EP2882758A1 - Polysilylierte organosilanverbindungen - Google Patents

Polysilylierte organosilanverbindungen

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Publication number
EP2882758A1
EP2882758A1 EP13734765.4A EP13734765A EP2882758A1 EP 2882758 A1 EP2882758 A1 EP 2882758A1 EP 13734765 A EP13734765 A EP 13734765A EP 2882758 A1 EP2882758 A1 EP 2882758A1
Authority
EP
European Patent Office
Prior art keywords
group
chosen
compound
formula
represent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP13734765.4A
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English (en)
French (fr)
Inventor
Michel Wong Chi Man
Xavier CATTOËN
Kristyna BÜRGLOVA
Jana HODACOVA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vysoka Skola Chemicko Technologicka V Praze
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Original Assignee
Vysoka Skola Chemicko Technologicka V Praze
Centre National de la Recherche Scientifique CNRS
Universite Montpellier 2 Sciences et Techniques
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
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Application filed by Vysoka Skola Chemicko Technologicka V Praze, Centre National de la Recherche Scientifique CNRS, Universite Montpellier 2 Sciences et Techniques, Ecole Nationale Superieure de Chimie de Montpellier ENSCM filed Critical Vysoka Skola Chemicko Technologicka V Praze
Publication of EP2882758A1 publication Critical patent/EP2882758A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings

Definitions

  • the present invention relates to a mono- or polyfunctional polysilyl organosilane compound, as well as to a process for its preparation.
  • the invention also relates to a functionalized organosilicon material derived from this compound.
  • Mono- or polyfunctional organosilane compounds are of major interest in many fields because they allow the manufacture of mono- or polyfunctionalized organosilicon materials, which may be in the form of powder, coating or polymer. They also make it possible to manufacture products in the form of functionalized particles, in particular functionalized nanoparticles, for example with an active remainder, which can in particular be released in a controlled manner under the action of one or more parameters.
  • the known compounds are monosilylated, polysilylated compounds in which the organic function is bridging, and comprising simple functionalities, such as amine, alcohol, thiol, halide, alkyl, alkylene, phenyl or phenylene derivatives.
  • a first object of the invention is to provide mono-or polyfunctional polysilyl organosilane compounds which overcome the problems of the state of the art and which provide a solution to all or part of the problems of the state of the art. technical.
  • Another object of the invention is to provide mono- or polyfunctional polysilyl organosilane compounds whose preparation process is easy to implement and high yield.
  • Another object of the invention is to provide polysilylated organosilane compounds for the preparation of mono- or polyfunctional organosilicon materials that may comprise one or more complex functionalities.
  • the subject of the present invention is a compound of formula (I)
  • ⁇ Z 1 represents a group of formula
  • ⁇ and Z 2 represents a group of formula
  • Z 1 and Z 2 simultaneously represent a group chosen from the groups R 7 R 8 Si (OH), R 9 Si (OH) 2 , Si (OH) 3 , R 7 R 8 SiO 1/2 , R 9 SiO or SiO 3/2 ;
  • R 1, R 2, R 3, R 4, R 5 and R 6, identical or different, represent a hydrogen atom, a Ci-C 6 alkyl, an aryl group, a Ci-C 6 alkoxy, a group C 3 -C 8 alkylene alkenyl;
  • ⁇ d, e, f, g, h, i, identical or different, represent 0, 1, 2, 3, 4, 5, 6;
  • ⁇ j, k, I, m, n, o, identical or different, represent 0, 1, 2, 3;
  • R 7, R 8 and R 9, identical or different, represent a group C-
  • ⁇ a is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12;
  • ⁇ B identical or different, represents a group -CR 12 R 13 or a group selected from the groups of formulas
  • ⁇ b represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12;
  • ⁇ V identical or different, represents a group selected from the groups of formulas
  • ⁇ c 0, 1, 2 or 3;
  • ⁇ Q identical or different, represents a hydrogen atom, a group
  • CIC-10 alkyl a C 1 -C 10 alkoxy group, a C 3 -C 10 cycloalkyl group, an aryl group; at least 2 groups Q and the carbon atoms to which they are bonded form a carbocycle with 5, 6, 7, 8, 9 or 10 carbon atoms, substituted or unsubstituted, aromatic or nonaromatic, saturated, partially or totally unsaturated, merged or unmerged;
  • ⁇ q is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12;
  • E 7 , E 8 , E 9 , E 10 , E 11 and E 12 identical or different, represent a group CR 14 R 15 , a group OCR 16 R 17 ;
  • ⁇ s, t, u and v identical or different, represent 0.1, 2, 3, 4, 5, 6;
  • T 1 and T 2 identical or different, represent a group (E 13 ) x Si (R 18 ) (R 19 ) (R 20 ); ⁇ E 13 represents a group - CR 21 R 22;
  • R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21 and R 22, identical or different, represent a hydrogen atom a C 1 -C 6 -alkyl group, a C 1 -C 6 -alkoxy group, a C 3 -C 8 -alkylene-alkenyl group, an aryl group, an aryloxy group;
  • ⁇ J represents an atom or a terminal group, an atom or a divalent group, trivalent, tetravalent, pentavalent or hexavalent, mono- or polyfunctional;
  • ⁇ p, w and x identical or different, represent 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12;
  • ⁇ Z " is an anion selected from halides, BF 4", B (Ph) 4 ", C0 3 2", R 23 C0 2 ", R 24 S0 3", S0 4 2 ", P0 4 3” HP0 3 2 ⁇ N0 3 " ;
  • ⁇ R 23 represents a group CC 3 alkyl or aryl group
  • ⁇ R 24 is a CC pack 3 alkyl, aryl or -CF 3;
  • the substituent groups may be present on one of the aryl groups forming the naphthyl residue or on each of the aryl groups forming the naphthyl residue.
  • the nitrogen atom binds with the remainder of the compound of formula (I).
  • the sulfur atom binds with the rest of the compound of formula (I).
  • the compound according to the invention may be a compound of formula (II)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , A, U, Q, V, B, a , b, c, d, e, f, g, h, i, j, k, I, m, n, o and q for the compound of formula (I) according to the invention apply to the compound of formula ( II) according to the invention.
  • the invention also provides a compound of formula (IIa) or (Mb)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , E 7 , E 12 , A, B, Q , a, b, c, d, e, f, g, h, i, j, k, I, m, n, o, p, q, w and J for the compound of formula (I) according to the invention apply to the compounds of formula (IIa) and (Mb) according to the invention.
  • the invention also provides a compound of formula (IIc) or (IId)
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , E 1 , E 2 , E 3 , E 4 , E 5 , E 6 , A, U, Q, V, B, a , b, d, e, f, g, h, i, j, k, I, m, n, o and q for the compound of formula (I) according to the invention apply to compounds of formula (IIc) and (lld) according to the invention.
  • the invention also provides a compound of formula (IIc), (IIf), (IIg) or (IIh)
  • the invention also provides a compound of formulas (III) to (VIII)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, may independently represent a hydrogen atom, a CrC 6 -alkyl group, an aryl group or a CrC 6 -alkoxy group; a C 3 -C 8 alkylene-alkenyl group;
  • - J 1 may represent a divalent, trivalent, tetravalent, pentavalent or hexavalent, mono- or polyfunctional atom or group;
  • y can represent 2, 3, 4, 5 or 6.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, may independently represent a hydrogen atom, a CrC 6 -alkyl group, an aryl group or a CrC 6 -alkoxy group; a C 3 -C 8 alkylene-alkenyl group;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, may independently represent a hydrogen atom, a CC 6 -alkyl group, a aryl group, a group -C 6 - alkoxy, C 3 -C 8 -alkylene-alkenyl;
  • - J 3 represents a trivalent atom or group, mono- or polyfunctional.
  • the invention also provides a compound of formulas (IIIc) or (IVc)
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, may independently represent a hydrogen atom, a C 6 -C 6 alkyl group, an aryl group or a C 1 -C 6 alkoxy group; a C 3 -C 8 -alkylene-alkenyl group;
  • R 7 , R 8 , R 9 , A, U, Q, V, B, a, b, c and q for the compound of formula (I) according to the invention apply to the compounds of formula (IX ), (X) and (XI) according to the invention.
  • the invention also provides a compound of formula (XII), (XIII) or (XIV), respectively obtained by polycondensation of a compound of formula (IX), (X) or (XI).
  • z may represent an integer ranging from 2 to 2,000,000.
  • R 7 , R 8 , R 9 , A, U, Q, V, B, a, b, c and q for the compound of formula (I) according to the invention apply to compounds of formulas (XII ), (XIII) and (XIV) according to the invention.
  • formulas (XII), (XIII) or (XIV) are units present within polymeric structures.
  • the compounds of formulas (XII), (XIII) or (XIV) represent monomers or oligomers for the preparation of other oligomers or polymers.
  • a and B represent a group - (CH 2 ) -;
  • Q represents a hydrogen atom
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a group Me or Et;
  • b represents 1, 2 or 3;
  • q 0, 1, 2, 3 or 4;
  • R 7 represents a methyl, ethyl or phenyl group
  • R 8 represents a methyl, ethyl or phenyl group
  • R 9 represents a methyl, ethyl or phenyl group
  • R 28 represents a methyl group or a phenyl group
  • R 29 represents a methyl group, a phenyl group or a -CF 3 group.
  • the compound according to the invention is a compound of formulas (II), (IIa), (Mb), (IIe), (IId), (IIe), (IIf), (IIg), (IIh) , (III), (IV), (V), (VI), (VII) or (VIII) in which:
  • a and B represent a group - (CH 2 ) -;
  • Q represents a hydrogen atom
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent a group Me or Et;
  • b represents 1, 2 or 3;
  • q 0, 1, 2, 3 or 4;
  • R 28 represents a methyl group or a phenyl group
  • R 29 represents a methyl group, a phenyl group or a -CF 3 group.
  • the compound according to the invention is a compound of formulas (II), (IIa), (Mb), (IIe), (IId), (IIe), (IIf), (IIg), (IIh) ), (III), (IV), (V), (VI), (VII) or (VIII) wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent an alkoxy group, preferably methoxy or ethoxy.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently represent an alkoxy group, j, k, I, m, n and o do not represent 0.
  • the compound according to the invention is a compound of formula (IX), (X), (XI), (XII), (XII) or (XIV) in which:
  • a and B represent a group - (CH 2 ) -;
  • Q represents a hydrogen atom
  • b represents 1, 2 or 3;
  • q 0, 1, 2, 3 or 4;
  • R 7 represents a methyl group, ethyl or phenyl
  • R 8 represents a methyl group, ethyl or phenyl
  • J, J 1 , J 2 , J 3 and J 4 may independently represent a mono- or polyfunctional group comprising at least one functional group chosen from a dye group, a catalyst group and a group allowing a molecular recognition, a biologically active group, a redox group, a hydrophilic group, a hydrophobic group, a decontaminating complexing group, a complexing catalyst group, a crosslinking group or a structuring group.
  • the functional group can be chosen from:
  • a coloring group chosen from an azo, triphenylmethane, a phthalein, a quinone, an indigoid, an azine, a porphyrin, a phthalocyanine, boron-dipyromethene, a naphthalimide, a polyaromatic, a pyrene, acridine, and their derivatives, a dye comprising a conjugated ⁇ system, a fluorescent dye or a phosphorescent dye;
  • a catalyst group chosen from proline, prolinamide, diaryl-prolinol, 1,1'-bis-2-naphthol, trans-1, 2-diaminocyclohexane, tartaric acid, 1,2-diphenylethylenediamine, bisoxazoline, phosphine-oxazoline, pyridine-bisoxazoline, triarylphosphine, diphosphine, imidazolium salt, N-heterocyclic metal-carbene complex, bipyridine, pyridine, phenanthroline, cyclopentadiene and derivatives thereof;
  • an oxido-reducing group chosen from a metallocene, 1,4 (4-aminophenyl) butadiene, a fullerene, a carbon nanotube and their derivatives;
  • hydrophobic group chosen from a group C Cso alkyl, unsubstituted or substituted by at least one fluorine atom, an aryl group;
  • a decontaminating complexing group chosen from an amine, an alcohol, a pyridine, a bipyridine, a triarylphosphine, a malonamide, a diacid, a diketone and their derivatives;
  • a complexing catalyst group chosen from a proline, a diarylprolinol and their derivatives
  • crosslinking group chosen from butadiene, butadiyne, an acrylate, a methacrylate, vinyl, styryl and their derivatives,
  • a structuring group chosen from a pyrrole, a thiophene, an alkylene or a phenylene.
  • J may represent a mono- or polyfunctional group comprising at least one functional group chosen from: a coloring group chosen from boron dipyromethene, a naphthalimide, a porphyrin, a phthalocyanine, an azo, an indigoid, a phthalein, a quinone and their derivatives;
  • a decontaminating complexing group chosen from an amine, an alcohol, a pyridine, a triarylphosphine, a malonamide, a diacid, a diketone and their derivatives;
  • a complexing catalyst group chosen from a proline, a diarylprolinol and their derivatives
  • an oxido-reducing group chosen from a metallocene
  • hydrophobic group chosen from a C1-C30 alkyl group, unsubstituted or substituted by at least one fluorine atom;
  • a structuring group chosen from a pyrrole or a thiophene.
  • J represents a group of formulas (J-1) to (J-46)
  • Cbz is meant a carboxybenzyl group.
  • Boc means a tert-butoxycarbonyl group.
  • the linkage with the triazole group is via an alkylene chain comprising from 0 to at 15, preferably from 0 to 12 units - (CH 2 ) -.
  • the number of -CF 2 - units ranges from 4 to 18.
  • J 2 may represent a mono- or polyfunctional group comprising at least one functional group chosen from:
  • a coloring group chosen from boron-dipyromethene, a porphyrin, a phthalocyanine, an azo, an indigoid, a phthalein, a quinone, triphenylmethane, a dye comprising at least one conjugated ⁇ system, a pyrene and their derivatives;
  • a decontaminating complexing group chosen from a pyridine, a bipyridine, a triarylphosphine, a malonamide, a diketone and their derivatives;
  • a group allowing a molecular recognition chosen from a melamine and its derivatives a catalyst group chosen from a binol, a 2,2'-bis (diphenylphosphino) -1,1'-benzaphthyl derivative (BINAP), a 2,2'-diamino-1,1'-binaphthyl derivative (BINAM); ), trans-1, 2-diaminocyclohexane, 1,2-diphenylethylene-1,2-diamine, tartaric acid and their derivatives;
  • an oxido-reducing group chosen from 1,4 (4-aminophenyl) butadiene, a metallocene and their derivatives;
  • hydrophobic group selected from a group Ci-C 30 alkyl, unsubstituted or substituted by at least one fluorine atom, an aryl group;
  • a structuring group chosen from a thiophene, an alkylene.
  • the linkage with the triazole groups is via an alkylene chain comprising 0 to 15, preferably from 0 to 12 units - (CH 2 ) -.
  • the number of units goes from 1 to 20.
  • J 3 can represent a mono- or polyfunctional group comprising at least one functional group chosen from:
  • a decontaminating complexing group chosen from a triarylphosphine and its derivatives
  • a structuring group such as phenylene.
  • J 3 represents a group of formulas (J 3 -1) to (J 3 -3)
  • the binding with the triazole groups is by an alkylene chain comprising from 0 to 15, preferably from 0 to 12 units - (CH 2 ) -.
  • J 4 can represent a mono- or polyfunctional group comprising at least one functional group chosen from: a dye group chosen from a porphyrin, a phthalocyanine, an azine, an azo, an indigo, a triphenylmethane, a polyaromatic and their derivatives;
  • a decontaminating complexing group chosen from a malonamide and its derivatives
  • a catalyst group chosen from trans-1, 2-diaminocyclohexane and 1,2-diphenylenediamine and their derivatives
  • an oxido-reducing group chosen from 1,4 (4-aminophenyl) butadiene and its derivatives;
  • a structuring group such as phenylene.
  • the linkage with the triazole groups is via an alkylene chain. comprising from 0 to 15, preferably from 0 to 12 units - (CH 2 ) -.
  • Another subject of the present invention relates to a process for the preparation of a compound of formula (II)
  • U represents a group U, U, U or U;
  • V represents a group V 2 , V 4 , V 6 or V 8 ;
  • U A represents a group chosen from groups of formula:
  • V A represents a group chosen from groups of formula.
  • the copper-based catalyst may be chosen from a halogenated derivative or a carbon-based derivative of copper.
  • halogenated derivatives of copper mention may be made of Cu iodide or copper iodide complexed with tris (1,2,3-triazolyl) methylamine, tris (1-benzyl-1H-1) , 2,3-triazol-4-yl) methylamine (TBTA), tris (1-tert-butyl-1H-1,2,3-triazol-4-yl) methylamine (TTTA) or tris ( benzimidazole) methyl amine (TBIA) (cf Hein et al, Chem Soc Rev., 2010, 39, 1302-1315).
  • Examples of copper carbon derivatives include the complex of the formula Cu (NHC) X wherein NHC is an N-heterocyclic carbene and X is a halogen
  • the copper-based catalyst is bromo tris (triphenylphosphine) copper (I) of formula [CuBr (PPh 3 ) 3 ] according to the invention, the compound (II) can be obtained from the reaction between equivalent of a compound of formula (XV) and (c + 1) equivalents of compound of formula (XVI) in solution.
  • c is identical to the definition of c defined for the compound of formula (XV) and can thus represent 0, 1, 2 or 3.
  • the solution comprises a mixture of solvents.
  • the solution comprises a 1: 1 mixture of dry tetrahydrofuran and triethylamine.
  • the molar concentration of compound of formula (XV) in the solution can range from 0.01 to 5 mol / l, preferably from 0.5 to 2 mol / l.
  • the molar concentration of compound of formula (XVI) in the solution may range from 0.01 to 5 mol / l, preferably from 0.5 to 2 mol / l.
  • the molar content of copper-based catalyst in the solution can range from 0.5 to 5% relative to the compound of formula (XV).
  • the reaction takes place at 100 ° C. under microwave irradiation (maximum power 200 W) for 1 to 20 minutes or between 15 and 25 ° C. for 24 hours.
  • Another subject of the present invention relates to a process for the preparation of a compound of formula (II)
  • U represents a group U 1 , U 3 , U 5 or U 7 ;
  • V represents a group V 1 , V 3 , V 5 or V 7 ;
  • V represents a group chosen from groups of formula:
  • the copper-based catalyst may be chosen from a halogenated derivative or a carbon-based derivative of copper.
  • halogenated derivatives of copper mention may be made of Cu iodide or copper iodide complexed with tris (1,2,3-triazolyl) methylamine, tris (1-benzyl-1H-1) , 2,3-triazol-4-yl) methylamine (TBTA), tris (1-tert-butyl-1H-1,2,3-triazol-4-yl) methylamine (TTTA) or tris ( benzimidazole) methyl amine (TBIA) (cf Hein et al, Chem Soc Rev., 2010, 39, 1302-1315).
  • Examples of copper carbon derivatives include the complex of the formula Cu (NHC) X wherein NHC is an N-heterocyclic carbene and X is a halogen
  • the copper catalyst is bromo tris (triphenylphosphine) copper (I) of formula [CuBr (PPh 3 ) 3 ]
  • the compound of formula (II) can be obtained from the reaction between an equivalent of compound of formula (XVII) and c + 1 equivalents of compound of formula (XVIII) in solution.
  • the definition of c is identical to the definition of c for the compound of formula (XVII) and can thus represent 0, 1, 2 or 3.
  • the solution comprises a mixture of solvents.
  • the solution comprises a 1: 1 mixture of dry tetrahydrofuran and triethylamine.
  • the molar concentration of compound of formula (XVII) in the solution can range from 0.01 to 5 mol / l, preferably from 0.5 to 2 mol / l.
  • the molar concentration of compound of formula (XVIII) in the solution may range from 0.01 to 5 mol / l, preferably from 0.5 to 2 mol / l.
  • the molar content of copper catalyst in the solution is from 0.5 to 5% relative to the compound (XVII).
  • the reaction takes place at 100 ° C. under microwave irradiation (maximum power 200 W) for 1 to 20 minutes or between 15 and 25 ° C. for 24 hours.
  • microwave irradiation maximum power 200 W
  • Another subject of the present invention relates to a process for the preparation of a compound of formula (XII) comprising the hydrolysis of a compound of formula (XIX)
  • R may represent a hydrogen atom, a C 1 -C 6 alkyl group, an aryl group, a C 1 -C 6 -alkoxy group or a C 3 -C 8 alkylene group. alkenyl.
  • the compound of formula (XII) can be obtained according to a method (P1).
  • the process (P1) comprises dissolving the compound of formula (XIX) in the presence of water, a catalyst and optionally in the presence of a surfactant.
  • the catalyst may be chosen from an acid catalyst, a basic catalyst or a nucleophilic catalyst.
  • the surfactant may be chosen from ammonium and phosphonium salts comprising at least one long alkyl chain, preferably the surfactant is sodium hexadecyl sulphate (SHS) containing 40% by weight of sodium steraryl sulphate. sodium relative to the total weight of the surfactant.
  • SHS sodium hexadecyl sulphate
  • the reaction can take place with or without an organic solvent.
  • the solvent may be chosen from water, alcohols comprising 1 to 8 carbon atoms, ethyl ether, THF, DMF or DMSO.
  • the alcohols comprising 1 to 8 carbon atoms are chosen from methanol, ethanol or propan-1-ol.
  • the reaction takes place at a temperature ranging from 20 to 100 ° C.
  • the reaction is conducted until a gel or a precipitate is obtained and then the final material is allowed to age for 2 to 7 days.
  • the compound of formula (XII) can also be obtained by a process (P2).
  • the process (P2) can lead to a siloxane-silica composite material of (IX) type, xSiO 2 , and siloxane-silsesquioxane (SQ) such as a composite (IX); BTSE-SQ or a composite (IX); BTSB-SQ.
  • a siloxane-silica composite material of (IX) type, xSiO 2 , and siloxane-silsesquioxane (SQ) such as a composite (IX); BTSE-SQ or a composite (IX); BTSB-SQ.
  • a composite (XII) -BTSE-SQ can be defined by the following formula:
  • a composite (XII) -BTSB-SQ can be defined by the following formula:
  • the compound of formula (XII) can be obtained by a process (P3).
  • the process (P3) comprises the co-hydrolysis of the compound of formula (XIX) with a source of silicone such as diethoxydimethylsilane.
  • the characteristics of the solvent, the catalyst and the temperature for the process (P1) apply to the process (P3).
  • the process (P3) can lead to a siloxane-silicone composite polymer of the type (XII) xMe 2 SiO.
  • Another subject of the present invention relates to a process for the preparation of a compound of formula (XIII) comprising the hydrolysis of a compound of formula (XX)
  • R 26 and R 27, identical or different, may represent a hydrogen atom, a C 6 -alkyl group, an aryl group, a group -C 6 - alkoxy, C 3 -C 8 -alkylene -alkenyl.
  • the compound of formula (XIII) can be obtained by the process (P1) or (P2) applied to the compound of formula (XX).
  • the process (P2) makes it possible to produce a siloxane-silica composite material of the type (XIII), xSiO 2 , and silicone-silsesquioxane (SQ) such as a composite (XI II); BTSE-SQ or a composite (XIII); BTSB-SQ.
  • a siloxane-silica composite material of the type (XIII), xSiO 2 , and silicone-silsesquioxane (SQ) such as a composite (XI II); BTSE-SQ or a composite (XIII); BTSB-SQ.
  • Another subject of the present invention relates to a process for the preparation of a compound of formula (XIV) comprising the hydrolysis of a compound of formula (XXI)
  • R, R and R which may be identical or different, may represent a hydrogen atom, a C 1 -C 6 -alkyl group, an aryl group or a C 1 -C 6 -alkoxy group, a C 3 -C 8 -alkylene-alkenyl group.
  • the compound of formula (XIV) can be obtained by the process (P1) or (P2) applied to the compound of formula (XXI).
  • the process (P2) can lead to a siloxane-silica composite material of (XIV) type), xSiO 2 , and siloxane-silsesquioxane (SQ) such as a composite (XIV)); -SQ or a composite (XIV)); BTSB-SQ.
  • XIV siloxane-silica composite material of (XIV) type
  • xSiO 2 siloxane-silsesquioxane
  • SQ siloxane-silsesquioxane
  • the NMR spectra were obtained in solution on Bruker instruments operating at 400 or 250 MHz, in CDCI 3 dry at 298 K.
  • Solid state NMRs were measured on a Varian ASX400 instrument.
  • the high resolution mass spectra were made by electrospray ionization. Infrared spectra were obtained by ATR on a Perkin 100 spectrometer.
  • Table I shows the structures of the organic azides used and the structures of the corresponding polysilyl organosilane compounds 2 to 11.
  • Table II shows the structures of the organic azides used and the structures of the corresponding polysilyl organosilane compounds 13 and 14.
  • a material of formula 18 has been prepared by two different methods:
  • IR (wavenumber in cm -1 ): 706, 842, 1023, 1186, 1456, 1589, 2880, 2931, 3047.
  • IR (wavenumber in cm -1 ): 706, 842, 1045, 1086, 1455, 1589, 2880, 2929, 2972, 3329.
  • IR number of waves in cm -1 : 705, 758, 926, 1045, 1092, 1,185, 1320, 1436, 1460, 1590, 1605, 2819, 2933, 3040, 3144.
  • NMR CP-MAS 13 C ( ⁇ , ppm): 146; 126; 58; 52; 21; 12.
  • the solvent was evaporated to give the material (23).
  • the powder was washed with methanol and dried under reduced pressure at 40 ° C for 6 hours.
  • the compound (22) (0.42 mmol) was added to a mixture of SHS (sodium hexadecyl sulfate containing 40% by weight of sodium steraryl sulfate relative to the total weight of the surfactant, 130 mg, 0.38 mmol) distilled water (20 mL, 1.1 mol) and HCl (1 M, 4 mL, 4 mmol) heated to 60 ° C.
  • SHS sodium hexadecyl sulfate containing 40% by weight of sodium steraryl sulfate relative to the total weight of the surfactant
  • the product thus obtained has been characterized as follows:

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EP13734765.4A 2012-07-06 2013-07-08 Polysilylierte organosilanverbindungen Withdrawn EP2882758A1 (de)

Applications Claiming Priority (2)

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FR1256549A FR2992964B1 (fr) 2012-07-06 2012-07-06 Composes organosilanes polysilyles
PCT/EP2013/064375 WO2014006221A1 (fr) 2012-07-06 2013-07-08 Composés organosilanes polysilylés

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