EP4188975A1 - Rheology-modifying diurethane compound - Google Patents

Rheology-modifying diurethane compound

Info

Publication number
EP4188975A1
EP4188975A1 EP21755511.9A EP21755511A EP4188975A1 EP 4188975 A1 EP4188975 A1 EP 4188975A1 EP 21755511 A EP21755511 A EP 21755511A EP 4188975 A1 EP4188975 A1 EP 4188975A1
Authority
EP
European Patent Office
Prior art keywords
compound
polyethoxylated
carbon atoms
diisocyanate
diurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21755511.9A
Other languages
German (de)
French (fr)
Inventor
Yves MATTER
Denis Ruhlmann
Jean-Marc Suau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coatex SAS
Original Assignee
Coatex SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coatex SAS filed Critical Coatex SAS
Publication of EP4188975A1 publication Critical patent/EP4188975A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

  • the invention relates to a rheology modifying diurethane compound.
  • the invention also provides an aqueous composition comprising a diurethane compound according to the invention as well as a method for controlling the viscosity of an aqueous composition by means of the diurethane compound according to the invention.
  • aqueous coating compositions and in particular for aqueous paint or varnish compositions, it is necessary to control the viscosity both for low or medium shear gradients and for high shear gradients. Indeed, during its preparation, its storage, its application or its drying, a paint formulation undergoes many constraints requiring particularly complex rheological properties.
  • the pigment particles tend to settle by gravity. Stabilizing the dispersion of these pigment particles then requires having a paint formulation whose viscosity is high at very low shear gradients corresponding to the limit speed of the particles.
  • Paint pick-up is the amount of paint carried away by means of an application tool, such as a brush, brush or roller for example.
  • the tool immersed and then removed from the paint pot carrying a large quantity of paint will avoid having to be reloaded more frequently. Paint pick-up is an increasing function of viscosity.
  • the equivalent shear rate calculation is a function of the paint flow rate for a particular thickness of paint on the tool.
  • the paint formulation should therefore also have a high viscosity at low or medium shear rates.
  • a high filling power of the paint must be sought so that when it is applied to a substrate, a large quantity of paint is deposited during each pass. A high filling power then makes it possible to obtain a greater wet film during each pass of the tool.
  • a high viscosity of the paint formulation must therefore be sought at high shear rates. High viscosity at high shear rates will also reduce or eliminate the risk of spattering or dripping during paint application.
  • Reduced viscosity at low to medium shear rates will also provide a good taut appearance after application of paint, especially paint monolayer, on a substrate whose coated surface will then present a very regular appearance, without bumps or hollows. The final visual appearance of the dry film is then much better.
  • the paint after being deposited on a surface, in particular a vertical surface, the paint should not form a run. It is then necessary for the paint formulation to have a high viscosity at low and medium shear rates.
  • the paint should have a significant leveling capacity. Reduced viscosity at low to medium shear rates of the paint formulation is then required.
  • Document EP0761780 discloses thickening and heat-resistant diurethane compounds.
  • Document EP1908807 discloses aqueous paint compositions for metal which may comprise a diurethane compound.
  • Document JP2009001687 discloses emulsions for industrial paint which may comprise a diurethane compound.
  • Document LR2113316 discloses diurethane compounds for textile printing paste.
  • Compounds of the HEUR type hydrophobically modified ethoxylated urethanes or ethoxylated and hydrophobically modified urethanes
  • rheology modifying agents are known as rheology modifying agents.
  • the known HEUR-type compounds do not always make it possible to provide a satisfactory solution.
  • the rheology modifying compounds of the state of the art do not always allow effective control of the viscosity or do not always allow the compromise between Stormer viscosity (measured at low or medium shear gradients and expressed in KU units) and ICI viscosity (measured at high or very high shear rates and expressed in s 1 ).
  • the known rheology modifier compounds do not always make it possible to increase the ICI viscosity/Stormer viscosity ratio.
  • the diurethane compound according to the invention makes it possible to provide a solution to all or part of the problems of the rheology modifying agents of the state of the art.
  • the invention provides a diurethane compound T prepared by reacting: a. of a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 with 40 carbon atoms and polyethoxylated and the cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms and polyethoxylated.
  • a a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon
  • the diurethane compound T is prepared from at least one compound (a) comprising two isocyanate groups and from a compound (b) capable of reacting with these isocyanate groups and comprising a hydrocarbon chain - saturated, unsaturated or aromatic - combined with a polyalkoxylated chain.
  • this reactive compound (b) is a monohydroxylated compound.
  • the condensation of compounds (a) and (b) is carried out in the presence of a catalyst.
  • This catalyst can be chosen from an amine, preferably 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), a derivative of a metal chosen from Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Traces of water can also participate in the catalysis of the reaction.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • metal derivatives a derivative selected from dibutyl bismuth dilaurate, dibutyl bismuth diacetate, dibutyl bismuth oxide, bismuth carboxylate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, a derivative of mercury is preferred.
  • a derivative of lead zinc salts, manganese salts, a compound comprising chelated zirconium, a compound comprising chelated aluminium.
  • the preferred metal derivative is chosen from a derivative of Bi, a derivative of S n and a derivative of Ti.
  • the reaction implements a single compound (a) or else the reaction implements two or three different compounds (a).
  • the polyisocyanate compound (a) comprises on average 2 isocyanate groups.
  • the polyisocyanate compound (a) comprises on average 2 ⁇ 10 molar % isocyanate groups.
  • the diisocyanate compounds are symmetrical diisocyanate compounds or else unsymmetrical diisocyanate compounds. Symmetrical diisocyanate compounds include two isocyanate groups that have the same reactivity. Unsymmetrical diisocyanate compounds include two isocyanate groups that have different reactivities.
  • compound (a) is chosen from:
  • - symmetrical aromatic diisocyanate compounds preferably: ⁇ 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);
  • HnMDI methylene bis(4-cyclohexylisocyanate)
  • - symmetrical aliphatic diisocyanate compounds preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);
  • IPDI isophorone diisocyanate
  • compound (a) is chosen from IPDI, HDI, H12MDI and their combinations.
  • monoalcohols are compounds comprising a single hydroxyl group (OH) which is terminal.
  • the polyethoxylated monoalcohols are compounds comprising a hydrocarbon chain which comprises several ethoxylated groups and a terminal hydroxyl (OH) group.
  • the polyethoxylated monoalcohols are compounds of formula R-(LO) n -H in which R represents a hydrocarbon chain, n represents the number of polyethoxylations and L, identical or different, independently represents a linear alkylene group comprising 2 carbon atoms.
  • the number of carbon atoms defining the monoalcohols (b1) to (b3) therefore corresponds to the number of carbon atoms of the R groups.
  • the polyethoxylated monoalcohols comprise from 100 to 500 ethoxylated groups, preferably from 100 to 400 ethoxylated groups or from 100 to 200 ethoxylated groups.
  • the ethoxylated groups are oxyethylene groups (-CH2CH2O).
  • the monoalcohols (bl) comprise strictly less than 200 oxyethylene groups or strictly less than 180 oxyethylene groups or less than 170 oxyethylene groups.
  • the monoalcohols (b2) comprise strictly less than 200 oxyethylene groups or strictly less than 180 oxyethylene groups.
  • compound T is a compound comprising ethoxylated groups.
  • the compound T has a degree of polyethoxylation between 105 and 500 or between 100 and 502 or between 105 and 502 or else between 100 and 400 or between 105 and 400.
  • the degree of polyethoxylation defines the number of ethoxylated groups included in this compound.
  • the compound (b) is such that: - the hydrocarbon chain of the monoalcohol (bl) comprises from 6 to 30 carbon atoms or from 6 to 16 carbon atoms or else from 20 to 40 carbon, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (bl) is chosen from polyethoxylated n-octanol, polyethoxylated n-decanol, polyethoxylated n-dodecanol, polyethoxylated n-hexadecanol , or - the hydrocarbon chain of the monoalcohol (b2) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (b2) is chosen from ethyl- polyethoxylated hexanol, polyethoxylated iso-octanol, polye
  • the hydrocarbon chain of the monoalcohol (b3) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 20 carbon atoms, more preferably the monoalcohol (b3) is chosen from polyethoxylated ethyl-cyclohexanol , polyethoxylated n-nonyl-cyclohexanol, polyethoxylated n-dodecyl-cyclohexanol.
  • the compound T is prepared by means of a monoalcohol and in the absence of diol or triol or in the absence of a compound comprising at least two hydroxyl groups (OH).
  • the invention also relates to a method for preparing this compound.
  • the invention provides a method for preparing a diurethane compound T by reaction: a. of a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 containing 40 carbon atoms and polyethoxylated and cycloaliphatic monoalcohols (b3) containing from 6 to 40 carbon atoms and polyethoxylated
  • the condensation of the compounds (a) and (b) is carried out in the presence of a catalyst.
  • the reaction is catalyzed by means of an amine, preferably by means of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or at least one derivative of a metal chosen from Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Traces of water can also participate in the catalysis of the reaction.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • metal derivatives a derivative selected from dibutyl bismuth dilaurate, dibutyl bismuth diacetate, dibutyl bismuth oxide, bismuth carboxylate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, a derivative of mercury, a lead derivative, zinc salts, manganese salts, a compound comprising chelated zirconium, a compound comprising chelated aluminium.
  • the preferred metal derivative is chosen from a derivative of Bi, a derivative of S n and a derivative of Ti.
  • the condensation of compounds (a) and (b) is carried out in an organic solvent.
  • the preferred organic solvents are solvents which are non-reactive with the isocyanate functions of compound (a), in particular the solvents chosen from hydrocarbon solvents (in particular Cs to C30 petroleum fractions), aromatic solvents (in particular toluene and its derivatives) and their combinations.
  • the condensation is carried out directly with the various reagents or else is carried out in toluene.
  • a solution of the compound is obtained in an organic solvent. Such a solution can be implemented directly.
  • the organic solvent can be separated and the compound T dried.
  • Such a compound T according to the invention which is dried, can then be implemented in solid form, for example in the form of powder or granules.
  • the invention also relates to an aqueous composition comprising at least one diurethane compound T according to the invention.
  • the invention also relates to an aqueous composition comprising at least one diurethane compound T prepared according to the preparation method according to the invention.
  • the diurethane compound according to the invention is a compound having a hydrophilic character. It can be formulated in an aqueous medium.
  • the aqueous composition according to the invention may also comprise at least one additive, in particular one additive chosen from: - an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol;
  • an amphiphilic compound in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol;
  • a polysaccharide derivative for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides;
  • solvents in particular coalescence solvents, and hydrotropic compounds, for example glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, Dowanol products whose CAS number is 34590-94-8), Texanol products whose CAS number is 25265-77 -4); - anti-foaming agents, biocidal agents.
  • the invention also provides an aqueous formulation which can be used in many technical fields.
  • the aqueous formulation according to the invention comprises at least one composition according to the invention and may comprise at least one organic or inorganic pigment or organic, organo-metallic or inorganic particles, for example calcium carbonate, talc, kaolin, mica, silicates , silica, metal oxides, in particular titanium dioxide, iron oxides.
  • the aqueous formulation according to the invention may also comprise at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coalescing agent, a antifoam, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.
  • at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coalescing agent, a antifoam, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.
  • the formulation according to the invention can be implemented in many technical fields.
  • the formulation according to the invention can be a coating formulation.
  • the formulation according to the invention is an ink formulation, an adhesive formulation, a varnish formulation, a paint formulation, for example decorative paint or industrial paint.
  • the formulation according to the invention is a paint formulation.
  • the invention also provides a concentrated aqueous pigment paste comprising at least one diurethane compound T according to the invention or at least one diurethane compound T prepared according to the preparation method according to the invention and at least one organic or inorganic colored pigment.
  • the diurethane compound according to the invention has properties allowing it to be used to modify or control the rheology of the medium comprising it.
  • the invention also provides a method for controlling the viscosity of an aqueous composition.
  • This viscosity control method according to the invention comprises the addition of at least one diurethane compound according to the invention in an aqueous composition.
  • This viscosity control method can also comprise the addition of at least one diurethane compound prepared according to the preparation method according to the invention.
  • the viscosity control method according to the invention is implemented by means of an aqueous composition according to the invention.
  • the method for controlling the viscosity according to the invention is implemented by means of an aqueous formulation according to the invention.
  • the preferred, particular or advantageous characteristics of the diurethane compound T according to the invention define aqueous compositions according to the invention, formulations according to the invention, pigment pastes and viscosity control methods which are also preferred, particular or advantageous. .
  • Example 1 preparation of diurethane compounds according to the invention
  • Example 1-1 preparation of a compound T1 according to the invention
  • the quantity of isocyanate functions present in the reaction medium can then be deduced therefrom. If the latter is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound T1 obtained is formulated in water with the addition of 1000 ppm of a biocidal agent (Biopol SMV Chemipol) and 1000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 1 consisting of 20% by weight of compound T1 according to the invention and 80% by weight of water is obtained.
  • a biocidal agent Biopol SMV Chemipol
  • an anti-foaming agent Tego 1488 Evonik
  • Example 1-2 preparation of a compound T2 according to the invention
  • a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a jacket in which oil circulates
  • This product is dehydrated.
  • the isocyanate level is zero by back dosing. If this is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound T2 obtained is formulated in water with the addition of 1,000 ppm of a biocidal 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 1-3 preparation of a compound T3 according to the invention
  • Example 1-4 preparation of a compound T4 according to the invention
  • T4 obtained is formulated using a surfactant compound of the ethoxylated alcohol type (ethoxylated hexanol with five equivalents of ethylene oxide) in water with the addition of 1,000 ppm of a biocidal agent (Biopol SMV Chemipol) and 1000 ppm of an anti-foaming agent (Tego 1488 Evonik).
  • a composition 4 consisting of 20% by mass of compound T4 according to the invention, 15% of surfactant and 65% by mass of water is obtained.
  • Paint formulations F1 to F3 according to the invention are prepared respectively from aqueous compositions 1 to 3 of diurethane compounds T1 to T3 according to the invention. All the ingredients and proportions (% by mass) used are presented in Table 1.
  • Example 3 Characterization of Paint Formulations According to the Invention For the paint formulations according to the invention, 24 hours after their preparation, the Brookfield viscosity was determined, measured at 25° C. and at 10 rpm and at 100 rev/min (p Bki o and PBkioo in mPa.s) using a Brookfield DV-1 viscometer with RVT type spindles. The properties of the paint formulations are shown in Table 2.
  • the diurethane compounds according to the invention are very effective in obtaining excellent viscosities at low and medium shear gradients for paint compositions.
  • Example 4 Characterization of Paint Formulations According to the Invention
  • the Cone Plane viscosity or ICI viscosity measured at high shear gradient, was determined 24 hours after their preparation and at room temperature. (pi in mPa.s) and the Stormer viscosity, measured at medium shear rate (pS in Krebs Units or KU), using the standard module.
  • the properties of the paint formulations are shown in Table 3.
  • the diurethane compounds according to the invention make it possible to prepare paint formulations whose viscosities are particularly well controlled.
  • the viscosity pi is particularly high and the mi/ps ratio is then excellent.
  • the compounds according to the invention allow an excellent compromise between the viscosity at high shear gradient and the viscosity at low shear gradient.

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Abstract

The invention relates to a rheology-modifying diurethane compound. The invention also provides an aqueous composition comprising a diurethane compound according to the invention and a method for controlling the viscosity of an aqueous composition using the diurethane compound according to the invention.

Description

COMPOSÉ DIURÉTHANE MODIFICATEUR DE RHÉOLOGIE RHEOLOGY MODIFIER DIURETHANE COMPOUND
L’invention concerne un composé diuréthane modificateur de rhéologie. L’invention fournit également une composition aqueuse comprenant un composé diuréthane selon l’invention ainsi qu’une méthode de contrôle de la viscosité d’une composition aqueuse au moyen du composé diuréthane selon l’invention. The invention relates to a rheology modifying diurethane compound. The invention also provides an aqueous composition comprising a diurethane compound according to the invention as well as a method for controlling the viscosity of an aqueous composition by means of the diurethane compound according to the invention.
De manière générale pour les compositions aqueuses de revêtement, et en particulier pour les compositions aqueuses de peinture ou de vernis, il est nécessaire de contrôler la viscosité tant pour de faibles ou moyens gradients de cisaillement que pour des gradients de cisaillement élevés. En effet, au cours de sa préparation, de son stockage, de son application ou de son séchage, une formulation de peinture subit de nombreuses contraintes nécessitant des propriétés rhéologiques particulièrement complexes. In general, for aqueous coating compositions, and in particular for aqueous paint or varnish compositions, it is necessary to control the viscosity both for low or medium shear gradients and for high shear gradients. Indeed, during its preparation, its storage, its application or its drying, a paint formulation undergoes many constraints requiring particularly complex rheological properties.
Lors du stockage de la peinture, les particules de pigment tendent à sédimenter par gravité. Stabiliser la dispersion de ces particules de pigment nécessite alors de disposer d’une formulation de peinture dont la viscosité est élevée à de très faibles gradients de cisaillement correspondant à la vitesse limite des particules. During paint storage, the pigment particles tend to settle by gravity. Stabilizing the dispersion of these pigment particles then requires having a paint formulation whose viscosity is high at very low shear gradients corresponding to the limit speed of the particles.
La prise de peinture est la quantité de peinture emportée au moyen d’un outil d’application, tel qu’un pinceau, une brosse ou un rouleau par exemple. L’outil plongé puis retiré du pot de peinture emportant une quantité élevée de peinture évitera de devoir être rechargé plus fréquemment. La prise de peinture est fonction croissante de la viscosité. Le calcul du gradient de cisaillement équivalent est fonction de la vitesse d’écoulement de la peinture pour une épaisseur particulière de peinture sur l’outil. La formulation de peinture devrait donc également avoir une viscosité élevée à des gradients de cisaillement faibles ou moyens. De plus, un pouvoir garnissant élevé de la peinture doit être recherché afin que lors de son application sur un subjectile, une quantité importante de peinture soit déposée lors de chaque passage. Un pouvoir garnissant élevé permet alors d’obtenir un feuil humide plus important lors de chaque passage de l’outil. Une viscosité élevée de la formulation de peinture doit donc être recherchée à des gradients de cisaillement élevés. Une viscosité élevée à des gradients de cisaillement élevés permettra également de réduire ou d’éliminer le risque de formation d’éclaboussures ou de gouttelettes lors de l’application de la peinture. Paint pick-up is the amount of paint carried away by means of an application tool, such as a brush, brush or roller for example. The tool immersed and then removed from the paint pot carrying a large quantity of paint will avoid having to be reloaded more frequently. Paint pick-up is an increasing function of viscosity. The equivalent shear rate calculation is a function of the paint flow rate for a particular thickness of paint on the tool. The paint formulation should therefore also have a high viscosity at low or medium shear rates. In addition, a high filling power of the paint must be sought so that when it is applied to a substrate, a large quantity of paint is deposited during each pass. A high filling power then makes it possible to obtain a greater wet film during each pass of the tool. A high viscosity of the paint formulation must therefore be sought at high shear rates. High viscosity at high shear rates will also reduce or eliminate the risk of spattering or dripping during paint application.
Une viscosité réduite à de faibles ou moyens gradients de cisaillement permettra également d’obtenir un bon aspect tendu après application de la peinture, notamment d’une peinture monocouche, sur un subjectile dont la surface revêtue présentera alors un aspect très régulier, sans bosses ni creux. L’aspect visuel final du feuil sec est alors bien meilleur.Reduced viscosity at low to medium shear rates will also provide a good taut appearance after application of paint, especially paint monolayer, on a substrate whose coated surface will then present a very regular appearance, without bumps or hollows. The final visual appearance of the dry film is then much better.
De plus, après son dépôt sur une surface, notamment une surface verticale, la peinture ne devrait pas former de coulure. Il est alors nécessaire que la formulation de peinture possède une viscosité élevée à de faibles et moyens gradients de cisaillement. In addition, after being deposited on a surface, in particular a vertical surface, the paint should not form a run. It is then necessary for the paint formulation to have a high viscosity at low and medium shear rates.
Enfin, après son dépôt sur une surface, la peinture devrait posséder une capacité de nivellement importante. Une viscosité réduite à de faibles et moyens gradients de cisaillement de la formulation de peinture est alors requise. Finally, after being deposited on a surface, the paint should have a significant leveling capacity. Reduced viscosity at low to medium shear rates of the paint formulation is then required.
Le document EP0761780 divulgue des composés diuréthanes épaississants et thermorésistants. Le document EP1908807 divulgue des compositions aqueuses de peinture pour métal pouvant comprendre un composé diuréthane. Le document JP2009001687 divulgue des émulsions pour peinture industrielle pouvant comprendre un composé diuréthane. Le document LR2113316 divulgue des composés diuréthanes pour pâte d’impression textile. Des composés de type HEUR ( hydrophobically modified ethoxylated urethanes ou uréthanes éthoxylés et modifiés de manière hydrophobe) sont connus comme agents modificateurs de rhéologie. Document EP0761780 discloses thickening and heat-resistant diurethane compounds. Document EP1908807 discloses aqueous paint compositions for metal which may comprise a diurethane compound. Document JP2009001687 discloses emulsions for industrial paint which may comprise a diurethane compound. Document LR2113316 discloses diurethane compounds for textile printing paste. Compounds of the HEUR type (hydrophobically modified ethoxylated urethanes or ethoxylated and hydrophobically modified urethanes) are known as rheology modifying agents.
Toutefois, les composés de type HEUR connus ne permettent pas toujours d’apporter de solution satisfaisante. Notamment, les composés modificateurs de rhéologie de l’état de la technique ne permettent pas toujours un contrôle efficace de la viscosité ou ne permettent pas toujours d’améliorer de manière satisfaisante le compromis entre viscosité Stormer (mesurée à faibles ou moyens gradients de cisaillement et exprimée en unité KU) et viscosité ICI (mesurée à hauts ou très hauts gradients de cisaillement et exprimée en s 1). En particulier, les composés modificateurs de rhéologie connus ne permettent pas toujours d’augmenter le rapport viscosité ICI/viscosité Stormer. However, the known HEUR-type compounds do not always make it possible to provide a satisfactory solution. In particular, the rheology modifying compounds of the state of the art do not always allow effective control of the viscosity or do not always allow the compromise between Stormer viscosity (measured at low or medium shear gradients and expressed in KU units) and ICI viscosity (measured at high or very high shear rates and expressed in s 1 ). In particular, the known rheology modifier compounds do not always make it possible to increase the ICI viscosity/Stormer viscosity ratio.
Il existe donc un besoin de disposer d’agents modificateurs de rhéologie améliorés. Le composé diuréthane selon l’invention permet d’apporter une solution à tout ou partie des problèmes des agents modificateurs de rhéologie de l’état de la technique. There is therefore a need for improved rheology modifying agents. The diurethane compound according to the invention makes it possible to provide a solution to all or part of the problems of the rheology modifying agents of the state of the art.
Ainsi, l’invention fournit un composé diuréthane T préparé par réaction : a. d’un équivalent molaire d’au moins un composé diisocyanate (a) et b. de deux équivalents molaires d’un même composé (b) polyéthoxylé comprenant de 100 à 500 groupements oxyéthylène choisi parmi les monoalcools (bl) aliphatiques linéaires comprenant de 6 à 40 atomes de carbone et polyéthoxylés, les monoalcools (b2) aliphatiques ramifiés comprenant de 6 à 40 atomes de carbone et polyéthoxylés et les monoalcools (b3) cycloaliphatiques comprenant de 6 à 40 atomes de carbone et polyéthoxylés. Thus, the invention provides a diurethane compound T prepared by reacting: a. of a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 with 40 carbon atoms and polyethoxylated and the cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms and polyethoxylated.
De manière essentielle selon l’invention, le composé diuréthane T est préparé à partir d’au moins un composé (a) comprenant deux groupements isocyanates et d’un composé (b) susceptible de réagir avec ces groupements isocyanates et comportant une chaîne hydrocarbonée - saturée, insaturée ou aromatique - combinée à une chaîne polyalkoxylée. De préférence selon l’invention, ce composé réactif (b) est un composé monohydroxylé. De manière préférée selon l’invention, la condensation des composés (a) et (b) est conduite en présence d’un catalyseur. Ce catalyseur peut être choisi parmi une amine, de préférence l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), un dérivé d’un métal choisi parmi Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Des traces d’eau peuvent également participer à la catalyse de la réaction. Comme exemples de dérivés métalliques, on préfère un dérivé choisi parmi dilaurate de dibutyl bismuth, diacétate de dibutyl bismuth, oxyde de dibutyl bismuth, carboxylate de bismuth, dilaurate de dibutyl étain, diacétate de dibutyl étain, oxyde de dibutyl étain, un dérivé du mercure, un dérivé du plomb, des sels de zinc, des sels de manganèse, un composé comprenant du zirconium chélaté, un composé comprenant de l’aluminium chélaté. Le dérivé métallique préféré est choisi parmi un dérivé de Bi, un dérivé de S n et un dérivé de Ti. Essentially according to the invention, the diurethane compound T is prepared from at least one compound (a) comprising two isocyanate groups and from a compound (b) capable of reacting with these isocyanate groups and comprising a hydrocarbon chain - saturated, unsaturated or aromatic - combined with a polyalkoxylated chain. Preferably according to the invention, this reactive compound (b) is a monohydroxylated compound. Preferably according to the invention, the condensation of compounds (a) and (b) is carried out in the presence of a catalyst. This catalyst can be chosen from an amine, preferably 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), a derivative of a metal chosen from Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Traces of water can also participate in the catalysis of the reaction. As examples of metal derivatives, a derivative selected from dibutyl bismuth dilaurate, dibutyl bismuth diacetate, dibutyl bismuth oxide, bismuth carboxylate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, a derivative of mercury is preferred. , a derivative of lead, zinc salts, manganese salts, a compound comprising chelated zirconium, a compound comprising chelated aluminium. The preferred metal derivative is chosen from a derivative of Bi, a derivative of S n and a derivative of Ti.
De manière préférée selon l’invention, la réaction met en œuvre un unique composé (a) ou bien la réaction met en œuvre deux ou trois composés (a) différents. Preferably according to the invention, the reaction implements a single compound (a) or else the reaction implements two or three different compounds (a).
Selon l’invention, le composé polyisocyanate (a) comprend en moyenne 2 groupements isocyanates. Généralement, le composé polyisocyanate (a) comprend en moyenne 2 ± 10 % molaire groupements isocyanates. Selon l’invention, les composés diisocyanates sont des composés diisocyanates symétriques ou bien des composés diisocyanates dissymétriques. Les composés diisocyanates symétriques comprennent deux groupements isocyanates qui ont la même réactivité. Les composés diisocyanates dissymétriques comprennent deux groupements isocyanates qui ont des réactivités différentes. According to the invention, the polyisocyanate compound (a) comprises on average 2 isocyanate groups. Generally, the polyisocyanate compound (a) comprises on average 2±10 molar % isocyanate groups. According to the invention, the diisocyanate compounds are symmetrical diisocyanate compounds or else unsymmetrical diisocyanate compounds. Symmetrical diisocyanate compounds include two isocyanate groups that have the same reactivity. Unsymmetrical diisocyanate compounds include two isocyanate groups that have different reactivities.
De manière préférée selon l’invention, le composé (a) est choisi parmi : Preferably according to the invention, compound (a) is chosen from:
- les composés diisocyanates aromatiques symétriques, de préférence : · 2,2'-diisocyanate de diphénylméthylène (2,2'-MDI) et 4,4'-diisocyanate de diphénylméthylène (4,4'-MDI) ; - symmetrical aromatic diisocyanate compounds, preferably: · 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);
• 4,4’-dibenzyl diisocyanate (4,4’-DBDI) ; • 4,4'-dibenzyl diisocyanate (4,4'-DBDI);
• 2,6-diisocyanate de toluène (2,6-TDI) ; • m-xylylène diisocyanate (m-XDI) ; • 2,6-toluene diisocyanate (2,6-TDI); • m-xylylene diisocyanate (m-XDI);
- les composés diisocyanates alicycliques symétriques, de préférence méthylène bis(4-cyclohexylisocyanate) (HnMDI) ; - symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (HnMDI);
- les composés diisocyanates aliphatiques symétriques, de préférence diisocyanate d'hexaméthylène (HDI), diisocyanate de pentaméthylène (PDI) ; - symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI);
- les composés diisocyanates aromatiques dissymétriques, de préférence : - unsymmetrical aromatic diisocyanate compounds, preferably:
• 2,4'-diisocyanate de diphénylméthylène (2,4'-MDI) ; • 2,4'-diisocyanate of diphenylmethylene (2,4'-MDI);
• 2,4’-dibenzyl diisocyanate (2,4’-DBDI) ; • 2,4'-dibenzyl diisocyanate (2,4'-DBDI);
• 2,4-diisocyanate de toluène (2,4-TDI) ; • 2,4-diisocyanate of toluene (2,4-TDI);
- les composés diisocyanates alicycliques dissymétriques, de préférence diisocyanate d'isophorone (IPDI). - unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).
De manière préférée selon l’invention, le composé (a) est choisi parmi IPDI, HDI, H12MDI et leurs combinaisons. Preferably according to the invention, compound (a) is chosen from IPDI, HDI, H12MDI and their combinations.
Selon l’invention, les monoalcools sont des composés comprenant un seul groupement hydroxyle (OH) qui est terminal. Selon l’invention, les monoalcools polyéthoxylés sont des composés comprenant une chaîne hydrocarbonée qui comprend plusieurs groupements éthoxylés et un groupement hydroxyle (OH) terminal. Selon l’invention, les monoalcools polyéthoxylés sont des composés de formule R-(LO)n-H dans laquelle R représente une chaîne hydrocarbonée, n représente le nombre de polyéthoxylations et L, identique ou différent, représente indépendamment un groupement alkylène linéaire comprenant 2 atomes de carbone. Selon l’invention, le nombre d’atomes de carbones définissant les monoalcools (bl) à (b3) correspond donc au nombre d’atomes de carbones des groupements R. According to the invention, monoalcohols are compounds comprising a single hydroxyl group (OH) which is terminal. According to the invention, the polyethoxylated monoalcohols are compounds comprising a hydrocarbon chain which comprises several ethoxylated groups and a terminal hydroxyl (OH) group. According to the invention, the polyethoxylated monoalcohols are compounds of formula R-(LO) n -H in which R represents a hydrocarbon chain, n represents the number of polyethoxylations and L, identical or different, independently represents a linear alkylene group comprising 2 carbon atoms. According to the invention, the number of carbon atoms defining the monoalcohols (b1) to (b3) therefore corresponds to the number of carbon atoms of the R groups.
Selon l’invention, les monoalcools polyéthoxylés comprennent de 100 à 500 groupements éthoxylés, de préférence de 100 à 400 groupements éthoxylés ou de 100 à 200 groupements éthoxylés. Selon l’invention, les groupements éthoxylés sont des groupements oxyéthylène (-CH2CH2O). De manière préférée selon l’invention, les monoalcools (bl) comprennent strictement moins de 200 groupements oxyéthylène ou strictement moins de 180 groupements oxyéthylène ou moins de 170 groupements oxyéthylène. De manière également préférée selon l’invention, les monoalcools (b2) comprennent strictement moins de 200 groupements oxyéthylène ou strictement moins de 180 groupements oxyéthylène. De manière essentielle selon l’invention, le composé T est un composé comprenant des groupements éthoxylés. Préférentiellement selon l’invention, le composé T a un degré de polyéthoxylation compris entre 105 et 500 ou entre 100 et 502 ou entre 105 et 502 ou bien entre 100 et 400 ou entre 105 et 400. Le degré de polyéthoxylation définit le nombre de groupements éthoxylés compris dans ce composé. According to the invention, the polyethoxylated monoalcohols comprise from 100 to 500 ethoxylated groups, preferably from 100 to 400 ethoxylated groups or from 100 to 200 ethoxylated groups. According to the invention, the ethoxylated groups are oxyethylene groups (-CH2CH2O). Preferably according to the invention, the monoalcohols (bl) comprise strictly less than 200 oxyethylene groups or strictly less than 180 oxyethylene groups or less than 170 oxyethylene groups. Also preferably according to the invention, the monoalcohols (b2) comprise strictly less than 200 oxyethylene groups or strictly less than 180 oxyethylene groups. Essentially according to the invention, compound T is a compound comprising ethoxylated groups. Preferably according to the invention, the compound T has a degree of polyethoxylation between 105 and 500 or between 100 and 502 or between 105 and 502 or else between 100 and 400 or between 105 and 400. The degree of polyethoxylation defines the number of ethoxylated groups included in this compound.
De manière préférée selon l’invention, le composé (b) est tel que : - la chaîne hydrocarbonée du monoalcool (bl) comprend de 6 à 30 atomes de carbone ou de de 6 à 16 atomes de carbone ou bien de 20 à 40 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 16 atomes de carbone, plus préférentiellement le monoalcool (bl) est choisi parmi n-octanol polyéthoxylé, n-décanol polyéthoxylé, n-dodécanol polyéthoxylé, n-hexadécanol polyéthoxylé, ou - la chaîne hydrocarbonée du monoalcool (b2) comprend de 6 à 30 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 16 atomes de carbone, plus préférentiellement le monoalcool (b2) est choisi parmi ethyl-hexanol polyéthoxylé, iso-octanol polyéthoxylé, iso-nonanol polyéthoxylé, iso-décanol polyéthoxylé, propyl-heptanol polyéthoxylé, butyl-octanol polyéthoxylé, iso-dodécanol polyéthoxylé, iso-hexadécanol polyéthoxylé, un alcool oxo polyéthoxylé, un alcool de Guerbet polyéthoxylé, ou Preferably according to the invention, the compound (b) is such that: - the hydrocarbon chain of the monoalcohol (bl) comprises from 6 to 30 carbon atoms or from 6 to 16 carbon atoms or else from 20 to 40 carbon, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (bl) is chosen from polyethoxylated n-octanol, polyethoxylated n-decanol, polyethoxylated n-dodecanol, polyethoxylated n-hexadecanol , or - the hydrocarbon chain of the monoalcohol (b2) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (b2) is chosen from ethyl- polyethoxylated hexanol, polyethoxylated iso-octanol, polyethoxylated iso-nonanol, polyethoxylated iso-decanol, polyethoxylated propyl-heptanol, polyethoxylated butyl-octanol, polyethoxylated iso-dodecanol, polyethoxylated iso-hexadecanol, a polyethoxylated oxo alcohol, a polyethoxylated Guerbet alcohol, or
- la chaîne hydrocarbonée du monoalcool (b3) comprend de 6 à 30 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 20 atomes de carbone, plus préférentiellement le monoalcool (b3) est choisi parmi ethyl-cyclohexanol polyéthoxylé, n-nonyl-cyclohexanol polyéthoxylé, n-dodécyl-cyclohexanol polyéthoxylé. - the hydrocarbon chain of the monoalcohol (b3) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 20 carbon atoms, more preferably the monoalcohol (b3) is chosen from polyethoxylated ethyl-cyclohexanol , polyethoxylated n-nonyl-cyclohexanol, polyethoxylated n-dodecyl-cyclohexanol.
De manière essentielle selon l’invention, le composé T est préparé au moyen d’un monoalcool et en l’absence de diol ou de triol ou en l’absence de composé comprenant au moins deux groupements hydroxyles (OH). Essentially according to the invention, the compound T is prepared by means of a monoalcohol and in the absence of diol or triol or in the absence of a compound comprising at least two hydroxyl groups (OH).
Outre un composé diuréthane T, l’invention concerne également une méthode de préparation de ce composé. In addition to a diurethane compound T, the invention also relates to a method for preparing this compound.
Ainsi, l’invention fournit une méthode de préparation d’un composé diuréthane T par réaction : a. d’un équivalent molaire d’au moins un composé diisocyanate (a) et b. de deux équivalents molaires d’un même composé (b) polyéthoxylé comprenant de 100 à 500 groupements oxyéthylène choisi parmi les monoalcools (bl) aliphatiques linéaires comprenant de 6 à 40 atomes de carbone et polyéthoxylés, les monoalcools (b2) aliphatiques ramifiés comprenant de 6 à 40 atomes de carbone et polyéthoxylés et les monoalcools (b3) cycloaliphatiques comprenant de 6 à 40 atomes de carbone et polyéthoxylés De manière préférée selon l’invention pour la méthode de préparation selon l’invention, la condensation des composés (a) et (b) est conduite en présence d’un catalyseur. De manière plus préférée, la réaction est catalysée au moyen d’une amine, de préférence au moyen de l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), ou d’au moins un dérivé d’un métal choisi parmi Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Des traces d’eau peuvent également participer à la catalyse de la réaction. Comme exemples de dérivés métalliques, on préfère un dérivé choisi parmi le dilaurate de dibutyl bismuth, diacétate de dibutyl bismuth, oxyde de dibutyl bismuth, carboxylate de bismuth, dilaurate de dibutyl étain, diacétate de dibutyl étain, oxyde de dibutyl étain, un dérivé du mercure, un dérivé du plomb, des sels de zinc, des sels de manganèse, un composé comprenant du zirconium chélaté, un composé comprenant de l’aluminium chélaté. Le dérivé métallique préféré est choisi parmi un dérivé de Bi, un dérivé de S n et un dérivé de Ti. Thus, the invention provides a method for preparing a diurethane compound T by reaction: a. of a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 containing 40 carbon atoms and polyethoxylated and cycloaliphatic monoalcohols (b3) containing from 6 to 40 carbon atoms and polyethoxylated Preferably according to the invention for the method of preparation according to the invention, the condensation of the compounds (a) and (b) is carried out in the presence of a catalyst. More preferably, the reaction is catalyzed by means of an amine, preferably by means of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or at least one derivative of a metal chosen from Al, Bi, Sn, Hg, Pb, Mn, Zn, Zr, Ti. Traces of water can also participate in the catalysis of the reaction. As examples of metal derivatives, a derivative selected from dibutyl bismuth dilaurate, dibutyl bismuth diacetate, dibutyl bismuth oxide, bismuth carboxylate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, a derivative of mercury, a lead derivative, zinc salts, manganese salts, a compound comprising chelated zirconium, a compound comprising chelated aluminium. The preferred metal derivative is chosen from a derivative of Bi, a derivative of S n and a derivative of Ti.
De manière avantageuse selon l’invention, la condensation des composés (a) et (b) est conduite dans un solvant organique. Les solvants organiques préférés sont des solvants non-réactifs avec les fonctions isocyanates du composé (a), en particulier les solvants choisis parmi les solvants hydrocarbonés (notamment des coupes pétrolières en Cs à C30), les solvants aromatiques (notamment toluène et ses dérivés) et leurs combinaisons. De manière plus préférée selon l’invention, la condensation est conduite directement avec les différents réactifs ou bien est conduite dans le toluène. À l’issue de la préparation du composé T selon l’invention, on obtient une solution du composé dans un solvant organique. Une telle solution peut être mise en œuvre directement. Également selon l’invention, le solvant organique peut être séparé et le composé T séché. Un tel composé T selon l’invention, qui est séché, peut alors être mis en œuvre sous forme solide, par exemple sous forme de poudre ou de granulés. Outre le composé diuréthane T et une méthode de préparation de ce composé, l’invention concerne également une composition aqueuse comprenant au moins un composé diuréthane T selon l’invention. L’invention concerne également une composition aqueuse comprenant au moins un composé diuréthane T préparé selon la méthode de préparation selon l’invention. De manière avantageuse, le composé diuréthane selon l’invention est un composé possédant un caractère hydrophile. Il peut être formulé en milieu aqueux. Advantageously according to the invention, the condensation of compounds (a) and (b) is carried out in an organic solvent. The preferred organic solvents are solvents which are non-reactive with the isocyanate functions of compound (a), in particular the solvents chosen from hydrocarbon solvents (in particular Cs to C30 petroleum fractions), aromatic solvents (in particular toluene and its derivatives) and their combinations. More preferably according to the invention, the condensation is carried out directly with the various reagents or else is carried out in toluene. At the end of the preparation of compound T according to the invention, a solution of the compound is obtained in an organic solvent. Such a solution can be implemented directly. Also according to the invention, the organic solvent can be separated and the compound T dried. Such a compound T according to the invention, which is dried, can then be implemented in solid form, for example in the form of powder or granules. In addition to the diurethane compound T and a method for preparing this compound, the invention also relates to an aqueous composition comprising at least one diurethane compound T according to the invention. The invention also relates to an aqueous composition comprising at least one diurethane compound T prepared according to the preparation method according to the invention. Advantageously, the diurethane compound according to the invention is a compound having a hydrophilic character. It can be formulated in an aqueous medium.
La composition aqueuse selon l’invention peut également comprendre au moins un additif, en particulier un additif choisi parmi : - un composé amphiphile, notamment un composé tensio-actif, de préférence un composé tensio-actif hydroxylé, par exemple alkyl-polyalkyleneglycol, notamment alkyl-polyethyleneglycol et alkyl-polypropyleneglycol ; The aqueous composition according to the invention may also comprise at least one additive, in particular one additive chosen from: - an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol;
- un dérivé de polysaccharide, par exemple cyclodextrine, dérivé de cyclodextrine, polyéthers, alkyl-glucosides ; - a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides;
- solvants, notamment solvants de coalescence, et composés hydrotropes, par exemple glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, produits Dowanol dont le numéro CAS est 34590-94-8), produits Texanol dont le numéro CAS est 25265-77-4) ; - agents anti-mousse, agents biocides. - solvents, in particular coalescence solvents, and hydrotropic compounds, for example glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, Dowanol products whose CAS number is 34590-94-8), Texanol products whose CAS number is 25265-77 -4); - anti-foaming agents, biocidal agents.
L’invention fournit également une formulation aqueuse qui peut être utilisée dans de nombreux domaines techniques. La formulation aqueuse selon l’invention comprend au moins une composition selon l’invention et peut comprendre au moins un pigment organique ou minéral ou des particules organiques, organo-métalliques ou minérales, par exemple carbonate de calcium, talc, kaolin, mica, silicates, silice, oxydes métalliques, notamment dioxyde de titane, oxydes de fer. La formulation aqueuse selon l’invention peut également comprendre au moins un agent choisi parmi un agent espaceur de particules, un agent dispersant, un agent stabilisant stérique, un agent stabilisant électrostatique, un agent opacifiant, un solvant, un agent de coalescence, un agent anti-mousse, un agent de conservation, un agent biocide, un agent d’étalement, un agent épaississant, un copolymère filmogène et leurs mélanges. The invention also provides an aqueous formulation which can be used in many technical fields. The aqueous formulation according to the invention comprises at least one composition according to the invention and may comprise at least one organic or inorganic pigment or organic, organo-metallic or inorganic particles, for example calcium carbonate, talc, kaolin, mica, silicates , silica, metal oxides, in particular titanium dioxide, iron oxides. The aqueous formulation according to the invention may also comprise at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, an opacifying agent, a solvent, a coalescing agent, a antifoam, a preservative, a biocidal agent, a spreading agent, a thickening agent, a film-forming copolymer and mixtures thereof.
Selon le composé diuréthane particulier ou les additifs qu’elle comprend la formulation selon l’invention peut être mise en œuvre dans de nombreux domaines techniques. Ainsi, la formulation selon l’invention peut être une formulation de revêtement. De préférence, la formulation selon l’invention est une formulation d’encre, une formulation d’adhésif, une formulation de vernis, une formulation de peinture, par exemple de peinture décorative ou de peinture industrielle. De préférence, la formulation selon l’invention est une formulation de peinture. Depending on the particular diurethane compound or the additives that it comprises, the formulation according to the invention can be implemented in many technical fields. Thus, the formulation according to the invention can be a coating formulation. Preferably, the formulation according to the invention is an ink formulation, an adhesive formulation, a varnish formulation, a paint formulation, for example decorative paint or industrial paint. Preferably, the formulation according to the invention is a paint formulation.
L’invention fournit également une pâte pigmentaire aqueuse concentrée comprenant au moins un composé diuréthane T selon l’invention ou au moins un composé diuréthane T préparé selon la méthode de préparation selon l’invention et au moins un pigment coloré organique ou minéral. Le composé diuréthane selon l’invention possède des propriétés permettant de G utiliser pour modifier ou contrôler la rhéologie du milieu le comprenant. Ainsi, l’invention fournit également une méthode de contrôle de la viscosité d’une composition aqueuse. The invention also provides a concentrated aqueous pigment paste comprising at least one diurethane compound T according to the invention or at least one diurethane compound T prepared according to the preparation method according to the invention and at least one organic or inorganic colored pigment. The diurethane compound according to the invention has properties allowing it to be used to modify or control the rheology of the medium comprising it. Thus, the invention also provides a method for controlling the viscosity of an aqueous composition.
Cette méthode de contrôle de la viscosité selon l’invention comprend l’addition d’au moins un composé diuréthane selon l’invention dans une composition aqueuse. Cette méthode de contrôle de la viscosité peut également comprendre l’addition d’au moins un composé diuréthane préparé selon la méthode de préparation selon l’invention. This viscosity control method according to the invention comprises the addition of at least one diurethane compound according to the invention in an aqueous composition. This viscosity control method can also comprise the addition of at least one diurethane compound prepared according to the preparation method according to the invention.
De manière préférée, la méthode de contrôle de la viscosité selon l’invention est mise en œuvre au moyen d’une composition aqueuse selon l’invention. De manière également préférée, la méthode de contrôle de la viscosité selon l’invention est mise en œuvre au moyen d’une formulation aqueuse selon l’invention. Preferably, the viscosity control method according to the invention is implemented by means of an aqueous composition according to the invention. Also preferably, the method for controlling the viscosity according to the invention is implemented by means of an aqueous formulation according to the invention.
Les caractéristiques préférées, particulières ou avantageuses du composé diuréthane T selon l’invention définissent des compositions aqueuses selon l’invention, des formulations selon l’invention, des pâtes pigmentaires et des méthodes de contrôle de la viscosité qui sont également préférées, particulières ou avantageuses. The preferred, particular or advantageous characteristics of the diurethane compound T according to the invention define aqueous compositions according to the invention, formulations according to the invention, pigment pastes and viscosity control methods which are also preferred, particular or advantageous. .
Les exemples qui suivent permettent d’illustrer les différents aspects de l’invention. The following examples illustrate the various aspects of the invention.
EXEMPLES EXAMPLES
Exemple 1 : préparation de composés diuréthanes selon l’invention Exemple 1-1 : préparation d’un composé Tl selon l’invention Example 1: preparation of diurethane compounds according to the invention Example 1-1: preparation of a compound T1 according to the invention
Dans un réacteur en verre de 3 L équipé d’une agitation mécanique, d’une pompe à vide, d’une entrée d’azote et chauffé au moyen d’une double enveloppe dans laquelle circule de l’huile, on introduit 451,2 g de dodécanol éthoxylé avec 140 moles d’oxyde d’éthylène (MM = 6 355 Da) que l’on chauffe à 90°C sous atmosphère inerte. Ce produit est déshydraté. 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 is introduced, 2 g of dodecanol ethoxylated with 140 moles of ethylene oxide (MM=6355 Da) which is heated to 90° C. under an inert atmosphere. This product is dehydrated.
Sous agitation et atmosphère inerte, on ajoute alors en une heure 5,97 g d’HDI (MM = 168,2 g/mol) en présence de 200 ppm de catalyseur dilaurate de dibutyle d’étain. Après addition complète, le mélange réactionnel est laissé sous agitation pendant 60 minutes à 90°C ± 1°C. Puis, on vérifie que le taux d’isocyanate est nul par un dosage en retour. On prélève 1 g du milieu réactionnel auquel on ajoute un excès de dibutylamine (1 molaire par exemple) qui réagit avec les fonctions isocyanates potentiellement présentes dans le milieu. La dibutylamine n'ayant éventuellement pas réagi est ensuite dosée avec de l’acide chlorhydrique (1 N par exemple). On peut alors en déduire la quantité de fonctions isocyanates présentes dans le milieu réactionnel. Si celui-ci est non nul, la réaction est prolongée par période de 15 minutes jusqu’à achèvement de la réaction. Lorsque le taux atteint zéro, le composé Tl obtenu est formulé dans l’eau avec adjonction de 1 000 ppm d’un agent biocide (Biopol SMV Chemipol) et de 1 000 ppm d’un agent anti-mousse (Tego 1488 Evonik). On obtient une composition 1 constituée de 20 % en masse de composé Tl selon l’invention et de 80 % en masse d’eau. With stirring and an inert atmosphere, 5.97 g of HDI (MW=168.2 g/mol) are then added in one hour in the presence of 200 ppm of tin dibutyl dilaurate catalyst. After complete addition, the reaction mixture is left under stirring for 60 minutes at 90°C ± 1°C. Then, it is checked that the level of isocyanate is zero by a back dosing. 1 g of the reaction medium is taken, to which an excess of dibutylamine (1 molar for example) is added, which reacts with the isocyanate functions potentially present in the medium. Any unreacted dibutylamine is then dosed with hydrochloric acid (1 N for example). The quantity of isocyanate functions present in the reaction medium can then be deduced therefrom. If the latter is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound T1 obtained is formulated in water with the addition of 1000 ppm of a biocidal agent (Biopol SMV Chemipol) and 1000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 1 consisting of 20% by weight of compound T1 according to the invention and 80% by weight of water is obtained.
Exemple 1-2 : préparation d’un composé T2 selon l’invention Dans un réacteur en verre de 3 L équipé d’une agitation mécanique, d’une pompe à vide, d’une entrée d’azote et chauffé au moyen d’une double enveloppe dans laquelle circule de l’huile, on introduit 448,7 g de dodécanol éthoxylé avec 140 moles d’oxyde d’éthylène (MM = 6 355 Da) que Ton chauffe à 90°C sous atmosphère inerte. Ce produit est déshydraté. Sous agitation et atmosphère inerte, on ajoute alors en une heure 7,85 g d’IPDI (MM = 222,3 g/mol) en présence de 200 ppm de catalyseur carboxylate de bismuth. Après addition complète, le mélange réactionnel est laissé sous agitation pendant 60 minutes à 90°C ± 1°C. Comme décrit dans l’exemple 1-1, on vérifie que le taux d’isocyanate est nul par un dosage en retour. Si celui-ci est non nul, la réaction est prolongée par période de 15 minutes jusqu’à achèvement de la réaction. Lorsque le taux atteint zéro, le composé T2 obtenu est formulé dans l’eau avec adjonction de 1 000 ppm d’un agent biocide (Biopol SMV Chemipol) et de 1 000 ppm d’un agent anti-mousse (Tego 1488 Evonik). On obtient une composition 2 constituée de 20 % en masse de composé T2 selon l’invention et de 80 % en masse d’eau. Example 1-2: preparation of a compound T2 according to the invention In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of a jacket in which oil circulates, 448.7 g of dodecanol ethoxylated with 140 moles of ethylene oxide (MM=6355 Da) are introduced, which is heated to 90° C. under an inert atmosphere. This product is dehydrated. With stirring and an inert atmosphere, 7.85 g of IPDI (MW=222.3 g/mol) are then added in one hour in the presence of 200 ppm of bismuth carboxylate catalyst. After complete addition, the reaction mixture is left under stirring for 60 minutes at 90°C ± 1°C. As described in example 1-1, we check that the isocyanate level is zero by back dosing. If this is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound T2 obtained is formulated in water with the addition of 1,000 ppm of a biocidal 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.
Exemple 1-3 : préparation d’un composé T3 selon l’invention Example 1-3: preparation of a compound T3 according to the invention
Dans un réacteur en verre de 3 L équipé d’une agitation mécanique, d’une pompe à vide, d’une entrée d’azote et chauffé au moyen d’une double enveloppe dans laquelle circule de l’huile, on introduit 449,3 g de dodécanol éthoxylé avec 140 moles d’oxyde d’éthylène (MM = 6 355 Da) que Ton chauffe à 90°C sous atmosphère inerte. Ce produit est déshydraté. 449, 3 g of dodecanol ethoxylated with 140 moles of ethylene oxide (MM=6355 Da) which is heated to 90° C. under an inert atmosphere. This product is dehydrated.
Sous agitation et atmosphère inerte, on ajoute alors en une heure 9,27 g d’HuMDI (MM = 262,3 g/mol) en présence de 200 ppm de catalyseur carboxylate de bismuth. Après addition complète, le mélange réactionnel est laissé sous agitation pendant 60 minutes à 90°C ± 1°C. Comme décrit dans l’exemple 1-1, on vérifie que le taux d’isocyanate est nul par un dosage en retour. Si celui-ci est non nul, la réaction est prolongée par période de 15 minutes jusqu’à achèvement de la réaction. Lorsque le taux atteint zéro, le composé T3 obtenu est formulé dans l’eau avec adjonction de 1 000 ppm d’un agent biocide (Biopol SMV Chemipol) et de 1 000 ppm d’un agent anti-mousse (Tego 1488 Evonik). On obtient une composition 3 constituée de 20 % en masse de composé T3 selon l’invention et de 80 % en masse d’eau. With stirring and an inert atmosphere, 9.27 g of HuMDI (MW=262.3 g/mol) are then added in one hour in the presence of 200 ppm of bismuth carboxylate catalyst. After complete addition, the reaction mixture is left under stirring for 60 minutes at 90°C ± 1°C. As described in example 1-1, it is verified that the isocyanate content is zero by a back assay. If the latter is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound T3 obtained is formulated in water with the addition of 1000 ppm of a biocidal agent (Biopol SMV Chemipol) and 1000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 3 consisting of 20% by mass of compound T3 according to the invention and 80% by mass of water is obtained.
Exemple 1-4 : préparation d’un composé T4 selon l’invention Dans un réacteur en verre de 3 L équipé d’une agitation mécanique, d’une pompe à vide, d’une entrée d’azote et chauffé au moyen d’une double enveloppe dans laquelle circule de l’huile, on introduit 449,3 g d’octadécanol éthoxylé avec 132 moles d’oxyde d’éthylène (MM moyenne = 6078 Da) que l’on chauffe à 90°C sous atmosphère inerte. Ce produit est déshydraté. Sous agitation et atmosphère inerte, on ajoute alors en une heure 6,23 g d’HDI (MM = 168,2 g/mol) en présence de 200 ppm de catalyseur carboxylate de bismuth. Après addition complète, le mélange réactionnel est laissé sous agitation pendant 60 minutes à 90°C ± 1°C. Comme décrit dans l’exemple 1-1, on vérifie que le taux d’isocyanate est nul par un dosage en retour. Si celui-ci est non nul, la réaction est prolongée par période de 15 minutes jusqu’à achèvement de la réaction. Lorsque le taux atteint zéro, le composéExample 1-4: preparation of a compound T4 according to the invention In a 3 L glass reactor equipped with mechanical stirring, a vacuum pump, a nitrogen inlet and heated by means of 449.3 g of octadecanol ethoxylated with 132 moles of ethylene oxide (mean MW=6078 Da) are introduced into a jacket in which oil circulates, which is heated to 90° C. under an inert atmosphere. This product is dehydrated. With stirring and 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. After complete addition, the reaction mixture is left under stirring for 60 minutes at 90°C ± 1°C. As described in example 1-1, we check that the isocyanate level is zero by back dosing. If this is non-zero, the reaction is prolonged for periods of 15 minutes until the reaction is complete. When the rate reaches zero, the compound
T4 obtenu est formulé à l’aide d’un composé tensio-actif de type alcool éthoxylé (hexanol éthoxylé avec cinq équivalents d’oxyde d’éthylène) dans l’eau avec adjonction de 1 000 ppm d’un agent biocide (Biopol SMV Chemipol) et de 1 000 ppm d’un agent anti-mousse (Tego 1488 Evonik). On obtient une composition 4 constituée de 20 % en masse de composé T4 selon l’invention, de 15 % de tensio-actif et de 65 % en masse d’eau. T4 obtained is formulated using a surfactant compound of the ethoxylated alcohol type (ethoxylated hexanol with five equivalents of ethylene oxide) in water with the addition of 1,000 ppm of a biocidal agent (Biopol SMV Chemipol) and 1000 ppm of an anti-foaming agent (Tego 1488 Evonik). A composition 4 consisting of 20% by mass of compound T4 according to the invention, 15% of surfactant and 65% by mass of water is obtained.
Exemple 2 : préparation de formulations de peinture selon l’invention On prépare les formulations de peinture Fl à F3 selon l’invention respectivement à partir des compositions aqueuses 1 à 3 de composés diuréthanes Tl à T3 selon l’invention. L’ensemble des ingrédients et proportions (% en masse) mis en œuvre sont présentés dans le tableau 1. Example 2 Preparation of Paint Formulations According to the Invention Paint formulations F1 to F3 according to the invention are prepared respectively from aqueous compositions 1 to 3 of diurethane compounds T1 to T3 according to the invention. All the ingredients and proportions (% by mass) used are presented in Table 1.
Tableau 1 Table 1
Exemple 3 : caractérisation de formulations de peinture selon l’invention Pour les formulations de peinture selon l’invention, on a déterminé, 24 h après leur préparation, la viscosité Brookfield, mesurée à 25°C et à 10 tr/min et à 100 tr/min (pBkio et PBkioo en mPa.s) au moyen d’un viscosimètre Brookfield DV-1 à mobiles de type RVT. Les propriétés des formulations de peinture sont présentées dans le tableau 2. Example 3 Characterization of Paint Formulations According to the Invention For the paint formulations according to the invention, 24 hours after their preparation, the Brookfield viscosity was determined, measured at 25° C. and at 10 rpm and at 100 rev/min (p Bki o and PBkioo in mPa.s) using a Brookfield DV-1 viscometer with RVT type spindles. The properties of the paint formulations are shown in Table 2.
Tableau 2 Table 2
Les composés diuréthanes selon l’invention sont très efficaces pour obtenir d’excellentes viscosités à bas et moyens gradients de cisaillement pour des compositions de peinture. The diurethane compounds according to the invention are very effective in obtaining excellent viscosities at low and medium shear gradients for paint compositions.
Exemple 4 : caractérisation de formulations de peinture selon l’invention Pour les formulations de peinture selon l’invention, on a déterminé, 24 h après leur préparation et à température ambiante, la viscosité Cône Plan ou viscosité ICI, mesurée à haut gradient de cisaillement (pi en mPa.s) et la viscosité Stormer, mesurée à moyen gradient de cisaillement (pS en Krebs Units ou KU), au moyen du module standard. Les propriétés des formulations de peinture sont présentées dans le tableau 3. Example 4 Characterization of Paint Formulations According to the Invention For the paint formulations according to the invention, the Cone Plane viscosity or ICI viscosity, measured at high shear gradient, was determined 24 hours after their preparation and at room temperature. (pi in mPa.s) and the Stormer viscosity, measured at medium shear rate (pS in Krebs Units or KU), using the standard module. The properties of the paint formulations are shown in Table 3.
Tableau 3 Table 3
Les composés diuréthanes selon l’invention permettent de préparer des formulations de peinture dont les viscosités sont particulièrement bien contrôlées. Notamment, la viscosité pi est particulièrement élevée et le rapport mi/ps est alors excellent. Les composés selon l’invention permettent un excellent compromis entre la viscosité à haut gradient de cisaillement et la viscosité à bas gradient de cisaillement. The diurethane compounds according to the invention make it possible to prepare paint formulations whose viscosities are particularly well controlled. In particular, the viscosity pi is particularly high and the mi/ps ratio is then excellent. The compounds according to the invention allow an excellent compromise between the viscosity at high shear gradient and the viscosity at low shear gradient.

Claims

REVENDICATIONS
1. Composé diuréthane T préparé par réaction : a. d’un équivalent molaire d’au moins un composé diisocyanate (a) et b. de deux équivalents molaires d’un même composé (b) polyéthoxylé comprenant de 100 à 500 groupements oxyéthylène choisi parmi les monoalcools (bl) aliphatiques linéaires comprenant de 6 à 40 atomes de carbone et polyéthoxylés, les monoalcools (b2) aliphatiques ramifiés comprenant de 6 à 40 atomes de carbone et polyéthoxylés et les monoalcools (b3) cycloaliphatiques comprenant de 6 à 40 atomes de carbone et polyéthoxylés. 1. Diurethane compound T prepared by reaction: a. of a molar equivalent of at least one diisocyanate compound (a) and b. of two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from linear aliphatic monoalcohols (bl) comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 containing 40 carbon atoms and polyethoxylated and cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms and polyethoxylated.
2. Composé diuréthane T selon la revendication 1 pour lequel la réaction met en œuvre un unique composé (a) ou bien pour lequel la réaction met en œuvre deux ou trois composés (a) différents. 2. Compound diurethane T according to claim 1 for which the reaction implements a single compound (a) or for which the reaction implements two or three different compounds (a).
3. Composé diuréthane T selon l’une des revendications 1 ou 2 pour lequel le composé (a) est choisi parmi : les composés diisocyanates aromatiques symétriques, de préférence : 3. Diurethane compound T according to one of claims 1 or 2 for which compound (a) is chosen from: symmetrical aromatic diisocyanate compounds, preferably:
• 2,2'-diisocyanate de diphénylméthylène (2,2'-MDI) et 4,4'-diisocyanate de diphénylméthylène (4,4'-MDI) ; • 2,2'-diphenylmethylene diisocyanate (2,2'-MDI) and 4,4'-diphenylmethylene diisocyanate (4,4'-MDI);
• 4,4’-dibenzyl diisocyanate (4,4’-DBDI) ; • 4,4'-dibenzyl diisocyanate (4,4'-DBDI);
• 2,6-diisocyanate de toluène (2,6-TDI) ; • 2,6-toluene diisocyanate (2,6-TDI);
• m-xylylène diisocyanate (m-XDI) ; les composés diisocyanates alicycliques symétriques, de préférence méthylène bis(4-cyclohexylisocyanate) (HnMDI) ; les composés diisocyanates aliphatiques symétriques, de préférence diisocyanate d'hexaméthylène (HDI), diisocyanate de pentaméthylène (PDI) ; les composés diisocyanates aromatiques dissymétriques, de préférence : • m-xylylene diisocyanate (m-XDI); symmetrical alicyclic diisocyanate compounds, preferably methylene bis(4-cyclohexylisocyanate) (HnMDI); symmetrical aliphatic diisocyanate compounds, preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI); unsymmetrical aromatic diisocyanate compounds, preferably:
• 2,4'-diisocyanate de diphénylméthylène (2,4'-MDI) ; • 2,4'-diisocyanate of diphenylmethylene (2,4'-MDI);
• 2,4’-dibenzyl diisocyanate (2,4’-DBDI) ; • 2,4'-dibenzyl diisocyanate (2,4'-DBDI);
• 2,4-diisocyanate de toluène (2,4-TDI) ; les composés diisocyanates alicycliques dissymétriques, de préférence diisocyanate d'isophorone (IPDI). • 2,4-diisocyanate of toluene (2,4-TDI); unsymmetrical alicyclic diisocyanate compounds, preferably isophorone diisocyanate (IPDI).
4. Composé diuréthane T selon l’une des revendications 1 à 3 pour lequel le composé (a) est choisi parmi IPDI, HDI, H12MDI et leurs combinaisons. 4. Diurethane compound T according to one of claims 1 to 3 for which compound (a) is chosen from IPDI, HDI, H12MDI and their combinations.
5. Composé diuréthane T selon l’une des revendications 1 à 4 : pour lequel le degré de polyéthoxylation est compris entre 105 et 500 ou entre 100 et 502 ou entre 105 et 502 ou entre 100 et 400 ou entre 105 et 400, ou pour lequel les monoalcools polyéthoxylés comprennent de 100 à 500 groupements éthoxylés, de préférence de 100 à 400 groupements éthoxylés ou de 100 à 200 groupements éthoxylés. 5. Diurethane compound T according to one of claims 1 to 4: for which the degree of polyethoxylation is between 105 and 500 or between 100 and 502 or between 105 and 502 or between 100 and 400 or between 105 and 400, or for wherein the polyethoxylated monoalcohols comprise from 100 to 500 ethoxylated groups, preferably from 100 to 400 ethoxylated groups or from 100 to 200 ethoxylated groups.
6. Composé diuréthane T selon l’une des revendications 1 à 5 pour lequel le composé (b) est tel que : la chaîne hydrocarbonée du monoalcool (b 1 ) comprend de 6 à 30 atomes de carbone ou de 6 à 16 atomes de carbone ou bien de 20 à 40 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 16 atomes de carbone, plus préférentiellement le monoalcool (bl) est choisi parmi n-octanol polyéthoxylé, n-décanol polyéthoxylé, n-dodécanol polyéthoxylé, n-hexadécanol polyéthoxylé, ou la chaîne hydrocarbonée du monoalcool (b2) comprend de 6 à 30 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 16 atomes de carbone, plus préférentiellement le monoalcool (b2) est choisi parmi ethyl-hexanol polyéthoxylé, iso-octanol polyéthoxylé, iso-nonanol polyéthoxylé, iso-décanol polyéthoxylé, propyl-heptanol polyéthoxylé, butyl-octanol polyéthoxylé, iso-dodécanol polyéthoxylé, iso-hexadécanol polyéthoxylé, un alcool oxo polyéthoxylé, un alcool de Guerbet polyéthoxylé, ou la chaîne hydrocarbonée du monoalcool (b3) comprend de 6 à 30 atomes de carbone, de préférence de 6 à 20 atomes de carbone ou de 8 à 20 atomes de carbone, plus préférentiellement le monoalcool (b3) est choisi parmi ethyl-cyclohexanol polyéthoxylé, n-nonyl-cyclohexanol polyéthoxylé, n-dodécyl-cyclohexanol polyéthoxylé. 6. Diurethane compound T according to one of claims 1 to 5 for which compound (b) is such that: the hydrocarbon chain of the monoalcohol (b 1 ) comprises from 6 to 30 carbon atoms or from 6 to 16 carbon atoms or else from 20 to 40 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (bl) is chosen from polyethoxylated n-octanol, polyethoxylated n-decanol, n- polyethoxylated dodecanol, polyethoxylated n-hexadecanol, or the hydrocarbon chain of the monoalcohol (b2) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 16 carbon atoms, more preferably the monoalcohol (b2 ) is chosen from polyethoxylated ethyl-hexanol, polyethoxylated iso-octanol, polyethoxylated iso-nonanol, polyethoxylated iso-decanol, polyethoxylated propyl-heptanol, polyethoxylated butyl-octanol, polyethoxylated iso-dodecanol, polyethoxylated iso-hexadecanol, a polyethoxylated oxo alcohol, a polyethoxylated Guerbet alcohol, or ch hydrocarbon amine of the monoalcohol (b3) comprises from 6 to 30 carbon atoms, preferably from 6 to 20 carbon atoms or from 8 to 20 carbon atoms, more preferably the monoalcohol (b3) is chosen from polyethoxylated ethyl-cyclohexanol, n -polyethoxylated nonyl-cyclohexanol, polyethoxylated n-dodecyl-cyclohexanol.
7. Méthode de préparation d’un composé diuréthane T par réaction : a. d’un équivalent molaire d’au moins un composé diisocyanate (a) et b. de deux équivalents molaires d’un même composé (b) polyéthoxylé comprenant de 100 à 500 groupements oxyéthylène choisi parmi les monoalcools (bl) aliphatiques linéaires comprenant de 6 à 40 atomes de carbone et polyéthoxylés, les monoalcools (b2) aliphatiques ramifiés comprenant de 6 à 40 atomes de carbone et polyéthoxylés et les monoalcools (b3) cycloaliphatiques comprenant de 6 à 40 atomes de carbone et polyéthoxylés. 7. Method for preparing a diurethane compound T by reaction: a. of a molar equivalent of at least one diisocyanate compound (a) and b. two molar equivalents of the same polyethoxylated compound (b) comprising from 100 to 500 oxyethylene groups chosen from monoalcohols (bl) linear aliphatics comprising from 6 to 40 carbon atoms and polyethoxylated, branched aliphatic monoalcohols (b2) comprising from 6 to 40 carbon atoms and polyethoxylated and cycloaliphatic monoalcohols (b3) comprising from 6 to 40 carbon atoms and polyethoxylated.
8. Méthode selon la revendication 7 pour la préparation d’un composé diuréthane T selon l’une des revendications 2 à 6. 8. Method according to claim 7 for the preparation of a diurethane compound T according to one of claims 2 to 6.
9. Composition aqueuse comprenant : au moins un composé choisi parmi un composé diuréthane T selon l’une des revendications 1 à 6 et un composé diuréthane T préparé selon la méthode des revendications 7 ou 8, et éventuellement au moins un additif choisi parmi : 9. Aqueous composition comprising: at least one compound chosen from a diurethane compound T according to one of claims 1 to 6 and a diurethane compound T prepared according to the method of claims 7 or 8, and optionally at least one additive chosen from:
• un composé amphiphile, notamment un composé tensio-actif, de préférence un composé tensio-actif hydroxylé, par exemple alkyl-polyalkyleneglycol, notamment alkyl-polyethyleneglycol et alkyl-polypropyleneglycol ; • an amphiphilic compound, in particular a surfactant compound, preferably a hydroxylated surfactant compound, for example alkyl-polyalkylene glycol, in particular alkyl-polyethylene glycol and alkyl-polypropylene glycol;
• un dérivé de polysaccharide, par exemple cyclodextrine, dérivé de cyclodextrine, polyéthers, alkyl-glucosides ; • a polysaccharide derivative, for example cyclodextrin, cyclodextrin derivative, polyethers, alkyl-glucosides;
• solvants, notamment solvants de coalescence, et composés hydrotropes, par exemple glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, produits Dowanol dont le numéro CAS est 34590-94-8), produits Texanol dont le numéro CAS est 25265-77-4) ; • solvents, in particular coalescence solvents, and hydrotropic compounds, for example glycol, butylglycol, butyldiglycol, monopropyleneglycol, ethyleneglycol, ethylenediglycol, Dowanol products whose CAS number is 34590-94-8), Texanol products whose CAS number is 25265-77 -4);
• agents anti-mousse, agents biocides. • anti-foaming agents, biocidal agents.
10. Formulation aqueuse comprenant : au moins une composition selon la revendication 9; éventuellement au moins un pigment organique ou minéral ou des particules organiques, organo-métalliques ou minérales, par exemple carbonate de calcium, talc, kaolin, mica, silicates, silice, oxydes métalliques, notamment dioxyde de titane, oxydes de fer ; et éventuellement au moins un agent choisi parmi un agent espaceur de particules, un agent dispersant, un agent stabilisant stérique, un agent stabilisant électrostatique, un agent opacifiant, un solvant, un agent de coalescence, un agent anti-mousse, un agent de conservation, un agent biocide, un agent d’étalement, un agent épaississant, un copolymère filmogène et leurs mélanges. 10. Aqueous formulation comprising: at least one composition according to claim 9; optionally at least one organic or mineral pigment or organic, organometallic or mineral particles, for example calcium carbonate, talc, kaolin, mica, silicates, silica, metal oxides, in particular titanium dioxide, iron oxides; and optionally at least one agent chosen from a particle spacer, a dispersing agent, a steric stabilizing agent, an electrostatic stabilizing agent, a opacifier, solvent, coalescing agent, anti-foaming agent, preservative, biocidal agent, spreading agent, thickening agent, film-forming copolymer and mixtures thereof.
11. Formulation selon la revendication 10 de revêtement, notamment une formulation d’encre, une formulation de vernis, une formulation d’adhésif, une formulation de peinture, par exemple de peinture décorative ou de peinture industrielle. 11. Formulation according to claim 10 of coating, in particular an ink formulation, a varnish formulation, an adhesive formulation, a paint formulation, for example decorative paint or industrial paint.
12. Pâte pigmentaire aqueuse concentrée comprenant au moins un composé diuréthane T selon l’une des revendications 1 à 6 ou au moins un composé diuréthane T préparé selon la méthode de préparation des revendications 7 ou 8 et au moins un pigment coloré organique ou minéral. 12. Concentrated aqueous pigment paste comprising at least one diurethane compound T according to one of claims 1 to 6 or at least one diurethane compound T prepared according to the preparation method of claims 7 or 8 and at least one organic or inorganic colored pigment.
13. Méthode de contrôle de la viscosité d’une composition aqueuse comprenant l’addition d’au moins un composé diuréthane T selon l’une des revendications 1 à 6 ou d’au moins un composé diuréthane T préparé selon la méthode des revendications 7 ou 8. 13. Method for controlling the viscosity of an aqueous composition comprising the addition of at least one diurethane compound T according to one of claims 1 to 6 or of at least one diurethane compound T prepared according to the method of claims 7 or 8.
14. Méthode selon la revendication 13 pour laquelle la composition aqueuse est une composition selon la revendication 9 ou bien une formulation définie selon l’une des revendications 10 et 11. 14. Method according to claim 13 for which the aqueous composition is a composition according to claim 9 or else a formulation defined according to one of claims 10 and 11.
EP21755511.9A 2020-07-27 2021-07-26 Rheology-modifying diurethane compound Pending EP4188975A1 (en)

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