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 same polyethoxylated compound (b) including from 100 to 500 oxyethylene groups selected from the group consisting of straight aliphatic monoalcohols (b1) including from 6 to 40 carbon atoms, branched aliphatic monoalcohols (b2) including from 6 to 40 carbon atoms, and cycloaliphatic monoalcohols (b3) including from 6 to 40 carbon atoms.

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 same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups selected from the group consisting of straight aliphatic monoalcohols (b1) comprising from 6 to 40 carbon atoms, branched aliphatic monoalcohols (b2) comprising from 6 to 40 carbon atoms, and cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms.

2. The diurethane compound T according to claim 1, wherein the reacting comprises 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 polyethoxylation is between 105 and 500, and wherein the polyethoxylated compound (b) comprises from 100 to 500 ethoxylated groups.

6. The diurethane compound T according to claim 1, wherein the polyethoxylated compound (b) is selected from the group consisting of the straight aliphatic monoalcohol (b1) having a hydrocarbon chain with 6 to 30 carbon atoms, the branched aliphatic monoalcohol (b2) having a hydrocarbon chain with 6 to 30 carbon atoms, and the cycloaliphatic monoalcohol (b3) having a hydrocarbon chain with 6 to 30 carbon atoms.

7. A method for preparing a diurethane compound T, comprising by reacting: a. one molar equivalent of at least one diisocyanate compound (a) and b. two molar equivalents of a same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups selected from the group consisting of straight aliphatic monoalcohols (b 1) comprising from 6 to 40 carbon atoms, branched aliphatic monoalcohols (b2) comprising from 6 to 40 carbon atoms, and cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms.

8. The method according to claim 7, comprising a single compound (a) or two or three different compounds (a).

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

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 stabilising agent, an opacifying agent, a solvent, a coalescing agent, an anti-foaming agent, a preservative agent, a biocide, 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, an adhesive formulation, or a paint formulation.

12. A concentrated aqueous pigment pulp comprising at least one diurethane compound T according to claim 1 and at least one coloured organic or mineral pigment.

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

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

Description

EXAMPLES

Example 1

Preparation of Diurethane Compounds According to the Invention

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

[0062] In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 451.2 g of ethoxylated dodecanol are introduced with 140 mol of ethylene oxide (MM=6,355 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0063] Under stirring and in an inert atmosphere, 5.97 g of HDI (MM=168.2 g/mol) are then added in one hour in the presence of 200 ppm of dibutyltin dilaurate 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. 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 are added 1,000 ppm of a biocide (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

[0064] In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 448.7 g of ethoxylated dodecanol are introduced with 140 mol of ethylene oxide (MM=6,355 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0065] Under stirring and in an inert atmosphere, 7.85 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. As described in Example 1-1, 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 are added 1,000 ppm of a biocide (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 1-3: Preparation of a Compound T3 According to the Invention

[0066] In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 449.3 g of ethoxylated dodecanol are introduced with 140 mol of ethylene oxide (MM=6,355 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0067] Under stirring and in an inert atmosphere, 9.27 g of H.sub.12MDI (MM=262.3 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. As described in Example 1-1, 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 T3 obtained is formulated in water to which are added 1,000 ppm of a biocide (Biopol SMV Chemipol) and 1,000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 3 is obtained consisting of 20% by mass of compound T3 according to the invention and 80% by mass of water.

Example 1-4: Preparation of a Compound T4 According to the Invention

[0068] In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 449.3 g of ethoxylated octadecanol are introduced with 132 mol of ethylene oxide (mean MM=6,078 Da) that is heated to 90° C. in an inert atmosphere. This product is dehydrated.

[0069] Under stirring and in an inert atmosphere, 6.23 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. As described in Example 1-1, 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 T4 obtained is formulated using a surfactant compound such as ethoxylated alcohol (ethoxylated hexanol with five ethylene oxide equivalents) in water to which are added 1,000 ppm of a biocide (Biopol SMV Chemipol) and 1,000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 4 is obtained consisting of 20% by mass of compound T4 according to the invention, 15% of surfactant and 65% by mass of water.

Example 2

Preparation of Paint Formulations According to the Invention

[0070] Paint formulations F1 to F3 according to the invention are prepared respectively from aqueous compositions 1 to 3 of diurethane compounds Ti to T3 according to the invention. 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 (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.3 pigment (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 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.Math.s) was determined 24 hours after their preparation using a Brookfield DV-1 viscometer with RVT spindles. The properties of the paint formulations are listed in Table 2.

TABLE-US-00002 TABLE 2 Formulation Compound μ.sub.Bk10 μ.sub.Bk100 F1 T1 2,980 1,810 F2 T2 6,100 3,110 F3 T3 4,160 2,070

[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), and the Stormer viscosity, measured at medium shear gradient (μS in Krebs Units or KUs), were determined 24 hours after the preparation of the formulations and at room temperature, using the reference module. The properties of the paint formulations are listed in Table 3.

TABLE-US-00003 TABLE 3 Formulation Compound μ.sub.I μ.sub.S μ.sub.I/μ.sub.S F1 T1 270 99 2.7 F2 T2 310 115 2.7 F3 T3 260 101 2.6

[0074] The diurethane compounds according to the invention make it possible to prepare paint formulations with particularly well-controlled viscosities. In particular, the μI viscosity is particularly high and the μI/μs ratio is therefore excellent. The compounds according to the invention allow for an excellent compromise between high shear gradient viscosity and low shear gradient viscosity.