WO2008015072A1 - Crystalline zirconium and/or titanium phosphate, having a lamellar structure and including a diamine as intercalation agent, method of preparation and use in a macromolecular material - Google Patents

Abstract

The zirconium and/or titanium phosphate of the invention is a crystalline phosphate having a lamellar structure and including an interlamellar intercalation agent, and it is characterized in that the intercalation agent is a diamine having a primary amine functional group and a second amine functional group, which is a secondary or tertiary amine functional group. The invention also relates to a macromolecular material which comprises or is prepared using such a zirconium and/or titanium phosphate.

Description

 ZIRCONIUM PHOSPHATE AND / OR CRYSTALLIZED TITANIUM,

LAMELLAR STRUCTURE AND COMPRISING AS AGENT

INTERCALATION DIAMINE, PREPARATION METHOD AND

USE IN MACROMOLECULAR MATERIAL

The present invention relates to a zirconium phosphate and / or crystallized titanium, having a lamellar structure and having as interlamellar intercalation agent a diamine, its method of preparation and its use in a macromolecular material.

To modify the thermomechanical and impermeability properties of macromolecular materials, it is known to use mineral particles. 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. In some cases, such as the materials obtained from latex, it is also sought to improve the characteristics of water uptake and water vapor permeability of the materials.

Thus, it is known to strengthen macromolecular materials, and in particular thermoplastic materials, with platelet particles of nanometric thickness, in particular particles obtained by exfoliation from a compound based on zirconium phosphate and / or titanium with lamellar structure. The compound with lamellar structure is treated with an organic swelling agent, before incorporation into the material to be reinforced, to ensure its exfoliation, exfoliation which is important for improving the properties of the material in which it is introduced.

The phosphates of this type currently available already give satisfactory results. However, products are sought which could have a function capable of reacting with the polymer matrix in which they are incorporated or with the monomers used in the preparation of these matrices. The presence of such a reactive function can improve the compatibility and interaction of phosphate with the matrix. The object of the invention is to provide such a type of product. For this purpose, the zirconium phosphate and / or titanium phosphate of the invention is a crystallized phosphate with lamellar structure and comprising an interlamellar intercalation agent and it is characterized in that the intercalation agent is a diamine comprising a primary amine function and a second amine function which is a secondary or tertiary amine function. Other features, details and advantages of the invention will appear even more fully on reading the description which follows, as well as various concrete but non-limiting examples intended to illustrate it.

The phosphate of the invention more particularly corresponds to the formula Zr (HPO ₄ ) ₂ or Ti (HPO ₄ ) ₂ . It can be anhydrous or hydrated. Furthermore, the zirconium may be partially substituted by another tetravalent element such as titanium, cerium and tin, for example in a proportion of up to 0.2 mol% (molar ratio substituent / zirconium).

This zirconium phosphate and / or titanium is crystallized and has a lamellar structure, that is to say that the atoms constituting the phosphate are arranged in lamellae or sheets, the phosphate consisting of a stack of several of these lamellae or leaflets. In addition, the phosphate comprises an intercalation agent, interposed between the lamellae and bonded thereto.

Without wishing to be bound by a theory, it may be thought that this binding is done by deprotonation of the POH function and protonation of the intercalation agent, for example it may be a PO ^" type bond ... H ₃ ⁺ N .

According to the invention, this intercalation agent is chosen from diamines comprising both a primary amine function and a second amine function which is a secondary or tertiary amine function. According to a preferred embodiment of the invention, the intercalation agent is chosen from diamines comprising both a primary amine function and a tertiary amine function.

Several variants of the invention are possible.

According to a first variant and in the case of a primary / tertiary diamine, the intercalation agent is bound to the phosphate via the tertiary amine function. In the case of a primary / secondary diamine, the intercalation agent is bound to the phosphate via the secondary amine function.

According to a second variant, the intercalation agent is bound to the phosphate via the primary amine function.

It may be noted that in the two variants which have been described, the function of the diamine which does not participate in the bond with the phosphate remains free.

It should also be noted that the phosphate of the invention may be in an intermediate variant between the two which have just been described above, that is to say a variant in which for part of the phosphate the agent of intercalation is linked via the tertiary or secondary amine function and, for another part, the intercalating agent is linked through the primary amine function. In the case of the second variant, the zirconium phosphate and / or titanium phosphate of the invention generally comprises two layers of intercalation agent arranged between the lamellae. The first layer consists of the diamine bonded to a first layer of phosphate by its primary amine function. The lamella which faces the first also has a layer consisting of the diamine bonded to the lamella by its primary amine function. It is still possible in the case of this two-layer arrangement to have in addition the presence of a zirconium phosphate and / or titanium in which the intercalation agent is present with bonding by the tertiary amine or secondary in a single layer or in two layers.

The type of bond, that is to say the nature of the function which participates in the bonding of diamine with phosphate (primary, secondary or tertiary function) can be demonstrated by NMR (single-pulse ³¹ P NMR high-power decoupling in rotation at the magic angle, the measurements given in the examples of the descrition having been made with a Spectro AVANCE 300 SOLID BRUKER), more precisely by the type of displacement which is observed on the NMR diagrams by compared to non-intercalated phosphate. Thus, for zirconium phosphate, the primary amine bonds sheets give a displacement of between -10 and -17 ppm. Moreover, the peak corresponding to the non-intercalated phosphate is at -19 ppm, that corresponding to an intercalation in which the bond is made by the primary amine is located at -14 ppm and that corresponding to an intercalation in which the bond is made by the tertiary amine is between -20 and -22 ppm. In the case of the intermediate variant described above and for the phosphates of the invention for which the bonds are of several types, the NMR diagrams then have several peaks.

The zirconium phosphate and / or titanium may further contain an alkaline cation such as Na ⁺ , K ⁺ , Li ⁺ or the NH ₄ ⁺ ammonium ion. These ions can act as an intercalating agent at least in part in place of the diamine. It may be thought, without wishing to be bound by theory, that these cations can be exchanged with protons of zirconium phosphate and / or titanium to create a PO-cation bond.

The intercalating agent may be chosen from the amines of the following generic formulas: H ₂ NR ₃ -NR ₁ R ₂ or also H ₂ NR ₃ -NHR 1 depending on whether the primary / tertiary diamines or the primary / secondary diamines are used .

In these formulas, the symbol R ₃ represents a linear or branched, cycloaliphatic or aromatic aliphatic polyvalent hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by, or containing, one or more heteroatoms such as oxygen, nitrogen, sulfur or phosphorus, said residue optionally carrying functional groups or functional groups that are not capable of reacting with the functions of zirconium phosphate. The symbols R 1, R ₂ represent monovalent hydrocarbon residues, analogous to the definition of R ₃ . Ri and R ₂ may be the same or different.

The intercalating agents may be chosen more particularly from the dialkylaminoalkylamines of the above formulas in which R 1 and R ₂ are both alkyl radicals or alternatively amino-cycloaliphatic amino-type diamines containing oxygen as hetero atoms.

By way of example only, there may be mentioned, as dialkylaminoalkylamine, dimethylaminopropylamine (DMPA) and diethylaminopropylamine (DEAPA) and as diamino amino cycloaliphatic type containing oxygen as a heteroatom, aminopropylmorpholine.

Other non-limiting examples are N- (2-aminoethyl) piperidine, 2-methyl-1-pipahdino-2-propanamine, 2- (4-benzylpiperidino) -1-ethanamine,

N- (2-aminoethyl) pyrrolidine, N- (3-aminopropyl) pyrrolidine, 2- (4-benzylpiperazino) ethan-1-amine of formula:

r ^'f Υ Λ ^"'" '^ 4-amino-1 -benzylpipéridine of the formula:

- ^{"V * N} ° ^x i - ^v" - - ^"" NH, 4-amino-1, 2,2,6,6-pentamethylpiperidine having the formula:.

Still as non-limiting examples of primary / secondary diamine which may be used in the context of the present invention, mention may be made of N-methylethylenediamine, N-ethylethylenediamine, N-ethylenediamine and the like. phenyl ethylenediamine, N-benzyl ethylenediamine, N-methyl-1,3-propane diamine, N- (2-hydroxyethyl) -1,3-propanediamine, histidine of formula:

le tryptophane de formule

the tryptophan of formula

H the guanine of formula o

The interlamellar distance of the phosphate of the invention can vary over a wide range, depending on the diamine used and the length thereof, that is to say on its number of carbon atoms, and also as a function of the chosen variant. This distance is generally at least about 10 Å, more preferably at least about 15 Å and even more preferably at least about 20 Å. It is measured by the X-ray diffraction technique (XRD) and is characterized by the peak of the plane (002) (monoclinic structure), it being understood that in the case of products in which there are several types of bonds, it is possible to obtain several distances. measured at the peak of plane 002. The highest values for this distance are generally obtained for the variant with two layers of intercalation agent.

The diamine / phosphate mass ratio of zirconium and / or titanium is generally between 10% and 50%.

The process for preparing the phosphate according to the invention essentially consists in reacting a crystalline zirconium phosphate and / or titanium phosphate in liquid medium with the intercalation agent of the type described above.

Starting from a zirconium phosphate and / or crystallized titanium that can be obtained by any known means. It is more particularly possible to use a zirconium phosphate of the type described in patent application WO 2006/008388 to the description to which reference may be made. This phosphate consists of particles in the form of wafer. These particles have a thickness of at most 30 nm, more particularly at most 20 nm and which may be for example between 1 nm and 20 nm and a length of between about 0.1 μm and about 2 μm, more particularly between 0.2 μm and 0.5 μm, these dimensions being determined by TEM analysis.

The wafers that make up the particles are themselves formed of superimposed leaflets whose thickness is of the order of a few angstroms (5 to 7 Å), the space between the leaflets being of the order of 7 to 8 Å. .

The liquid medium used is generally water and the phosphate is dispersed in this medium. It may be useful to wash the phosphate before it is dispersed so as to obtain a relatively pure dispersion, this purity being measured by the conductivity of the dispersion. A conductivity of at most 2 mS.cm can avoid precipitation of parasitic phases in the subsequent preparation of the phosphate according to the invention.

The intercalation agent is introduced into the medium thus formed, generally in the form of a solution. The reaction is generally carried out at room temperature.

The reaction is carried out under conditions such that the molar ratio of amine / P (N / P) is generally between 0.5 and 2. For values of this ratio of at most about 1, the binding with phosphate by the tertiary amine whereas for values of at least about 1.5, the binding with the phosphate by the primary amine is favored. For the ratios whose value is between those given above, it is favored the preparation of a phosphate according to the intermediate variant which has been described above. The values given above may vary depending on the amine. At the end of the reaction, the process can take place according to several variants.

Thus, it is possible to leave the product obtained, as it is, in the form of an aqueous suspension. It is also possible to transfer it in a solvent medium. Finally, the solid product can be separated from the reaction medium by any known means and dried.

In a preferred manner, it is spray-dried. 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 using any sprayer known per se, for example by a spraying nozzle of the watering apple or other type. It is also possible to use so-called turbine atomizers. On the various spraying techniques that may be used, reference may be made in particular to the MASTERS basic work entitled "SPRAYD DRYING" (second edition, 1976, George Godwin-London Editions).

Thanks to intercalation, the intercalation agent is stabilized in the phosphate, in the sense of a thermal stabilization, which makes possible the use of this type of drying. This therefore makes it possible to have a product which has the advantages associated with spray drying, that is to say a morphology and a particle size which facilitates the use of zirconium phosphate and / or titanium in the macromolecular material.

The phosphate of the invention can be used in the preparation of macromolecular materials. The invention therefore also relates to a macromolecular material which is characterized in that it comprises or is prepared by using a zirconium phosphate and / or titanium having the characteristics which have been described above or a phosphate of zirconium and / or titanium obtained by the preparation method described above.

The macromolecular material can be of different types: elastomeric, thermoplastic, thermosetting.

The macromolecular material may be more particularly a thermoplastic polymer. By way of example of polymers that may be suitable, mention may be made of: 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, 3,3'-dimethyl-4,4'-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 diols with long linear chains 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 the same family; polycarbonates such as poly [methane bis (4-phenyl) carbonate], poly [1,1-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 poly (4-aminobutyric 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 (1-aminodecanoic acid) and (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 (para-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 poly (phenylene sulfide) 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-styrene methacrylate 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), and polymers of the same family; mixtures of at least two of the above polymers. Among these thermoplastic polymers, polyamides, such as polyamide 6, polyamide 66, polyamide 12, polyamide 11, semi-aromatic polyamides, PVC, PET, PPO and the mixtures and co-polymers, are particularly preferred. copolymers based on these polymers. Any method can be implemented to use the phosphate of the invention in the macromolecular material. A first method consists in mixing a phosphate in a thermoplastic material 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. Another method consists in mixing a phosphate to be dispersed with the monomers in the polymerization medium and then in carrying out the polymerization. Another method comprises mixing a thermoplastic polymer in molten form with a concentrated mixture of a thermoplastic polymer and a phosphate. There is no limitation to the form in which the phosphate is introduced into the synthesis medium of the macromolecular material, or into the molten thermoplastic macromolecular material. 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 phosphate in the composition based on a macromolecular material is preferably less than or equal to 5%.

The phosphate of the invention may 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 organic 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, lauryl acrylate, isoamyl acrylate, ethyl acrylate and the like. 2 hexyl), octyl acrylate, methyl methacrylate, chloroethyl methacrylate, butyl methacrylate, (3,3-dimethylbutyl) methacrylate, ethyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, phenyl methacrylate, butyl chloroacrylate, methyl chloroacrylate, ethyl chloroacrylate, isopropyl chloroacrylate, cyclohexyl chloroacrylate; b): 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 vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, vinyl versatate (registered trademark for C ₉ -C n alpha-branched acid esters), vinyl laurate vinyl benzoate, trimethyl vinyl acetate, 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-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): the 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 latices, in particular polyvinyl acetate latexes.

It is also possible to use copolymers of some of the aforementioned 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, methacrylic, maleic, itaconic, fumaric acid, etc.); an ethylenic monomer comprising secondary, tertiary or quaternized amino groups (vinyl- pyridines, diethylaminoethyl methacrylate, etc.),

a sulfonated ethylenic monomer (vinylsulphonate, styrene-sulphonate, etc.), a Zwitterionic ethylenic monomer (sulfopropyl- (dimethylaminopropyl) acrylate, or a nonionic acid, in particular unsaturated carboxylic acid amides (acrylamide, methacrylamide, etc.), (meth) acrylate esters, and polyhydroxypropyl or polyhydroxyethylated alcohols.

More particularly, copolymers of styrene with acrylates and styrene-butadiene copolymers may be mentioned.

It will be noted here that in the case of latices, the introduction of the phosphate of the invention can also be done by simply stirring the phosphate with the latex.

Finally, the phosphate of the invention may also be used in any mixture or copolymer of at least two macromolecular materials taken indifferently in the list of thermoplastics mentioned above and polymers described in the latex heading.

Examples will now be given. In these examples, the following reagents are used: Hydrochloric acid (Prolabo 36%, d = 1, 19) Phosphoric acid (Prolabo 85% d = 1.695) Deionized water

Zirconium oxychloride (in powder form) at 32.8% ZrO ₂ .

To characterize the products, an X-ray analysis is carried out with a PW1700 diffractometer equipped with fixed slots and a copper anode (λ _m = 1, 5418 Å). The operating conditions are 5 ° to 70 ° (degrees 2Θ), with a step of

0.020 ° and a time of 1 second per step.

The BET surface indicated is that determined by nitrogen adsorption in accordance with ASTM D 3663-78 established from the BRUNAUER-EMMETT-TELLER method described in the journal "The Journal of the American Chemical Society, 60, 309 (1938). ). "

EXAMPLE 1

1) A crystalline zirconium phosphate of the type described in WO 2006/008388 is first prepared. An aqueous solution of zirconium oxychloride at 2.1 moles per liter of ZrO ₂ is prepared beforehand.

In a stirred reactor of 500 ml the following solutions are added at ambient temperature: Hydrochloric acid: 50 ml

Phosphoric acid: 50 ml

Deionized water: 150 ml

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

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

After removal of the mother liquor the precipitate is washed with 1.2 I of H ₃ PO ₄ at 20 g / l and then with 4 liters of 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 moles / liter), the dispersion thus obtained is transferred to a 1-liter 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) and therefore the shape in wafer. 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 Å.

The solids content is 13%. The specific surface area measured in BET is 37 m ² / g.

2) 38.3 g of the previously obtained suspension of zirconium phosphate with a solids content of 13% are diluted with deionized water so as to obtain a solids content of 5%. The conductivity of this starting dispersion is less than 2 mS.cm, the pH is 2.4. A molar solution of DMPA (ie 10.2 g of DMPA in

100 ml of water).

16.6 ml of this DMPA solution are added over 30 minutes to the ZrP suspension. The amount of DMPA implemented is such that the N / P ratio is 1. The suspension is stirred during this addition, the reaction is carried out at room temperature. The pH after addition is 10.7.

The suspension is centrifuged at 4500 rpm for 30 minutes, the supernatant is removed. The pellet is dried at 50 ° C for 48 hours. The amount of amine intercalated is determined by chemical analysis (powder). The effective ratio N / P is 0.8 which shows that the effective amount of diamine present in intercalation relative to the amount engaged is 50%.

XRD analysis (peak of the 002 plane) shows the presence of two types of zirconium phosphate, one whose interlamellar distance is 21.3 Å and the other whose interlamellar distance is 12.6 Å. .

The ³¹ P NMR analysis shows chemical shifts of between -15 ppm and -22 ppm, which is in agreement with the phosphate type detection and which also shows the presence of tertiary amine bonds and by primary amine.

EXAMPLE 2

Starting from the same suspension of zirconium phosphate as that of Example 1 (dry extract of the suspension adjusted to 5%). A molar solution of DEAPA is prepared. 16.66 ml of this DEAPA solution are added over 30 minutes in the zirconium phosphate suspension. The amount of DEAPA used is such that the N / P ratio is 1. The suspension is stirred during this addition, the reaction is carried out at room temperature. The pH after addition is 10.7. The suspension is centrifuged at 4500 rpm for 30 minutes. The pellet is dried at 50 ° C for 48 hours.

XRD analysis revealed the presence of two types of zirconium phosphate, one with an interlamellar distance of 21.3 Å and the other with an interlamellar distance of 16.5 Å. The effective N / P ratio is 0.85.

Phosphorus NMR analysis performed on the powder shows 2 chemical shifts at about -18.4 ppm and -22 ppm (main peak). This analysis makes it possible to see that the intercalation agent is bound to phosphate via the tertiary amine function.

EXAMPLE 3

Starting from the same zirconium phosphate suspension as that of Example 1 (dry extract of the suspension of 5%). A molar solution of aminopropylmorpholine (APM) is prepared. 33.32 ml of this solution are added over 30 minutes to the zirconium phosphate suspension. The amount of APM used is such that the N / P ratio is 2. The suspension is stirred during this addition, the reaction is carried out at room temperature. The pH after addition is 10.5.

The suspension is centrifuged at 4500 rpm for 30 minutes. The pellet is dried at 50 ° C for 48 hours.

The N / P ratio (chemical analysis) is 1, 57.

The interlamellar distance is 22 Å. NMR analysis revealed a chemical shift of between -13 ppm and -15 ppm characteristic of the bonding of diamine to phosphate by the primary amine function. It can be seen from the X-ray and NMR analyzes that there are two layers of intercalation agent.

EXAMPLE 4

230 g of the suspension of zirconium phosphate obtained as in Example 1 with a solids content of 13% are diluted with deionized water so as to obtain a solids content of 5%. The conductivity of this starting dispersion is less than 2 mS.cm, the pH is 2.4. 7.11 g of DMPA is added to the zirconium phosphate suspension. The amount of DMPA implemented is such that the ratio N / P is equal to 0.7. The suspension is stirred during this addition, the reaction is carried out at room temperature. 363 g of deionized water are added.

The suspension obtained is atomized using a Bϋchi atomizer, the inlet temperature is 240 ° C. and the outlet temperature is 110 ^° C. The powder obtained has the following characteristics: The interlamellar distance is 12, 4 Â.

The chemical composition is as follows: P = 16.6%, N = 4.93%, ie a N / P ratio of 0.66. The NMR analysis of the phosphorus carried out on the powder shows 2 chemical shifts of between -15 ppm and -20 ppm. This analysis makes it possible to see that the intercalation agent is bound to the phosphate of the leaflets via the tertiary amine function.

Measurements by ATD-ATG technique (samples analyzed from 25 ° C. to 800 ° C. in air (30 ml / min) and rate of temperature rise of 10 ° C./min) show that DMPA is detected only from 225 ° C which indicates a good thermal stability of the intercalation agent. The size of the particles is measured by the light diffraction technique. A COULTER LS 230 (small volume) apparatus associated with a 100 W ultrasonic probe was used. The measurement is made by diluting 1 g of the sample in 25 ml of water. Magnetic stirring is then carried out for a few minutes in order to allow good wetting of the suspension. The suspension thus prepared is subjected to ultrasound 100 watts for 3 minutes.

The results obtained are given below.

Claims

1 - crystalline zirconium and / or titanium phosphate, having a lamellar structure and comprising an interlamellar intercalating agent, characterized in that the intercalating agent is a diamine comprising a primary amine function and a second amine function which is a secondary or tertiary amino function. 2- phosphate according to claim 1, characterized in that the intercalation agent is bound to the phosphate via the tertiary amine function. 3. Phosphate according to claim 1, characterized in that the intercalation agent is bound to the phosphate via the primary amine function. 4. Phosphate according to claim 3, characterized in that it comprises two layers of intercalation agent arranged between the lamellae of the lamellar structure. 5. Phosphate according to one of the preceding claims, characterized in that the intercalation agent is chosen from amines of the following formulas: H ₂ NR ₃ -NR ₁ R ₂ or H ₂ NR ₃ -NHR 1 in which R ₃ represents a linear or branched, cycloaliphatic or aromatic aliphatic polyvalent hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by or containing one or more heteroatoms such as oxygen, nitrogen, sulfur or the phosphorus and R 1, R ₂ , which are identical or different, represent monovalent hydrocarbon residues of the same type as R ₃ . 6. Phosphate according to claim 5, characterized in that the intercalation agent is chosen from amines of the dialkylaminoalkylamine type. 7. The phosphate according to claim 5, characterized in that the intercalating agent is chosen from amines of the amino alkyl cycloaliphatic type containing oxygen as heteroatom. 8. The phosphate according to one of the preceding claims, characterized in that the interlamellar distance is at least 10 Å, more particularly at least 15 Å. 9- Process for the preparation of a zirconium phosphate and / or titanium according to one of the preceding claims, characterized in that is reacted in liquid medium a zirconium phosphate and / or titanium crystallized with the agent d intercalation mentioned above. 10- Process according to claim 9, characterized in that the phosphate and the intercalation agent are reacted under conditions such that the molar ratio amine / P function is between 0.5 and 2. 1 1 - Process according to claim 9 or 10, characterized in that a crystallized zirconium phosphate consisting of particles having a thickness of at most 30 nm and a length of between 0.1 μm and 2 μm is reacted. 12- macromolecular material characterized in that it comprises or that it is prepared using a zirconium phosphate and / or titanium according to one of claims 1 to 8 or a zirconium phosphate and / or titanium obtained by the method according to one of claims 9 to 11.