FR2753971A1 - New metallic and metalloid tetravalent phosphonates and their preparation - Google Patents

Abstract

New phosphonates of tetravalent elements of general formula (I): M(O3PR)2 (I) -M = a tetravalent element of group IVa or IVb; -R = H or a monovalent 1 - 40C hydrocarbyl radical. Also claimed, is their method of preparation.

Description

NEW PHOSPHONATES OF TETRAVALENT ELEMENTS AND THEIR
PROCESS FOR PREPARATION

 The present invention relates to novel phosphonates of tetravalent elements and their method of preparation. The invention more particularly relates to phosphonates of metalloids such as silicon or metals such as titanium, tin and zirconium.

 The present invention also relates to the preparation of said phosphonates according to several alternative embodiments.

 Metal phosphonates are organic-organic hybrid materials that can be used as catalysts, absorbers or ion exchangers. It is important to have new ones to develop new applications.

It has now been found and this is the object of the present invention, new phosphonates of tetravalent elements corresponding to the general formula:
M (03PR) 2 (I) in which:
M represents a tetravalent element belonging to groups (IVa) or (IVb)
of the periodic table,
R represents a hydrogen atom or a monovalent hydrocarbon radical,
optionally substituted having from 1 to 40 carbon atoms.

 In the present text, reference is made hereinafter to the Periodic Table of Elements published in the Bulletin of the Chemical Society of France, No. 1 (1966).

 The phosphonates of the invention more particularly correspond to the formula (I) in which M represents an element of the group (IVa) such as titanium, zirconium, hafnium, and preferably titanium or zirconium.

 With regard to the elements of the group (lob), M represents silicon, germanium, tin and lead, preferably silicon or tin.

 The metalloid or metal phosphonates of the invention are products with lamellar structure.

A preferred class of phosphonates are silicon phosphonates of formula (I '):
If (03PR) 2 (I ') in which R has the meaning given above.

 The silicon phosphonates obtained according to the invention have the characteristic demonstrated by 29Si NMR analysis, of having a hexacoordinated silicon atom. The spectrum of the products obtained is reduced to a peak at 6 = -211.9ppm.

 In the phosphonates of formula (I), the nature of the radical R is highly variable.

 R represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon radical which may be a saturated or unsaturated, linear or branched acyclic aliphatic radical; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic radical.

 R can have various meanings. Different examples are given below but they are in no way limiting.

 In the compounds of formula (I), R preferably represents an acyclic aliphatic radical, saturated or unsaturated, linear or branched.

 More specifically, R represents a linear or branched acyclic aliphatic radical preferably having from 1 to 12 carbon atoms, saturated or comprising one to more unsaturations on the chain, generally 1 to 3 unsaturations which may be single or conjugated double bonds or triple connections.

The hydrocarbon chain can be optionally:
- interrupted by one of the following groups Z: -O-; -CO-; COO; -NR1-; -CO-NR 1; -S-; -SO 2 - -NR 1 -CO-;
in said formulas R1 represents a hydrogen atom, an alkyl group
linear or branched having 1 to 6 carbon atoms, preferably a
methyl or ethyl radical,
and / or carrier of one of the following substituents:
-OH; -COOH; -COOX; -CO-N (R1) (R2) -COOR1; -CHO; -COR 1; -NO 2; -X;
-CF3.

in these formulas, R2 having the same meaning as R1 given
previously.

 It is also possible that R represents an acyclic aliphatic radical, saturated or unsaturated, linear or branched optionally carrying a cyclic substituent. By ring is meant a carbocyclic or heterocyclic ring, saturated, unsaturated or aromatic.

 The acyclic aliphatic radical can be linked to the ring by a valency bond or by one of the aforementioned Z groups.

 As examples of cyclic substituents, it is possible to envisage cycloaliphatic, aromatic or heterocyclic substituents, in particular cycloaliphatic ring substituents comprising 6 ring carbon atoms or benzenes, these cyclic substituents being themselves optionally carrying one or more substituents.

 Examples of such radicals include, among others, the benzyl radical.

 In the general formula (I), R may also represent a saturated carbocyclic radical or comprising 1 or 2 unsaturations in the ring, generally having from 3 to 7 carbon atoms, preferably 6 carbon atoms in the ring.

 Preferred examples of R radicals include cyclohexyl or cyclohexene-yl radicals.

dans ladite formule (Il):
- n est un nombre entier de O à 5, de préférence de O à 3,
- Q représente R3, I'un des groupes ou fonctions suivantes:
un radical alkyle, linéaire ou ramifié, ayant de 1 à 6 atomes de carbone, de
préférence de 1 à 4 atomes de carbone, tel que méthyle, éthyle1 propyle,
isopropyle, butyle, isobutyle, sec-butyle, tert-butyle,
un radical alcényle linéaire ou ramifié ayant de 2 à 6 atomes de carbone, de
préférence, de 2 à 4 atomes de carbone, tel que vinyle, allyle,
. un radical alkoxy linéaire ou ramifié ayant de 1 à 6 atomes de carbone, de
préférence de 1 à 4 atomes de carbone tel que les radicaux méthoxy, éthoxy,
propoxy, isopropoxy, butoxy,
un groupe acyle ayant de 2 à 6 atomes de carbone,
un radical de formule: -R5-OH
-R5-COOR7
-R5-CHO
-R5-N02
-R5-CN
-R5-N(R7)(Ri
-R5-CO-N(R7)(R8)
-R5-SH
-R5-X
-R5-CF3 dans lesdites formules, R5 représente un lien valentiel ou un radical hydrocarboné divalent, linéaire ou ramifié, saturé ou insaturé, ayant de 1 à 6 atomes de carbone tel que, par exemple, méthylène, éthylène, propylène, isopropylène, isopropylidène ; les radicaux R7 et R8, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone ; X symbolise un atome d'halogène, de préférence un atome de chlore, de brome ou de fluor.The radical R may preferably represent an aromatic carbocyclic radical. and in particular benzenium corresponding to the general formula (II):

in said formula (II):
n is an integer of from 0 to 5, preferably from 0 to 3,
Q represents R3, one of the following groups or functions:
a linear or branched alkyl radical having from 1 to 6 carbon atoms,
preferably from 1 to 4 carbon atoms, such as methyl, ethylpropyl,
isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
a linear or branched alkenyl radical having from 2 to 6 carbon atoms,
preferably from 2 to 4 carbon atoms, such as vinyl, allyl,
. a linear or branched alkoxy radical having 1 to 6 carbon atoms,
preferably from 1 to 4 carbon atoms such as methoxy, ethoxy,
propoxy, isopropoxy, butoxy,
an acyl group having 2 to 6 carbon atoms,
a radical of formula: -R5-OH
-R 5 COOR 7
-R 5 CHO
-R 5 N02
-R5-CN
-R5-N (R7) (R
-R5 -CO-N (R7) (R8)
-R5-SH
-R 5 X
-R5-CF3 in said formulas, R5 represents a valency bond or a divalent hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene ; the radicals R7 and R8, which are identical or different, represent a hydrogen atom or a linear or branched alkyl radical having from 1 to 6 carbon atoms; X symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.

dans lequel:
- m est un nombre entier de 0 à 5, de préférence de 0 à 3,
. Ro ayant la signification donnée précédemment pour R3
R6 représente un lien valentiel ; un groupe hydrocarboné divalent, linéaire
ou ramifié, saturé ou insaturé ayant de 1 à 6 atomes de carbone tel que par
exemple, méthylène, éthylène, propylène, isopropylèn e, isopropylidène ou
l'un des groupes suivants dénommés Z:
-O-; -CO-; COO-; -N R7- ; -CO-NR7-; -S-; -S02- ; -NR7-CO-;
dans lesdites formules R7 représente un atome d'hydrogène, un groupe
alkyle linéaire ou ramifié ayant de 1 à 6 atomes de carbone, de préférence,
un radical méthyle ou éthyle.Q is Ri, one of the following more complex radicals:

in which:
m is an integer from 0 to 5, preferably from 0 to 3,
. Ro having the meaning given above for R3
R6 represents a valency bond; a divalent hydrocarbon group, linear
or branched, saturated or unsaturated having 1 to 6 carbon atoms such as
example, methylene, ethylene, propylene, isopropylene, isopropylidene or
one of the following groups called Z:
O-; -CO-; COO; -N R7-; -CO-NR7-; -S-; -SO2-; -NR7-CO-;
in said formulas R7 represents a hydrogen atom, a group
linear or branched alkyl having from 1 to 6 carbon atoms, preferably
a methyl or ethyl radical.

 Examples of radicals R corresponding to formula (II) are phenyl, tolyl or xylyl, methoxyphenyl, 2-nitrophenyl and biphenyl, 1,1'-ethylenebiphenyl, 1,1'-isopropylidenebiphenyl, , 1'-carboxybiphenyl, 1,1'-oxybiphenyl, 1,1'-iminobiphenyl: said radicals may be substituted with one or more radicals Q as predefined.

 R may also represent a polycyclic aromatic hydrocarbon radical; the cycles can form between them ortho-condensed, ortho- and peri-condensed systems. More particularly, a naphthalenic radical may be mentioned.

 In the general formula (I), R may also represent a saturated, unsaturated or aromatic heterocyclic radical containing in particular 5 or 6 atoms in the ring, including 1 or 2 heteroatoms such as nitrogen, sulfur and oxygen atoms. .

 It should be noted that if the radical R comprises any cycle, it is possible for this cycle to carry a substituent. The nature of the substituent is any as long as it does not interfere with the desired product. R3 illustrates the type of substituents commonly encountered. The substituents most often carried by the ring are one or more alkyl or alkoxy radicals preferably having from 1 to 4 carbon atoms, a halogen atom.

 Among all the aforementioned R radicals, the phosphonates of the invention preferably comprise, as R radicals, a linear or branched alkyl radical having from 1 to 6, preferably from 1 to 4, carbon atoms optionally carrying an acid function, amide or ester, or a phenyl radical.

 The present invention provides access according to the method of the invention described below to phosphonates of formula (II ') difficult to obtain because of their propensity to hydrolyze.

 The preferred silicon phosphonates according to the invention correspond to the formula (II ') in which R represents a linear or branched alkyl radical having from 1 to 6, preferably 1 to 4 carbon atoms or a phenyl radical.

 Another object of the invention resides in the process for preparing said phosphonates.

 A first preparation variant consists in reacting in an anhydrous medium, an organic phosphonate and a tetravalent element halide.

 A second variant is to make the reaction in an anhydrous medium, between a dihalogenated organic phosphonate and a tetravalent element alkoxide.

 Another variant is to always contact in an anhydrous medium, a dihalogenated organic phosphonate and a tetravalent element halide, in the presence of an organic solvent, oxygenated, polar.

More precisely, according to the first mode of preparation, an organic phosphonate corresponding to formula (III) is reacted:
R-PO- (OR ') 2 (III) in said formula (III):
R has the meaning given above,
R 'is a hydrocarbon group of any kind, and - a tetravalent element halide (IV):
MX4 (IV) in said formula (IV):
X represents a halogen atom such as chlorine, bromine and iodine,
preferably, chlorine,
M represents a tetravalent element belonging to groups (IVa) or (IVb)
of the periodic table.

 Regarding more specifically the nature of the organic phosphonates of formula (III) used in the process of the invention, it can be said that they are known products and / or easily accessible by a synthetic route.

Thus, one can refer to synthesize them to a process of preparation according to the reaction of Arbuzov mentioned in the work of Jerry MARC H -
Advanced Organic Chemistry, chapter 6-47, page 959, 4th edition (1992).

 The reagents used preferentially in the process of the invention are for the compounds of formula (III), dimethylphenylphosphonate, dimethylethylphosphonate, diethylphenylphosphonate and for the halides of formula (IV), TiCl4, TiBr4, Tir4, ZrCl4, ZrBr4 , Zr1 SnC4, SnBr4, Sn4, SiC4, SiBr4, Sil4.

 The reagents of formula (III) or (IV) are used in an amount close to the stoichiometry, namely 90 to 120% of the stoichiometric amount.

 Indeed, if one deviates too much from the stoichiometry, poorly condensed products are obtained, which can include halogen atoms.

 According to the process of the invention, the reaction is carried out under anhydrous conditions, preferably in an organic solvent.

 The choice of the solvent is determined according to several parameters.

 It must be inert under the reaction conditions.

 It is preferable that it allows at least partial dissolution of the halide of the tetravalent element.

 An aprotic, organic, aprotic, non-oxygenated solvent is preferably used, and more particularly an aprotic, slightly polar or slightly polar solvent.

 As examples of suitable solvents for the present invention, there may be mentioned in particular aliphatic or aromatic hydrocarbons, halogenated or not.

 As examples of aliphatic hydrocarbons, mention may be made more particularly of paraffins, such as in particular hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane or cyclohexane. , and naphthalene and aromatic hydrocarbons and more particularly aromatic hydrocarbons such as benzene, toluene, xylenes, cumene, petroleum fractions consisting of a mixture of alkylbenzenes, especially the Solvesso type cuts.

 As regards the aliphatic or aromatic halogenated hydrocarbons, there may be mentioned more particularly perchlorinated hydrocarbons such as in particular tetrachloromethane, tetrachlorethylene, hexachloroethane; partially chlorinated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, trichlorethylene, 1chlorobutane, 2-dichlorobutane; monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,4-trichlorobenzene or mixtures of different chlorobenzenes; bromoform, bromoethane or 1,2-dibromoethane; monobromobenzene or mixtures of monobromobenzene with one or more dibromobenzenes; 1bromonaphthalene.

 The preferred solvents are dichloromethane and p-xylene.

 It is also possible to use a mixture of organic solvents.

 The concentration of the halide of the tetravalent element in the solvent can vary within wide limits. Thus, it is generally used from 0.1 to 10 mol of halide per liter of solvent. It is not disadvantageous to be at low concentrations except for the problem of productivity of the apparatus.

 The temperature at which the reaction is carried out is preferably selected from a temperature range of from room temperature to 200 ° C, preferably from 100 ° C to 1500 ° C. By "ambient temperature" is meant a temperature generally between 15 ° C and 250 ° C.

 The reaction may be carried out under atmospheric pressure or at pressures greater than atmospheric pressure, for example from 1 to 100 bar, and preferably between 5 and 20 bar.

 According to a preferred variant of the process of the invention, the process of the invention is carried out under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economical to use nitrogen.

 From a practical point of view, the method according to the invention is simple to implement.

 A preferred mode is first to put the organic phosphonate in solution in the organic solvent, to add the halide of the tetravalent element.

Since the reaction is exothermic, the temperature is controlled by cooling if necessary so that the temperature is between OOC and 20 ° C.

 Crystallization of the product obtained is effected by heating under pressure preferably the reaction mixture at a temperature between room temperature and 2000C, preferably between 100 "C and 150" C.

 As an indication, the duration of the heating can be between 2 and 24 hours.

 The phosphonate obtained precipitates.

 It is separated according to conventional solid / liquid separation techniques, optionally washed, preferably with the same organic solvent as that of the reaction. A solid, generally white solid is obtained which can be dried at a temperature between room temperature and 7000 ° C, preferably between 40 ° C and 200 ° C.

 It should be noted that if the temperature of the reaction and (or the duration of the reaction are insufficient, the condensation is not complete and a phosphonate can be obtained in which halogen atoms and R residues are left behind. These can be removed by continuing crystallization.

 For this purpose, it is possible to carry out a recrystallization operation in an organic solvent.

 To do this, use is made of a solvent which is chosen from aliphatic and preferably aliphatic alcohols, and more particularly secondary or tertiary alcohols. Thus, sec-butanol and tert-butanol are the preferred solvents.

 Generally, the phosphonate obtained is suspended in the organic solvent, for example, from 20 to 25 moles of alcohol per mole of tetravalent element.

 It is then heated to a temperature preferably between 100 ° C and 150 ° C for a period of at least 1 hour and up to 200 hours and more.

 Then, the crystallized product is recovered in a conventional manner.

 According to the second variant of the process of the invention, the reaction is carried out in anhydrous medium, between a dihalogenated organic phosphonate and a tetravalent element alkoxide.

Thus, a dihalogenated organic phosphonate having the formula (V) is reacted:
R-PO- (X) 2 (V) in said formula (V):
R has the meaning given above,
X represents a halogen atom such as chlorine, bromine and iodine,
preferably, chlorine, and - a tetravalent element alkoxide (VI):
M (OR ') 4 (VI) in said formula (VI):
R 'is a hydrocarbon group of any kind,
M represents a tetravalent element belonging to groups (IVa) or (IVb)
of the periodic table.

 As regards the halogenated organic phosphonates of formula (V) used in the process of the invention, it can be said that they are known products and / or easily accessible by a synthetic route.

 For this purpose, reference may be made to the preparation thereof, in the article by A. M. Kinnear et al., J. Chem. Soc. pp.3437 (1952) which describes the reaction of an alkyl halide, phosphorus trichloride and aluminum chloride, followed by a hydrolysis reaction.

 As regards the alkoxides of formula (VI), many are commercially available. They can be prepared in a known manner, in particular by reaction of a metal halide (or metalloid) and an alcohol [Metal alkoxides. D.C. Bradley, R.C. Mehrotra, D. T. Gaur, Academic Press pp.10-41 (1978)].

 The reagents used preferentially in the process of the invention are for the compounds of formula (V), dichloromethylphosphonate, dichloroethylphosphonate, dichlorophenylphosphonate and for the alkoxides of formula (VI), tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium , tetraethoxyzirconium, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane.

 The process for using the reagents is identical to that described above. The reaction is conducted under anhydrous conditions, preferably in an organic solvent as mentioned above.

 It is also possible to perform the crystallization operation to obtain well crystallized products.

 Another variant consists in always bringing into contact, in an anhydrous medium, a dihalogenated organic phosphonate and a tetravalent element halide, in the presence of an aprotic oxygen-containing polar solvent, for example an ether-oxide or protic agent, especially an alcohol. .

 It is thus possible to use a dihalogenated organic phosphonate having the formula (V) and a tetravalent element halide corresponding to the formula (IV).

 The nature of said compounds has already been clarified in the present text.

 As regards the ether-type or alcohol-type reagent, it is specified that an ether-oxide is used which may be chosen in particular from aliphatic, cycloaliphatic or aromatic ether-oxides and, more particularly, diethyloxide. , dipropyl ether, diisopropyloxide, dibutyloxide, methyltertiobutylether, dipentyloxide, diisopentyloxide, ethyleneglycol dimethylether (or 1,2-dimethoxyethane), diethylene glycol dimethyl ether (or 1,5-dimethoxy-3-oxapentane); Biphenyl or benzyloxide; dioxane, tetrahydrofuran (THF).

 In the case of the implementation of an alcohol, preference is given to an aliphatic alcohol, preferably secondary or tertiary, having at least 3 carbon atoms. Tert-butanol is advantageously chosen.

 The amount of oxygenated solvent used is very variable. Thus, it can be set so that the concentration of the halide of the tetravalent element in the solvent varies between 0.4 and 40 mol of halide per liter of solvent.

 It should be noted that it is also possible to also have a non-oxygenated, apolar or slightly polar organic solvent, preferably of the aliphatic or aromatic hydrocarbon type, halogenated or not. It is necessary to refer to what has been previously described on the nature of the solvents and the quantities used.

 The reagents of formula (V) or (IV) are used in an amount close to the stoichiometry, namely 90 to 120% of the stoichiometric amount.

 The conditions of temperature and pressure are identical.

 In a preferred manner, use is made of the halide of the tetravalent element, the oxygenated organic solvent and then the dihalogenated phosphonate, optionally in a non-oxygenated, apolar or slightly polar organic solvent.

 At the end of the reaction, the product precipitates. It is separated and if desired, recrystallized as previously described.

 It should be noted that the phosphonates of the invention can be manufactured in various ways. The choice of the one more particularly will be guided according to the availability or accessibility of more or less of the starting reagents.

 The process of the invention is particularly advantageous because it makes it possible to prepare phosphonates of tetravalent elements which are sensitive to water, either because of the presence of a hydrocarbon radical carrying a function capable of hydrolyzing (for example ester or amide), or because the material itself is susceptible to hydrolysis and this is the case of silicon phosphonates.

 Examples of embodiments of the invention are given below.

Examples 1 to 5, 10, relate to a titanium phosphonate, Example 6, a zirconium phosphonate, Examples 7 and 9, a tin phosphonate,
Example 8, a silicon phosphonate.

 Examples 11 and 12 relate to the recrystallization of a tin phosphonate and a titanium phosphonate, respectively.

Example 1
Synthesis of titanium phenylphosphonate by reaction between titanium tetraisopropoxide and dichloroDhénvlDhosDhonate.

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb> Ti (OiPr) 4 <SEP> 1.60 <SEP> 9 <SEP><SEP> 0.004
<tb> PhPOCl <SEP> 1.13 <SEP> a <SEP><SEP> 0.008
<tb><SEP> CH2C12 <SEP> 5 <SEP> ml
<Tb>
The addition at 0 ° C. of titanium tetraisopropoxide to dichlorophenylphosphonate dissolved in dichloromethane gives a yellow-orange solution.

 The reaction is very exothermic.

 After 5 hours at 110 ° C, a light yellow monolithic gel is obtained.

 After aging at 110 ° C. for 91 hours, the gel is white and the syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 10 ml), the solid is dried under reduced pressure (10 mm Hg) at 100 ° C. for 3 hours.

 1.39 g of a white powder are collected, the analysis of which is given below.

Elemental analysis (percentages given in mass)

<tb><SEP>% Ti <SEP>% P <SEP><SEP>% O <SEP><SEP>% C <SEP>% H <SEP><SE>% CI <SEP>
<tb> found <SEP> 11.45 <SEP> 16.15 <SEP> 25.89 <SEP> 39.43 <SEP> 3.08 <SEP> 4.00
<tb> calculated <SEP> 13.30 <SEP> 17.23 <SEP> 26.68 <SEP> 40.01 <SEP> 2.78 <SEP> 0
<Tb>
The analysis corresponds to a product corresponding to the formula
TiP2,19O6.77C13,74H12,88Cl0,47 and which can be compared with the following theoretical formula: TiP2O6C12H1o.

X-ray energy dispersive spectroscopic analysis (Structural and chemical analysis of materials, J.-P. Eberhart, Ed. Dunod, Paris, 1989):

<tb><SEP> (P / Ti) <SEP> (Cl / Ti) <SEP> homogeneity
<tb> atomic <SEP> atomic <SEP> to <SEP> scale
<tb><SEP> average <SEP> average <SEP> microns <SEP> use <SEP>
<tb><SEP> 2.21 <SEP> 0.43 <SEP> homogeneous
<tb> Thermogravimetric analysis between room temperature and 1200 C 1200 C:

<tb><SEP> Amim * <SEP> (%) <SEP> observed <SEP> Am / m <SEP> (%)
<tb><SEP> between <SEP> 180 <SEP> and <SEP> 300 <SEP> C <SEP> observed <SEP> after <SEP> 400 C <SEP>
<tb><SEP> 2.3 <SEP> 40.5
<tb> Th. <SEP>: <SEP> Ti (O3Pph) 2 <SEP> TiP2O7 <SEP> 38.4
<tb> * = Am / m (%) is the mass loss relative to the starting mass.

 Nuclear magnetic resonance of phosphorus 31 in the solid state.

 The chemical shift of the majority peak is at -3.9 ppm.

 By X-ray diffraction an interlamellar distance of 15.1 is determined.

 The specific surface area determined by the BET method (S. BRUNAUER, P.H.

EMMETT, E. TELLER, J. Am. Chem. Soc., 1968, 309, 60) is 171 m 2 / g.

Example 2
Synthesis of titanium phenylphosphonate by reaction between titanium tetrachloride and dichlorophenyl-doponate in the presence of isopropyl ether.

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb><SEP> TiCl4 <SEP> 0.87 <SEP> g <SEP><SEP> 0.005
<tb> PhPOCl2 <SEP> 1.68 <SEP> g <SEP> 0.009
<tb><SEP> iPr20 <SEP> 2.5 <SEP> ml <SEP> 0.018
<tb><SEP> CHCl <SEP> 5 <SEP> ml
<Tb>
The addition at 0 ° C. of titanium tetrachloride to dichlorophenylphosphonate in solution in dichloromethane gives a yellow-orange solution.

 The reaction is very exothermic.

 The isopropyl ether is then added.

 After 24 hours at 00C, a clear yellow gel is obtained.

 After aging at 00C for 82 hours, the gel is still yellow.

The Li
The analysis corresponds to a product corresponding to the formula TiP2, o9O5,95C12,76H12,91Cl1,35 and which can be compared with the following theoretical formula: TiP2O6Cl2H10.

X-ray energy dispersion spectroscopic analysis (Structural and chemical analysis of materials, J.-P. Eberhart, Ed. Dunod, Paris, 1989):

<tb><SEP> (pee) <SEP> (Cl / Ti) <SEP> homogeneity
<tb> atomic <SEP> atomic <SEP> to <SEP> scale
<tb><SEP> medium <SEP> medium <SEP> micron
<tb><SEP> 2.14 <SEP> 1.30 <SEP> homogeneous
<Tb>
Thermogravymetric analysis between room temperature and 1200 C:

<tb><SEP># m / m * <SEP><SEP> (%) <SEP> observed <SEP># m / m <SEP><SEP> (%)
<tb><SEP> between <SEP> 180 <SEP> and <SEP> 300 <SEP> C <SEP> observed <SEP> at <SEP> 4000C
<tb><SEP> 5.7 <SEP> 36.8
<tb> Th. <SEP>: Ti (O3PPh) 2 <SEP>#, O2 <SEP>-><SEP> TiP2O7 <SEP> 38.4
<tb> * = Am / m (%) is the mass loss relative to the starting mass.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is at -3.3 ppm.

 By diffraction of ravons X. an interlamellar distance of 15.1 A. is determined.

 The specific surface area determined by the BET method is 500 m 2 / g.

Example 3
Synthesis of titanium phenylphosphonate by reaction between titanium tetrachloride and diisopropylphosphonate

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol) <SEP>
<tb><SEP> TiCI <SEP> 0.74 <SEP> a <SEP><SEP> 0.004
<tb><SEP> 0.008
<tb> PhPO (OiPr) 2 <SEP> 2.05 <SEP> g <SEP><SEP> 0.008
<tb><SEP> CH <SEP> I <SEP> 5m1 <SEP>
<Tb>
The addition at 0 ° C. of titanium tetrachloride to diisopropylphenylphosphonate dissolved in dichloromethane gives a yellow-orange solution.

 The reaction is very exothermic.

 After 24 hours at 110 ° C., a light yellow monolithic gel is obtained.

 After aging at 00C for 82 hours, the gel is white.

 The syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 10 ml), the solid is dried under reduced pressure (10 mm Hg) at 110 ° C. for 3 hours.

 1.38 g of a white powder are collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Ti <SEP>% P <SEP>% O <SEP><SEP>% C <SEP>% H <SE>% CI <SEP>
<tb> Found <SEP> 10.10 <SEP> 12.73 <SEP> 29.41 <SEP> 41.09 <SEP> 3.49 <SEP> 3.18
<tb> calculated <SEP> 13.30 <SEP> 17.23 <SEP> 26.68 <SEP> 40.01 <SEP> 2.78 <SEP> 0
<Tb>
The analysis corresponds to a product corresponding to the formula TiP1.9408.71 C16.23Hi6.54C10.47 and which can be compared with the following theoretical formula: TiP2o6C12H1o.

Energy dispersive spectroscopic analysis of X-rays

<tb><SEP> (P / Ti) <SEP> (CliTi) <SEP> homogeneity <SEP>
<tb> atomic <SEP> atomic <SEP> to <SEP> scale
<tb><SEP> medium <SEP> medium <SEP> micron
<tb><SEP> 1.99 <SEP> 0.44 <SEP> homogeneous
<Tb>
Thermogravimetric analysis between room temperature and 1200 C:

<tb><SEP> limim * <SEP> (%) <SEP> observed <SEP># m / m <SEP><SEP> (%)
<tb><SEP> between <SEP> 180 <SEP> and <SEP> 300 <SEP> C <SEP> observed <SEP> after <SEP> 400 C <SEP>
<tb><SEP> 8.4 <SEP> 36.0
<tb><SEP> a, <SEP> O2 <SEP>
<tb> Th. <SEP>: <SE> Ti (O3PPh) 2 <SEP> 2 <SEP> w <SEP> TiP207 <SEP> 38.4
<tb> * = Am / m (%) is the mass loss relative to the starting mass.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is -4.3 ppm.

 By X-ray diffraction an interlamellar distance of 14.9 is determined.

Example 4
Synthesis of titanium phenylphosphonate by rection between titanium tetrachloride and dichlorophenylphosphonate in the presence of an excess of tert-butanol.

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb><SEP> TiCl4 <SEP> 1.0 <SEP> ml <SEP> 0.009
<tb> PhPOCl2 <SEP> 2.6 <SEP> ml <SEP> 0.018
<tb> tBuOH <SEP> 15.0 <SEP> ml <SEP> 0.163
<Tb>
Titanium tetrachloride is dissolved in dichloromethane.

 The addition of tert-butanol is exothermic and is accompanied by a gassing and the formation of a light yellow precipitate.

 The dichlorophenylphosphonate is then added.

 There is then dissolution of the precipitate.

 The light yellow solution obtained is colored very quickly in purple then in green then thickens.

 After 24 hours at 110 ° C., a white gel is obtained The syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 5 ml), the solid is dried under reduced pressure (10 mm Hg) at 110 ° C. for 3 hours.

 2.65 g of a white powder are then collected, the analysis of which is given below.

Elementary analvse (percentages given in mass).

<Tb>

<SEP>% Ti <SEP>% P <SEP> I <SEP>% O <SEP>% C <SEP>% H <SEP><SEP>% CI <SEP>
<tb> found <SEP> 12.30 <SEP> 1 <SEP> 17.15 <SEP> 26.90 <SEP> I <SEP> 40.02 <SEP> 2.97 <SE> 0.66
<tb> calculated <SEP> 13.30 <SEP> 17.23 <SEP> 26.68 <SEP> 40.01 <SEP> i <SEP> 2.78 <SE> O <SEP>
<Tb>
The analysis corresponds to a product corresponding to the formula
TiP2,15O6,54C12,98H11,56Cl0,47 and which can be compared with the following theoretical formula: TiP2O6C12H1o.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is -4.0 ppm.

 By diffraction of ravons X, an interlamellar distance of 15.2 is determined.

Example 5
Synthesis of Titanium Methyl Dhosonate by Reaction Between Titanium Tetrasopropoxide and Dichloromethyl Phosphonate

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb> Ti (OiPr) <SEP> 4.92 <SEP> g <SEP> 0.035
<tb> MePOCI2 <SEP> 4.6 <SEP> 9 <SEP><SEP> 0.017
<tb><SEP> CH2Ch <SEP> 10 <SEP> ml
<Tb>
The addition at 0 ° C. of titanium tetraisopropoxide with dichloromethylphosphonate dissolved in dichloromethane gives a yellow solution.

 The reaction is very exothermic.

 After 5 hours at 00C, a light yellow monolith gel is obtained.

 After aging at 110 ° C. for 91 hours, the gel is white.

 The syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 10 ml), the solid is dried under reduced pressure (10 mm Hg) at 110 ° C. for 3 hours.

 3.69 g of a white powder are then collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Ti <SEP>% P <SEP>% O <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SEP>% H <SE>% CI <SEP>
<tb> found <SEP> 19.35 <SEP> 25.35 <SEP> 39.21 <SEP> 11.32 <SEP> 2.83 <SEP> 1.94
<tb> calculated <SEP> 20.34 <SEP> 26.27 <SEP> 40.68 <SEP> 10.17 <SEP> 2.54 <SEP> 0
<Tb>
The analysis corresponds to a product corresponding to the formula TiP2, o2O6.06C2.33H7, ooClo, 13 and which can be compared with the following theoretical formula: TiP2O6C2H6.

Thermogravimetric analysis between room temperature and 1000 C 1000 C:

<tb><SEP> i \ mim * <SEP> (%) <SEP> total <SEP> / vmim <SEP> (%)
<tb><SEP> observed <SEP> after <SEP> 400 C <SEP>
<tb><SEP> 7.1 <SEP> 1.2
<tb> Th. <SEP>: Ti (O3PMe) 2 <SEP>#, O2 <SEP>-><SEP> TiP2O7 <SEP><SEP> 5.9
<tb> * = Am / m (%) is the mass loss relative to the starting mass.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is at 8.5 ppm.

 By X-ray diffraction, an interlamellar distance of 9.4 is determined.

 The specific surface area determined by the BET method is 640 m 2 / g.

Example 6
Synthesis of zirconium phenylphosphonate by reaction between zirconium tetraethoxide and dichloroDhenylphosphonate

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb> PhPOCl2 <SEP> 1.49 <SEP> g <SEP><SEP> 0.008
<tb> Zr (OEt) <SEP> 1.03 <SEP> a <SEP><SEP> 0.004
<tb><SEP> CH <SEP> I <SEP> 6 <SEP> ml
<Tb>
Zirconium tetraethoxide is only partially soluble in dichloromethane, the addition of dichlorophenylphosphonate results in slight exotherm.

 After 25 hours at 1500C, a brown monolithic gel is obtained.

 The syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 5 ml), the solid is dried under reduced pressure (10 mm Hg) at 150 ° C. for 3 hours.

 1.66 g of a light brown powder are collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Zr <SEP>% P <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SE>% H <SEP>
<tb> Found <SEP> 19.00 <SEP> 13.30 <SEP> 23.18 <SEP> 34.86 <SEP> 2.82 <SEP> 6.84
<tb> calculated <SEP> 22.62 <SEP> 15.38 <SEP> 23.81 <SEP> 35.71 <SEP> 2.48 <SEP> 0
<Tb>
The analysis corresponds to a product corresponding to the formula
ZrP2.06O6.96C13.95H13.54C10.93 and which can be compared with the following theoretical formula: zrp2o6c12H1o.

 Nuclear magnetic resonance of phosphorus 31 in the solid state.

The chemical shift in ppm is: -3.3 (50% integration)
6.0 (integration 50%).

 By diffraction of ravons X, an interlamellar distance of 14.3 A.

Example 7
Synthesis of tin phenylphosphonate by reaction between tin tetrachloride and dichlorophenylphosphonate in the presence of isopropyl ether.

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb><SEP> PhPOCi2 <SEP> 4.95 <SEP> g <SEP> 0.011
<tb><SEP> SnC4 <SEP> 11.4 <SEP> ml <SEP> 0.023
<tb> (1 <SEP> mol <SEP> in <SEP> CH2C12)
<tb><SEP> iPr <SEP> O <SEP> 6.7 <SEP> ml <SEP> 0.048
<Tb>
The dichlorophenylphosphonate is added to the tin tetrachloride dissolved in dichloromethane.

 The reaction is exothermic, a white precipitate appears.

 The addition of isopropyl ether makes it possible to dissolve this precipitate.

 After 15 hours of heating at 150 ° C, a brown precipitate appears.

 The syneresis liquid is light brown.

 After 121 hours at 1500 ° C., this precipitate is separated from the syneresis liquid and washed with dichloromethane (3 × 10 ml) and then dried under reduced pressure (10 mm Hg) at 150 ° C. for 3 hours.

 2.75 g of a brown powder are then collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Sn <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SE>% CI <SEP>
<tb> found <SEP> 24.25 <SEP> 14.10 <SEP> 22.15 <SEP> 32.72 <SEP> 2.60 <SEP> 4.61
<tb> calculated <SEP> 27.56 <SEP> 14.40 <SEP> 22.29 <SEP> 33.43 <SEP> 2.32
<Tb>
The analysis corresponds to a product corresponding to the formula
SnP2,23O6,78C13,35H12,73Cl0,64 and which can be compared with the following theoretical formula: SnP206C12H1o.

 Nuclear magnetic resonance of tin 119 in the solid state.

 The chemical shift is at -222.9 ppm.

 Nuclear magnetic resonance of phosphorus 31 in the solid state.

 The chemical shift of the majority peak is 4.5 ppm.

 By X-ray diffraction, an interlamellar distance of 16.1 is determined.

Example 8
Synthesis of silicon methylphosphonate by reaction between tetraethoxysilane and dichloromethylphosphonate.

The amounts of reagents and solvent are specified in the table
following:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb> MePOCI2 <SEP> 3.819 <SEP> 0.029
<tb> Si (OEt) 4 <SEP> 2.92 <SEP> g <SEP> 0.014
<Tb>
The tetraethoxysilane is added to the dichloromethylphosphonate.

 After 24 hours at 150 ° C, a brown precipitate is obtained.

 There is no syneresis fluid.

 After washing with dichloromethane (3 × 5 ml), the solid is dried under reduced pressure (10 mm Hg) at 150 ° C. for 3 hours.

 2.44 g of a light brown powder are collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% If <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SE>% Cl <SEP>
<tb> found <SEP> 13.55 <SEP> 25.70 <SEP> 44.52 <SEP> 12.24 <SEP> 3.69 <SE> 0.30
<tb> calculated <SEP> 12.96 <SEP> 28.70 <SEP> 44.44 <SEP> 11.11 <SEP> 2.77
<Tb>
The analysis corresponds to a product corresponding to the formula
SiP1,79gO5,77C2,11H7,64Cl0,02 and which can be compared to the following theoretical formula: SiP206C2H6.

 Nuclear Magnetic Resonance of Silicon 29 in the Solid State.

 The chemical shift is -212.9 ppm.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is at -5.0 ppm.

By X-ray diffraction, an interlamellar distance of
7.3 A.

Example 9
Synthesis of tin methylphosphonate by reaction between tetrachloride
of tin and dichloromethylphosphonate in the presence of isopropyl ether.

The amounts of reagents and solvent are specified in the table
following:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb><SEP> MePOCI <SEP> 2.34 <SEP> g <SEP><SEP> 0.018
<tb><SEP> SnC4 <SEP> 9.0 <SEP> mi <SEP> 0.009
<tb> (1 <SEP> mol <SEP> in <SEP> CH2Cl2) <SEP>
<tb><SEP> iPr <SEP> 5.0 <SEP> ml <SEP> 1 <SEP> 0.035
<Tb>
The addition of dichloromethylphosphonate to tin tetrachloride dissolved in dichloromethane is slightly exothermic.

 The isopropyl ether is then added.

 After 1 hour of heating at 150 C, a white monolithic gel appears.

 The syneresis liquid is colorless.

 After 25 hours at 1500C, this gel is separated from the syneresis liquid and washed with dichloromethane (3 × 10 ml) and then dried under reduced pressure (10 mm Hg) at 150 ° C. for 3 hours.

 2.86 g of a white powder (solid A) are collected, the analysis of which is given below.

Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Sn <SEP>% Sn <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SE>% Cl <SEP>
<tb> found <SEP> 31.15 <SEP> 16.70 <SEP> 31.89 <SEP> 8.87 <SEP> 2.58 <SEP> 8.75
<tb> calculated <SEP> 38.70 <SEP> 20.22 <SEP> 31.30 <SEP> 7.82 <SEP> ~ <SEP><SEP> 1.96
<Tb>
The analysis corresponds to a product corresponding to the formula
SnP2, o507.59C2.82Hg, 83C10.92 and which can be compared with the following theoretical formula: SnP206C2H6.

Nuclear magnetic resonance of tin 119 in solid state:
The chemical shift is at -222.9 ppm.

 Nuclear magnetic resonance of phosphorus 31 in the solid state.

 The chemical shift of the majority peak is at 14.4 ppm.

 By diffraction of ravons X, an interlamellar distance of 10.4 A.

Example 10
Synthesis of titanium phenylphosphonate by reaction between titanium tetraisopropoxide and dichlorophenylphosphonate

The amounts of reagents and solvent are specified in the following table:

<tb><SEP> reagents <SEP> quantities <SEP> n <SEP> (mol)
<tb> Ti (OiPr) 4 <SEP> 1.60 <SEP> 9 <SEP><SEP> 0.004
<tb> PhPOC12 <SEP> 1.13 <SEP> g <SEP> 0.008
<tb><SEP> CH2C12 <SEP> ml <SEP>
<Tb>
The addition at 0 ° C. of titanium tetraisopropoxide to dichlorophenylphosphonate in solution in dichloromethane gives a yellow-orange solution.

 The reaction is very exothermic.

* After 1 hour at 1500C, a light yellow monolithic gel is obtained.

 After aging at 1500C for 25 hours, the gel is white.

 The syneresis liquid is colorless.

 After separation of the syneresis liquid and washing with dichloromethane (3 × 10 ml), the solid is dried under reduced pressure (10 mm Hg) at 1500 ° C. for 3 hours.

 1.35 g of a white powder (solid B) are collected, the analysis of which is given below.

Elementary analysis (percentages given in mass).

<Tb>

<SEP>% Ti <SEP>% P <SEP>% O <SEP> 96C <SEP>% H <SE>% CI <SEP>
<tb> Found <SEP> 13.40 <SEP> 17.25 <SEP> 24.04 <SEP> 39.93 <SEP> 2.83 <SE> 2.55
<tb> calculated <SEP> 13.30 <SEP> 17.23 <SEP> 26.68 <SEP> 40.01 <SEP> 2.78 <SEP> 0
<Tb>
The analysis corresponds to a product corresponding to the formula
TiP1,99O5,37C11,89H10,11Cl0,28 and which can be compared with the following theoretical formula: TiP2O6Cl2H10.

Thermogravimetric analysis between room temperature and 1200 C 1200 C:

<tb><SEP> brn / m <SEP> * (%) <SEP> observed <SEP>: 'm! tn <SEP> (%)
<tb><SEP> between <SEP> 200 <SEP> and <SEP> 250 <SEP> C <SEP> total
<tb><SEP> 2.9 <SEP> 35.8
<tb><SEP>#,<SEP> O2
<tb> Th.:Ti(O3PPh)2 <SEP> - <SEP>#<SEP> TiP2O7 <SEP><SEP> 38.4
<tb> * = am / m (%) is the mass loss relative to the starting mass.

Nuclear magnetic resonance of phosphorus 31 in solid state:
The chemical shift of the majority peak is -4.0 ppm.

 By X-ray diffraction an interlamellar distance of 15.9 is determined.

 The specific surface area determined by the BET method is 350 m2ig.

Example 11
Recrystallization in tert-butanol of tin methylphosphonate.

 500 mg (1.6 mmol) of tin methylphosphonate synthesized in Example 9 (solid A) is suspended in 3.5 ml of tert-butanol (37.9 mmol).

 The whole is then heated in a sealed tube at 110 ° C for one week.

 The solid is then separated from the liquid and washed with dichloromethane and dried under reduced pressure (10 mm Hg) at 110 ° C for 3 hours.

484 mg of a white powder is then collected, the analysis of which is given below:
Nuclear magnetic resonance of phosphorus 31 in the solid state:
The chemical shift of the majority peak is at 14.4 ppm.

 By X-ray diffraction an interlamellar distance of 10.4 ° is determined.

Figure 1: diffractograrrirnes of powder.

Theta (degree)
Example 12
Recrystallization in tert-butanol of titanium dhénylphosphonate.

 600 mg (1.6 mmol) of titanium phenylphosphonate synthesized in Example 10 (solid B) is suspended in 3.5 ml of tert-butanol (37.9 mmol).

 The whole is then heated in a sealed tube at 110 ° C for one week.

 The solid is then separated from the liquid and then washed with dichloromethane and dried under reduced pressure (10 mm Hg) at 1100C for 3 hours.

580 mg of a white powder is then collected, the analysis of which is given below:
Elemental analysis (percentages given in mass).

<Tb>

<SEP>% Ti <SEP>% Ti <SEP>% P <SEP>% O <SEP>% C <SEP>% H <SE>% CI <SEP>
<tb> found <SEP> 12.10 <SEP> 17.65 <SEP> 27.17 <SEP> 40.07 <SEP> 2.81 <SEP><0.20<SEP>
<tb> calculated <SEP> 13.30 <SEP> 17.15 <SEP> 26.68 <SEP> 40.01 <SEP> 2.78 <SE> 0
<Tb>
The analysis corresponds to a product corresponding to the formula
TiP2,25O6,72C13,20H11,12Cl <0,02 and which can be compared with the following theoretical formula: TiP206C12H10.

 Nuclear magnetic resonance of phosphorus 31 in the solid state.

 The chemical shift of the majority peak is -4.2 ppm.

By X-ray diffraction, an interlamellar distance of
15.1 A.

Theta (degree)

Claims (30)

 optionally substituted having from 1 to 40 carbon atoms.  R represents a hydrogen atom or a monovalent hydrocarbon radical,  of the periodic table,  M represents a tetravalent element belonging to groups (IVa) or (IVb)  M (03PR) 2 (I) in which:  1 - tetravalent element phosphonate corresponding to the general formula (I): 2 - Phosphonate according to claim 1, characterized in that it corresponds to the formula (I) in which M represents an element of the group (IVa), preferably titanium, zirconium, hafnium or an element of the group (IVb), preferably silicon, germanium, tin and lead. 3 - Phosphonate according to claim 1 characterized in that it corresponds to the formula (I) wherein M represents titanium, zirconium, tin or silcium. 4- Silicon phosphonate corresponding to formula (I '):  If (O3PR) 2 (I ') in which R has the meaning given above in claim 1. 5 - phosphonate of silicon according to claim 4 characterized in that it comprises a hexacoordinated silicon atom. 6 - Phosphonate according to one of claims i to 5 characterized in that it corresponds to the formula (I) wherein R represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon radical which may be an aliphatic radical acyclic saturated or unsaturated, linear or branched; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic radical. 7- Phosphonate according to one of claims 1 to 6 characterized in that it corresponds to formula (I) wherein R represents a linear or branched acyclic aliphatic radical, saturated or unsaturated. 8. Phosphonate according to claim 7, characterized in that it corresponds to formula (I) in which R represents a linear or branched acyclic aliphatic radical preferably having from 1 to 12 carbon atoms, saturated or comprising one to more unsaturations. on the chain, generally, 1 to 3 unsaturations which can be single or conjugated double bonds or triple bonds the hydrocarbon chain possibly being:  - interrupted by one of the following groups Z: -O-; -CO-; COO; -NR1-; -CO-NR 1; -S-; -SO2- -N; -NR1-CO-;  in said formulas R1 represents a hydrogen atom, an alkyl group  linear or branched having 1 to 6 carbon atoms, preferably a  methyl or ethyl radical,  andlor carrying one of the following substituents:  -OH; -COOH; -COOX; -CO-N (R1) (R2) -COOR1; -CHO; -COR 1; -NO 2; -X;  -CF3.  previously.  in these formulas, R2 having the same meaning as R1 given 9 - Phosphonate according to one of claims 1 to 8 characterized in that it corresponds to the formula (I) wherein R represents a linear or branched, saturated or unsaturated, acyclic aliphatic radical which may optionally carry a substituent cyclic: said acyclic aliphatic radical can be connected to the ring by a valency bond or by one of the groups Z cited above in claim 8. 10 - phosphonate according to one of claims 1 to 6 characterized in that it corresponds to formula (I) wherein R represents a carbocyclic radical saturated or comprising 1 or 2 unsaturations in the ring, generally having 3 to 7 carbon atoms, preferably 6 carbon atoms in the ring. 11 - Phosphonate according to one of claims 1 to 6 characterized in that it corresponds to the formula (I) wherein R represents an aromatic carbocyclic radical. and in particular benzenial acid, which is redundant with the general formula (II):

 in said formula (II):  n is an integer from 0 to 5, preferably from 0 to 3,  Q represents R3, one of the following groups or functions: a linear or branched alkyl radical having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isopropyl; , butyl, isobutyl, sec-butyl, tert-butyl, a linear or branched alkenyl radical having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl, a linear alkoxy radical or branched group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, an acyl group having 2 to 6 carbon atoms, a radical of the formula:  -R5-OH  -R 5 COOR 7  -R5-CHO -R5-NO2  -R5-CN  -R5-N (R7) (R8)  -R5 -CO-N (R7) (R8)  -R5-S H  -R 5 X  - R5-CF3 in said formulas R5 represents a valency bond or a divalent hydrocarbon radical, linear or branched, saturated or unsaturated, having 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene; the radicals R7 and R8, which are identical or different, represent a hydrogen atom or a linear or branched alkyl radical having from 1 to 6 carbon atoms; X symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.  a methyl or ethyl radical.  linear or branched alkyl having from 1 to 6 carbon atoms, preferably  in said formulas R7 represents a hydrogen atom, a group  wherein: - m is an integer from 0 to 5, preferably from 0 to 3, Ro having the meaning given above for R3,. R6 represents a valency bond; a divalent, linear or branched, saturated or unsaturated hydrocarbon group having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene or one of the following groups designated Z: -O-; -CO-; COO; -NR7-; -CO-NRR; -S-; -SO2-; -NR7-CO-;

Q represents RAI one of the following more complex radicals: 12 - Phosphonate according to one of claims 1 to 6, characterized in that it corresponds to the formula (I) wherein R represents a polycyclic aromatic hydrocarbon radical; the cycles can form between them ortho-condensed, ortho- and peri-condensed systems. or a saturated, unsaturated or aromatic heterocyclic radical containing in particular 5 or 6 atoms in the ring, including 1 or 2 heteroatoms such as nitrogen, sulfur and oxygen atoms. 13 - Phosphonate according to one of claims 1 to 6 characterized in that it corresponds to the formula (I) wherein R represents a linear or branched alkyl radical having from 1 to 6, preferably 1 to 4 atoms of carbon optionally carrying an acid, amide or ester function, or a phenyl radical. Characterized in that it corresponds to the formula (II ') in which R represents a linear or branched alkyl radical having from 1 to 6, preferably 1 to 4 carbon atoms or a phenyl radical. 15 - Process for preparing a tetravalent element phosphonate described in one of claims 1 to 14 characterized in that it consists in reacting in an anhydrous medium, an organic phosphonate and a tetravalent element halide. 16 - Process for preparing a tetravalent element phosphonate described in one of claims 1 to 14 characterized in that it consists in reacting in an anhydrous medium, a dihalogenated organic phosphonate and a tetravalent element alkoxide. 17 - Process for preparing a tetravalent element phosphonate described in one of claims 1 to 14, characterized in that it consists in reacting in an anhydrous medium, a dihalogenated organic phosphonate and a tetravalent element halide, in the presence of an organic solvent, oxygenated, polar. 18 - Process according to claim 15, characterized in that an organic phosphonate corresponding to formula (III) is reacted:  R-PO- (OR ') 2 (III) in said formula (III):  R has the meaning given above,  R 'is a hydrocarbon group of any kind, and - a tetravalent element halide (IV):  MX4 (IV) in said formula (IV):  X represents a halogen atom such as chlorine, bromine and iodine,  preferably, chlorine,  M represents a tetravalent element belonging to groups (IVa) or (IVb)  of the periodic table. 19 - Process according to claim 18, characterized in that a dimethylphenylphosphonate, a dimethylethylphosphonate, a diethylphenylphosphonate and a halide of formula (IV), TiCl4, TiBr4, Tri4, ZrCl4, ZrBr4, Zr4, SnCl4 and SnBr4 are reacted. SnCl4, SiCl4, SiBr4, Si4. 20- Process according to claim 16 characterized in that it consists in reacting a dihalogenated organic phosphonate corresponding to formula (V):  R-PO- (X) 2 (V) in said formula (\ /):  R has the meaning given above,  X represents a halogen atom such as chlorine, bromine and iodine,  preferably, chlorine, and - a tetravalent element alkoxide (VI):  M (OR ') 4 (VI) in said formula (VI):  R 'is a hydrocarbon group of any kind,  M represents a tetravalent element belonging to groups (IVa) or (IVb)  of the periodic table. 21- A method according to claim 17 characterized in that it consists in reacting, in the presence of an organic solvent, oxygenated, polar, a dihalogenated organic phosphonate corresponding to formula (V):  R-PO- (X) 2 (V) in said formula (V):  R has the meaning given above,  X represents a halogen atom such as chlorine, bromine and iodine,  preferably, chlorine, and - a tetravalent element halide (IV):  MX4 (IV) in said formula (IV):  X represents a halogen atom such as chlorine, bromine and iodine,  preferably, chlorine,  M represents a tetravalent element belonging to groups (IVa) or (IVb)  of the periodic table. 22- Method according to one of claims 15 to 21 characterized in that the reactants of formula (III) to (VI) are implemented in an amount close to the stoichiometry, namely 90 to 120% of the stoichiometric amount. 23- A method according to claim 22 characterized in that it implements a propylene organic solvent slightly or slightly polar. 24. A process according to claim 23, characterized in that the organic solvent is chosen from aliphatic or aromatic hydrocarbons, halogenated or not, preferably dichloromethane or p-xylene. 25 - Method according to one of claims 15 to 24 characterized in that the temperature at which the reaction is carried out is chosen in a temperature range from room temperature to 200 "C, preferably between 100" C and 1500C. 26 - Process according to one of claims 15 to 25, characterized in that the reaction is carried out under atmospheric pressure or at pressures greater than atmospheric pressure, ranging from 1 to 10 bar, and preferably located between 5 and 20 bar. 27- Process according to claim 17, characterized in that an oxygen-containing organic solvent is used chosen from aliphatic, cycloaliphatic or aromatic ether-oxides and, more particularly, diethyloxide, Dipropyloxide, diisopropyloxide, dibutyloxide, methyltertiobutylether, dipentyloxide, diisopentyloxide, ethyleneglycol dimethylether (or 1,2-dimethoxyethane), dimethylether diethylene glycol (or 1,5-dimethoxy-3-oxapentane); Biphenyl or benzyloxide; dioxane, tetrahydrofuran (THF) or alcohols, preferably aliphatic alcohols, preferably secondary or tertiary, having at least 3 carbon atoms and more preferably tert-butanol. 28 - Method according to one of claims 15 to 27 characterized in that one proceeds to an operation of recrystallization of the phosphonate obtained in an organic solvent. 29- A method according to claim 28 characterized in that the solvent is selected from alcohols, preferably aliphatic and more particularly secondary or tertiary alcohols. 30 - Process according to claim 29, characterized in that the solvent is tert-butanol.