RHEOLOGY-MODIFYING DIFUNCTIONAL COMPOUND

Abstract

A rheology-modifying difunctional compound prepared by reacting one molar equivalent of a non-alkoxylated compound (a) and one molar equivalent of a polyethoxylated compound (b). A method for preparing the difunctional compound by reacting one molar equivalent of a non-alkoxylated compound (a) and one molar equivalent of a polyethoxylated compound (b). An aqueous composition with the difunctional compound and an additive. An aqueous formulation with the aqueous composition, an organic or mineral pigment, and an agent. A coating formulation with the aqueous formulation. A concentrated aqueous pigment pulp with the difunctional compound and coloured organic or mineral pigment. A method for controlling the viscosity of an aqueous composition.

Claims

1. A difunctional compound T, obtained by reacting: one molar equivalent of at least one non-alkoxylated compound (a) selected from the group consisting of: straight aliphatic monoisocyanate compounds (a1) comprising from 6 to 40 non-alkoxylated carbon atoms, branched aliphatic monoisocyanate compounds (a2) comprising from 6 to 40 non-alkoxylated carbon atoms, cycloaliphatic monoisocyanate compounds (a3) comprising from 6 to non-alkoxylated carbon atoms, monoaromatic monoisocyanate compounds (a4) comprising from 6 to non-alkoxylated carbon atoms, polyaromatic monoisocyanate compounds (a5) comprising from 10 to 80 non-alkoxylated carbon atoms, straight aliphatic monohalogen compounds (a6) comprising from 6 to non-alkoxylated carbon atoms, branched aliphatic monohalogen compounds (a7) comprising from 6 to 40 non-alkoxylated carbon atoms, cycloaliphatic monohalogen compounds (a8) comprising from 6 to non-alkoxylated carbon atoms, monoaromatic monohalogenoalkylene compounds (a9) comprising from 7 to 30 non-alkoxylated carbon atoms, and polyaromatic monohalogenoalkylene compounds (a10) comprising from 10 to 80 non-alkoxylated carbon atoms; and one molar equivalent of at least one polyethoxylated compound (b) selected from the group consisting of: straight aliphatic monoalcohols (b1) comprising from 6 to 40 polyethoxylated carbon atoms comprising strictly more than 100 and up to 500 oxyethylene groups, branched aliphatic monoalcohols (b2) comprising from 6 to 40 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups, cycloaliphatic monoalcohols (b3) comprising from 6 to 40 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups, monoaromatic monoalcohols (b4) comprising from 6 to 30 polyethoxylated carbon atoms comprising strictly more than 100 and up to 500 oxyethylene groups, and polyaromatic monoalcohols (b5) comprising from 10 to 80 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups.

2. The difunctional compound T according to claim 1, wherein the reaction is with a single compound (a) or two or three different compounds (a).

3. The difunctional compound T according to claim 1, wherein the monohalogen compound is at least one selected from the group consisting of a chlorine compound, a bromine compound, an iodine compound and combinations thereof.

4. The difunctional compound T according to claim 1, wherein: a degree of polyalkoxylation is from 100 and 500; or the polyethoxylated monoalcohols (b1) and (b3) comprise from 105 to 400 ethoxylated groups or from 105 to 200 ethoxylated groups; or polyethoxylated monoalcohols (b2), (b4) and (b5) comprise from 80 to 400 ethoxylated groups or from 100 to 200 ethoxylated groups; or the polyethoxylated compound (b) comprises a number of ethoxylated groups that is identical or different.

5. The difunctional compound T according to claim 1, wherein compound (a) is: a hydrocarbon chain of compound (a1) or of compound (a6) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (a2) or of compound (a7) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (a3) or of compound (a8) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (a4) or of compound (a9) comprising from 12 to 30 carbon atoms or from 12 to 22 carbon atoms; and a hydrocarbon chain of compound (a5) or of compound (a10) comprising from 10 to 60 carbon atoms.

6. The difunctional compound T according to claim 1, wherein compound (b) is: a hydrocarbon chain of compound (b1) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (b2) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (b3) comprising from 6 to 30 carbon atoms; a hydrocarbon chain of compound (b4) comprising from 12 to 30 carbon atoms or from 12 to 22 carbon atoms; a hydrocarbon chain of compound (b5) comprising from 10 to 60 carbon atoms.

7. A method for preparing a difunctional compound T, comprising reacting: one molar equivalent of at least one non-alkoxylated compound (a) selected from the group consisting of: straight aliphatic monoisocyanate compounds (a1) comprising from 6 to 40 non-alkoxylated carbon atoms, branched aliphatic monoisocyanate compounds (a2) comprising from 6 to 40 non-alkoxylated carbon atoms, cycloaliphatic monoisocyanate compounds (a3) comprising from 6 to non-alkoxylated carbon atoms, monoaromatic monoisocyanate compounds (a4) comprising from 6 to non-alkoxylated carbon atoms, polyaromatic monoisocyanate compounds (a5) comprising from 10 to 80 non-alkoxylated carbon atoms, straight aliphatic monohalogen compounds (a6) comprising from 6 to non-alkoxylated carbon atoms, branched aliphatic monohalogen compounds (a7) comprising from 6 to 40 non-alkoxylated carbon atoms, cycloaliphatic monohalogen compounds (a8) comprising from 6 to non-alkoxylated carbon atoms, monoaromatic monohalogenoalkylene compounds (a9) comprising from 7 to 30 non-alkoxylated carbon atoms, and polyaromatic monohalogenoalkylene compounds (a10) comprising from 10 to 80 non-alkoxylated carbon atoms; and one molar equivalent of at least one polyethoxylated compound (b) selected from the group consisting of: straight aliphatic monoalcohols (b1) comprising from 6 to 40 polyethoxylated carbon atoms comprising strictly more than 100 and up to 500 oxyethylene groups, branched aliphatic monoalcohols (b2) comprising from 6 to 40 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups, cycloaliphatic monoalcohols (b3) comprising from 6 to 40 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups, monoaromatic monoalcohols (b4) comprising from 6 to 30 polyethoxylated carbon atoms comprising strictly more than 100 and up to 500 oxyethylene groups, and polyaromatic monoalcohols (b5) comprising from 10 to 80 polyethoxylated carbon atoms comprising from 80 to 500 oxyethylene groups.

8. The method according to claim 7, wherein the reaction employs a single compound (a).

9. An aqueous compositions comprising: at least one a difunctional compound T according to claim 1, and optionally at least one additive selected from the group consisting of: an amphiphilic compound; a polysaccharide derivative; solvents; and anti-foaming agents or biocides.

10. An aqueous formulation comprising: the composition according to claim 9; and optionally at least one organic or mineral pigment or organic, organo-metallic or mineral particle selected from the group consisting of calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and optionally 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. A coating formulation, comprising the aqueous formulation according to claim 10.

12. A concentrated aqueous pigment pulp comprising: the difunctional compound T according to claim 1 and a coloured organic or mineral pigment.

13. A method for controlling the viscosity of an aqueous composition, comprising: adding the difunctional compound T according to claim 1 to the aqueous solution.

14. The method according to claim 13, wherein the aqueous composition a coating formulation.

15. The difunctional compound T according to claim 3, wherein the monohalogen compound is bromine.

16. The difunctional compound T according to claim 5, wherein the hydrocarbon chain of compound (a1) or of compound (a6) has from 6 to 20 carbon atoms or from 8 to 16 carbon atoms and is at least one selected from the group consisting of a non-alkoxylated n-octanyl, non-alkoxylated n-decanyl, non-alkoxylated n-dodecanyl, and non-alkoxylated n-hexadecanyl; the hydrocarbon chain of compound (a2) or of compound (a7) has from 6 to 20 carbon atoms or from 8 to 16 carbon atoms and is at least one selected from the group consisting of non-alkoxylated ethyl hexanyl, non-alkoxylated isooctanyl, non-alkoxylated isononanyl, non-alkoxylated isodecanyl, non-alkoxylated propyl heptanyl, non-alkoxylated butyloctanyl, non-alkoxylated isododecanyl, non-alkoxylated isohexadecanyl, an alkyl group derived from a non-alkoxylated oxo alcohol, and an alkyl group derived from a non-alkoxylated Guerbet alcohol; the hydrocarbon chain of compound (a3) or of compound (a8) has from 6 to 20 carbon atoms or from 8 to 20 carbon atoms and is at least one selected from the group consisting of non-alkoxylated ethyl-cyclohexanyl, non-alkoxylated n-nonyl-cyclohexanyl, and non-alkoxylated n-dodecyl-cyclohexanyl; the compound (a4) or compound (a9) is a non-alkoxylated n-pentadocecyl phenyl; and the compound (a5) or compound (a10) is at least one selected from the group consisting of non-alkoxylated naphtyl, non-alkoxylated distyrylphenyl, non-alkoxylated tristyrylphenyl, non-alkoxylated pentastyrylcumyl phenyl.

17. The difunctional compound T according to claim 6, wherein the hydrocarbon chain of compound (b1) comprises from 6 to 20 carbon atoms or from 8 to 16 carbon atoms and is at least one selected from the group consisting of polyethoxylated n-octanol, polyethoxylated n-decanol, polyethoxylated n-decanol, polyethoxylated n-dodecanol, and polyethoxylated n-hexandecanol; the hydrocarbon chain of compound (b2) comprises from 6 to 20 carbon atoms or from 8 to 16 carbon atoms and is at least one selected from the group consisting of polyethoxylated ethylhexanol, polyethoxylated isooctanol, polyethoxylated isononanol, polyethoxylated isodecanol, polyethoxylated propyl heptanol, polyethoxylated butyl octanol, polyethoxylated isododecanol, polyethoxylated isohexadecanol, a polyethoxylated oxo alcohol, and a polyethoxylated Guerbet alcohol; the hydrocarbon chain of compound (b3) comprises from 6 to 20 carbon atoms or from 8 to 20 carbon atoms and is at least one selected from the group consisting of polyethoxylated ethylcyclohexanol, polyethoxylated n-nonyl-cyclohexanol, and polyethyoxylated n-dodecyl-cyclohexanol; the hydrocarbon chain of compound (b4) is a polyethoxylated n-pentadocecylphenol; and the hydrocarbon chain of compound (b5) is at least one selected from the group consisting of polyethoxylated naphthol, polyethoxylated distyrylphenol, polyethoxylated tristyrylphenol, and polyethoxylated pentastyrylcumylphenol.

18. The aqueous composition of claim 9, wherein the amphiphilic compound is at least one surfactant compound selected from the group consisting of alkyl-polyalkylene glycol, alkyl-polyethylene glycol, and alkyl-polypropylene glycol; the polysaccharide derivative is at least one selected from the group consisting of cyclodextrin, cyclodextrin derivative, polyethers, and alkyl-glucosides; and the solvent is at least one selected from the group consisting of glycol, butyl glycol, butyldiglycol, mono propylene glycol, ethylene glycol, and ethylenediglycol,

19. The coating formulation of claim 11, wherein the coating formulation is an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation for decorative paint, and a paint formulation for an industrial paint.

Description

EXAMPLES

Example 1: Preparation of Difunctional Compounds According to the Invention

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

[0114] In a 3 L glass reactor (container 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 450.60 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.

[0115] At the same time, in a 100 mL glass three-neck flask (container 2), 15.76 g of IPDI are introduced, to which 400 ppm of bismuth carboxylate catalyst is added. The medium is flushed with nitrogen, then heated to 50° C. When this temperature is reached, 9.23 g of octanol are gradually introduced.

[0116] When the injection is completed, the reaction mixture is left to stir for 15 minutes. Then, back titration is used to check that the theoretical level of NCO groups has been reached. 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 present in the medium. The unreacted dibutylamine is then dosed with hydrochloric acid (for example 1 N). The number of isocyanate groups present in the reaction medium can then be deduced.

[0117] Then, the contents of container 2 are poured into container 1. Stirring is continued for 60 minutes at 90±1° C. Then, the NCO group level is checked to ensure it is zero, indicating the end of the reaction. 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 (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

[0118] In a 3 L glass reactor (container 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 448.10 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.

[0119] At the same time, in a 100 mL glass three-neck flask (container 2), 15.67 g of IPDI are introduced, to which 400 ppm of bismuth carboxylate catalyst is added. The medium is flushed with nitrogen, then heated to 50° C. When this temperature is reached, 11.16 g of decanol are gradually introduced.

[0120] When the injection is completed, the reaction mixture is left to stir for 15 minutes. Then, back titration is used to check that the theoretical level of NCO groups has been reached.

[0121] Then, the contents of container 2 are poured into container 1. Stirring is continued for 60 minutes at 90±1° C. Then, the NCO group level is checked to ensure it is zero, indicating the end of the reaction. 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 (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

[0122] In a 3 L glass reactor (container 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 453.00 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.

[0123] At the same time, in a 100 mL glass three-neck flask (container 2), 15.85 g of IPDI are introduced, to which 400 ppm of bismuth carboxylate catalyst is added. The medium is flushed with nitrogen, then heated to 50° C. When this temperature is reached, 13.28 g of dodecanol are gradually introduced.

[0124] When the injection is completed, the reaction mixture is left to stir for 15 minutes. Then, back titration is used to check that the theoretical level of NCO groups has been reached.

[0125] Then, the contents of container 2 are poured into container 1. Stirring is continued for 60 minutes at 90±1° C. Then, the NCO group level is checked to ensure it is zero, indicating the end of the reaction. 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 is 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

[0126] In a 3 L glass reactor (container 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 449.80 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.

[0127] At the same time, in a 100 mL glass three-neck flask (container 2), 15.73 g of IPDI are introduced, to which 400 ppm of bismuth carboxylate catalyst is added. The medium is flushed with nitrogen, then heated to 50° C. When this temperature is reached, 17.16 g of hexadecanol are gradually introduced.

[0128] When the injection is completed, the reaction mixture is left to stir for 15 minutes. Then, back titration is used to check that the theoretical level of NCO groups has been reached.

[0129] Then, the contents of container 2 are poured into container 1. Stirring is continued for 60 minutes at 90±1° C. Then, the NCO group level is checked to ensure it is zero, indicating the end of the reaction. 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 is formulated using a surfactant compound such as ethoxylated alcohol (ethoxylated octanol with ten ethylene oxide equivalents) in water to which is 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, 10% of surfactant compound and 70% by mass of water.

Example 1-5: Preparation of a Compound T5 According to the Invention

[0130] In a 3 L glass reactor (container 1) equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a double jacket in which oil circulates, 452.50 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.

[0131] At the same time, in a 100 mL glass three-neck flask (container 2), 15.83 g of IPDI are introduced, to which 400 ppm of bismuth carboxylate catalyst is added. The medium is flushed with nitrogen, then heated to 50° C. When this temperature is reached, 19.08 g of 4-dodecylcyclohexanol are gradually introduced.

[0132] When the injection is completed, the reaction mixture is left to stir for 15 minutes. Then, back titration is used to check that the theoretical level of NCO groups has been reached.

[0133] Then, the contents of container 2 are poured into container 1. Stirring is continued for 60 minutes at 90±1° C. Then, the NCO group level is checked to ensure it is zero, indicating the end of the reaction. 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 T5 is formulated using a surfactant compound such as ethoxylated alcohol (ethoxylated octanol with ten ethylene oxide equivalents) in water to which is added 1,000 ppm of a biocide (Biopol SMV Chemipol) and 1,000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 5 is obtained consisting of 20% by mass of compound T5 according to the invention, 10% of surfactant compound and 70% by mass of water.

Example 2: Preparation of Paint Formulations According to the Invention

[0134] Paint formulations F1 to F5 according to the invention are prepared respectively from aqueous compositions 1 to 5 of difunctional compounds T1 to T5 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) 1.0 aqueous composition 1 according to the 28.7 invention added water q.s.p. 650 g total

Example 3: Characterisation of Paint Formulations According to the Invention

[0135] 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

TABLE-US-00002 TABLE 2 Formulation Compound μ.sub.BK10 μ.sub.BK100 F1 T1 1,020 590 F2 T2 1,380 810 F3 T3 1,530 940 F4 T4 3,250 1,720 F5 T5 3,150 1,570

[0136] properties of the paint formulations are listed in Table 2.

[0137] The difunctional 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

[0138] 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 μI/μS F1 T1 150 72 2.0 F2 T2 150 78 1.9 F3 T3 140 82 1.7 F4 T4 250 96 2.6 F5 T5 250 94 2.6

[0139] The difunctional compounds according to the invention make it possible to prepare paint formulations with particularly well-controlled viscosities. In particular, the μ.sub.I viscosity is particularly high and the μ.sub.I/μ.sub.s 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.