Materials comprising organic groups containing sulphur and phosphorous bonded to a mineral oxide via oxygen atoms

The invention describes materials comprising organic groups containing sulphur and phosphorous bonded together by a hydrocarbon chain and bonded via phosphorous and oxygen atoms to a mineral oxide of an element M, said materials being characterized in that they comprise M—O—M′ bonds, M′ representing an element of a mineral oxide identical to or different from M, in that the ratio of the element M to the phosphorous is about 0.5: 1 to about 500:1 and in that each phosphorous atom of the phosphorous-containing groups forms at least one P—O—M bond and/or P—O—M′ bond. The invention also describes a process for preparing such materials.

EXAMPLE 1 In this example, a functionalised solid was prepared containing a bromo group that was then transformed into a functionalised solid containing a thiol group. In a first step, the Arbuzov reaction (J. March, Advanced Organic Chemistry, 3 rd Edition, John Wiley & Sons, New York, 1985, p. 848) was used to prepare a phosphonate with formula Br(CH 2 ) 3 PO 3 Et 2 (I′). The second step of this preparation was hydrolysis of the P—OEt bonds to a P—OH bond that produced phosphonic acid with formula Br(CH 2 ) 3 PO 3 H 2 (I). P(OEt) 3 &plus;Br—(CH 2 ) 3 —Br→Br(CH 2 ) 3 PO 3 Et 2 &plus;EtBr Br(CH 2 ) 3 PO 3 Et 2 &plus;2HCI→Br(CH 2 ) 3 PO 3 H 2 &plus;2 EtCl 1 equivalent of triethylphosphite and 1.5 equivalents of 1,3-dibromopropane were introduced into a reactor in a nitrogen atmosphere. The reactor was heated to 140° C. and held at that temperature, with stirring, for 24 h. After distilling at a pressure of 0.1 millibars (mbar) (10 pascals) at an average column bottom temperature of 90° C., diethylbromopropylphosphonate with formula Br(CH 2 ) 3 PO 3 Et 2 (I′) was obtained in a yield of 60 mole % with respect to the triethylphosphite introduced. This compound with formula (I′) was then heated under reflux for 24 hours in concentrated hydrochloric acid (HCl) then after evaporation at a pressure of 10 mbar at a temperature of 90° C. for 1 hour. Re-crystallisation from acetonitrile produced the phosphonic acid with formula Br(CH 2 ) 3 PO 3 H 2 (I) was obtained. 2.028 g, i.e., 0.01 moles, of the phosphonic acid with formula (I), Br(CH 2 ) 3 PO 3 H 2 , dissolved in 15 milliliters (ml) of dry tetrahydrofuran (THF) was introduced into a reactor at ambient temperature, then 0.03 moles, i.e., 8.53 g, of tetraisopropoxytitanate with formula Ti(O 1 Pr) 4 was introduced in a nitrogen atmosphere, with stirring. 0.05 moles, i.e., 0.9 g of water diluted in 10 ml of THF was then added dropwise. After stirring for 2 hours at ambient temperature, the solid obtained was washed successively with THF, methanol then acetone. This solid was then dried at a pressure of 0.05 mbar at 100° C. for 5 hours to produce a solid A. Solid A was then functionalised using the procedure given below using a conventional reaction for replacing a halogen atom by a thiol atom described in the book by J. March, Advanced Organic Chemistry, 3 rd Edition, John Wiley & Sons, New York, 1985, p. 360. 1.3 g of solid gel A was added to 0.56 g, i.e. 10 millimoles, of sodium hydrosulphide in solution in 25 ml of methanol in a reactor. This was then heated under reflux for 10 hours in a nitrogen atmosphere. After filtering, a solid was recovered that was washed successively with methanol, water and acetone. The solid was then dried at a pressure of 0.05 mbars at 100° C. for 5 hours to produce a solid B. Elemental analysis of solid B gave the following results: Ti, 31.9%; P, 6.1%; S, 4.4%, Br, less than 0.1%. The Ti/P ratio was 3.4 and the S/P ratio was 0.7. The phosphorous-31 NMR spectrum of solid B (see FIG. 1 ) carried out using a 300 MHz Bruker Avance apparatus showed a broad peak at 26.2 ppm corresponding to phosphonate groups bonded to titanium atoms; the carbon-13 NMR spectrum of solid B, carried out using a 300 MHZ Bruker Avance apparatus, showed three peaks at 25.9 ppm, 22.2 ppm and 39.3 ppm, corresponding to three methylene groups in the P—CH 2 —CH 2 —CH 2 -—S concatenation. 
 EXAMPLE 2 In this example, a functionalised solid containing a sulphonic acid group was prepared. In a first step, the phosphonate with formula Br(CH 2 ) 3 PO 3 Et 2 (I′) was prepared using the procedure described above. This phosphonate was then functionalised using the procedure given below using a conventional reaction for replacing a halogen atom by a sulphonate group as described in the book by J. March, Advanced Organic Chemistry, 3 rd Edition, John Wiley & Sons, New York, 1985, p. 363, to obtain the phosphonate with formula NaSO 3 (CH 2 ) 3 PO 3 Et 2 (II). The last step of this preparation was hydrolysis of the P—OEt bonds to a P—OH bond to produce the phosphonic acid with formula HSO 3 (CH 2 ) 3 PO 3 H 2 (II′). Br(CH 2 ) 3 PO 3 Et 2 &plus;Na 2 SO 3 →NaSO 3 (CH 2 ) 3 PO 3 Et 2 &plus;NaBr NaSO 3 (CH 2 ) 3 PO 3 Et 2 &plus;2HCl→HSO 3 (CH 2 ) 3 PO 3 H 2 &plus;2 Et 0.1 equivalents (25.91 g) of diethyl bromopropylphosphonate Br(CH 2 ) 3 PO 3 Et 2 (I′) was added to a boiling solution of 0.13 equivalents (12.61 g) of sodium sulphite NaSO 3 in 50 ml of water in a reactor in a nitrogen atmosphere. After refluxing for 1 hour, the solution was cooled then eluted through a Dowex 50W-X8 (H &plus; ) resin. After evaporation under reduced pressure (15 mbar) at 100° C., an oil was obtained which was refluxed for 24 hours in concentrated hydrochloric acid (HCl) (32% by weight). After evaporation under reduced pressure (15 mbar) at 100° C., a viscous liquid was obtained. This liquid was taken up in 250 ml of boiling water. The solution obtained was eluted through Dowex 50W-XB (H &plus; ) resin. The precipitate obtained was filtered, then taken up in 250 ml of water and concentrated hydrochloric acid was added to dissolve it. The solution obtained was eluted through a Dowex 50W-X8 (H &plus; ) resin. After evaporation under reduced pressure (10 mbar) at 90° C. then under reduced pressure (0.05 mbar) at 90° C. for 15 hours, a phosphonic acid with formula HSO 3 (CH 2 ) 3 PO 3 H 2 (II′) was obtained. 1.56 g, i.e., 0.01 moles, of phosphonic acid with formula HSO 3 (CH 2 ) 3 PO 3 H 2 (II′) dissolved in 25 milliliters (ml) of dimethylsulphoxide (DMSO) was introduced into a reactor at ambient temperature then 0.05 moles, i.e., 14.21 g of tetraisopropoxytitanate with formula Ti(O 1 Pr) 4 was added, with stirring and in a nitrogen atmosphere. 0.1 moles, i.e., 1.8 g of water diluted in 15 ml of THF was then added dropwise. After stirring for 2 hours at ambient temperature, a solid was isolated by filtering and washed successively with THF, methanol, water and acetone. The solid was then dried at a pressure of 0.05 mbar at 100° C. for 5 hours to produce solid C. Elemental analysis of solid C gave the following results. Ti, 35.6%, P, 4.8%, S, 6.5. The Ti/P ratio was 4.8 and the S/P ratio was 0.8. The phosphorous-31 NMR spectrum of solid C (see FIG. 1 ) carried out using a 300 MHz Bruker Avance apparatus showed a broad peak at 25.1 ppm corresponding to phosphonate groups bonded to titanium atoms; the carbon-13 NMR spectrum of solid B, carried out using a 300 MHz Bruker Avance apparatus, showed three peaks at 26.2 ppm, 19.9 ppm and 53.1 ppm, corresponding to three methylene groups in the P—CH 2 —CH 2 —CH 2 —S concatenation. The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples. Also, the preceding specific embodiments are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. The entire disclosure of all applications, patents and publications, cited above and below, and of corresponding French application 00/06.803, are hereby incorporated by reference. From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.