EP0986583A1 - Stable small sized particle water-in-water emulsions, synthesis method and application as thickening agents - Google Patents

Stable small sized particle water-in-water emulsions, synthesis method and application as thickening agents

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Publication number
EP0986583A1
EP0986583A1 EP99909066A EP99909066A EP0986583A1 EP 0986583 A1 EP0986583 A1 EP 0986583A1 EP 99909066 A EP99909066 A EP 99909066A EP 99909066 A EP99909066 A EP 99909066A EP 0986583 A1 EP0986583 A1 EP 0986583A1
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EP
European Patent Office
Prior art keywords
monomer
water
aqueous dispersion
dispersion according
polymerization
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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.)
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EP99909066A
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German (de)
French (fr)
Inventor
Denis Tembou Nzudie
Karine Loyen
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Arkema France SA
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Elf Atochem SA
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Publication of EP0986583A1 publication Critical patent/EP0986583A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent

Definitions

  • the present invention relates to water-in-water emulsions, and in particular to aqueous dispersions based on water-soluble polymers intended for use as a thickener in aqueous systems.
  • Water-in-water emulsions can be used as a thickener for aqueous systems used in particular in textile and paint applications.
  • Viscosifying water-soluble polymers are used for various applications and in particular in the field of paints, glues and adhesives, construction, textiles and paper.
  • the aqueous and / or pigmented compositions often dealt with by a person skilled in the art, for example aqueous paints, consist of a liquid phase which can be water or a mixture of water with a miscible organic solvent with water, a polymer dispersed in the liquid phase, commonly called “binder", fillers and / or pigments, a dispersing agent for fillers and / or pigments, which can be a water-soluble polymer, as well as the various adjuvants such as coalescing agents, biocides, defoamers or others, finally one or more viscosifying agents (or thickeners) which are natural or synthetic polymers.
  • polymers increase the viscosity of the solutions in which they are dissolved.
  • the water-soluble polymers generally used as viscosifiers of aqueous solutions have various structures; by way of indication, mention may be made of polyacrylamides, optionally partially hydrolyzed, sodium poly (meth) acrylates, cellulose derivatives, poly (ethylene oxide) or also polysaccharides. It is well known that the aqueous systems of such water-soluble polymers with a high solids content are gelatinous and have very high viscosities, which make their handling and storage difficult. The problem posed to a person skilled in the art is the production of such aqueous systems but having both a high dry extract and a low viscosity.
  • a new polymerization technique has been developed leading to aqueous dispersions of water-soluble polymers whose originality lies in terms of presentation, that is to say free of polluting solvent, not generating of dust, quickly soluble in water, of low viscosity even at high polymer content, and ready for use.
  • this technology requires the development of a polymer dispersant suitable for the stability of the dispersed polymer in a saline or non-saline medium.
  • Such a dispersant must be chosen and used under conditions which make it possible to generate the incompatibility with the polymer formed during synthesis in order to induce the formation of a dispersed phase. It can also generate specific interactions with the polymer in order to make it insoluble in an aqueous medium and generate particles.
  • EP 1 70 394 describes a dispersion of a polymer gel particle of size greater than 20 ⁇ m in a solution of dispersant of poly (sodium acrylate) or of poly (DADMAC), designating polydiallyldimethylammonium chloride.
  • this product has the disadvantage of having insufficient stability and a high viscosity after a long period of storage. The viscosity can only be reduced after shearing or stirring.
  • US Patent 5403883 describes a technique for obtaining dispersions of cationic polymers without salt, and of low viscosity by polymerization in the presence of the dispersant poly-DADMAC, of a mixture of at least one water-soluble monomer, at least one hydrophobic monomer and if necessary an amphiphilic monomer.
  • Post-addition of the same poly-DADMAC dispersant makes it possible to reduce the viscosity (CA 31 23460). However, it has the effect of increasing the level of dispersant and leading to a dispersion having a low level of dispersed polymer.
  • the problem that the invention seeks to solve is therefore the preparation of aqueous dispersions of water-soluble polymers which are stable on storage and do not contain an organic solvent.
  • the Applicant has now developed new water-in-water emulsions which do not have the drawbacks of the dispersions mentioned above. Because on the one hand, they have particles with an average diameter of less than 3 ⁇ m. This guarantees the absence of sedimentation and therefore good stability during storage. On the other hand, such particles can be obtained without incorporating a complexing dispersant. In fact, thanks to the use of specific monomers, it is possible to induce the formation of inter and intrapolymer complexes. However, the introduction of dispersant in small quantities is recommended in order to increase the fluidity of the emulsion. The Applicant has found that the incorporation into the mixture of water-soluble monomers to be polymerized of a monomer having a radical (R) containing both a block 4
  • polyethoxylated and a hydrophobic block and of a monomer which can form specific interactions with the polyethoxylated block, allows intra and interpolymer complexation and the formation of particles of small diameter.
  • the dispersions of the invention keep their particles in the state at the time of dilution with water even under the conditions of high dilution.
  • the dispersed polymer becomes water-soluble, generating an increase in viscosity, under the basic conditions of paint application or pigment printing.
  • the first object of the invention is an aqueous dispersion containing:
  • a complexing dispersant capable of forming complexes with the water-soluble polymer by interpolymer interactions such as hydrogen bonds or polar interactions.
  • the polymers of the invention consist essentially of water-soluble monomers. They contain units derived by polymerization of at least one neutral or anionic monomer (A), at least one monomer (B) having a polyethoxylated radical ending in a hydrophobic group and at least one monomer (C) capable of complex with the monomer (B) by polar interactions or by hydrogen bonds.
  • A neutral or anionic monomer
  • B monomer having a polyethoxylated radical ending in a hydrophobic group
  • C monomer capable of complex with the monomer (B) by polar interactions or by hydrogen bonds.
  • They can also contain units derived from at least one polyunsaturated monomer (D) and this in order to have crosslinked polymer particles.
  • the polymers of the invention contain:
  • Another object of the invention is the process for the synthesis of water-in-water emulsions containing water-soluble polymers dispersed in the form of particles with a diameter of less than 3 ⁇ m.
  • the dispersions of the invention are prepared by radical polymerization of an aqueous solution containing: from 0 to 98.98 mol% of at least one monomer A from 0.02 to 5 mol% of at least one monomer B from 1 to 99.98% by mole of at least one monomer C from 0 to 2% by mole of at least one monomer D in the presence of 0 to 15% by weight relative to the total weight of the monomers of at least a complexing dispersant.
  • the monomers A are chosen from the group consisting of acrylamide, methacrylamide, N-alkylacrylamide, N, N di-alkylacrylamide, N-vinyl methacetamide, N-vinyl methylformamide, N-vinyl pyrolidone, ( meth) acrylates comprising a polyethoxylated side chain terminated by a hydrogen or a CH3 and their mixtures.
  • the preferred monomer A is acrylamide.
  • the monomers B are chosen from the group corresponding to the following formula:
  • R- is hydrogen or methyl n is an integer between 2 and 50
  • R 2 is either a C2-C40 alkyl radical, or a C5-C40 aryl radical, or a C7-C40 alkylaryl radical, or a C5-C40 cycloalkyl, or an alkylene and propylene or higher homolog.
  • the preferred monomer B of the invention is polyethoxylated tristyryl phenol methacrylate corresponding to the formula
  • the monomers C are vinyl or acrylic monomers comprising functional groups chosen from acid groups (carboxylic, sulfonic, phosphoric, sulfuric) and their salts, sulfuric ester, sulfone, hydroxyl, amino, imino, tertiary amino, quaternary ammonium, pyrolidone , and hydrazino.
  • the preferred monomer C of the invention is acrylic acid.
  • the monomer D is chosen from the group consisting of N, N methylene-bis acrylamide, a di-acrylate such as ethylene glycol di-acrylate, or polyethylene glycol di-acrylate, a di-allyl compound such as diallylacetic acid or diallyl phthalate, an ethylene glycol allyl acrylate or a polyethylene glycol allyl acrylate.
  • the preferred monomer D of the invention is N, N methylene-bis acrylamide.
  • the complexing dispersant according to the invention is generally a water-soluble polymer of average mass by weight of 300 to 500,000 and preferably comprising one or more functional groups chosen from ether, hydroxyl, carboxyl, sulfone, sulfuric ester, amino, imino, amino tertiary, quaternary ammonium, and hydrazino, among which particular preference is given to the ether, hydroxyl, and carboxyl groups.
  • Typical examples of these dispersants are poly (ethylene oxide), polyvinyl alcohol, and poly (N vinyl pyrolidone).
  • the polymerization is carried out as follows:
  • the mixture of monomers represents from 10 to 40% and preferably 15 to 30% by weight of the reaction mixture consisting of water, of dispersant, and of monomers, the dispersant representing from 0 to 6% and preferably from 0.5 to 3% by weight.
  • the polymerization can be initiated by various means, such as free radical generators such as peroxides, diazo compounds or persulfates, or by irradiation.
  • the preferred mode according to the invention is the initiation with potassium, sodium or ammonium persulfate. These initiators can be combined with a decomposition accelerator.
  • the polymerization temperature is between 0 and 100 ° C and preferably 40 and 95 ° C. The conversion is greater than 99%.
  • the water-in-water emulsions obtained can be used to thicken aqueous systems such as latex in an alkaline medium, for paint and textile applications, in particular pigment printing.
  • Example 1 illustrates the invention without limiting it. In all the examples below, the parts are given by weight.
  • Example 1 illustrates the invention without limiting it. In all the examples below, the parts are given by weight.
  • Ot7 obtains a stable dispersion of Brooklield 19,000 cp viscose polymer at 25 ° C and an average particle diameter determined by light scattering of 0.725 ⁇ m.
  • Comparison of Examples 1 and 2 shows that the presence of the special polyethoxylated tristyryl phenol methacrylate monomer is necessary to form water-in-water emulsion particles.
  • Example 2 The same synthesis is repeated as in Example 1, but removing the polyethylene oxide dispersant. A stable dispersion of polymer with a Brookfie viscosity / d 47,000 cp at 25 ° C. and an average particle diameter determined by light scattering of 1.13 ⁇ m is obtained.
  • Example 2 The same synthesis is repeated as in Example 1 but incorporating 500 ppm by weight of N N methylene bisacrylamide relative to all of the monomers. A stable dispersion of polymer with Brookfield viscosity 48,000 cp at 25 ° C. and an average particle diameter determined by light scattering of 1 ⁇ m is obtained.

Abstract

The invention concerns water soluble polymers obtained by radical polymerisation in water-in-water emulsion of a mixture of substantially water soluble monomers containing a particular monomer having a polyethoxylated radical terminated by a hydrophobic group. Said polymers can be used as thickening agents for aqueous solutions.

Description

EMULSIONS EAU DANS EAU, STABLES ET DE FAIBLE TAILLE DE PARTICULES, LEUR PROCEDE DE SYNTHESE ET APPLICATION EN TANT QU'EPAISSISSANTSWATER-TO-WATER, STABLE AND LOW-SIZE PARTICLE EMULSIONS, THEIR SYNTHESIS PROCESS AND APPLICATION AS THICKENERS
La présente invention se rapporte aux émulsions eau dans eau, et en particulier aux dispersions aqueuses à base de polymères hydrosolubles destinées à être utilisées comme épaississant des systèmes aqueux.The present invention relates to water-in-water emulsions, and in particular to aqueous dispersions based on water-soluble polymers intended for use as a thickener in aqueous systems.
Elle concerne aussi le procédé de synthèse de ces dispersions aqueuses obtenues par polymérisation en emulsion eau dans eau d'un mélange de monomères hydrosolubles et hydrosolubles contenant un groupe polyéthoxylé et un motif hydrophobe.It also relates to the process for the synthesis of these aqueous dispersions obtained by water-in-water emulsion polymerization of a mixture of water-soluble and water-soluble monomers containing a polyethoxylated group and a hydrophobic unit.
Les émulsions eau dans eau peuvent être utilisées comme épaississant des systèmes aqueux utilisés en particulier dans les applications textile et peintures.Water-in-water emulsions can be used as a thickener for aqueous systems used in particular in textile and paint applications.
Les polymères hydrosolubles viscosifiants sont utilisés pour différentes applications et en particulier dans le domaine des peintures, colles et adhésifs, bâtiment, textile et papier. Les compositions aqueuses et/ou pigmentées auxquelles a souvent affaire l'homme de l'art, par exemple les peintures aqueuses, sont constituées d'une phase liquide qui peut être de l'eau ou un mélange d'eau avec un solvant organique miscible à l'eau, d'un polymère dispersé dans la phase liquide, nommé couramment "liant", des charges et/ou des pigments, d'un agent dispersant des charges et/ou pigments, qui peut être un polymère hydrosoluble, ainsi que les divers adjuvants tels que agents de coalescence, biocides, antimousses ou autres, enfin d'un ou plusieurs agents viscosifiants (ou épaississants) qui sont des polymères naturels ou de synthèse.Viscosifying water-soluble polymers are used for various applications and in particular in the field of paints, glues and adhesives, construction, textiles and paper. The aqueous and / or pigmented compositions often dealt with by a person skilled in the art, for example aqueous paints, consist of a liquid phase which can be water or a mixture of water with a miscible organic solvent with water, a polymer dispersed in the liquid phase, commonly called "binder", fillers and / or pigments, a dispersing agent for fillers and / or pigments, which can be a water-soluble polymer, as well as the various adjuvants such as coalescing agents, biocides, defoamers or others, finally one or more viscosifying agents (or thickeners) which are natural or synthetic polymers.
En général, les polymères augmentent la viscosité des solutions dans lesquelles ils sont dissous. Les polymères hydrosolubles généralement utilisés comme viscosifiants des solutions aqueuses ont des structures variées ; on peut citer à titre indicatif les polyacrylamides, éventuellement partiellement hydrolyses, les poly(méth)acrylates de sodium, les dérivés de la cellulose, les poly(oxyde d'éthylène) ou encore les polysaccharides. Il est bien connu que les systèmes aqueux de tels polymères hydrosolubles à haut extrait-sec sont gélatineux et présentent des viscosités très élevées, qui rendent leur manipulation et stockage difficiles. Le problème posé à l'homme du métier est la réalisation de tels systèmes aqueux mais ayant à la fois un extrait-sec élevé et une faible viscosité.In general, polymers increase the viscosity of the solutions in which they are dissolved. The water-soluble polymers generally used as viscosifiers of aqueous solutions have various structures; by way of indication, mention may be made of polyacrylamides, optionally partially hydrolyzed, sodium poly (meth) acrylates, cellulose derivatives, poly (ethylene oxide) or also polysaccharides. It is well known that the aqueous systems of such water-soluble polymers with a high solids content are gelatinous and have very high viscosities, which make their handling and storage difficult. The problem posed to a person skilled in the art is the production of such aqueous systems but having both a high dry extract and a low viscosity.
Les procédés conventionnels de synthèse de ces polymères comprennent la polymérisation en solution, suspension inverse et emulsion inverse. La solution 2Conventional processes for the synthesis of these polymers include solution polymerization, reverse suspension and reverse emulsion. The solution 2
et la suspension inverse conduisent à des produits à l'état de poudre qui présentent l'inconvénient de générer de la poussière au moment de l'utilisation, de se dissoudre difficilement dans l'eau et de ne pas pouvoir former des solutions aqueuses de polymères de concentration élevée qui puissent être manipulées aisément. Outre cette mise en oeuvre incommode qui est propre à l'état pulvérulent du produit, ces deux procédés sont handicapés en terme de productivité, d'une part en raison de la faible concentration en monomère utilisée en cours de polymérisation, et d'autre part à cause d'une étape de séchage et/ou broyage induisant une augmentation du temps de cycle et un surcoût de consommation d'énergie. Le procédé en emulsion inverse conduit quant à lui à un produit ayant un solvant organique polluant.and the reverse suspension lead to powdered products which have the drawback of generating dust at the time of use, of being difficult to dissolve in water and of being unable to form aqueous solutions of polymers high concentration that can be easily handled. In addition to this inconvenient implementation which is specific to the pulverulent state of the product, these two processes are handicapped in terms of productivity, on the one hand because of the low concentration of monomer used during polymerization, and on the other hand because of a drying and / or grinding step inducing an increase in the cycle time and an additional cost of energy consumption. The reverse emulsion process results in a product having a polluting organic solvent.
Pour remédier à ces inconvénients, il a été développé une nouvelle technique de polymérisation conduisant à des dispersions aqueuses de polymères hydrosolubles dont l'originalité réside sur le plan de la présentation, c'est-à-dire exemptes de solvant polluant, ne générant pas de poussière, rapidement solubles dans l'eau, de faible viscosité même à taux de polymère élevé, et prêtes à l'emploi. En revanche cette technologie nécessite la mise au point de dispersant polymère adapté pour la stabilité du polymère dispersé en milieu salin ou non salin. Tel dispersant doit être choisi et utilisé dans des conditions qui permettent de générer l'incompatibilité avec le polymère formé en cours de synthèse afin d'induire la formation d'une phase dispersée. Il peut également engendrer des interactions spécifiques avec le polymère afin de le rendre insoluble en milieu aqueux et générer des particules.To overcome these drawbacks, a new polymerization technique has been developed leading to aqueous dispersions of water-soluble polymers whose originality lies in terms of presentation, that is to say free of polluting solvent, not generating of dust, quickly soluble in water, of low viscosity even at high polymer content, and ready for use. However, this technology requires the development of a polymer dispersant suitable for the stability of the dispersed polymer in a saline or non-saline medium. Such a dispersant must be chosen and used under conditions which make it possible to generate the incompatibility with the polymer formed during synthesis in order to induce the formation of a dispersed phase. It can also generate specific interactions with the polymer in order to make it insoluble in an aqueous medium and generate particles.
Certains auteurs ont préparé des polymères hydrosolubles cationiques, anioniques ou non ioniques par polymérisation de monomères hydrosolubles en présence de dispersant polymère de faible masse. Par exemple, EP 1 70 394 décrit une dispersion de particule de gel de polymère de taille supérieure à 20 μm dans une solution de dispersant de poly(acrylate de sodium) ou de poly(DADMAC), désignant le chlorure de polydiallyldiméthylammonium. Cependant ce produit présente l'inconvénient d'avoir une stabilité insuffisante et une viscosité élevée après une longue période de stockage. La viscosité ne pouvant être diminuée qu'après cisaillement ou agitation.Some authors have prepared cationic, anionic or nonionic water-soluble polymers by polymerization of water-soluble monomers in the presence of low-mass polymer dispersant. For example, EP 1 70 394 describes a dispersion of a polymer gel particle of size greater than 20 μm in a solution of dispersant of poly (sodium acrylate) or of poly (DADMAC), designating polydiallyldimethylammonium chloride. However, this product has the disadvantage of having insufficient stability and a high viscosity after a long period of storage. The viscosity can only be reduced after shearing or stirring.
Les documents US 1 83466, EP 525751 A1 , EP 71 7056 A2, US 4929655, US 5006590, EP 657478 A2 et EP 637598 A2 proposent le cas de polymérisation précipitante en milieu salin de monomères hydrosolubles dont le polymère précipité sous forme de particules, puis dispersé par le biais de l'agitation et stabilisé par des dispersants polymères de faible masse, solubles quant à eux en milieu salin. Les dispersants typiques de ces polymérisations sont 3Documents US 1 83466, EP 525751 A1, EP 71 7056 A2, US 4929655, US 5006590, EP 657478 A2 and EP 637598 A2 propose the case of precipitating polymerization in saline medium of water-soluble monomers including the polymer precipitated in the form of particles, then dispersed by means of agitation and stabilized by low-mass polymer dispersants, which are soluble in saline medium. The typical dispersants for these polymerizations are 3
le poly-DADMAC ou le copo-DADMAC/(M)ADAMQUAT C1 6, ce dernier monomère désignant le chlorure depoly-DADMAC or copo-DADMAC / (M) ADAMQUAT C1 6, the latter monomer denoting chloride
(méth)acryloxyéthyldimétylhexadecylammonium (EP 657478 A2) .(meth) acryloxyethyldimetylhexadecylammonium (EP 657478 A2).
Le brevet US 5403883 décrit une technique d'obtention des dispersions de polymères cationiques sans sel, et de faible viscosité par polymérisation en présence du dispersant poly-DADMAC, d'un mélange d'au moins un monomère hydrosoluble, au moins un monomère hydrophobe et si nécessaire un monomère amphiphile. Une post-addition du même dispersant poly-DADMAC permet de diminuer la viscosité (CA 31 23460) . Cependant, elle a pour effet d'augmenter le taux de dispersant et de conduire à une dispersion ayant un faible taux de polymère dispersé.US Patent 5403883 describes a technique for obtaining dispersions of cationic polymers without salt, and of low viscosity by polymerization in the presence of the dispersant poly-DADMAC, of a mixture of at least one water-soluble monomer, at least one hydrophobic monomer and if necessary an amphiphilic monomer. Post-addition of the same poly-DADMAC dispersant makes it possible to reduce the viscosity (CA 31 23460). However, it has the effect of increasing the level of dispersant and leading to a dispersion having a low level of dispersed polymer.
Les documents EP 2429225 et US 4380600 décrivent des dispersions de polymères hydrosolubles anioniques obtenues par polymérisation en emulsion eau dans eau d'un mélange de monomères hydrosolubles comprenant de l'acrylate de sodium (AANa) dans une solution aqueuse de dispersant tel que le poly(oxyde d'éthylène) (POE). Les particules sont générées en cours de polymérisation par formation de complexe interpolymère entre le POE et le poly(acrylate de sodium) (PAANa), et des dispersions aqueuses sont obtenues pour un ratio molaire POE/PAANa supérieur à 1 . Ces dispersions présentent deux inconvénients : d'une part elles nécessitent l'utilisation d'un taux important de polymère dispersant complexant qui peut perturber les propriétés applicatives finales. D'autre part, elles sont constituées de grosses particules de 1 0 à 1 00 μm qui ont tendance à sédimenter, induisant un problème de stabilité au cours du stockage.The documents EP 2429225 and US 4380600 describe dispersions of anionic water-soluble polymers obtained by water-in-water emulsion polymerization of a mixture of water-soluble monomers comprising sodium acrylate (AANa) in an aqueous dispersant solution such as poly ( ethylene oxide) (POE). The particles are generated during polymerization by the formation of an interpolymer complex between POE and poly (sodium acrylate) (PAANa), and aqueous dispersions are obtained for a POE / PAANa molar ratio greater than 1. These dispersions have two drawbacks: on the one hand they require the use of a high level of complexing dispersing polymer which can disturb the final application properties. On the other hand, they are made up of large particles of 1 0 to 1 00 μm which tend to sediment, inducing a problem of stability during storage.
Le problème que cherche à résoudre l'invention est donc la préparation de dispersions aqueuses de polymères hydrosolubles stables au stockage et ne contenant pas de solvant organique.The problem that the invention seeks to solve is therefore the preparation of aqueous dispersions of water-soluble polymers which are stable on storage and do not contain an organic solvent.
La demanderesse a maintenant mis au point de nouvelles émulsions eau dans eau ne présentant pas les inconvénients des dispersions citées précédemment. Car d'une part, elles présentent des particules de diamètre moyen inférieur à 3 μm. Ceci garantit l'absence de sédimentation et donc la bonne stabilité au cours du stockage. D'autre part, de telles particules peuvent être obtenues sans incorporation de dispersant complexant. En effet, grâce à l'utilisation de monomères spécifiques on peut induire la formation de complexe inter et intrapolymère. Cependant, l'introduction de dispersant en faible quantité est recommandée afin d'augmenter la fluidité de i'émulsion. La demanderesse a trouvé que l'incorporation dans le mélange de monomères hydrosolubles à polymériser d'un monomère ayant un radical (R) contenant à la fois une séquence 4The Applicant has now developed new water-in-water emulsions which do not have the drawbacks of the dispersions mentioned above. Because on the one hand, they have particles with an average diameter of less than 3 μm. This guarantees the absence of sedimentation and therefore good stability during storage. On the other hand, such particles can be obtained without incorporating a complexing dispersant. In fact, thanks to the use of specific monomers, it is possible to induce the formation of inter and intrapolymer complexes. However, the introduction of dispersant in small quantities is recommended in order to increase the fluidity of the emulsion. The Applicant has found that the incorporation into the mixture of water-soluble monomers to be polymerized of a monomer having a radical (R) containing both a block 4
polyéthoxylée et une séquence hydrophobe et d'un monomère pouvant former des interactions spécifiques avec la séquence polyéthoxylée, permet la complexation intra et interpolymère et la formation de particules de faible diamètre.polyethoxylated and a hydrophobic block and of a monomer which can form specific interactions with the polyethoxylated block, allows intra and interpolymer complexation and the formation of particles of small diameter.
Ces comonomères complexants présentent un second avantage dans la mesure où ils confèrent au copolymère un caractère associatif.These complexing comonomers have a second advantage insofar as they give the copolymer an associative character.
Il faut préciser aussi que les dispersions de l'invention conservent leurs particules en l'état au moment de la dilution à l'eau même dans les conditions de forte dilution. Le polymère dispersé devient hydrosoluble en générant une augmentation de la viscosité, dans les conditions basiques d'application peinture ou impression pigmentaire.It should also be specified that the dispersions of the invention keep their particles in the state at the time of dilution with water even under the conditions of high dilution. The dispersed polymer becomes water-soluble, generating an increase in viscosity, under the basic conditions of paint application or pigment printing.
Le premier objet de l'invention est une dispersion aqueuse contenant :The first object of the invention is an aqueous dispersion containing:
- de 10 à 40 % en poids d'au moins un polymère hydrosoluble dispersé sous la forme de particules de diamètre inférieur à 3 μm- from 10 to 40% by weight of at least one water-soluble polymer dispersed in the form of particles with a diameter of less than 3 μm
- de 0 à 6 % en poids d'un dispersant complexant apte à former des complexes avec le polymère hydrosoluble par interactions interpolymères telles que les liaisons hydrogènes ou les interactions polaires.- from 0 to 6% by weight of a complexing dispersant capable of forming complexes with the water-soluble polymer by interpolymer interactions such as hydrogen bonds or polar interactions.
Les polymères de l'invention sont constitués essentiellement de monomères hydrosolubles. Ils renferment des motifs dérivés par polymérisation d'au moins un monomère (A) neutre ou anionique, d'au moins un monomère (B) ayant un radical polyéthoxylé se terminant par un groupe hydrophobe et d'au moins un monomère (C) pouvant se complexer avec le monomère (B) par interactions polaires ou par liaisons hydrogènes.The polymers of the invention consist essentially of water-soluble monomers. They contain units derived by polymerization of at least one neutral or anionic monomer (A), at least one monomer (B) having a polyethoxylated radical ending in a hydrophobic group and at least one monomer (C) capable of complex with the monomer (B) by polar interactions or by hydrogen bonds.
Ils peuvent renfermer aussi des motifs dérivés d'au moins un monomère (D) polyinsaturé et ceci dans le but d'avoir des particules de polymères réticulés.They can also contain units derived from at least one polyunsaturated monomer (D) and this in order to have crosslinked polymer particles.
Les polymères de l'invention contiennent :The polymers of the invention contain:
- de 0 à 98,98 % en mole de motifs dérivés par polymérisation d'au moins un monomère hydrosoluble A- from 0 to 98.98% by mole of units derived by polymerization of at least one water-soluble monomer A
- de 0,02 à 5 % en mole de motifs dérivés par polymérisation d'au moins un monomère B- from 0.02 to 5 mol% of units derived by polymerization of at least one monomer B
- de 1 à 99,98 % en mole de motifs dérivés par polymérisation d'au moins un monomère C- from 1 to 99.98% by mole of units derived by polymerization of at least one monomer C
- de 0 à 2 % en mole de motifs dérivés par polymérisation d'au moins un monomère D.- from 0 to 2% by mole of units derived by polymerization of at least one monomer D.
Un autre objet de l'invention est le procédé de synthèse des émulsions eau dans eau contenant des polymères hydrosolubles dispersés sous la forme de particules de diamètre inférieur à 3 μm. oAnother object of the invention is the process for the synthesis of water-in-water emulsions containing water-soluble polymers dispersed in the form of particles with a diameter of less than 3 μm. o
Les dispersions de l'invention sont préparées par polymérisation radicalaire d'une solution aqueuse contenant : de 0 à 98,98 % en mole d'au moins un monomère A de 0,02 à 5 % en mole d'au moins un monomère B de 1 à 99,98 % en mole d'au moins un monomère C de 0 à 2 % en mole d'au moins un monomère D en présence de 0 à 15 % en poids par rapport au poids total des monomères d'au moins un dispersant complexant.The dispersions of the invention are prepared by radical polymerization of an aqueous solution containing: from 0 to 98.98 mol% of at least one monomer A from 0.02 to 5 mol% of at least one monomer B from 1 to 99.98% by mole of at least one monomer C from 0 to 2% by mole of at least one monomer D in the presence of 0 to 15% by weight relative to the total weight of the monomers of at least a complexing dispersant.
Les monomères A sont choisis dans le groupe constitué de l'acrylamide, le méthacrylamide, les N-alkylacrylamide, les N,N di-alkylacrylamide, le N-vinyl méthacétamide, le N-vinyl méthylformamide, le N-vinyl pyrolidone, les (méth)acrylates comportant une chaîne latérale polyéthoxylée terminée par un hydrogène ou un CH3 et leurs mélanges.The monomers A are chosen from the group consisting of acrylamide, methacrylamide, N-alkylacrylamide, N, N di-alkylacrylamide, N-vinyl methacetamide, N-vinyl methylformamide, N-vinyl pyrolidone, ( meth) acrylates comprising a polyethoxylated side chain terminated by a hydrogen or a CH3 and their mixtures.
Le monomère A préféré est l'acrylamide.The preferred monomer A is acrylamide.
Les monomères B sont choisis dans le groupe répondant à la formule suivante :The monomers B are chosen from the group corresponding to the following formula:
CH2 =C -Ç -O^CH2 -CH2 -O^R2 O dans laquelleCH2 = C -Ç -O ^ CH 2 -CH 2 -O ^ R2 O in which
R-| est un hydrogène ou un méthyl n est un nombre entier compris entre 2 et 50R- | is hydrogen or methyl n is an integer between 2 and 50
R2 est soit un radical alkyl en C2-C40, soit un radical aryl en C5-C40, soit un radical alkylaryl en C7-C40, soit un cycloalkyle en C5-C40, soit un alkylène et propylène ou homologue supérieur.R 2 is either a C2-C40 alkyl radical, or a C5-C40 aryl radical, or a C7-C40 alkylaryl radical, or a C5-C40 cycloalkyl, or an alkylene and propylene or higher homolog.
Le monomère B préféré de l'invention est le méthacrylate de tristyryl phénol polyéthoxylé répondant à la formuleThe preferred monomer B of the invention is polyethoxylated tristyryl phenol methacrylate corresponding to the formula
/ : \ T V . //: \ T V. /
C H .C H.
CH9=C-C-O CH -CH -O V I I 25CH 9 = CCO CH -CH -OVII 25
OO
6 6
Les monomères C sont des monomères vinyliques ou acryliques comportant des groupes fonctionnels choisis parmi les groupes acides (carboxylique, sulfonique, phosphorique, sulfurique) et leur sels, ester sulfurique, sulfone, hydroxyle, amino, imino, amino-tertiaire, amonium quaternaire, pyrolidone, et hydrazino.The monomers C are vinyl or acrylic monomers comprising functional groups chosen from acid groups (carboxylic, sulfonic, phosphoric, sulfuric) and their salts, sulfuric ester, sulfone, hydroxyl, amino, imino, tertiary amino, quaternary ammonium, pyrolidone , and hydrazino.
Le monomère C préféré de l'invention est l'acide acrylique.The preferred monomer C of the invention is acrylic acid.
Le monomère D est choisi dans le groupe constitué de N,N méthylène-bis acrylamide, un di-acrylate tel que le di-acrylate d'éthylène glycol, ou le di-acrylate de polyéthylène glycol, un composé di-allylique tel que le diallylacetique ou le diallyl phtalate, un allyl acrylate d'éthylène glycol ou un allyl acrylate de polyéthylène glycol.The monomer D is chosen from the group consisting of N, N methylene-bis acrylamide, a di-acrylate such as ethylene glycol di-acrylate, or polyethylene glycol di-acrylate, a di-allyl compound such as diallylacetic acid or diallyl phthalate, an ethylene glycol allyl acrylate or a polyethylene glycol allyl acrylate.
Le monomère D préféré de l'invention est le N,N méthylène-bis acrylamide.The preferred monomer D of the invention is N, N methylene-bis acrylamide.
Le dispersant complexant selon l'invention est généralement un polymère hydrosoluble de masse moyenne en poids de 300 à 500 000 et comportant de préférence un ou plusieurs groupes fonctionnels choisis parmi les groupes éther, hydroxyle, carboxyle, sulfone, ester sulfurique, amino, imino, amino-tertiaire, amonium quaternaire, et hydrazino, parmi lesquels on donne une préférence particulière aux groupes éther, hydroxyle, et carboxyle. Des exemples typiques de ces dispersants sont le poly(oxyde d'éthylène), l'alcool polyvinylique, et le poly(N vinyl pyrolidone).The complexing dispersant according to the invention is generally a water-soluble polymer of average mass by weight of 300 to 500,000 and preferably comprising one or more functional groups chosen from ether, hydroxyl, carboxyl, sulfone, sulfuric ester, amino, imino, amino tertiary, quaternary ammonium, and hydrazino, among which particular preference is given to the ether, hydroxyl, and carboxyl groups. Typical examples of these dispersants are poly (ethylene oxide), polyvinyl alcohol, and poly (N vinyl pyrolidone).
La polymérisation est conduite de la manière suivante :The polymerization is carried out as follows:
Le mélange de monomères représente de 10 à 40 % et de préférence 1 5 à 30 % en poids du mélange réactionnel constitué de l'eau, de dispersant, et de monomères, le dispersant représentant de 0 à 6 % et de préférence de 0.5 à 3 % en poids. La polymérisation peut être amorcée par différents moyens, comme les générateurs de radicaux libres tels que les peroxydes, les composés diazoïques ou les persulfates, ou par irradiation. Le mode préféré selon l'invention est l'amorçage par le persulfate de potassium, de sodium ou d'ammonium. Ces amorceurs peuvent être combinés avec un accélérateur de décomposition. La température de polymérisation est comprise entre 0 et 100° C et de préférence 40 et 95 °C. La conversion est supérieure à 99 %.The mixture of monomers represents from 10 to 40% and preferably 15 to 30% by weight of the reaction mixture consisting of water, of dispersant, and of monomers, the dispersant representing from 0 to 6% and preferably from 0.5 to 3% by weight. The polymerization can be initiated by various means, such as free radical generators such as peroxides, diazo compounds or persulfates, or by irradiation. The preferred mode according to the invention is the initiation with potassium, sodium or ammonium persulfate. These initiators can be combined with a decomposition accelerator. The polymerization temperature is between 0 and 100 ° C and preferably 40 and 95 ° C. The conversion is greater than 99%.
Les émulsions eau dans eau obtenues peuvent être utilisées pour épaissir en milieu alcalin des systèmes aqueux tels que des latex, pour les applications peintures et textile en particulier l'impression pigmentaire.The water-in-water emulsions obtained can be used to thicken aqueous systems such as latex in an alkaline medium, for paint and textile applications, in particular pigment printing.
Les exemples suivants illustrent l'invention sans la limiter. Dans tous les exemples ci-après, les parts sont données en poids. Exemple 1The following examples illustrate the invention without limiting it. In all the examples below, the parts are given by weight. Example 1
Dans un réacteur de 1 litre, sous agitation on introduit sous balayage d'azote, 320 parts d'eau, 1 36,8 parts d'acrylamide à 50 % dans l'eau, 1 0,98 parts d'acide acrylique, 2,66 parts d'acide méthacrylique, 1 3,98 parts de méthacrylate de tristyryl phénol polyoxyéthyléné avec 25 moles d'oxyde d'éthylène, 8,8 parts de poly(oxyde d'éthylène) de masse molaire 6000 et 1 part de solution d'acide sulfurique à 20 % . On porte le réacteur à 80°C pendant 30 minutes sous balayage d'azote et on introduit 0,045 part de persulfate d'ammonium dilué dans 4 parts d'eau. La température est maintenue à 80°C pendant 2 h 30. Ensuite on ajoute 0,045 part de persulfate d'ammonium dilué dans 4 parts d'eau et on laisse la réaction se faire pendant 2 h supplémentaires. On refroidit à 30° C et on vide le réacteur.320 parts of water, 1 36.8 parts of acrylamide at 50% in water, 1 0.98 parts of acrylic acid, 2 , 66 parts of methacrylic acid, 1 3.98 parts of polyoxyethylene tristyryl phenol methacrylate with 25 moles of ethylene oxide, 8.8 parts of poly (ethylene oxide) with a molecular weight of 6000 and 1 part of solution 20% sulfuric acid. The reactor is brought to 80 ° C. for 30 minutes with nitrogen sweeping and 0.045 part of ammonium persulfate diluted in 4 parts of water is introduced. The temperature is maintained at 80 ° C. for 2 h 30 min. Then 0.045 part of ammonium persulfate diluted in 4 parts of water is added and the reaction is allowed to proceed for an additional 2 h. Cool to 30 ° C and empty the reactor.
Ot7 obtient une dispersion stable de polymère de viscosté Brooklield 19000 cp à 25 °C et de diamètre moyen de particule déterminé par diffusion de la lumière de 0, 725 μm.Ot7 obtains a stable dispersion of Brooklield 19,000 cp viscose polymer at 25 ° C and an average particle diameter determined by light scattering of 0.725 μm.
Exemple 2 (comparatif)Example 2 (comparative)
On refait la même synthèse que précédemment mais en supprimant le méthacrylate de tristyryl phénol polyéthoxylé. On obtient une solution gélatineuse homogène transparente de polymère hydrosoluble.The same synthesis is repeated as above, but by removing the polyethoxylated tristyryl phenol methacrylate. A transparent homogeneous gelatinous solution of water-soluble polymer is obtained.
La comparaison des exemples 1 et 2 permet de constater que la présence du monomère spécial méthacrylate de tristyryl phénol polyéthoxylé est nécessaire pour former des particules d' emulsion eau dans eau.Comparison of Examples 1 and 2 shows that the presence of the special polyethoxylated tristyryl phenol methacrylate monomer is necessary to form water-in-water emulsion particles.
Exemple 3Example 3
On refait la même synthèse que dans l'exemple 1 mais en supprimant le dispersant polyoxyde d'éthylène. On obtient une dispersion stable de polymère de viscosité Brookfie/d 47 000 cp à 25°C et de diamètre moyen de particule déterminé par diffus on de la lumière de 1, 13 μm.The same synthesis is repeated as in Example 1, but removing the polyethylene oxide dispersant. A stable dispersion of polymer with a Brookfie viscosity / d 47,000 cp at 25 ° C. and an average particle diameter determined by light scattering of 1.13 μm is obtained.
L 'incorporation de faible quantité de dispersant poly (oxyde d'éthylène) permet de réduire la viscosité de l' emulsion eau dans eau.The incorporation of a small amount of poly (ethylene oxide) dispersant makes it possible to reduce the viscosity of the water-in-water emulsion.
Exemple 4Example 4
On refait la même synthèse que dans l'exemple 1 mais en y incorporant 500 ppm en poids de N N méthylène bisacrylamide par rapport à la totalité des monomères. On obtient une dispersion stable de polymère de viscosité Brookfield 48 000 cp à 25° C et de diamètre moyen de particule déterminé par diffusion de la lumière de 1 μm. The same synthesis is repeated as in Example 1 but incorporating 500 ppm by weight of N N methylene bisacrylamide relative to all of the monomers. A stable dispersion of polymer with Brookfield viscosity 48,000 cp at 25 ° C. and an average particle diameter determined by light scattering of 1 μm is obtained.

Claims

oREVENDICATIONS o CLAIMS
1. Dispersion aqueuse contenant :1. Aqueous dispersion containing:
- de 10 à 40 % en poids d'au moins un polymère hydrosoluble dispersé sous la forme de particules de diamètre inférieur à 3 μm.- from 10 to 40% by weight of at least one water-soluble polymer dispersed in the form of particles with a diameter of less than 3 μm.
- de 0 à 6 % en poids d'au moins un dispersant complexant caractérisée en ce que le polymère hydrosoluble est constitué :- from 0 to 6% by weight of at least one complexing dispersant, characterized in that the water-soluble polymer consists of:
- de 0 à 98,98 % en mole de motifs dérivés par polymérisation d'au moins un monomère hydrosoluble (A) neutre ou anionique- from 0 to 98.98% by mole of units derived by polymerization of at least one neutral or anionic water-soluble monomer (A)
- de 0,02 à 5 % en mole de motifs dérivés par polymérisation d'au moins un monomère (B) ayant un radical polyéthoxylé se terminant par un groupe hydrophobe- from 0.02 to 5 mol% of units derived by polymerization of at least one monomer (B) having a polyethoxylated radical ending in a hydrophobic group
- de 1 à 99,98 % en mole de motifs dérivés par polymérisation d'au moins un monomère hydrosoluble (C) pouvant se complexer avec le monomère (B)- from 1 to 99.98% by mole of units derived by polymerization of at least one water-soluble monomer (C) which can complex with the monomer (B)
- de 0 à 2 % en mole de motifs dérivés par polymérisation d'au moins un monomère polyinsaturé (D).- from 0 to 2 mol% of units derived by polymerization of at least one polyunsaturated monomer (D).
2. Dispersion aqueuse selon la revendication 1 caractérisée en ce que le monomère A est choisi dans le groupe constitué de l'acrylamide, le méthacrylamide, les N-alkylacrylamide, les N,N-di-alkylacrylamide, le N-vinyl méthacétamide, le N-vinyl méthylformamide, le N-vinyl pyrolidone, les (meth)acrylates comportant une chaîne latérale polyéthoxylée terminée par un hydrogène ou un CH3 et leurs mélanges.2. Aqueous dispersion according to claim 1 characterized in that the monomer A is chosen from the group consisting of acrylamide, methacrylamide, N-alkylacrylamide, N, N-di-alkylacrylamide, N-vinyl methacetamide, N-vinyl methylformamide, N-vinyl pyrolidone, (meth) acrylates comprising a polyethoxylated side chain terminated by hydrogen or CH3 and their mixtures.
3. Dispersion aqueuse selon la revendication 2 caractérisée en ce que le monomère A est l'acrylamide.3. Aqueous dispersion according to claim 2 characterized in that the monomer A is acrylamide.
4. Dispersion aqueuse selon l'une des revendications 1 à 3 caractérisée en ce que le monomère B est choisi parmi les molécules répondant à la formule4. Aqueous dispersion according to one of claims 1 to 3 characterized in that the monomer B is chosen from the molecules corresponding to the formula
R .R.
C H = C -C - θ C H l - C~> H π 20 - 0 R-CH = C -C - θ CH l - C ~> H π 2 0 - 0 R-
O dans laquelleO in which
R-] est un hydrogène ou un méthyl n est un nombre entier compris entre 2 et 50 R2 est soit un radical alkyl en C2-C40, soit un radical aryl en C6- 40, soit un radical alkylaryl en C7-C40, soit un cycloalkyle en C6-C40, soit un alkylène et propylène ou homologue supérieur.R-] is hydrogen or methyl n is an integer between 2 and 50 R 2 is either a C2-C40 alkyl radical, or a C6-40 aryl radical, or a C7-C40 alkylaryl radical, or a C6-C40 cycloalkyl, or an alkylene and propylene or higher homolog.
5. Dispersion aqueuse selon la revendication 4 caractérisée en ce que le monomère B est le méthacrylate de tristyryl phénol polyéthoxylé répondant à la formule5. Aqueous dispersion according to claim 4 characterized in that the monomer B is polyethoxylated tristyryl phenol methacrylate corresponding to the formula
CH .CH.
C H =C - C - O CH o -C H - OlC H = C - C - O CH o -C H - Ol
25 O25 O
6. Dispersion aqueuse selon l'une quelconque des revendications 1 à 5 caractérisée en ce que le monomère (C) est choisi dans le groupe constitué des monomères vinyliques ou acryliques comportant des groupes fonctionnels choisis parmi les groupes acides (carboxylique, sulfonique, phosphorique, sulfurique) et leurs sels, ester sulfurique, sulfone, hydroxyle, amino, imino, amino-tertiaire, amonium quaternaire, pyrolidone et hydrazino.6. Aqueous dispersion according to any one of claims 1 to 5, characterized in that the monomer (C) is chosen from the group consisting of vinyl or acrylic monomers comprising functional groups chosen from acid groups (carboxylic, sulfonic, phosphoric, sulfuric) and their salts, sulfuric ester, sulfone, hydroxyl, amino, imino, amino-tertiary, quaternary ammonium, pyrolidone and hydrazino.
7. Dispersion aqueuse selon la revendication 6 caractérisée en ce que le monomère (C) est l'acide acrylique.7. Aqueous dispersion according to claim 6 characterized in that the monomer (C) is acrylic acid.
8. Dispersion aqueuse selon l'une quelconque des revendications 1 à 7 caractérisée en ce que le monomère D est choisi parmi le N,N méthylène-bis acrylamide, les di-acrylates tels que le di-acrylate d'éthylène glycol, ou le di- acrylate de polyéthylène glycol, les composés di-allyliques tels que le diallylacetique ou le diallyl phtalate, un allyl acrylate d'éthylène glycol ou un allyl acrylate de polyéthylène glycol.8. Aqueous dispersion according to any one of claims 1 to 7 characterized in that the monomer D is chosen from N, N methylene-bis acrylamide, di-acrylates such as ethylene glycol di-acrylate, or polyethylene glycol di-acrylate, di-allyl compounds such as diallylacetic or diallyl phthalate, an ethylene glycol allyl acrylate or a polyethylene glycol allyl acrylate.
9. Dispersion aqueuse selon l'une quelconque des revendications 1 à 8 caractérisée en ce que le dispersant complexant est un polymère hydrosoluble ayant au moins un groupe fonctionnel choisi parmi les groupes éther, hydroxyle carboxyle, sulfone, ester sulfurique, amino, imino, amino-tertiaire, amonium quaternaire et hydrazino.9. Aqueous dispersion according to any one of claims 1 to 8 characterized in that the complexing dispersant is a water-soluble polymer having at least one functional group chosen from ether and hydroxyl groups carboxyl, sulfone, sulfuric ester, amino, imino, amino-tertiary, quaternary ammonium and hydrazino.
10. Dispersion aqueuse selon la revendication 9 caractérisée en ce que le dispersant complexant est le poly(oxyde d'éthylène).10. Aqueous dispersion according to claim 9 characterized in that the complexing dispersant is poly (ethylene oxide).
11. Procédé d'obtention des dispersions aqueuses des revendications 1 à 10 caractérisé en ce qu'on polymérise par amorçage radicalaire à une température allant de 0 à 100°C une solution aqueuse contenant :11. A process for obtaining the aqueous dispersions of claims 1 to 10, characterized in that an aqueous solution containing: a. Radical polymerization at a temperature ranging from 0 to 100 ° C.
1 - de 10 à 40 % en poids d'un mélange de monomères hydrosolubles constitué :1 - from 10 to 40% by weight of a mixture of water-soluble monomers consisting of:
- de 0 à 98,98 % en mole d'au moins un monomère A- from 0 to 98.98 mol% of at least one monomer A
- de 0,02 à 5 % en mole d'au moins un monomère B- from 0.02 to 5 mol% of at least one monomer B
- de 1 à 99,98 % en mole d'au moins un monomère C- from 1 to 99.98 mol% of at least one monomer C
- de 0 à 2 % en mole d'au moins un monomère D.- from 0 to 2% by mole of at least one monomer D.
2 - de 0 à 6% en poids d'un dispersant complexant. 2 - from 0 to 6% by weight of a complexing dispersant.
EP99909066A 1998-04-01 1999-03-22 Stable small sized particle water-in-water emulsions, synthesis method and application as thickening agents Withdrawn EP0986583A1 (en)

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FR9804033A FR2777011B1 (en) 1998-04-01 1998-04-01 WATER-TO-WATER, STABLE AND LOW-SIZE EMULSIONS OF PARTICLES, THEIR SYNTHESIS PROCESS AND APPLICATION AS THICKENERS
PCT/FR1999/000663 WO1999050308A1 (en) 1998-04-01 1999-03-22 Stable small sized particle water-in-water emulsions, synthesis method and application as thickening agents

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