) was determined 24 hours after their preparation and at room temperature, using a Cone & Plate Research Equipment London (REL) viscometer having a measuring range of 0 to 5 poise, and the Stormer viscosity, measured at medium shear gradient (μS in Krebs Units or KUs), was determined using the reference module of a Brookfield KU-2 viscometer. The properties of the paint formulations are listed in Table 3.

TABLE-US-00003 TABLE 3 Formulation Compound μI μS F1 T1 120 122 F2 T2 130 124

[0074] The diurethane compounds according to the invention make it possible to prepare paint formulations with particularly well-controlled viscosities. In particular, the viscosity μ.sub.I is particularly high. The compounds according to the invention allow for good control of the viscosity at high shear gradients and of the viscosity at low shear gradients.