Continuous or semi - continuous process for producing a pre - activated organogelator paste

Abstract

The present invention relates to a continuous or semi - continuous process for producing a pre - activated organic gelling agent paste, the process comprising: (1) mixing at least one amide compound with at least one liquid carrier to provide a mixture, the mixing being carried out at a temperature T1 below the activation temperature of the amide compound; (2) continuously flowing the mixture through a heat exchanger to raise its temperature to a temperature T2 above the activation temperature of the amide compound to obtain a paste; (3) filling the paste into a container maintained at a temperature above the activation temperature; and (4) removing and cooling the container.

Description

Technical Field

[0001] The present invention relates to a continuous or semi - continuous process for producing a pre - activated organic gelling agent paste, which process comprises: (1) mixing at least one amide compound with at least one liquid carrier to provide a mixture, wherein the mixing is carried out at a temperature T1 below the activation temperature of the amide compound; (2) continuously flowing the mixture through a heat exchanger to raise its temperature to a temperature T2 above the activation temperature of the mixture to obtain a paste; (3) filling the paste into a container maintained at a temperature above the activation temperature; and (4) removing and cooling the container.

Background Art

[0002] Many rheology additives are used to increase the viscosity of coating compositions such as mastics, glues, or adhesive compositions, paints, varnishes, gel coats, or inks, or molding compositions, or even electrolyte compositions. Among these, mention may be made in particular of polyamide powders, powders of hydrogenated castor oil - based derivatives, fumed silica, precipitated calcium carbonate, or ground calcium carbonate. Fumed silica and calcium carbonate are inorganic substances and require the mixture to be dispersed very rapidly. However, these inorganic fillers exhibit problems of stability and precipitation over time and have an adverse effect on the mechanical properties of the final system. Another particular drawback of polyamide powders and powders of hydrogenated castor oil derivatives is that the user (formulator) needs to activate the system when producing the final composition. This activation requires high - speed shearing, heating corresponding to a temperature rise of up to about 120 °C depending on the product, and a minimum time required depending on the temperature conditions and the system to obtain optimal final rheological properties.

[0003] The applicant has already proposed a rheology additive in the form of a pre - activated paste that can impart thixotropic properties simply by blending it into the final formulation, thus eliminating the need for an activation step by the end - user.

[0004] Therefore, in European Patent Application Publication No. 1935934, a rheology additive containing at least one fatty acid diamide introduced in powder form and at least one organic plasticizer has been proposed.

[0005] An improved method has been proposed in which the diamide contains a reaction product of 12-hydroxystearic acid (HSA) and a linear aliphatic diamine, and the plasticizer is replaced by a reactive (meth)acrylic solvent containing at least one alicyclic group (European Patent Application Publication No. 3371253).

[0006] Therefore, it has been proposed to use 14-hydroxyicosanoic acid (14-HEA) derived from Lesquerella seeds instead of 12-HSA derived from castor oil (U.S. Patent Application Publication No. 2015 / 0274644).

[0007] All of the above additives impart thixotropic behavior to the formulated composition, characterized by significant shear thinning, i.e., the viscosity decreases as the shear increases and then recovers time-dependently (corresponding to the hysteresis effect).

[0008] These provide excellent properties to the final composition, characterized by high viscosity at rest, good stability of this viscosity during storage, good resistance to sedimentation, ease of application and extrusion, and good resistance to sagging after application. In addition, it has been demonstrated that these rheology additives can be used immediately in various solvent-based formulations or solvent-free formulations. However, they always involve a batch process that includes a first step of mixing the diamide with the plasticizer or a reactive or non-reactive solvent in an open container at a temperature below room temperature to obtain a homogeneous mixture, followed by closing the container and heating the mixture in an oven at an activation temperature (i.e., 35 - 120°C) for 1 - 100 hours in a second step.

[0009] This activation step can be difficult to control and reproduce, resulting in a paste that may not be easy to disperse in the final formulation, and whose rheological properties may vary depending on the container used in manufacturing. In addition, this batch process is expensive in terms of time and energy, and the start and stop of manufacturing take time, which has an adverse effect on economy. Furthermore, given that the reactor needs to be placed in an oven afterwards, only a small amount of diamide and plasticizer or solvent can be prepared. Moreover, this process is limited to using only solvents with low vapor pressure, which is necessary to avoid the internal pressure of the container rising during heating or dropping excessively during cooling. Due to these safety issues, this process would not be applicable to reactive solvents such as methyl methacrylate unless expensive containers that can withstand such pressures are used.

[0010] Therefore, it would be desirable to provide a cost-effective and safe process for activating such rheological additives that is more reproducible, versatile, and can be used on an industrial scale, even with solvents having a low vapor pressure.

Summary of the Invention

[0011] The inventors have shown that it is possible to produce, on a large scale in a reproducible manner, a pre-activated paste of an organic gelling agent based on an amide compound using a continuous or semi-continuous process that includes an activation step carried out in a continuous flow mode.

[0012] Accordingly, the present invention is directed to a process for producing a pre-activated organic gelling agent paste, the process comprising: (1) mixing at least one amide compound with at least one liquid carrier to provide a mixture, wherein the mixing is carried out at a temperature T1 below the activation temperature of the amide compound; (2) continuously flowing the mixture through a heat exchanger to raise its temperature to a temperature T2 above the activation temperature of the amide compound to obtain a paste; (3) filling the paste into a container maintained at a temperature equal to or higher than the activation temperature, and (4) removing and cooling the container are included.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] The present invention relates to a method for producing a pre - activated organic gelling agent paste.

[0015] An organic gelling agent (also called a rheology additive or a thixotropic agent) can correspond to an organic molecule of low molecular weight (i.e., less than 2000 g / mol) that can form a thermoreversible organic gel in an organic liquid, particularly at a relatively low concentration (i.e., less than 1% by weight based on the weight of the organic liquid). The organic gelling agent can change the rheology of the formulation into which it is introduced. In particular, the organic gelling agent can impart a pseudoplastic effect or a thixotropic effect to this formulation. Thus, the organic gelling agent can increase the viscosity of the formulation when the formulation is at rest (when no shear stress is applied) and decrease the viscosity of the formulation when the formulation is subjected to shear stress. The increase and decrease in viscosity can be determined with reference to a control formulation that does not contain the organic gelling agent.

[0016] In order to exhibit pseudoplastic or thixotropic properties, it is necessary to activate the organic gelling agent. This activation generally involves applying specific heating conditions for a specific time under shear. This activation step is generally carried out by the end user, i.e., the formulator who desires to impart thixotropic or pseudoplastic properties to the formulation by adding the organic gelling agent. For example, the end user can activate the organic gelling agent before introducing it into the formulation, or the end user can also activate the organic gelling agent in situ (directly within the formulation).

[0017] Advantageously, the process of the present invention provides an organic gelling agent paste in a pre-activated form. The expression "pre-activated" should be considered to mean that the organic gelling agent has thixotropic or pseudoplastic properties and is thus in a state that can be used by the end user. Thus, the pre-activated organic gelling agent can simply be mixed into the formulation and will not require further activation to exhibit pseudoplastic or thixotropic properties.

[0018] The pre-activated organogelator obtained in the process of the present invention is in the form of a paste. The expression "paste" should be considered to mean that the pre-activated organogelator is dispersed in the liquid in which it is carried, and preferably, the pre-activated organogelator is in the form of an organogel. An organogel can be defined as a non-crystalline, non-glassy, thermoreversible solid or semi-solid (jelly-like) material consisting of an organic liquid trapped within a three-dimensional cross-linked network based on the self-assembly of a structuring agent (in this case an amide compound) by non-covalent interactions (such as hydrogen bonding, van der Waals interactions, π-π stacking ion pairs, solvophobic forces, and / or ion coordination). These interactions result in the formation of a 3D network of microfibrils that immobilize the organic liquid. The organogel can be stable for several months at 25 °C, i.e., it does not phase-separate in the bulk. By heating and stirring, the 3D network is reversibly fragmented, the viscosity of the organogel decreases, and when heating under stirring is stopped, the 3D network of microfibrils can be reformed.

[0019] The pre-activated organogelator paste obtained in the process of the present invention comprises at least one amide compound and at least one liquid carrier.

[0020] The amide compound can be selected from monoamides and / or diamides. A monoamide is a compound having one amide bond (-NH-C(=O)-). Such a compound can be the reaction product of at least one monoamine and at least one monocarboxylic acid. A diamide is a compound having two amide bonds (-NH-C(=O)-). Such a compound can be the reaction product of at least one diamine and at least one monocarboxylic acid. An asymmetric diamide can be obtained by the reaction of a diamine with a mixture of monocarboxylic acids. A mixture of diamides can be obtained when a mixture of diamines and / or a mixture of monocarboxylic acids participates in the reaction.

[0021] Suitable amide compounds are a) aliphatic C2-C24 Monoamine and / or diamine, alicyclic C6-C 18 Monoamine and / or diamine, aromatic C6-C 18 At least one amine selected from monoamine and / or diamine, and combinations thereof b) At least one hydroxylated C3-C 36 Monocarboxylic acid c) Optionally, at least one saturated straight-chain non-hydroxylated C2-C 18 Monocarboxylic acid can be obtained by polycondensation of

[0022] The amide compound can optionally be combined with hydrogenated castor oil. In this case, the content of the amide compound can be in the range of 10 to 99% by weight, preferably 20 to 99% by weight, based on the total weight of the amide compound and hydrogenated castor oil.

[0023] Component (a) comprises at least one amine selected from monoamine, diamine, and mixtures thereof. As used herein, monoamine is a compound having a single secondary amine group (-NH2), and diamine is a compound having two secondary amine groups. When component (a) comprises monoamine, the reaction product comprises monoamide. When component (a) comprises diamine, the reaction product comprises diamide. When component (a) comprises both monoamine and diamine, the reaction product comprises both monoamide and diamide. When component (a) comprises a mixture of diamines, the reaction product comprises a mixture of diamides.

[0024] Component (a) is aliphatic C2-C 24 Monoamine and / or diamine, alicyclic C6-C 18 Monoamine and / or diamine, aromatic C6-C 18 comprises at least one amine selected from monoamine and / or diamine, and combinations thereof.

[0025] As used herein, aliphatic C2-C 24The monoamine and each diamine are acyclic monoamines and each diamine, respectively, containing 2 to 24 carbon atoms. The aliphatic monoamine and / or diamine may be linear or branched, preferably linear. The aliphatic monoamine and / or diamine preferably contain 2 to 12, more preferably 2 to 8, even more preferably 2 to 6 carbon atoms.

[0026] Examples of aliphatic diamines include 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, and combinations thereof; preferably 1,2-ethylenediamine or 1,6-hexamethylenediamine; more preferably 1,6-hexamethylenediamine.

[0027] Examples of linear aliphatic monoamines suitable for component (a) can include ethylamine, propylamine, butylamine, pentylamine, hexylamine, ethanolamine, and combinations thereof, preferably ethylamine, propylamine, hexylamine, or ethanolamine.

[0028] As used herein, alicyclic C6-C 18 The monoamine and each diamine are monoamines and each diamine, respectively, containing 6 to 18 carbon atoms and at least one non-aromatic ring. The alicyclic monoamine and / or diamine preferably contain at least one 6-membered non-aromatic ring which may be crosslinked or condensed with another non-aromatic ring.

[0029] Examples of alicyclic diamines suitable for component (a) include C6-C 12 Alicyclic amines, especially the following, can be mentioned: Cyclohexane-1,3-, -1,4-, or -1,2-diamine, especially -1,3- or -1,4-diamine, 2- or 4-methylcyclohexane-1,3-diamine, isophoronediamine, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane (each derived from the hydrogenation of m-, p-, or o-xylylenediamine), preferably 1,3- or 1,4-bis(aminomethyl)1,4-cyclohexane, decahydronaphthalenediamine, bis(3-methyl-4-aminocyclohexyl)methane (BMACM), bis(4-aminocyclohexyl)methane (BACM), 1-{[4-(aminomethyl)cyclohexyl]oxy}propane-2-amine, and combinations thereof. Preferred alicyclic diamines are selected from cyclohexane-1,3- or -1,4-diamine, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, or bis(4-aminocyclohexyl)methane.

[0030] Examples of alicyclic monoamines suitable for component (a) include cyclohexylamine, isophorylamine, and combinations thereof.

[0031] As used herein, aromatic C6-C 18 The monoamine and diamine, respectively, are monoamines and diamines containing 6 to 18 carbon atoms and at least one aromatic ring. The aromatic monoamine and / or diamine preferably contains at least one 6-membered ring aromatic ring which may be crosslinked or condensed with another non-aromatic ring. Suitable and preferred examples of aromatic diamines as component (a) include C6-C 14 Aromatic amines, especially the following: m- or p-xylylenediamine, m- or p-phenylenediamine, m- or p-tolylenediamine, 3,4'- or 4-4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and combinations thereof.

[0032] Examples of aromatic monoamines include benzylamine, xylylamine, and toluidine.

[0033] Preferably, component (a) is at least one C2-C 24 and, in particular, C2-C 12 more specifically a C2-C8 linear aliphatic diamine; and optionally an alicyclic C6-C 18 diamine, an aromatic C6-C 18 diamine, and at least one other diamine selected from combinations thereof.

[0034] Component (b) comprises at least one hydroxylated C3-C 36 monocarboxylic acid, i.e., a compound containing from 3 to 36 carbon atoms, a single carboxy group (-COOH), and one or more hydroxy groups (-OH), preferably a single hydroxy group. This hydroxylated C3-C 36 monocarboxylic acid may be saturated or unsaturated (in which case the trans form is preferred) and may preferably be saturated.

[0035] The hydroxylated monocarboxylic acid is preferably a C 16 -C 22 monohydroxylated monocarboxylic acid, preferably 14-hydroxyeicosanoic acid, and / or 9-, 10- and / or 12-hydroxystearic acid (9-HSA, 10-HSA and / or 12-HSA). 12-Hydroxystearic acid can be obtained by hydrogenating castor oil and then hydrolyzing the resulting hydrogenated castor oil. 14-Hydroxyeicosanoic acid can be obtained from lesquerol oil, which is produced by extraction from Lesquerella seeds and thus by cultivation of Lesquerella. Lesquerella oil is typically subjected to a transesterification reaction with methanol, the resulting product is hydrogenated, and finally hydrolyzed to obtain 14-hydroxyeicosanoic acid. An example of a polyhydroxylated monocarboxylic acid is 9,10-dihydroxystearic acid.

[0036] Preferably, component (b) contains 12-hydroxystearic acid.

[0037] Optional component (c) is at least one saturated straight-chain non-hydroxylated C2-C 18 monocarboxylic acid, i.e., a straight-chain saturated compound containing from 2 to 18 carbon atoms and a single carboxy group (-COOH) and not containing a hydroxy group (-OH). The non-hydroxylated monocarboxylic acid preferably contains from 2 to 15 carbon atoms, more preferably from 6 to 12 carbon atoms. Examples of non-hydroxylated monocarboxylic acids suitable for component (c) include acetic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and stearic acid. The following non-hydroxylated monocarboxylic acids are preferred: hexanoic acid, octanoic acid, nonanoic acid, and decanoic acid.

[0038] According to one embodiment of the present invention, the amide compound is a diamide compound obtained by polycondensation of 12-hydroxystearic acid and 1,6-hexamethylenediamine.

[0039] The polycondensation reaction of the above components (a) and (b) and optionally (c) can be carried out at a temperature in the range of 140 to 250 °C, preferably 150 to 200 °C. The reaction is preferably carried out under an inert atmosphere. The molar ratio of the amine group of component (a) to the carboxy groups of components (b) and (c) is typically in the range of 0.9 to 1.1, preferably 1:1. In addition, when component (c) is present, the molar ratio of component (b) to component (c) is generally in the range of 1:2 to 4:1.

[0040] This polycondensation reaction enables the recovery of the amide compound. This expression is intended to refer to one or more monoamide compounds, one or more diamide compounds, and mixtures thereof. The preferred amide compound is a diamide compound optionally mixed with a monoamide compound.

[0041] The amide compound obtained after the polycondensation reaction is typically solid. To facilitate the mixing of the amide compound with the liquid carrier in the first step of the process of the present invention, the amide compound is preferably particulate. In particular, the amide compound can be in the form of a powder or a fine powder. For example, the amide compound can be micronized by mechanical grinding (ball milling) or by an air jet. Preferably, the amide compound has a volume particle size Dv(90) of less than 30 μm, preferably less than 25 μm, more preferably less than 20 μm, and even more preferably less than 15 μm. In particular, Dv(90) can be greater than 5 μm and less than 30 μm. The Dv(90) particle size can be understood as a volume-based size distribution that includes 90% of the particles present in a given sample. The said size can be determined by laser diffraction using the method described herein.

[0042] Next, this amide compound can be converted into a pre-activated organogelator paste using the process according to the present invention. In particular, the amide compound is mixed with a liquid carrier and heated to a temperature above its activation temperature to enable self-organization of the molecules by non-covalent bonds and obtain microfibrils.

[0043] The first step of the process of the present invention involves the use of a liquid carrier. The liquid carrier can be used to at least partially solubilize or disperse the amide compound.

[0044] The liquid carrier can be any organic compound that is liquid at a temperature T1 (for example, 30 °C). Preferably, the liquid carrier is an organic compound that is liquid over the entire temperature range from 0 °C to T1 (for example, from 0 to 30 °C). Preferably, the liquid carrier is an organic compound that is liquid over the entire temperature range from T1 to T2 (for example, from 30 °C to 120 °C).

[0045] The liquid carrier may include one or more plasticizers, one or more reactive solvents, and one or more non-reactive solvents, or mixtures thereof. Thus, in this description, the terms "plasticizer" or "solvent" cover both a single compound and a mixture of compounds, unless otherwise specified.

[0046] As used herein, the term "solvent" means a compound that can at least partially solubilize an amide compound, optionally under heating conditions. The solvent is preferably an aprotic organic solvent. More preferably, the solvent is a polar aprotic organic solvent.

[0047] As used herein, the term "reactive solvent" means a solvent that contains a reactive functional group, i.e., a functional group that can react with at least one component of a formulation to which a pre-activated organic gelling agent paste is added. For example, the reactive solvent may contain at least one polymerizable carbon-carbon double bond and / or at least one epoxide ring.

[0048] As used herein, the term "non-reactive solvent" means a solvent that is inert to the components of a formulation to which a pre-activated organic gelling agent paste is added. Typically, the non-reactive solvent lacks the reactive functional groups defined above.

[0049] As used herein, the term "plasticizer" means a compound that can modify the mechanical and / or thermal properties of a formulation to which a pre-activated organic gelling agent paste is added, optionally under heating conditions. For example, the plasticizer may have one or more of the following effects on a formulation to which a pre-activated organic gelling agent paste is added: a decrease in viscosity, a decrease in glass transition temperature, an improvement in flexibility, etc.

[0050] Examples of non-reactive solvents include xylene; alcohols such as methanol, ethanol, butanol, and benzyl alcohol; cyclic saturated hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, and decalin; alkyl esters of monocarboxylic acids such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, heptyl acetate, methyl propionate, ethyl propionate, amyl propionate, and ethyl ethoxypropionate; alkyl esters of dicarboxylic acids such as methyl glutarate, methyl succinate, and methyl adipate; lactones such as γ-butyrolactone; ethers such as dimethoxyethane (DME), methyl ethers of oligoethylene glycol having 2 to 5 ethylene oxide units, 1,3-dioxolane, dioxane, dibutyl ether, and tetrahydrofuran; ketones such as cyclohexanone; phosphate esters or sulfite esters; nitriles such as acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile, and malononitrile; carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate, methyl phenyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, vinylene carbonate, fluoroethylene carbonate, and trifluoropropylene carbonate; and mixtures thereof.

[0051] An example of a mixture of non-reactive solvents is, for example, a mixture of xylene and ethanol or butanol in a weight ratio of 1:1 to 4:1.

[0052] When a reactive solvent is used, it is typically selected from ethylenically unsaturated compounds (i.e., compounds containing a polymerizable carbon-carbon double bond) or epoxides (i.e., compounds containing an epoxy ring). A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Polymerizable carbon-carbon double bonds are generally included in the group selected from acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, maleates, fumarates, itaconates, allyls, propenyls, vinyls, and combinations thereof, preferably selected from acrylates, methacrylates, and vinyls, and more preferably selected from acrylates and methacrylates.

[0053] In particular, the reactive solvent may contain one or more ethylenically unsaturated compounds selected from (meth)acrylic monomers, styrenic monomers, vinyl monomers, olefinic monomers, unsaturated polyacids, or derivatives thereof, and mixtures thereof.

[0054] As used herein, the term "(meth)acrylic monomer" means a monomer containing a carbon-carbon double bond conjugated with a carbonyl (-C(=O)-) bond. Such monomers typically contain a (meth)acryloyl group. Preferably, the (meth)acrylic monomer is a monofunctional (meth)acrylic monomer, i.e., containing only one (meth)acryloyl group. The term "(meth)acryloyl group" is used interchangeably to refer to an acryloyl group (-C(=O)-CH=CH2) or a methacryloyl group (-C(=O)-C(CH3)=CH2). The (meth)acrylic monomer can be selected from alkyl (meth)acrylates (especially methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, or 2-ethylhexyl (meth)acrylate); alicyclic (meth)acrylates (especially dicyclopentadienyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate (IBO(M)A), tert-butylcyclohexanol (meth)acrylate (TBCH(M)A), tricyclodecanemethanol mono(meth)acrylate, and 3,3,5-trimethylcyclohexanol (meth)acrylate (TMCH(M)A)); hydroxyalkyl (meth)acrylates (especially 2-hydroxyethyl (meth)acrylate); (meth)acrylic acid; (meth)acrylamide; (meth)acrylonitrile; or mixtures thereof.

[0055] As used herein, the term "styrenic monomer" refers to a monomer containing a carbon-carbon double bond at the alpha position of an aromatic ring. Styrenic monomers can be selected from styrene, alpha-methylstyrene, tert-butylstyrene, ortho-, meta-, or para-methylstyrene, ortho-, meta-, or para-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta-, or para-methoxystyrene, optionally substituted indene, optionally substituted vinylnaphthalene, acenaphthylene, diphenylethylene, vinylanthracene, or mixtures thereof.

[0056] As used herein, the term "vinyl monomer" refers to a monomer containing a vinyl group (-CH=CH2) that is not conjugated to a carbonyl (C=O) group or an aromatic group. Vinyl monomers differ from olefinic monomers in that they contain at least one heteroatom (i.e., an atom other than carbon or hydrogen). Vinyl monomers can be selected from vinyl halides (especially vinyl chloride); vinyl esters (especially vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl pelargonate, vinyl laurate, vinyl stearate, and vinyl versatate, i.e., esters of branched monocarboxylic acids having 6, 9, 10, or 11 carbon atoms and available under the reference numbers VeoVa® EH, VeoVa® 9, VeoVa® 10, or VeoVa® 11 from Hexion); vinyl ethers (especially methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, or isobutyl vinyl ether), or mixtures thereof.

[0057] As used herein, the term "olefinic monomer" refers to a non-aromatic hydrocarbon monomer containing one or more carbon-carbon double bonds. The olefinic monomer can be selected from ethylene, propylene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene, butadiene, or mixtures thereof.

[0058] As used herein, the term "unsaturated polyacid" means a compound containing at least one carbon-carbon double bond and at least two carboxy groups, and this carbon-carbon double bond is conjugated with at least one of the carboxy groups. The term "unsaturated polyacid derivative" means a compound that can generate an unsaturated polyacid in situ, for example, by hydrolysis or ring-opening. Examples of suitable unsaturated polyacid derivatives include alkyl esters and cyclic anhydrides of unsaturated polyacids. The unsaturated polyacid or its derivative can be selected from fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, their anhydrides, and mixtures thereof.

[0059] Alternatively, the reactive diluent can be a cardanol derivative or a glycidyl ether.

[0060] As used herein, the term "cardanol derivative" means a compound obtained by chemical modification of cardanol. Cardanol is a bio-based phenolic lipid extracted from cashew nut shell liquid (a by-product of cashew nut processing). Cardanol contains a phenolic ring substituted with an unsaturated fatty chain and can be chemically modified by various reactions. The OH group of the phenolic ring can be converted to an ester group, a phosphate group, an ether, or a glycidyl ether. Alternatively, the unsaturated fatty chain can be epoxidized. Examples of suitable cardanol derivatives include -{3-[(8E)-pentadeca-8-en-1-yl]phenoxymethyl}oxirane (Cardolite NC-513) or [(7Z)-pentadeca-7-en-1-yl]phenol (Cardolite NX-2022).

[0061] As used herein, the term "glycidyl ether" refers to a compound containing a glycidyl ether group of the following formula: TIFF2025519542000001.tif13170

[0062] Glycidyl ethers can be obtained by reacting an alcohol or a polyol with epichlorohydrin. Examples of suitable glycidyl ethers include C4-C20 alkyl glycidyl ethers (e.g., octyl, decyl, dodecyl, tetradecyl, or hexadecyl glycidyl ether), 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3-, or 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetraglycidyl ether, cyclohexane diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, hydrogenated bisphenol diglycidyl ether, bisphenol diglycidyl ether, glycidyloxypropyltrimethoxysilane, and mixtures thereof.

[0063] According to one embodiment, the reactive solvent is a monofunctional (meth)acrylic monomer, preferably an alkyl (meth)acrylate or an alicyclic (meth)acrylate. The pre-activated organic gelling agent paste obtained from these monomers is particularly suitable as an additive for a composition based on an epoxyamine two-component reaction system in which the reactive solvent can react with an epoxyamine-based amine (hardener).

[0064] When a plasticizer is used, the plasticizer is preferably selected from polar organic plasticizers containing at least one polar group generally selected from ether groups and / or ester groups and / or epoxy groups.

[0065] The plasticizer containing at least one ether group can be selected from polyethers, such as homopolymers and / or copolymers of ethylene oxide and / or propylene oxide, and / or blends of said polyethers (homopolymers and / or copolymers) and / or their derivatives, and these derivatives include, inter alia, said polyethers blocked at the chain ends with C1 (methoxy)-C4 (butoxy) alkoxy groups or C2 (acetate)-C4 (butyrate) ester groups, and said polyethers have a weight average molecular weight Mw in the range of 150 to 6000, preferably 1000 to 3000. The term "copolymer" is construed to include both random copolymers and block copolymers.

[0066] The plasticizer containing at least one ester group can be selected from monoesters and / or polyesters (polyfunctional esters) obtained from C4-C 21 monoalcohols, and these alcohols are optionally alkoxylated with 1 to 10 alkoxy units selected from, for example, oxyethylene (OE) units and / or oxypropylene (OP) units, and a monoacid or polyacid having a functionality in the range of 1 to 4 selected from the following: (a) aromatic acids (-CO2H free) having a chain length in the range of C6-C 10 and / or C4-C18 An aliphatic acid (-CO2H functional group absent) having a chain length in the range of, and / or a cycloaliphatic acid (-CO2H functional group absent) having a chain length in the range of C6-C 10 An organic acid selected from those having a chain length in the range of, and (b) an inorganic acid.

[0067] The esters of aromatic acids can be selected from phthalic acid esters (phthalates) and trimellitic acid esters (trimellitates). The aliphatic acid esters can be selected from adipic acid esters (adipates), citric acid esters (citrates), sebacic acid esters (sebacates), and azelaic acid esters (azelates). The esters of cycloaliphatic acids can be selected from tetrahydrophthalic acid esters (tetrahydrophthalates) and hexahydrophthalic acid esters (hexahydrophthalic acids). The esters of inorganic acids can be selected from sulfonic acid esters (sulfonates), especially C 10 -C 21 Alkyl sulfonic acid esters, sulfuric acid esters (sulfates), sulfinic acid esters (sulfinates), phosphoric acid esters (phosphates), phosphonic acid esters (phosphonates), and phosphinic acid esters (phosphinates).

[0068] Finally, when the plasticizer contains at least one epoxy group, it can be selected from epoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil, and epoxidized fatty acid alkyl esters such as methyl epoxidized oleate, isoamyl epoxidized stearate, or 2-ethylhexyl epoxidized stearate.

[0069] Among the preferred plasticizers, those having at least one C6-C 10 Aromatic acid ester group can be mentioned. In particular, the plasticizer is selected from monoalkyl phthalates and / or dialkyl phthalates, and more preferably from dialkyl phthalates or hexahydrophthalic acid, where the alkyls are the same or different and are C7-C 18 Alkyl, preferably C 10 -C 12It is selected from alkyl. The most preferred plasticizers in the ((hexahydro)phthalic acid dialkyl) family are diisodecyl phthalate and diisononyl hexahydrophthalate. The most preferred polyethers are polyethers which are homopolymers of propylene oxide (polypropylene glycol) having a weight average molecular weight Mw in the range of 1000 to 3000, more specifically, polypropylene glycol (PPG) having an Mw equal to 2000, and / or derivatives thereof, which are selected from mono-esters, preferably C2-C4 mono-esters, or C1-C4 mono-ethers such as monomethoxylated or monoethoxylated polypropylene glycol.

[0070] Generally, the amide compound is present in a weight ratio in the range of 5:1 to 1:20, preferably 2:1 to 1:15, more preferably 1:1 to 1:10, and even more preferably 1:3 to 1:6 with respect to the liquid carrier.

[0071] More specifically, the process of the present invention includes a first step (also referred to as the mixing step) of mixing an amide compound with a liquid carrier to provide a mixture. This step can be carried out in a tank or reactor equipped with a stirring system such as a rotating impeller and optionally one or more baffles. For example, the amide compound and the liquid carrier can be stirred at 1000 to 3000 rpm, preferably 1500 to 2000 rpm. Stirring can be carried out for 10 minutes to 1 hour, for example 15 to 30 minutes. Alternatively, the mixing step can be carried out in a static mixer, for example, in a tube or pipe equipped with fixed elements that redistribute the fluid laterally (i.e., radially and tangentially) with respect to the main flow. For example, the amide compound can be introduced into a continuous flow of the liquid carrier flowing through the static mixer. The mixing step is carried out at a temperature T1 lower than the activation temperature of the amide compound. Preferably, the temperature T1 should be at least 10 °C, or at least 20 °C, or at least 30 °C lower than the activation temperature of the amide compound. Such a temperature is advantageously selected so that the viscosity of the mixture does not increase significantly during the mixing step (so that there is no premature activation of the amide compound). In one embodiment, T1 is 30 °C or lower, preferably 25 °C or lower, more preferably from 0 to 25 °C. The temperature of the mixture during the mixing step can be controlled to be maintained below T1 by any suitable means, such as a cold bath or a double jacket cooling system. The temperature control can be useful to avoid overheating caused by shear during the mixing of the amide compound and / or to avoid premature and uncontrolled activation of the amide compound. The mixing step can be carried out until a homogeneous mixture is obtained. The homogeneity of the mixture can be characterized, in a laboratory-scale preparation, for volumes not exceeding 1 liter, preferably by the absence of sedimentation or the absence of visible particles when the amide compound is mixed with the liquid carrier at a shear rate of 2 to 6 m·s -1 −1.

[0072] In the second step of the process according to the present invention, the above mixture is continuously flowed through a heat exchanger, and its temperature is raised to temperature T2 (also called the activation step). Therefore, the temperature when the mixture enters the heat exchanger may be T1 or lower, which is lower than the activation temperature of the amide compound (for example, 0 to 30 °C), and the temperature when the mixture exits the heat exchanger is T2 (for example, 35 to 120 °C). The temperature T2 is at least equal to the activation temperature of the amide compound, that is, a temperature sufficient to form an organic gel. The activation temperature can be easily determined by those skilled in the art according to the properties of the amide compound and the properties of the liquid carrier used. For example, those skilled in the art can apply heat to the mixture of the amide and the liquid carrier in a container and observe when the gelation point is reached. The temperature T2 is typically in the range of 35 to 120 °C, for example, 50 to 100 °C. While staying in the heat exchanger, the temperature of the mixture gradually rises by the heat transfer fluid circulating in the heat exchanger. The temperature of the heat transfer fluid entering the heat exchanger can be equal to the temperature T2. The heat transfer fluid can circulate in parallel or countercurrent to the flow of the mixture. When the mixture exits the heat exchanger, it is in the form of a paste. The residence time of the mixture in the heat exchanger depends, inter alia, on the flow rate of the mixture, the target activation temperature, the flow rate of the heat transfer fluid, and the dimensions of the heat exchanger. Typically, the residence time can be less than 1 hour, preferably 30 seconds to 50 minutes, more preferably 1 minute to 30 minutes. This activation step can be carried out in any suitable heat exchanger that enables a continuous flow of the mixture and can control the residence time of the mixture. For example, the heat exchanger can be selected from a double-tube heat exchanger, a coil heat exchanger, a shell-and-tube heat exchanger, or a plate heat exchanger. The flow rate of the mixture can be adjusted to a set value according to the dimensions of the heat exchanger, whereby the residence time is within a predetermined optimal range.

[0073] The continuous flow of the mixture through the heat exchanger can be driven by a pump. The pump can be arranged upstream of the heat exchanger. The type of pump used is not important, for example, non-blocking pumps, impeller pumps, disc flow pumps, rotary piston pumps, eccentric single rotor screw pumps, cylindrical diaphragm pumps, etc. can be used. It is also not important whether the mixture is pumped in laminar flow or turbulent flow.

[0074] The paste material thus obtained after the second step is filled into a container maintained at a temperature above the activation temperature, for example, temperature T2. The container is then removed and cooled before use in the formulation. Thus, the process of the present invention enables the preparation of a pre-activated organic gelling agent paste in a continuous process. In one embodiment of the present invention, a semi-continuous process can be used if the paste is not fully activated when it exits the heat exchanger. Thus, this process can further include the step of transferring the container to an oven to complete the activation of the amide compound, typically for a predetermined time at a predetermined temperature (temperature T2) before removing and cooling the container.

[0075] In any case, when the gelation point is reached, in other words, when the paste reaches the Plateau value without significant subsequent change in its viscosity, activation is considered complete. The gel thus activated (also called pre-activated organic gelling agent paste) can first be characterized by a very simple test in which a wooden spatula is inserted into the gel or paste being tested and remains vertically immobile when the product being tested is sufficiently activated, the gel or paste remains single-phase, and no liquid carrier exudes. More specifically, the viscosity of the activated paste is measured in accordance with ASTM standard D217 (2010) under the conditions of a temperature of 23 °C, a cone of 30 degrees, a test speed of 5 mm / second, and a penetration force of 0.4 N such that the maximum penetration value of the formed paste is less than 15 mm, preferably less than 10 mm. Alternatively, when the dynamic elastic modulus E’ of the paste is at least 10 4 Pa at 23 °C and 1 Hz, it can also be considered that the appropriate viscosity has been reached.

[0076] An example of a setup that can be used to carry out the process of the present invention is shown in the accompanying drawings.

[0077] As shown in this figure, this equipment includes a reactor 1 equipped with stirring means 2 such as a stainless steel or copper tank with a rotating impeller. On a laboratory scale, a round-bottomed container equipped with a PTFE stirrer can be used. This reactor is fluid-connected to a container (not shown) containing an amide compound and a liquid carrier respectively, and is supplied to the reactor 1 via a pump (not shown). The reactor is immersed in a cold bath so as to maintain the temperature inside the reactor at a temperature T1 in the range of 0 to 5 °C. The homogeneous mixture prepared in the reactor 1 is transferred via a pump 3 such as a peristaltic pump to a heat exchanger 4 such as a coil heat exchanger connected to a heat bath 5 maintained at 60 - 65 °C. The heat exchanger is installed such that the mixture flows through the coil and warm water flows in a closed loop around the coil. The mixture continuously flows through the heat exchanger until it reaches a temperature T2 that is at least equal to the activation temperature (60 - 65 °C in this example). The residence time of the mixture in the heat exchanger 4 is controlled by adjusting the flow rate of the mixture by the pump 3. The activated paste thus produced is discharged from the heat exchanger 4 via a duct 6 and divided into containers 8 such as sample vials (three of which are shown in this figure). These containers are maintained at a temperature T2, i.e., 60 - 65 °C, by a heat bath 7 and are collected when filled. An oven 9 is optionally provided to maintain the containers at temperature T2 to complete the activation if necessary.

[0078] The pre-activated organogelator paste as described above can be added to formulations that can be coating compositions, molding compositions, or electrolyte compositions. The coating composition can be applied to various substrates and used as a protective coating and / or a decorative coating and / or a surface treatment coating. The coating composition can be selected from paints, varnishes, colored gel coats, or uncolored gel coats, inks, PVC-based plastisols. Alternatively, it may be a mastic, glue, adhesive, or sealant composition. In another embodiment, the coating composition may be a cosmetic composition such as a nail polish. In yet another embodiment, the coating composition may be a photocurable composition, particularly for stereolithography or 3D printing of objects by inkjet. This coating composition can be applied to the substrate, for example, by spraying with a spray gun or by brushing or rolling. When the formulation is a molding composition, it can be selected from molding compositions for composite materials such as SMC or BMC or laminated types (such as hulls or composite panels). Examples of electrolyte compositions for lithium-ion batteries are described in French Patent No. 3103637. These can include a lithium salt and an electrolyte additive such as fluoroethylene carbonate (FEC) or vinylene carbonate.

[0079] The pre-activated organogelator paste can be present in these formulations in a weight content in the range of 1 to 30%, preferably 2 to 25%, and the amide compound can be present in a weight content in the range of 0.2 to 8%, preferably 1 to 6%, based on the weight of the formulation as a dry active substance.

[0080] The formulation can include other components such as fillers, plasticizers, wetting agents, or pigments.

[0081] Typically, the complex contains an organic reactive binder. The pre-activated organic gelling agent paste described above can be used with both an organic reactive binder crosslinked by a radical pathway under radiation or by heat, or by an initiation system based on peroxides or hydroperoxides, and an organic reactive binder crosslinked by a reaction with a reactive amino component by a Michael addition reaction, such as an epoxyamine two-component reactive binder.

[0082] Accordingly, according to one embodiment, the organic reactive binder can be crosslinked by heat or by irradiation under radiation such as UV radiation (in the presence of at least one photoinitiator) and / or EB radiation (electron beam without initiator) (including those capable of self-crosslinking at room temperature), or is non-crosslinkable. The organic reactive binder can be single-component crosslinkable (with only one reactive component) or two-component crosslinkable (based on two components that react with each other by mixing during use).

[0083] The organic reactive binder can be selected from at least one epoxy / amine (crosslinkable two-component) reaction system, unsaturated polyester, vinyl ester, epoxidized resin, reactive silicone resin, alkyd grafted with polyester or polyamide, or diurea / diurethane type alkyd, or ungrafted alkyd, polyurethane or silicone, crosslinkable two-component polyurethane, polysiloxane, polysulfide polymer, reactive acrylic polymer, (meth)acrylate polyfunctional oligomer or acrylic oligomer or allyl polyfunctional oligomer, butyl rubber, polychloropene or SBR type elastomer, or silylated prepolymer, preferably silylated polyether or silylated polyurethane, or silylated polyether / urethane having -OH or -CO2H functionality.

[0084] In more specific examples, the organic reactive binder can be selected from the following crosslinkable two-component reaction systems: an epoxy / amine or epoxy / polyamide system comprising at least one epoxy resin containing at least two epoxy groups and a polyamide compound containing at least one amino or at least two amine groups, a polyurethane system comprising at least one polyisocyanate and at least one polyol, a polyol / melamine system, and a polyester system based on at least one epoxy or one polyol that reacts with at least one corresponding acid or anhydride.

[0085] According to other specific examples, the organic reactive binder can be a crosslinkable two-component polyurethane system or a crosslinkable two-component polyester system starting from an epoxy / carboxylic acid or anhydride reaction system, or a polyol / carboxylic acid or anhydride system, or a polyol / melamine reaction system, where the polyol is a hydroxylated acrylic resin, or a polyester, or a polyether polyol.

[0086] According to one embodiment, the formulation is self-crosslinkable and is a coating composition selected from mastic, paste, adhesive, or sealant compositions based on a polyether / silane or polyurethane / silane organic reactive binder.

[0087] Typically, the formulation is prepared by adding the above pre-activated organic gelling agent paste to the remaining components of the formulation and then homogenizing the mixture with a kneader and / or a planetary mixer and / or a high-speed disperser without the need to apply a heat activation treatment at this step, where "high-speed" means a tangential speed in the range of 2 to 15 m·s -1 of the range.

Examples

[0088] The present invention will be better understood in light of the following examples, which are presented for illustrative purposes only and are not intended to limit the scope of the present invention as defined by the appended claims.

[0089] Example 1 : Product : TIFF2025519542000002.tif51170

[0090] Synthesis Example 1: Preparation of diamide compound : 49.96 grams of HMDA (i.e., 0.43 mol, 0.86 amine equivalent) and 271.1 grams of 12-HSA (i.e., 0.86 mol, 0.86 acid equivalent) were placed in a 1-liter round-bottom flask equipped with a thermometer, a Dean-Stark apparatus, a condenser, and a stirrer under a nitrogen atmosphere. The mixture was heated to 200 °C under a nitrogen stream. Water was recovered in the Dean-Stark apparatus at 150 °C. The reaction was monitored by acid value and amine value. When the values of the acid value and the amine value became less than 10 mg KOH / g, the reaction mixture was cooled to 150 °C and discharged into a silicone-treated mold. After cooling to room temperature, the product was mechanically micronized by milling and sieving to obtain a fine and controlled particle size with a volume particle size Dv90 of less than 10 μm. The particle size can be measured by dry laser particle size analysis using a Mastersizer MS3000 (Malvern Panalytical) apparatus under the following conditions: Measurement range: 0.1 to 3500 μm Optical model: 1.30-0i Analysis mode: MS3000: Standard / Peak of fine powder Observation: 0.3 to 10% Number of measurements: 3

[0091] Experimental equipment: - Comparative example To reproduce the process disclosed in

[0122] -

[0123] of US Patent Application Publication No. 2015 / 0274644, the following equipment was used: TIFF2025519542000003.tif39170

[0092] - Example according to the present invention The process according to the present invention was reproduced using the equipment shown in and described in relation to FIG. 1. Here, the reactor was a 500 mL round-bottomed flask, and the sample vial was a 100 mL Erlenmeyer flask.

[0093] Example 1 (Comparative Example) 70 grams of the diamide compound prepared in Synthesis Example 1 and 280 grams of a solvent mixture (xylene:ethanol, 3:1) were placed in a 500 mL metal dish at room temperature (20 °C). Using an ATP Dispermill disperser equipped with a paddle with a diameter of 3 cm, by controlling the temperature by circulating cold water, the product was mixed at a speed of 1500 revolutions per minute (or rpm) for 30 minutes at a temperature not exceeding 20 °C. Activation was carried out by carefully closing the dish and placing it in an oven preheated to 60 °C for 24 hours. After cooling and leaving it to stand for 4 hours, the paste became hard enough to hold a metal spatula vertically.

[0094] Example 2 (According to the Present Invention) 40 grams of the diamide compound prepared in Synthesis Example 1 and 160 grams of a solvent mixture (xylene:ethanol, 3:1) were placed in a round-bottomed flask.

[0095] Next, the flask was placed at 5 °C under mechanical stirring for 30 minutes.

[0096] Next, the mixture was sent to a coil distillation condenser preheated to 60 °C using a peristaltic pump.

[0097] At the other end of the tube, the paste was collected in a sample vial, which was also preheated to 60 °C. The sample vial was removed from the heat bath after filling. Optionally, in a semi-continuous process, the sample vial may be placed in an oven preheated to 60 °C for 1 hour. After cooling and leaving it to stand for 4 hours, the paste became hard enough to hold a metal spatula vertically.

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