WO2008017755A2

WO2008017755A2 - Lamellar zirconium and/or titanium phosphate structure modified by an alkylamine or a diamine, method of preparation and use thereof

Info

Publication number: WO2008017755A2
Application number: PCT/FR2007/001322
Authority: WO
Inventors: Dominique Dupuis; Franck Touraud; Yves Bomal; Laurent Guy
Original assignee: Rhodia Operations
Priority date: 2006-08-02
Filing date: 2007-07-31
Publication date: 2008-02-14
Also published as: WO2008017755A3; FR2904619B1; FR2904619A1

Abstract

The object of the invention is a zirconium and/or titanium phosphate with a lamellar structure modified by interlamellar intercalating agents, in which the interlamellar intercalation agents comprise a combination of: (a) an alkylamine generating a specific interlamellar distance D in the zirconium phosphate, and (b) a diamine generating a specific interlamellar distance d in the zirconium phosphate less than the specific interlamellar distance D of the alkylamine. A further object of the invention is a method of preparation of the zirconium and/or titanium phosphate and uses for the zirconium and/or titanium phosphate, in particular as fillers in macromolecular materials, such as thermoplastic or elastomeric polymers.

Description

Zirconium and / or titanium phosphate with lamellar structure modified with an alkylamine or a diamine, its method of preparation and its use.

The present invention relates to a zirconium phosphate and / or titanium modified lamellar structure, a process for preparing said zirconium phosphate and / or titanium and uses of said zirconium phosphate and / or titanium, especially as a load in macromolecular materials, such as thermoplastic or elastomeric polymers.

It is known to use mineral particles as fillers in macromolecular materials, in particular to modify their thermomechanical properties. It is thus possible to modify, for example, the modulus of the materials, the impact resistance, the ductility, the dimensional stability, the deformation temperature under load, the abrasion resistance or the abrasive power. Certain mineral fillers also make it possible to reduce the impermeability to gases of materials, in particular to air or water vapor. In particular, it is known that the gas permeability of macromolecular materials can be reduced by introducing lamellar fillers, such as natural clays modified with quaternary ammoniums. When introduced into macromolecular materials, these lamellar fillers exfoliate at least partially in the form of lamellar particles of platelet form. The decrease in the permeability obtained is explained by the fact that the average free path of the gases to pass through a layer of macromolecular materials is increased by the presence of these lamellar particles in the material, according to the so-called "tortuosity" mechanism. For more details on this subject, reference may be made to the works of Nielsen described in particular in J. Macromol. Sci. (Chem.), A1 (5), 929-942 (1967). According to Nielsen's theory, a good gas impermeability depends, among other things, on the ratio between the length and the thickness of the lamellar particle. It is therefore important to control the size of the exfoliated lamellar particles.

In this context, the natural clays prove to be unsuitable, especially insofar as they lead to the formation of platelet particles having a wide distribution of size and shape. They prefer layer-structured compounds capable of exfoliating in the form of platelets of nanometric thickness whose dimensions are controlled. In particular, it has been described for this purpose the use of compounds based on zirconium phosphate and / or titanium lamellar structure. Whatever their nature, the lamellar structure compounds used for the reinforcement of macromolecular materials of the thermoplastic or elastomeric polymer type are generally treated with an interlamellar intercalation agent.

For the purposes of the present description, the term "interlamellar intercalating agent" is intended to mean an organic agent, such as an amine for example, which is localized in the interlamellar space of a zirconium phosphate-type layered compound and or titanium, which in particular has the effect of increasing the interlamellar distance. By "interlamellar distance" is meant here the spacing between the planes formed by the zirconium and / or titanium atoms in the compound with non-exfoliated lamellar structure, as measured by X-ray diffraction. introduction of the intercalation agent, an increase in this spacing between the planes is obtained, namely an increased interlamellar distance. An interlamellar intercalator induces, when introduced into a given lamellar material, a interlamellar distance characteristic of this agent, greater than the interlamellar distance of the material without intercalation agent. Here, the term "specific interlamellar distance" is used to denote the interlamellar distance induced by an intercalation agent after it has been introduced into the compound with a lamellar structure. This interlamellar distance increases with the size of the intercalator. For example, for primary alkylamines, the specific interlamellar distance increases with the number of atoms of the alkyl group.

The modification of the interlamellar distance as obtained with the above intercalation agents can in particular be used to modulate the exfoliation capacity of the lamellar compound, this increasing capacity with the interlamellar distance. By modulating the exfoliation capacity, partial exfoliation within the material can be obtained with a sufficient amount of exfoliated charges released sufficient to provide impermeability to the gases, while still retaining some of the lamellar filler in the unexfoliated state and "Swollen" by the interlamellar intercalator. The presence of the filler comprising an exfoliated part and another non-exfoliated part may in particular be used to confer on the material improved mechanical properties. Indeed, a non-exfoliated lamellar filler having a sufficiently large interlamellar distance can act as a micro-shock absorber.

However, this modulation of the interlamellar distance generally requires the introduction of protonated primary amine-type organic compounds, in an amount important, in compounds with lamellar structure, which has repercussions especially in terms of cost, or even environmental aspects. In addition, the organic compounds introduced are generally released into the materials when the charge is exfoliated, and they are likely to lead in some cases to parasitic reactions, which may for example induce a degradation of the properties of the material.

An object of the present invention is to provide novel materials suitable as fillers in macromolecular materials such as thermoplastic or elastomeric polymers, and having a reduced amount of organic agents, alkylamine type potentially harmful.

For this purpose, according to a first aspect, the invention provides a zirconium and / or titanium phosphate with lamellar structure modified by interlamellar intercalating agents, wherein said interlamellar intercalating agents comprise a combination of: (a) an alkylamine generating, in zirconium phosphate and / or titanium, a specific interlamellar distance D, and

(b) a diamine generating, in zirconium phosphate and / or titanium, a specific interlamellar distance of said specific interlamellar distance d being less than the specific interlamellar distance D of the alkylamine, preferably with a D / d ratio less than or equal to 5, preferably less than or equal to 4, for example between 3 and 4.

According to one embodiment, the modified phosphate of the invention is a zirconium phosphate. Alternatively, it may be a titanium phosphate or a mixed phosphate of zirconium and titanium.

In the modified zirconium and / or titanium phosphates of the invention, a large alkylamine (corresponding to a specific interlamellar distance D) associated with a shorter diamine (corresponding to a lower specific interlamellar distance) is specifically used. . Interestingly, it turns out that the combined use of the alkylamine and the diamine according to the invention makes it possible to increase the interlamellar distance of zirconium phosphate and / or titanium by employing a smaller quantity of agents. organic, alkylamine type, than that which would be necessary according to the usual method, namely by using only an amine of suitable size. Moreover, the inventors have surprisingly found that the diamine / alkylamine combination leads, in at least a part of the lamellar material, to an interlamellar distance which is intermediate between the specific interlamellar distances D and d of each of the amines. used. This result is unexpected, since we would rather have expected to obtain an interlamellar distance equal to the specific interlamellar distance D of the alkylamine. Indeed, in the most general case, it is known that, when a mixture of two alkylamines is introduced as an intercalating agent in a lamellar material, an interlamellar distance equal to the specific interlamellar distance of the the longest amine, which imposes its specific spacing. According to the invention, on the contrary, it is surprisingly obtained, for all or part of the zirconium phosphate and / or titanium according to the invention, an intermediate interlamellar distance between the specific distances D and d.

In fact, the alkylamine and the diamine together act as intercalating agents, and not separately in different parts of the lamellar compound.

This characteristic is reflected in particular by the fact that the modified zirconium phosphate and / or titanium phosphate according to the invention does not have an interlamellar distance equal to the specific interlamellar distance d. In particular, no X-ray diffraction pattern shows this characteristic distance. Without being bound to any theory, it appears that the diamine is intercalated between the lamellae of zirconium phosphate and / or titanium in the manner of alkylamine. The presence of the alkylamine induces a spacing of the lamella sufficiently large to avoid bridging by the diamines. Given this configuration where, schematically, some alkylamines are substituted by diamines, the effect of adjusting the desired interlamellar distance is obtained by employing a smaller amount of alkylamine than if the alkylamine alone had been used.

Together with this interesting effect, it is also found that at the same time diamines are introduced which are more interesting, insofar as they can in particular develop interactions with the matrix. Most often, at least one of the terminal amine functions of the diamine does not remain engaged in a bond or interaction with the zirconium phosphate and / or titanium according to the invention. A free amine function is thus obtained which can interact with certain matrices in which the zirconium phosphate and / or titanium phosphate can be introduced, which can improve certain mechanical properties of said material, In addition, even more surprisingly, the inventors have demonstrated that, for a given diamine / alkylamine pair, it is possible to modify the interlamellar distance by varying the amount of diamine introduced.

More precisely, for a molar ratio of diamine / alkylamine of less than about 0.05, the interlamellar distance obtained for the modified phosphate is equal to D. Without being bound to any theory, it seems possible to be advanced that zirconium phosphate and or titanium according to the invention would comprise between its lamellae two layers of interlamellar intercalation agents, and that the diamine would be intercalated between the alkylamines without modifying the interlamellar distance, in a state available to be engaged in an interaction or a binding with the matrix of the material in which the modified phosphate is introduced.

In other words, for a molar ratio of less than about 0.05, the zirconium phosphate and / or titanium phosphate behaves globally as if it contained only an alkylamine interlamellar intercalating agent, but with the additional advantages ( 1) using a reduced amount of alkylamine and (2) containing a diamine available to interact with the matrix.

For a diamine / alkylamine molar ratio greater than or equal to approximately 0.05, a more unexpected effect is obtained. For all or part of the zirconium phosphate and / or titanium according to the invention, an intermediate interlamellar distance is obtained between the specific distances D and d, said zirconium phosphate and / or titanium being called P2. For a diamine / alkylamine molar ratio of less than about 0.7, P2 has an interlamellar distance whose value is constant regardless of the diamine / alkylamine ratio. The value of interlamellar distance depends on the choice of alkylamine. Together with P2, some of the zirconium phosphate having an interlamellar distance equal to D remains, said phosphate of zirconium and / or titanium being called P1. The proportion of P1 with respect to P2 decreases when the molar ratio diamine / alkylamine increases. In particular, P1 is no longer detectable by known means, for example by X-ray diffraction, when the diamine / alkylamine molar ratio is greater than or equal to about 0.25.

Thus, for this ratio greater than or equal to about 0.05 and preferably greater than or equal to about 0.25, the abovementioned advantages are preserved, and it is also possible to modulate the level of exfoliation. Indeed, it is known that in the context of the use of alkylamines as intercalation agents, it is possible to modulate the interlamellar distance by varying the number of carbons of the alkylamine. However, interlamellar distances having a finite value characteristic of each alkylamine are obtained. The invention makes it possible to reach these interlamellar distances with a lesser amount of amines used. In particular, depending on the diamine / alkylamine molar ratio, it is also possible to obtain a zirconium and / or titanium phosphate having two parts whose lamellar distances have two different values, thus making it possible to modulate the exfoliation capacity. Thus, the invention provides a method of modifying the interlamellar distance more advantageous than those currently known.

By using the intercalating agents of the invention, a given interlamellar distance can be easily obtained. The value of the specific interlamellar distance is known for many amines and diamines. For the others, it is easily measurable, in particular by X-ray diffraction. According to the invention, a given interlamellar distance can be achieved by combining an alkylamine having a specific interlamellar distance greater than or equal to the desired distance and a diamine having a specific interlamellar distance less than the desired distance and one can reach the desired distance by adopting the molar ratio diamine / alkylamine. It is also possible to regulate the distance obtained by modifying the length of the chains of the two amines, in particular by varying their number of carbon atoms.

The interlamellar distance of the zirconium phosphate and / or titanium according to the invention can vary over a fairly wide range of values, depending on the nature of the diamines (b) and alkylamines (a).

As a general rule, the interlamellar distance obtained is between 10 Λ and

50 Λ. In order to obtain an exfoliation leading to good gas impermeability of the macromolecular material in which the zirconium phosphate and / or modified titanium phosphate is introduced, it is preferred that this distance be greater than 12 Λ, for example greater than 20 Å.

Furthermore, for some applications, it is advantageous for some of the zirconium phosphate and / or titanium to remain in the non-exfoliated form in the material where it is introduced. For this purpose, it is preferred that the interlamellar distance be less than

50, for example between 40 and 50.

Advantageously, the alkylamine (a) has the following formula (I):

R ¹ -NR ² R ³ (I), wherein each of R ¹ , R ² and R ³ denotes, independently, a hydrogen atom or an aliphatic monovalent hydrocarbon group, linear or branched (preferably linear), cycloaliphatic or aromatic , containing from 4 to 50 carbon atoms, for example from 8 to 40, which may comprise one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus, said residue carrying functional groups or functional groups that may not be susceptible to react with the functions of zirconium phosphate, and it being understood that at least one of the groups R ¹ , R ² and R ³ is a monovalent hydrocarbon group.

In the most general case, the alkylamine (a) may be chosen from primary, secondary or tertiary alkylamines. Nevertheless, it is preferred that the alkylamine (a) is a primary amine, preferably corresponding to the following formula (Ia): R ¹ NH ₂ (la) where R ¹ has the abovementioned meaning.

As a primary amine useful according to the invention, there may be mentioned amines containing from 4 to 20 carbon atoms.

Diamine (b) is a compound carrying at least two primary, secondary or tertiary amino functions.

According to an advantageous embodiment, the diamine (b) corresponds to the following formula (II):

R ⁴ R ⁵ NR ⁶ -NR ⁷ R ⁸ (II) wherein: - R ^δ is a divalent hydrocarbon chain, linear or branched (preferably linear) aliphatic, cycloaliphatic or aromatic group containing from 3 to 20 carbon atoms, e.g. between 5 and 15, which may comprise one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus, said remainder bearing functions or functional groups that may be incapable of reacting with the functions of zirconium phosphate, and

each of R ⁴ , R ⁵ , R ⁷ and R ⁸ is independently a hydrogen atom or a monovalent hydrocarbon group. Advantageously, the hydrocarbon chain R ⁶ of formula (II) does not develop any interaction with respect to the phosphate group of zirconium phosphate and / or titanium according to the invention.

In general, the diamine (b) may comprise primary, secondary and / or tertiary amine functions. However, preferably, the diamine (b) has at least one primary amine function.

According to one particular embodiment, the diamine (b) comprises two primary amine functions, preferably a diamine corresponding to the following formula (IIa):

H ₂ NR ⁶ -NH ₂ (IIa) where R 6 has the above meaning.

Suitable diamines according to the invention include, in addition to the diamines (IIa) above, the diamines carrying a primary amine group and a tertiary amine group, especially 3-aminopropyl dimethylamine (DMPA). ) and 3-aminopropyl diethylamine (PEAPA), 3-morpholine propylamine, among N- (2-aminoethyl) piperidine, 2-methyl-1-piperidino-2-propanamine, 2- (4-benzylpiperidino) - 1-ethanamine, N- (2-aminoethyl) -pyrrolidine, N- (3-aminopropyl) -pyrrolidine, 2- (4-benzylpiperazino) ethan-1-amine, 4-amino-1-benzylpiperidine and 4-amino-1,2,6,6-pentamethylpiperidine or alternatively N-methylethylenediamine, N-ethylethylenediamine, N-phenylethylenediamine, N-benzylethylenediamine, N-methyl-1,3-propane diamine, N- (2-hydroxyethyl) -1,3-propanediamine, histidine, tryptophan, guanine, 1- (2-aminoethyl) piperazine.

Regardless of the exact nature of amine (a) and diamine (b), it is generally preferred that, in the material of the invention, the molar ratio of intercalation to amines be between 0.3 and 0.6, preferably between 0.4 and 0.5. The molar ratio of organic intercalation is also a function of the desired diamine / alkylamine molar ratio. In the case of a contraction of the interlamellar distance with respect to the specific interlamellar distance D, said diamine / alkylamine molar ratio is preferably greater than or equal to about 0.05. By "molar ratio of intercalation" is meant here the ratio between the number of moles of amines intercalated (or N) and the initial number of protons of zirconium phosphate (or P).

The zirconium and / or titanium phosphate according to the invention may further comprise an interlamellar alkaline cation, in particular Na ⁺ , K ⁺ , Li ⁺ ions or NH ₄ ⁺ ammonium ions. The presence of cations avoids, among other things, the release of acids that may deteriorate the macromolecular material.

According to a second aspect, the subject of the invention is the process for preparing the zirconium and / or titanium phosphate according to the invention, comprising a step (E) in which a zirconium phosphate is placed in contact in a dispersing medium. and / or titanium P ⁰ with an alkylamine (a) and a diamine (b) as described above.

The dispersing medium in which the zirconium phosphate and / or titanium P ⁰ is contacted with the alkylamine and the diamine is typically a liquid medium comprising an aqueous solvent, especially water. It is possible to wash the zirconium phosphate and / or titanium before it is dispersed so as to purify the medium, which makes it possible to avoid precipitation of parasitic phases in the course of the preparation of the zirconium phosphate and / or of titanium according to the invention. The purity of the dispersion can be measured by conductivity. This is advantageously less than or equal to 2 mS.cm- ¹ The zirconium phosphate and / or titanium P ⁰ corresponds to the formula Zr (HPO ₄ ) 2 or Ti (HPO ₄ ) ₂ It can be anhydrous or zirconium may be partially substituted by another tetravalent element such as cerium and tin, for example, in a proportion of up to 0.2 mol% (ratio of the number of mole atoms of substituent on the zirconium phosphate and / or titanium P ⁰ can be obtained by any type of known means, in particular by the preparation method described in the patent application WO 2006/008388, in particular in Zirconium phosphate and / or titanium phosphate consists of wafer-shaped particles having a thickness of at most 30 nm, more particularly at most 20 nm, for example between 1 nm and 20 nm The length can be between Approximately 0.1 μm and 2 μm, more particularly between 0.2 μm and 0.5 μm, these dimensions being determined by transmission electron microscopy (TEM) analysis. The zirconium phosphate and / or titanium P ⁰ generally has a lamellar structure whose lamellae thickness is between 5 and 7 Λ and the space between said lamellae is less than 8 A. The atoms constituting each phosphate are arranged in slats or sheets. The two interlamellar intercalation agents are interposed between these lamellae and form bonds with said lamellae. The binding can be done by deprotonation of the POH function and protonation of the amine function of each intercalation agent, for example a proton bond of the type PO ^' ... H ₃ ⁺ N. The nature of said bond can be set For example, by ³¹ P NMR. According to ³¹ P NMR analysis, the main chemical shift is -15 ppm corresponding to PO ^" ... H ⁺ N, characteristic of the attachment of the amino functions on the lamellae. the amine linkage is visible on the ³¹ P NMR spectra relative to the ³¹ P NMR spectrum of the unmodified zirconium phosphorus and / or titanium phosphorus, the primary amine bonds such as PO ^', H ₃ ⁺ N modifying the displacement corresponding to the phosphate of zirconium phosphate and / or titanium unmodified in the opposite direction to those induced by the secondary or tertiary amine bonds such as PO ^" ... H ₂ ⁺ N or PO ^' ... H ⁺ N. More precisely, the peak corresponding to the phosphate of zirconium phosphate e t / or unmodified titanium is at -19 ppm, that corresponding to an intercalation in which the bond is made by a primary amine such that PO ^" ... H ₃ ⁺ N is located at -14 ppm and that corresponding to an intercalation in which the bond is via a tertiary amine such that PO ^" ... H ⁺ N is at -20 ppm.

The ratio β is defined as being equal to the molar ratio of the number of reactive amine functions and the number of moles of zirconium phosphate. The zirconium phosphate and / or titanium phosphate is reacted with each interlamellar intercalation agent with a β ratio in particular of between 0.25 and 1, preferably less than or equal to 0.6. By number of moles of reactive functions is meant the sum of the number of moles of each amine function capable of reacting on the phosphate functions.

According to one embodiment, the step (E) of bringing the intercalating agents into contact with the zirconium phosphate and / or titanium comprises:

(E1) contacting the zirconium phosphate and / or titanium with the diamine (b); then

(E2) contacting the zirconium phosphate and / or modified titanium obtained in step (E1) with the alkylamine (a). Typically, whatever the mode of implementation of the process, the molar ratio of intercalation to amines is between 0.3 and 0.6. The molar intercalation ratio is also a function of the desired diamine / alkylamine molar ratio. In the case of a contraction of the interlamellar distance with respect to the specific interlamellar distance D, said diamine / alkylamine molar ratio is greater than or equal to about 0.05

The reaction temperature is most often of the order of room temperature, for example between 20 ^° C. and 30 ^° C.

At the end of the reaction, the product according to the invention is separated from the liquid phase by any known means and dried. In a preferred manner, the drying is carried out by atomization. By spray drying is meant here and in a known manner, a spray drying of the mixture in a hot atmosphere (spray-drying).

The atomization can be carried out by means of any sprayer known per se, for example a spraying nozzle of the watering apple or other type. It is possible to use so-called turbine atomizers. On the various spraying techniques that can be used, reference may be made in particular to the basic work of

MASTERS entitled Spray-drying, second edition, 1976, Editions George Godwin-

London.

Thanks to intercalation, the two interlamellar intercalation agents are stabilized in zirconium phosphate and / or titanium making it possible to use this type of drying. In particular, spray drying makes it possible to obtain a certain morphology and particle size facilitating the use of zirconium phosphate and / or titanium in the macromolecular material.

According to a third aspect, the invention relates to the use of zirconium phosphate and / or titanium according to the invention as an exfoliation-capable filler in macromolecular materials, such as thermoplastic or elastomeric polymers.

According to a fourth aspect, the invention relates to macromolecular materials comprising zirconium phosphate and / or titanium according to the invention as a filler with exfoliation capacity.

According to a preferred embodiment, at least one of the interlamellar intercalation agents (a) and / or (b) (preferably diamine (b)) may comprise at least one reactive group with at least one of the compounds forming the macromolecular material. This makes it possible, for example, to improve the dispersion or the potential reactivity of the zirconium phosphate and / or titanium according to the invention in the matrix of the macromolecular material. The macromolecular material may in particular be an elastomeric polymer, a thermoplastic polymer or a thermosetting polymer.

Examples of thermoplastic polymers that may be mentioned include polylactones such as poly (pivalolactone), poly (caprolactone) and polymers of the same family; polyurethanes obtained by reaction between diisocyanates such as 1,5-naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3, 3-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 5'-dimethyl-4'-diphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate , 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate, toluidine diisocyanate, hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane and compounds of the same family and linear long-chain diols such as poly (tetramethylene adipate), poly (ethylene adipate), poly (1,4-butylene adipate), poly (ethylene succinate), poly (2,3-butylene succinate), polyether diols and compounds of same family; polycarbonates such as poly [methane bis (4-phenyl) carbonate], poly [1,1-ether bis (4-phenyl) carbonate], poly [diphenylmethane bis (4-phenyl) carbonate], poly [1 1-cyclohexane bis (4-phenyl) carbonate] and polymers of the same family; polysulfones; polyethers; polyketones; polyamides such as oleyl (4-amino butyric acid), poly (hexamethylene adipamide), poly (6-aminohexanoic acid), poly (m-xylylene adipamide), poly (p-xylylene sebacamide), poly (2 , 2,2-trimethyl hexamethylene terephthalamide), poly (metaphenylene isophthalamide), poly (p-phenylene terephthalamide), poly (12-aminododecanoic acid), poly (11-aminoundodecanoic acid) and the (co) polymers of the same family; polyesters such as poly (ethylene azelate), poly (ethylene-1,5-naphthalate, poly (1,4-cyclohexane dimethylene terephthalate), poly (ethylene oxybenzoate), poly (poly-hydroxy benzoate), poly ( 1,4-cyclohexylidene dimethylene terephthalate), poly (1,4-cyclohexylidene dimethylene terephthalate), polyethylene terephthalate, polybutylene terephthalate and polymers of the same family; poly (arylene oxides) such as poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,6-diphenyl-1,4-phenylene oxide) and polymers of the same family; poly (arylene sulfides) such as polyphenylene sulphide) and polymers of the same family; polyetherimides; vinyl polymers and their copolymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride; polyvinyl butyral, polyvinylidene chloride, ethylene-vinyl acetate copolymers, and polymers of the same family; acrylic polymers, polyacrylates and their copolymers such as polyethyl acrylate, poly (n-butyl acrylate), polymethyl methacrylate, polyethyl methacrylate, poly (n-butyl methacrylate), poly (n-propyl methacrylate), polyacrylamide, polyacrylonitrile, poly (acrylic acid), ethylene-acrylic acid copolymers, ethylene-vinyl alcohol copolymers, acrylonitrile copolymers, methyl methacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers methacrylate-butadiene-styrene copolymers, ABS, and polymers of the same family; polyolefins such as low density poly (ethylene), polypropylene, low density chlorinated poly (ethylene), poly (4-methyl-1-pentene), poly (ethylene), poly (styrene), and polymers of the same family; ionomers; poly (epichlorohydrins); furan resins such as poly (furan); cellulose-ester plastics such as cellulose acetate, cellulose acetate butyrate, cellulose propionate and polymers of the same family; silicones such as poly (dimethyl siloxane), poly (dimethyl siloxane co-phenylmethyl siloxane), polymers of the same family and mixtures of at least two of the above polymers.

Among the thermoplastic polymers, polyamides such as polyamide 6, polyamide 66, polyamide 12, polyamide 11, semi-aromatic polyamides, PVC, PET, PPO, blends and copolymers with base of these polymers.

The zirconium and / or titanium phosphate according to the invention can be used more particularly in the case where the macromolecular material is a latex. The latices are aqueous dispersions of polymer particles from conventional emulsion (co) polymerization processes of polymerizable organic monomers. These monomers may be chosen, for example, from: a) alkyl (meth) acrylates, the alkyl part of which preferably contains from 1 to 18 carbon atoms, in particular methyl acrylate, ethyl acrylate, , propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, acrylate, lauryl, isoamyl acrylate, (2-ethyl-2-hexyl) acrylate, octyl acrylate, methyl methacrylate, chloroethyl methacrylate, butyl methacrylate, (3-dimethyl methacrylate) Butyl), ethyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, phenyl methacrylate, butyl chloroacrylate, methyl chloroacrylate, ethyl chloroacrylate, isopropyl chloroacrylate, cyclohexyl chloroacrylate; b) the alpha, beta-ethylenically unsaturated esters of monocarboxylic acids whose acid part is non-polymerizable and whose unsaturated part preferably comprises 2 to 14 carbon atoms and the acid part of 2 to 12 carbon atoms, in particular the vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, vinyl versatate (registered trademark for C 8 -C 18 alpha-branched acid esters), vinyl laurate, vinyl vinyl benzoate, vinyl trimethylacetate, vinyl pivilate and vinyl trichloroacetate; c) esters and hemi-esters of alpha.beta.-ethylenically unsaturated polycarboxylic acids having from 4 to 24 carbon atoms, in particular dimethyl fumarate, diethyl maleate, methyl and ethyl fumarate, (2-ethylhexyl) fumarate; d) vinyl halides, in particular vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride; e) aromatic vinyls preferably having at most 24 carbon atoms and chosen in particular from styrene, alpha-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-methylstyrene, hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylsilylene, 2-chlorostyrene, chlorostyrene, 4-chloro-3-methylstyrene, 4-tert-butylstyrene, 4-dichlorostyrene, 2, 6-dichlorostyrene, 2,5-difluorostyrene, and 1-vinylnaphthalene; f) conjugated aliphatic dienes preferably having from 3 to 12 carbon atoms, in particular 1,3-butadiene, isoprene and 2-chloro-1,3-butadiene; g) alpha-, beta-ethylenically unsaturated nitriles preferably having from 3 to 6 carbon atoms such as acrylonitrile and methacrylonitrile. Mention may also be made of homopolymeric latexes, in particular polyvinyl acetate latexes. In the case of latices, the introduction of the zirconium phosphate and / or titanium according to the invention can be done by simply stirring mixture of zirconium phosphate and / or titanium according to the invention with the latex. It is possible to use copolymers of some of the above-mentioned main monomers with up to 50% by weight of other ionic isomers, in particular:

an alpha-, beta-ethylenically unsaturated carboxylic acid monomer mentioned above, including mono and polycarboxylic acids (acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, etc.),

an ethylenic monomer comprising secondary, tertiary or quaternized amine groups (vinylpyridines, diethylaminoethylmethacrylate, etc.),

a sulphonated ethylenic monomer (vinylsulphonate, styrene sulphonate, etc.), an ethylenic Zwitterionic monomer (sulphopropyl dimethylaminopropyl acrylate, etc.). or non-ionic character, in particular:

the amides of unsaturated carboxylic acids (acrylamide, methacrylamide, etc.)

esters of (meth) acrylates and of polyhydroxypropyl or polyhydroxyethylated alcohols.

More particularly, mention may be made of styrene-acrylate copolymers and styrene-butadiene copolymers.

Any method can be implemented to incorporate the zirconium phosphate and / or titanium according to the invention into the macromolecular material. A first method consists in mixing the zirconium phosphate and / or titanium according to the invention in a thermoplastic polymer in molten form and optionally subjecting the mixture to a large shear, for example in a twin-screw extrusion device, in order to achieve a good dispersion. A second method consists of mixing the zirconium and / or titanium phosphate according to the invention with the monomers present in the polymerization medium and then carrying out the polymerization. A third method consists of mixing with a thermoplastic polymer in molten form, a concentrated mixture of a thermoplastic polymer and zirconium phosphate and / or titanium according to the invention.

There is no limitation on the form in which the zirconium and / or titanium phosphate according to the invention can be introduced into the synthesis medium of the macromolecular material or into the thermoplastic macromolecular material. molten. It may for example be introduced in the form of a solid powder or in the form of a dispersion in water or in an organic dispersant.

The proportion by weight of the zirconium phosphate and / or titanium according to the invention in the base composition of a macromolecular material is preferably less than or equal to 5%, for example between 1 and 4%.

The macromolecular material may comprise other additives, including stabilizers, plasticizers, flame retardants, colorants, lubricants, catalysts, this list not being exhaustive. >

The invention will be further illustrated by reading the nonlimiting example which follows.

Example 1 Intercalation of Octadecylamine (ODA) and Hexamethylenediamine (HMD)

Intercalation of ODA and HMD

An unmodified zirconium phosphate corresponding to that described in the application WO 02/16264, the characteristics of which are as follows: dry extract equal to 26.9%, a conductivity of less than 2 mS · cm ^-1 , pH equal to 2 5

At 25 ^° C. with stirring, 371.7 g of ZrP slurry (ie 100 g in dry) are introduced. 77.69 g of a 5M aqueous sodium hydroxide solution are added thereto. The mixture is stirred for one hour.

33.2 ml of a molar aqueous solution of hexamethylenediamine are then added. The mixture is left stirring again for one hour at 25 ° C. and then a solution of 90% octadecylamine in purity, from the dissolution of 59.65 g of 90% IODA in 800 ml of ethanol, is added.

The HMD / ODA ratio is 0.165.

The reaction medium is stirred for 24 h at 25 ^° C.

Solid / liquid separation is carried out by centrifugation, the cake obtained is dried for 15 hours at 50 ^° C. Analysis

To characterize the products, a diffraction ray analysis (DRX) was carried out with a PW 1700 diffractometer equipped with fixed slots and a copper anode (λ _m = 1, 5418 A). The operating conditions were:

- variation from 5 ° to 70 ° (degree 2Θ)

a step of 0.020 °

- a time of 1 second per step.

The X-ray diffractogram shows a low intensity of 002 to 48 A lines corresponding to the specific interlamellar distance of I ¹ ODA and the more intense peaks corresponding to interlamellar distances of 23.8 A and 15.6 A. identifies the Na ₂ Zr phase (PO ₄ J ₂ , H ₂ O.

TEM Analysis: The MET area indicated is that determined by nitrogen adsorption according to the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method described in the journal The Journal of the American Chemical Society, 60, 309 (1938).

MET analysis revealed lamellar swelling by organic compounds. The specific surface is 31 m ² .g ^"1 .

The chemical composition is as follows:

Relative abundance in Zr: 16.6%

Relative Abundance in P: 11.1% Relative Abundance in Na: 4.0%

Relative abundance in N: 2.2%

Relative abundance in C: 29.6%

Let the following ratios be:

Zr / P: 0.51 Na / P: 0.49

N / P: 0.44

C / N: 15.7

The ratio β is equal to 0.44. Comparative Example 1 of a Synthetic Blend with 3 = 0.44

A mixture having the same β ratio as Example 1 was prepared with the following composition:

- 50% of protons exchanged by Na ⁺ such as Na / P = 1, corresponding to the structure Na ₂ Zr (PO ₄ ) ₂ , xH ₂ θ,

30% of protons exchanged by ODA such that β = 1, corresponding to the structure Zr (ODA, PO ₄ ) ₂ ,

- 20% protons exchanged by HMD such that β = 0.5, corresponding to the structure

(HMD, H) Zr (PO-O ₂ .

Zirconium phosphate as previously prepared was used. This zirconium phosphate was interposed separately with ODA, HMD and Na. The three zirconium phosphates thus obtained are dried separately at 50 ^° C. The mixture of the three powders of ZrP, each comprising ZrP modified solely with Na ⁺ , is then carried out solely by HMD and only by ODA.

X-ray diffraction analysis (XRD):

The interlamellar distances measured by DRX are 48 A corresponding to the structure Zr (ODA, PO ₄ ) ₂ and 12.6 A to the structure (HMD, H) Zr (PO ₄ ) ₂ . The Na ₂ Zr phase (PO ₄ J ₂ , 3H ₂ O is demonstrated by ³¹ P NMR analysis.

³¹ P NMR analysis revealed the structural differences between the intercalation mixture and the synthetic mixture. The phosphorus environment is different between the mixing of the powders and the direct intercalation. For direct intercalation, the characteristic PO-Na peaks are not observed. Peaks attributable to ZrP decreased in intensity, illustrating a change.

Example 1a. Intercalation with octadecylamine and HMD with β = 0.41

The same modified zirconium phosphate is prepared with the same proportion of ODA and HMD but with a P ⁰ zirconium phosphate prepared according to an experimental protocol different from Example 1. More specifically, the following protocol was implemented. . A zirconium phosphate corresponding to that described in patent application WO 2006/008388 is firstly prepared.

An aqueous solution of zirconium oxychloride at 2.1 mol.r ^-1 is prepared beforehand.

In a stirred reactor of 500 ml, the following solutions are added at ambient temperature:

Hydrochloric acid: 50ml Phosphoric acid: 50ml Deionized water: 150ml

After stirring the mixture, 140 ml of the 2.1M aqueous solution of zirconium oxychloride are added continuously.

Stirring is maintained for 1 hour after the end of the addition of the zirconium oxychloride solution. After removal of the mother liquors, the precipitate is washed with 1.2 I of H ₃ PO ₄ to

20 gl ^'1 and then with 4 I deionized water. A precipitate is obtained based on zirconium phosphate. Dry at 50 ^° C. for 15 hours and recover about 90 g of product. Part of the preceding precipitate (60 g) is dispersed in 230.6 g of 85% phosphoric acid and 524.9 g of water (ie an acid concentration of 3 mol.l ^-1 ), the dispersion thus obtained is transferred to a 1 L autoclave and then heated to a temperature of 150 ^° C. This temperature is maintained for 5 hours.

The dispersion obtained is washed with deionized water. The cake from the last centrifugation is redispersed.

A dispersion of a crystalline compound based on zirconium phosphate is obtained, the characteristics of which are as follows:

Electron transmission microscopic (TEM) analysis reveals particles of size between 150 and 400 nm.

The X-ray analysis indicates in particular by the high intensity of the peak of the plane (002) relative to that of the doublet of the planes (-113) and (202) a preferential growth of the particles in this plane (002). The shape is of the wafer type.

The thickness of the particle measured perpendicular to the plane (002) is 18 nm. The distance measured between the constituent leaflets of the platelets is 7.5 A.

The solids content is 13% and the specific surface area measured in BET is 37 m ² .g- ¹ . Intercalation of IODA and I ⁹ HMD

1 150.5 g of ZrP slurry prepared according to the experimental protocol described above is introduced into a reactor (25 ^° C.) equipped with stirring. 100 ml of a 5N sodium hydroxide solution are added over 15 minutes, the stirring is maintained for 2 hours at 25 ^° C. 50 ml of a solution of hexamethylenediamine molar are then added, the suspension is stirred for 2 hours. hours at 25 ^° C. Then 2 liters of a technical octadecylamine ethanol solution (purity of 90% - ACROS) at a concentration of 45 μl ^{-1 are added,} stirring is maintained for 16 hours at 25 ^° C. The reaction medium is separated by centrifugation, the solid fraction is dried at 50 ^° C. for 72 hours and the powder obtained is ground using a Retsch type mortar grinder.

The chemical composition of the product leads to the following ratios: Na / P ratio: 0.483

N / P ratio: 0.41 The ratio β is equal to 0.41.

The X-ray diffractogram revealed a low intensity of d002 lines at 48 A corresponding to the interlamellar distance specific to the ODA, and peaks corresponding to interlamellar distances of 23.8 A and 15.6 A, these peaks are more intense. The Na ₂ Zr phase (PO ₄ , H ₂ O.

Example 2 intercalation of octadecylamine (ODA) and hexamethylenediamine (HMD).

Experimental conditions

Preparation of zirconium phosphate according to the invention.

A modified zirconium phosphate according to the invention was prepared by intercalating octadecylamine (ODA) and hexamethylenediamine (HMD) with a zirconium phosphate base prepared according to the preparation method described in the patent application.

WO 2006/008388. Sodium has also been introduced into said zirconium phosphate. Specifically, the following protocol has been implemented.

Preparation of zirconium phosphate

A zirconium phosphate corresponding to that described in patent application WO 2006/008388 is firstly prepared.

Hydrochloric acid: 50ml Phosphoric acid: 50ml Deionized water: 150ml

Stirring is maintained for 1 hour after the end of the addition of the zirconium oxychloride solution.

After removing the mother liquor, the precipitate is washed with 1.2 I of H ₃ PO ₄ to 20 gl ^"1 then with 4 l of deionized water. A precipitate zirconium phosphate. It is dried at 50 ⁰ C for 15 hours and recovering about 90 g of product.A portion of the preceding precipitate (60 g) is dispersed in 230.6 g of 85% phosphoric acid and 524.9 g of water (ie an acid concentration). of 3 mol T ¹ ), the dispersion thus obtained is transferred to a 1 L autoclave and then heated to a temperature of 150 ^° C. This temperature is maintained for 5 hours The dispersion obtained is washed with deionized water The cake from the last centrifugation is redispersed.

The thickness of the particle measured perpendicular to the plane (002) is 18 nm. The distance measured between the constituent leaflets of the platelets is 7.5 A. The solids content is 13% and the specific surface area measured in BET is

37 m ² .g- ¹ .

Intercalation of ODA and HMD

At 25 ^° C. with stirring, 304.3 g of crystallized ZrP slurry prepared according to 1) and 139.8 g of aqueous 5M sodium hydroxide solution are introduced. The mixture is stirred for one hour. 74.7 ml of a molar aqueous solution of HMD are then added. The mixture is left stirring again for one hour and then 29.8 g of octadecylamine at 90% purity are added, the ODA being finely divided.

The HMD / ODA ratio is 0.75.

The reaction medium is stirred for 24 hours at 25 ^° C.

The suspension obtained is atomized using a Bϋchi atomizer. The inlet temperature is 240 ° C. and the outlet temperature is 110 ^° C.

X-ray diffraction analysis (XRD): The interlamellar distances are 23.8 A and 15.6 A with identification of the phase Na ₂ Zr (PO ₄ ) ₂ , H ₂ O.

Neither the phase (HMD, H) Zr (PO ₄ ) ₂ at 12.6 A, nor the Zr phase (ODA, PO ₄ ) ₂ at 48 A are observed.

The chemical composition is as follows: Na: 6.53%

N: 1, 64% P: 15.91% Na / P ratio: 0.55 N / P ratio: 0.23 The β ratio is 0.23.

Comparative Example 2 of a synthetic mixture with β = 0.23.

A mixture having the same β ratio as Example 2 was prepared with the following composition: 60% of protons exchanged with Na ⁺ such as Na / P = 1, - 10% of protons exchanged by ODA such that β = 0.5

- 30% of protons exchanged by HMD such that β = 0.5

The zirconium phosphate as prepared in the above Example 2 and separately intercalated with HMD, ODA and Na was used. The three products obtained are dried separately at 50 ^° C. The mixture of the three powders of ZrP, each comprising ZrP modified solely by Na ⁺ , was then carried out solely by HMD and only by ODA.

X-ray diffraction analysis (XRD):

The interlamellar distances measured by XRD was 12.6 A corresponding to the structure (HMD, H) Zr (PO ₄₎ ₂ and 48 A to the Zr structure (ODA PO ₄₎ _2. The Na ₂ Zr phase (PO ₄ , 3H ₂ O is evidenced.

Claims

A zirconium and / or titanium phosphate with lamellar structure modified with interlamellar intercalating agents, wherein said interlamellar intercalating agents comprise a combination of: (a) an alkylamine generating in zirconium phosphate a specific interlamellar distance D, and

(b) a diamine generating in the zirconium phosphate a specific interlamellar distance d less than the specific interlamellar distance D of the alkylamine.

2. Modified phosphate according to claim 1, wherein the phosphate used is zirconium phosphate.

3. Modified phosphate according to claim 1 or 2, wherein a D / d ratio is less than or equal to 5, preferably less than or equal to 4.

4. Modified phosphate according to one of claims 1 to 3, wherein the diamine / alkylamine molar ratio is greater than or equal to about 0.05.

5. Modified phosphate according to any one of claims 1 to 4, wherein the diamine / alkylamine molar ratio is greater than or equal to about 0.25.

6. Modified phosphate according to any one of claims 1 to 5, wherein the interlamellar distance is between 10 Λ and 50 A.

7. Modified phosphate according to any one of claims 1 to 6, wherein Talkylamine (a) has the following formula (I):

R ¹ -NR ² R ³ (I), wherein each of R ¹ , R ² and R ³ denotes, independently, a hydrogen atom or an aliphatic monovalent hydrocarbon group, linear or branched (preferably linear), cycloaliphatic or aromatic containing from 4 to 50 carbon atoms, which may contain one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus, and it being understood that at least one of the groups R ¹ , R ² and R ³ is a monovalent hydrocarbon group.

8. Modified phosphate according to any one of claims 1 to 7, wherein the alkylamine (a) has from 4 to 20 carbon atoms.

9. Modified phosphate according to any one of claims 1 to 8, wherein the diamine (b) has the following formula (II):

R ⁴ R ⁵ NR ⁶ -NR ⁷ R ⁸ (II) where:

R ⁵ represents a divalent, linear or branched (preferably linear), aliphatic, cycloaliphatic or aromatic hydrocarbon-based chain containing from 3 to 20 carbon atoms, for example between 5 and 15, which may comprise one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus, said moiety bearing functional groups or functional groups which may be incapable of reacting with the functions of zirconium phosphate and / or titanium, and

each of R ⁴ , R ⁵ , R ⁷ and R ⁸ is independently a hydrogen atom or a monovalent hydrocarbon group.

10. Modified phosphate according to any one of claims 1 to 9, wherein the diamine (b) comprises at least one primary amine function.

11. Modified phosphate according to any one of claims 1 to 10, wherein the diamine (b) is selected from diamines comprising two primary amine functions, including hexamethylene diamine (HMD), among dialkylaminoalkylamines including R ^{1 '} and R ² are hydrogen and R ^{1 "} and R ² are alkyl groups, in particular 3-aminopropyl dimethylamine (DMPA) and 3-aminopropyl diethylamine (PEAPA), among the amino-cycloaliphatic alkyls comprising oxygen, in particular 3 -morpholine propylamine, among N- (2-aminoethyl) piperidine, 2-methyl-1-piperidino-2-propanamine, 2- (4-benzylpiperidino) -1-ethanamine, N- (2-aminoethyl) - pyrrolidine, N- (3-aminopropyl) -pyrrolidine, 2- (4-benzylpiperazino) ethan-1-amine, 4-amino-1-benzylpiperidine and 4-amino-1,2,6,6 -pentamethylpiperidine or alternatively N-methylethylenediamine, N-ethylethylenediamine, N-phenylethylenediamine, N-benzylethylenediamine, N-methyl 1,3-propane diamine, N- (2-hydroxyethyl) -1,3-propanediamine, histidine, tryptophan, guanine, 1- (2-aminoethyl) piperazine.

12. Modified phosphate according to any one of claims 1 to 11, wherein the diamine is hexamethylenediamine and the alkylamine is octadecylamine.

13. Modified phosphate according to any one of claims 1 to 12 comprising an interlamellar alkaline cation.

14. A method for preparing a modified phosphate according to any one of claims 1 to 13, comprising a step E) which is contacted in a dispersing medium a zirconium phosphate and / or titanium P ⁰ with a diamine (b) and an alkylamine (a) as described in any one of the preceding claims.

15. Preparation process according to claim 14, wherein the zirconium phosphate and / or titanium reacts with each interlamellar intercalating agent with a β ratio of between 0.25 and 1.

16. Preparation process according to claim 14 or 15, wherein step (E) comprises:

(E2) contacting the zirconium phosphate and / or modified titanium obtained in step (E1) with the alkylamine (a).

17. Preparation process according to any one of claims 14 to 16, wherein the zirconium phosphate and / or titanium is composed of wafer thickness particles of at most 30 nm and length between 0, 1 μm and 2 μm.

18. Use of a modified phosphate according to any of claims 1 to 13 as an exfoliation-capable filler in macromolecular materials.

19. A macromolecular material comprising a zirconium and / or titanium phosphate according to any one of claims 1 to 13 or a zirconium and / or titanium phosphate obtainable by the process according to any one of claims 14 at 17 as a load with exfoliation ability.