WO2015128496A1 - Composé oligosiloxysilane hautement réactif - Google Patents

Composé oligosiloxysilane hautement réactif Download PDF

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WO2015128496A1
WO2015128496A1 PCT/EP2015/054212 EP2015054212W WO2015128496A1 WO 2015128496 A1 WO2015128496 A1 WO 2015128496A1 EP 2015054212 W EP2015054212 W EP 2015054212W WO 2015128496 A1 WO2015128496 A1 WO 2015128496A1
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highly reactive
oligosiloxysilane
silicate
silica
oligomers
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PCT/EP2015/054212
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English (en)
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Johan Martens
Pieter Verlooy
Sam Smet
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Katholieke Universiteit Leuven
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes

Definitions

  • the present invention relates generally to a new family of highly reactive silica oligosiloxysilane compounds, more particularly to a system and method for producing highly reactive oligosiloxysilane compounds based on silicate oligomers connected to reactive silane molecules (hereinafter called highly reactive oligosiloxysilane compounds (HROSiSil)) by a process of connecting at least partially stabilized silicate oligomers with reactive silane compounds with multiple reactive leaving groups.
  • HROSiSil highly reactive oligosiloxysilane compounds
  • Silicate hydrates are known (see P.L.H. Verlooy et al., Micropor. And Mesopor. Mater., 130 (2010) 14-20) crystalline materials in containing specific silicate oligomers (especially D3R, D4R and D6R). The organic cations are embedded in cages or pores formed by a network of hydrogen bonded water molecules and oligomeric silicate clusters. Some silicate hydrate materials have also been described in P.L.H. Verlooy et al., Micropor. And Mesopor. Mater., 130 (2010) 14-20 to contain, for example, some aluminum, Cobalt, Nickel copper, palladium or zinc atoms. Different arrangements of those silicate oligomers are known.
  • JP2009-173760A discloses a liquid polysiloxane compound having a polyhedron structure which has excellent molding processability and transparency and provides a composition using the polysiloxane-based compound having the polyhedron structure having a structural unit of formula [XR 2 SiO-Si0 3 /2] a [XR2SiO- (R 2 SiO) m -Si0 3 /2]b[R'-( R2SiO) n -Si0 3 2]c (wherein, each of a to c denotes an integer of 0 or 1 or more, a+b+c denotes an integer of 6 to 24, b+c denotes an integer of 1 or more, each of m and n denotes an integer of 1 or more, R denotes an alkyl group or an aryl group which may be equal to or different from each other when a plurality of groups exist, R' denotes an another polysiloxane having a polyhedron structure and X
  • Coatings and polymers containing highly reactive compounds will have a fast curing time compared to similar coatings and polymers without these highly reactive compounds. Coatings or polymers containing highly reactive compounds will have a better adhesion to a substrate. Highly reactive compounds are also an important ingredient in glue, paint and varnish whereby some of this paint, varnish or glues can also contain some oligomer or polymer material. Highly reactive nanoscopic building blocks offer large possibilities in the generation of membranes and new generations of hierarchical materials with potential applications in for example catalysis, separations, gas sensing, purification etc. (see C.A. Crock, A.R. Rogensues, W. Shan, V.V. Tarabara., Nanotechnology for water and wastewater treatment., 12 (2013) 3984-3996).
  • HROSiSil highly reactive oligosiloxysilane compounds
  • An further advantage of the present invention is that these highly reactive oligosiloxysilane compounds can be in polymers used as (a) crosslinker, (b) fire retardant, (c) to reduce the curing time, (d) to add functionalities, (e) to change the hydrophobic-hydrophilic properties of the polymer blend, (f) to change the oleophobic-oleophilic properties of the polymer blend or (g) for a better dispersion of additives in the polymer blend.
  • a further advantage of the present invention is that the highly reactive oligosiloxysilane compounds can be used in coatings as (a) crosslinker, (b) fire retardant, (c) to reduce the curing time, (d) to add functionalities, (e) to change the hydrophobic-hydrophilic properties of the coating, (f) to change the oleophobic- oleophilic properties of the coating.
  • the highly reactive oligosiloxysilane compounds can be used (a) as such, (b) as such without any other additive(s), (c) in as such in combination with silane monomers, (d) as such in combination with silane oligomers, (e) as such in combination with silane monomers, silane dimers, silane oligomers, silane polymers or any combination of silane monomers, dimers, oligomers or polymers, (f) as such in combination with organic solvent(s), (g) as such without any other additive(s) in combination with organic solvent(s), (h) in as such in combination with silane monomers in combination with organic solvent(s), (i) as such in combination with silane oligomers in combination with organic solvent(s), (j) as such in combination with silane monomers, silane dimers, silane oligomers, silane polymers or any combination of silane monomers, dimers, oligomers or polymers in combination with organic solvent(s).
  • a further advantage of the present invention is that the highly reactive oligosiloxysilane compounds can be used as building block(s) in the synthesis of hierarchical materials, these hierarchical materials can be constructed (a) using only of highly reactive oligosiloxysilane compounds, (b) using a combination of silane monomers and highly reactive oligosiloxysilane compounds, (c) using a combination of silane oligomers and highly reactive oligosiloxysilane compounds, (d) using a combination of silicate oligomers and highly reactive oligosiloxysilane compounds (e) using a combination of metal captions, metal anions, metal nan clusters and highly reactive oligosiloxysilane compounds, (f) using a combination of layered silica based materials and highly reactive oligosiloxysilane compounds, (g) using a combination of small reactive organic molecules and highly reactive oligosiloxysilane compounds.
  • a further advantage of the present invention is that the highly reactive oligosiloxysilane compounds can be used as one of the ingredients of glue, paints or varnish whereby the highly reactive oligosiloxy silane compound can act as a (a) crosslinker, (b) as a matrix, (c) as a means to stabilize other compounds, (d) as a means to make the glue, paint or varnish more resistant towards chemicals, sunlight, UV-light, temperature, water, mechanical stress, (e) as a means of a brightener of surfaces, (f) as a means for a better adhesion with on or more substrates, (g) as a means for a faster curing, (h) as a means to reduce migration, (i) as a fire retarder, (j) as a means to change to hydrophobility of the surface, or (k) as a means to change to oleophobility of the surface, etc.
  • a silicate oligomer is reacted with a reactive silane with multiple reactive leaving groups.
  • a method for the preparation of a highly reactive silica-based oligosiloxysilane compound comprising the following steps: provision of a source of cyclosilicate oligomer, for example cyclosilicate hydrate or cyclosilicate amine crystals; drying said cyclosilicate oligomer; mixing of said dried cyclosilicate oligomer as such or dissolved or suspended in an organic solvent or solvents, typically dry and alcohol- free, with one or more typically predried highly reactive silanes, -for example a silane having four substituents at least two of which are chlorine or acetoxy groups- as such or dissolved in a dry alcohol-free organic solvent or solvent mixture thereby forming a highly reactive silica-based oligosiloxysilane compound; at least partial stabilization of said dried cyclosilicate oligomer prior to or simultaneous with the contact of said one or more typically predried highly reactive silanes with
  • a highly reactive oligosiloxysilane compound is provided obtainable by the method of the first embodiment of the present invention.
  • a silica-based highly reactive oligosiloxysilane compound is provided with chemical composition with A being a Chlorine atom (-CI) or an acetoxy group (-OC(0)CH 3 ) and with all R and R'-groups being independently from each other an organic group or a reactive leaving group selected of the group of CI, Br, OH, H, OR", OC(0)CH 3 ⁇ , where OR" is an alkoxy group.
  • A being a Chlorine atom (-CI) or an acetoxy group (-OC(0)CH 3 ) and with all R and R'-groups being independently from each other an organic group or a reactive leaving group selected of the group of CI, Br, OH, H, OR", OC(0)CH 3 ⁇ , where OR" is an alkoxy group.
  • a silica-based highly reactive oligosiloxysilane compound with formula [Si 8 0 2 o][SiRR'A] 8 is provided with A being a Chlorine atom (-CI) or an acetoxy group (-OC(0)CH 3 ) and with all R and R'-groups being independently from each other an organic group or a reactive leaving group selected of the group of -CI, -Br, -OH, -H, -OR", -OC(0)CH 3 , where OR" is an alkoxy group.
  • a polymer comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.
  • a coating comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.
  • a hierarchical material comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.
  • a use is provided of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention in polymers, coatings, as building blocks for hierarchical materials, in glue, in paint or in varnish.
  • a polymer material is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • a coating is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • a hierarchical material is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • a glue is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • a paint is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • a varnish is provided obtained through the use of the silica-based highly reactive oligosiloxysilane compound of the second, third and fourth aspects of the present invention.
  • Figure 1 Schematic representation of the reaction of a cyclosilicate oligomer with a highly reactive silane SiKLMN.
  • Figure 2 a silicate octameric cube. a [Si 7 O 9 ][OH] 10 * , a silicate polyhedral with one of the corners missing.
  • TBA-CySH (TEA) crystals X-ray diffractogram of TBA-CySH (TEA) crystals.
  • silicate oligomer refers to silicon containing oligomer or polymer whereby every silicon atom is bound to four oxygen atoms.
  • silicate oligomer no direct Si-H bonds, no direct Si-C and no direct Si-Si bonds are present.
  • the dimensions of the silicate oligomer in minimum two orthogonal axes are smaller than 2 nm .
  • highly reactive silane refers to chemical compounds containing silicon, in which every silicon atom is involved into minimum two labile Si-(rlg) bonds with rig is a CI atom or acetoxy group, where rig is an abbreviation for reactive leaving group.
  • Highly reactive silanes may also contain one or several, equal or different Si-0 and/or Si-Si and/or Si-C bonds.
  • solvent can be used for any organic or inorganic liquid with a melting point below 100°C and that has a viscosity lower than 1000 centipoise. Furthermore the term solvent can both be used for solvent as well as for a mixture of solvents as well as for a solvent in combination with an acid, as well as for a solvent in combination with several different acid as well as for a mixture of solvents in combination with an acid, as well as for a mixture of solvents in combination with a mixture of solvents.
  • alcohol refers to any organic molecule or organic compound containing minimum one hydroxyl functional group (-OH) bound to a carbon atom and whereby this carbon center is saturated by three single bonds to other atoms or the carbon atom is part of an aromatic ring structure.
  • core in present invention relate to a compound obtained through reacting silicate oligomer with highly reactive silane whereby it is possible to draw two ellipsoids around the center of mass of a silicate oligomer in such a way that the center (core) inside the smallest ellipsoid especially consists of atoms of the former silicate oligomer and whereby the atoms of the compound in the outer layer (shell) in between the two ellipsoids originate especially from the former highly reactive silanes now bound to this silicate oligomer (see Figure 4).
  • saturated organic moiety means an organic moiety without carbon-carbon double or triple bonds and without an aromatic ring structure.
  • saturated organic moiety means an organic moiety with a carbon-carbon double or triple bond.
  • aromatic organic moiety means an organic moiety with an aromatic ring structure and no carbon-carbon double or triple bonds.
  • organic group encompasses saturated organic moieties unsaturated organic moieties and aromatic organic moieties.
  • compound as used in disclosing the present invention, means a chemical substance composed of two or more different chemical elements that are ion ically or covalently bound to one another.
  • Hierarchical structure means a material containing structural elements which themselves have structure.
  • silane as used in disclosing the present invention, is used both for a true silane with a chemical formula of the form SiKLMN whereby the K and L groups are reactive leaving groups, the remaining M and N groups being independently from each other a reactive leaving group or an organic moiety with a direct Si-C bond as for a -SiLMN group connected through a siloxane bond to a silicate oligomer (see Figure 1).
  • silanol groups can be deprotonated (-0 ), protonated (-OH) or doubly protonated (- OH 2 + ) depending on the exact environment of this oxygen, therefor for simplification and for clarity reasons the charge of molecules or particles is in some of those formulae omitted, moreover for simplification and clarity reasons the different possible silanol (-0 " , -OH, -0H 2 + ) groups are in many formulae simplified and represented by -OH groups or only the O atom of the silanol group. A person skilled in the art is expected to be able to understand this.
  • CySH stands for cyclosilicate hydrate
  • CySA stands for cyclosilicate amine
  • An example of a silicate octameric cube is shown in figure 2.
  • silicate polyhedral whereby one of the corners is missing.
  • An example of such a silicate oligomer with a missing corner is a [Si 7 0 9 ][OH] 10 * species as shown in figure 3.
  • the asterix indicates that as stated above depending on the environment of the silicate oligomers part or all of the silanols [OH] connected to the silicate oligomer could be deprotonated in the [O] " form or double protonated in the [H 2 0] + form.
  • Silicate oligomers can be obtained in different ways.
  • (Aqueous) suspensions of silicate oligomers can be obtained using the methods known by those skilled in the art. For example: double four ring silicate octamers can be obtained from an aqueous suspension containing a silica source, tetramethylammonium hydroxide and methanol.
  • the cyclosilicate oligomers can be in a crystalline form as found in amongst others in silicate hydrates, silicate amines, or cyclosilicate amines.
  • Cyclosilicate hydrates are silicate hydrate crystals whereby the silicate oligomer is a double ring silicate oligomer.
  • Cyclosilicate amines are silicate amines crystals whereby the silicate oligomer is a double ring silicate oligomer.
  • Silicate hydrate materials and silicate amines can be obtained from a variety of silicate suspensions.
  • double four ring silicate hydrate crystals can be formed in an aqueous suspension of (excess) hexamethyleneimine and a silica source.
  • silicate hydrate structures are changed through the use of a whole variety of small manipulations. This together with our knowledge about the synthesis of silicate hydrates makes it perfectly feasible for us to create a large set of ordered materials in which the oligomers are arranged in different ways.
  • the silicate oligomers in those materials are interconnected through a network of hydrogen bonds.
  • Silicate hydrates are positioned between zeolites and clathrate hydrates.
  • zeolites organic
  • template molecules are embedded in the pores of a four-connected silicon dioxide network. The template molecules reside in zero, one, two or three dimensional pores. In the crystal structure of clathrate hydrates, the template molecules are partially or entirely surrounded by water molecules.
  • the first silicate hydrate was reported in 1937 when Glixelli described a new type of crystal. From an aqueous suspension containing tetramethylammonium hydroxide (TMAOH) and silica gel the new kind of crystals were synthesized. Those crystals were slightly soluble in water, methanol and ethanol. In air the crystals decomposed. It was confirmed that the crystals contained water molecules. Similar crystals are obtained using tetraethylammonium hydroxide (TEAOH) as mineralized. It was only in 1952 that Prikid'ko described the structure of a silicate unit in a silicate hydrate. It took until the early seventies before the first silicate hydrate structures was solved.
  • TMAOH tetramethylammonium hydroxide
  • silicate hydrates So far three different silicate units have been found in silicate hydrates. Most silicate hydrates contain double four ring silicate units. Next to many four ring silicate hydrates only one double six ring silicate hydrate and a few double three ring silicate hydrates have been reported.
  • Silicate hydrates can also be effectively formed in, for instance, tetramethyl- (TMA), tetraethyl-(TEA) and tetrabutylammonium (TBA) aqueous suspensions.
  • TMA tetramethyl-
  • TEA tetraethyl-(TEA)
  • TBA tetrabutylammonium
  • the use of these TMA aqueous suspensions gives rise to hydrates with isolated D4R silicate units; TEA aqueous suspensions to D3R silicate units and TBA aqueous suspensions to D4R silicate cubes.
  • the cubes in the TBA based structure are interconnected by direct hydrogen bonds between the terminal oxygen (Si-O-) and silanol (Si-OH) groups.
  • Each of the terminal oxygen or silanol group is hydrogen bonded to a terminal oxygen or silanol group of a different silica cube.
  • the TBA- based silicate hydrate structure resembles closely the structure of zeolite A. The difference is that the TBA-silicate hydrate structure contains some Si-O-H-O-Si bonds instead of siloxane bonds in the LTA zeolite structure (see Fig.9).
  • charge compensation of the negatively charged silicate cubes occurs not only by TBA cations, but also by protonated water clusters. Inside of each " sodalite- like cage" a H 41 0 16 9+ cluster is located.
  • TBA-silicate hydrate Apart from this water cluster, no other water molecules are present in TBA-silicate hydrate.
  • the TBA template molecule resides in the "8+ -ring" pores with the nitrogen atom of TBA in the "8 + ring” pore and the butyl groups pointing two by two to different 'Ita- like” cages.
  • Structurally similar silicate hydrates were formed from ethylenediam ine containing clear solution of TBA, water and silicic acid. The structure resembled the TBA- silicate hydrate in which part of the water was replaced by ethylenediamine (en).
  • TBP- silicate hydrate In the presence of ethylenediamine and tetrabutylphosphonium (TBP) cations, TBP- silicate hydrate are prepared. The structure of this material seemed to be very similar to the TBA-silicate hydrate.
  • TBP- silicate hydrate The use of hexamethyleneimine (HMI) as a template give rise to yet another different silicate hydrate structure (HMI-CySH).
  • HMI-CySH hexamethyleneimine
  • the structure of HMI-CySH is described as a heteronetwork structure formed by both covalent and non-covalent interactions between the water, inorganic and organic species.
  • the crystal packing contains 16 D4R units on two crystallographic independent positions centered on inversion centers in the asymmetric unit.
  • the crystal packing shows that alternating cube 1 and cube 2 are stacked onto each other, forming columns of silicate species.
  • the terminal oxygen atoms (O ter m) on the silicate cubes are partly hydrated.
  • Six hydrogen atoms were localized in the difference maps for cube 1 [Si 8 0 14 (OH) 6 ] 2" , and two hydrogen atoms on the second silicate cube 2 [Si 8 0 18 (OH) 2 ] 6" .
  • the overall charge-compensation is achieved by eight protonated hexamethyleneimine molecules, hydrogen bonding two neighboring cubes within one stack. An extensive hydrogen bond network is present in the crystal structure.
  • Each oxygen in O term H and each O term acts as a proton acceptor in a hydrogen bond with a water molecule. This way eight water molecules are located in the direct vicinity of a silicate anion. In accordance with the 24 water rule, each terminal oxygen is involved in hydrogen bonding to three protons resulting in a tetrahedral oxygen environment.
  • One of the hydrogen bonds originates from the water molecules, one from a proton shared between cubes and the third from an hexamethyleneiminium ion, which in turn also binds to a neighboring cube in the same stack.
  • Silicate columns are connected through a network of water molecules. All terminal oxygen atoms are connected with a terminal oxygen atom of a neighboring silicate column through a chain of hydrogen bonds involving three water molecules, whereof one is not in direct interaction with any D4R unit.
  • the HMI molecules all hydrogen bonded to two D4R cubes in one stack, are grouped by four thus maximizing the shielding of their hydrophobic moieties from the polar silicate-water network.
  • the refined structure revealed that the hydrophobic parts of the HMI molecules are partially distorted.
  • HMI-CySH crystals Upon air drying HMI-CySH crystals lose most or all of their crystal water and the structure partially changes to form a new crystalline fase: HMI-CySA.
  • a silicate hydrate containing isolated cubes was formed in presence of Cu(en) 2 .
  • all terminal oxygens are stabilized by three hydrogen bonds and 4 out of the 8 terminal oxygens are hydrogen bonded to nitrogen atoms of the metal-ethylenediamine complex. Twenty further hydrogen bonds water molecules aligned with the edges of the silica cubes are involved.
  • Ni(en) 3 double three ring silicate units are formed .in which Ni(en) 3 molecules reside in channels formed by water molecules and the D3R silicate units.
  • silicates In the case of Co(en) 3 double four ring silicates are formed. These silicate units are directly linked to each other by hydrogen bridges between terminal oxygen atoms. Silica columns formed by silica cubes hydrogen linked though the edges are formed.
  • silicate hydrates are formed using ethylendiamine complexes of zinc and palladium. The crystal structure of these silicate hydrates has not been reported so far.
  • silanes there are several families of silanes that can undergo a hydrolysis reaction or that could react with silanol groups on silica based materials.
  • the ability of these groups to hydrolyse is dependent on the nature of the reactive leaving group connected to a silicon atom of the silane.
  • Some of the more reactive leaving groups are the halogen, particularly chlorine, and acyloxy, particularly acetoxy, groups.
  • Alkoxy (aryloxy) groups only react slowly with silanols especially in the absence of a catalyst.
  • the reaction of a alkoxy (aryloxy) group with a silanol forms an alcohol. In the absence of water this alcohol can also react with a silanol to form an alkoxy (aryloxy) bond.
  • This equilibrium reaction between silanols and alcohols makes the reaction between the silicate oligomers and alkoxysilanes (aryloxysilanes) less controllable.
  • reactive leaving groups are atoms or groups of atoms connected to a silicon atom of a silane that can be hydrolyzed upon addition of water alone or water in the presence of a catalyst; some examples or these reactive leaving groups are: -CI, -Br, -I, -OH, OR, -OC(0)R, where R is alkyl or aryl, with -CI and acetoxy being particularly preferred.
  • a Si-H group can also be hydrolyzed upon addition of water and a catalyst, except where explicitly stated, this hydrogen is not considered to be reactive leaving group, according to the present invention.
  • Silanes have four substituents and highly reactive silanes are defined as having at least two chloro or two acetoxy groups typically connected directly to the silicon atom and may also have substituents bonded to the silicon atom of the silane by Si-0 and/or Si-Si and/or Si-C bonds.
  • the highly reactive silane has the formula SiA 2 R 1 R 2 , where A is - CI or acetoxy and R 1 and R 2 are independently a reactive leaving group, a hydrogen atom or an organic moiety, with R 1 and R 2 being independently a reactive group or an organic moiety being preferred.
  • One substituent A reacts with silicate oligomer (typically originating from a cyclosilicate hydrate or cyclosilicate amine) and R 1 and R 2 and at least part of the other substituent A are retained in the oligosiloxysilane compounds of the present invention after reaction of the cyclosilicate oligomers with the reactive silanes.
  • Organic moieties include one or more organic moieties selected from the group consisting of organic moieties without carbon-carbon double or triple bonds and without an aromatic ring structure (saturated organic moieties), organic moieties with carbon-carbon double or triple bonds (unsaturated organic moieties) and organic moieties with an aromatic ring structure and no carbon-carbon double or triple bonds (aromatic organic moieties), with saturated or aromatic organic moieties being preferred and with organic moieties selected from the group consisting of organic moieties without carbon-carbon double or triple bonds and without an aromatic ring structure being more preferred.
  • Organic moieties without carbon-carbon double or triple bonds and without an aromatic ring structure include alkyl, aminoalkyl, cyanoalkyl, thionyl, cycloalkyl, epoxyalkyl, haloalkyl, glycidyl and imidoyl groups, and may further include iminoalkyl, imidoalkyl isocyanoalkyl, thiocyanoalkyl and carbonyl groups.
  • Organic moieties with carbon-carbon double or triple bonds include alkenyl, methacryl, alkynyl and norbornenyl groups.
  • Organic moieties with an aromatic ring structure and no carbon-carbon double or triple bonds include aryl, thioaryl, aminoaryl, cyanoaryl, epoxyaryl and haloaryl groups and may further include nitroaryl and sulfoaryl groups.
  • the highly reactive silane has the formula SiA 2 RR', where A, R and R' have the same meanings as defined for the highly reactive oligosiloxysilane.
  • highly reactive leaving groups on said highly reactive silane molecules and on said highly reactive oligosiloxysilane compounds can be Chlorine or Acetoxy groups.
  • all silane molecules with minimum two chlorine atoms or with minimum two acetoxy groups connected directly to the core silicon atom(s) of the silane molecule are considered to be highly reactive silanes.
  • Some examples of highly reactive silane molecules are amongst others: dimethyldichlorosilane, methyltrichlorosilane, tetrachlorosilane, dichlorosilane, trich lorosilane, dimethyldiacetoxysilane, dichlorodiphenylsilane, dichloromethyl- vinylsilane, etc.
  • Another aspect of the invention concerns the members of this group of highly reactive oligosiloxysilane compounds, whereby silicate oligomers are connected to reactive-silane molecules.
  • a silica-based highly reactive oligosiloxysilane compound is provided with chemical composition Si 16 0 2 oR 8 R'8A8 with A being a chlorine atom (-CI) or an acetoxy group (-OC(0)CH 3 ) and with all R and R'-groups being independently from each other an organic group or a reactive leaving group selected of the group of -CI, -Br, -OH, H,-OR", - OC(0)CH 3 , where OR" is an alkoxy group.
  • the oligosiloxysilane compound has the formula [Si 8 0 2 o][SiRR'A] 8 .
  • the silica-based highly reactive oligosiloxysilane compound comprises a silica core (X) and a silane shell (S) whereby the dimensions of said silica core in any direction is smaller than 2nm and whereby every silicon atom on the silane shell is directly connected to a minimum of one chlorine atom or to a minimum of one acetoxy group, with preferably at least 5% of the silicon atoms on the silane shell being directly connected to at least one chlorine atom or at least one acetoxy group, with more preferably at least 10% of the silicon atoms on the silane shell being directly connected to at least one chlorine atom or at least one acetoxy group, with particularly preferably at least 25% of the silicon atoms on the silane shell being directly connected to at least one chlorine atom or at least one acetoxy group and especially preferably at least 50% of the silicon atoms on the silane shell being directly connected to at least one chlorine atom or at least one acetoxy group and especially preferably at least 50% of the silicon
  • R, R' are independently selected from the group consisting of methyl, vinyl, allyl, ethyl, phenyl, benzyl, aminopropyl, cyanopropyl, H, CI, OC(0)CH 3 and OH groups, with R, R' being preferably selected from the group consisting of methyl, ethyl, aminopropyl, cyanopropyl, -CI, -OC(0)CH 3 and -OH groups.
  • a is a chorine atom.
  • A is an acetoxy group (-OC(0)CH 3 ).
  • R, R' are independently from each other selected from methyl, vinyl, allyl, ethyl, phenyl, benzyl, aminopropyl, cyanopropyl, H, CI, OC(0)CH 3 , or OH.
  • the silica-based highly reactive oligosiloxysilane compound has the formula [Si 8 O2 0 ][SiRR'A] 8 and whereby R, R' are independently from each other selected from methyl, vinyl, allyl, ethyl, phenyl, benzyl, aminopropyl, cyanopropyl, H, CI, OC(0)CH 3 , or OH.
  • R, R' are independently selected among the fluorinated hydrocarbons.
  • R, R' are independently selected among the fluorinated hydrocarbons.
  • the silica-based highly reactive oligosiloxysilane compound has a formula [Si 8 0 2 o][SiRR'A] 8 and whereby R, R' are independently selected among the fluorinated hydrocarbons.
  • said highly reactive oligosiloxysilane is capable of being dissolved in a dry alcohol-free solvent or solvent mixture.
  • a method for the preparation of a highly reactive oligosiloxysilane compound comprising the addition of one or more highly reactive silanes to silicate oligomers more preferably double four ring silicate octamers.
  • a method for the preparation of a highly reactive oligosiloxysilane compound comprising the addition of one or more highly reactive silanes -as such or dissolved in a dry alcohol-free organic solvent or solvent mixture- to double four ring silicate octamers that are in a solid form or in a solid matrix.
  • a method for the preparation of a highly reactive oligosiloxysilane compound comprising the addition of one of more highly reactive silanes -as such or dissolved in a dry alcohol-free organic solvent or solvent mixture- to double four ring silicate octamer that are in a solution or suspension in a dry alcohol-free organic solvent or solvents thereby forming the highly reactive oligosiloxysilane compounds.
  • a method for the preparation of a highly reactive oligosiloxysilane compound comprising the addition of one or more highly reactive silanes as such or dissolved in a dry alcohol- free organic solvent or solvent mixture to especially double four ring silicate octamer that are dry and in a solid form or to double four ring silicate octamers that are in a solution or suspension in a dry alcohol-free organic solvent or solvents thereby forming the highly reactive oligosiloxysilane compounds characterised in that the highly reactive oligosiloxysilane comprises highly reactive leaving groups said CI or acetoxy groups.
  • a highly reactive oligosiloxysilane compound is provided obtainable by one of the methods of fifteenth, sixteenth, seventeenth or eighteenth aspect of the present invention.
  • said highly reactive oligosiloxysilane is capable of being suspended in a dry alcohol-free solvent or solvent mixture.
  • highly reactive oligosiloxysilane comprises a silica core and a highly reactive silane shell.
  • the highly reactive oligosiloxysilane compound is a core-shell compound in which the core originates especially from the silica oligomer and the shell originates especially from the highly reactive silanes, with the core typically containing one or more silanol groups.
  • the highly reactive oligosiloxysilane compound is a core-shell compound whereby the core originates especially from the silica oligomer and the shell originates especially from the highly reactive silanes and whereby two cores are typically connected through a siloxane bond.
  • the highly reactive oligosiloxysilane compound is a core-shell compound whereby the core originates especially from the silica oligomer and the shell originates especially from the highly reactive silanes and whereby core and shell of different core-shell are typically connected through a siloxane bridge.
  • the highly reactive oligosiloxysilane compound can contain one or more direct siloxane bonds and typically contain one or more siloxane bridges between the former silica oligomers.
  • two or more silicate oligomers can be bridged by one or more siloxane bridges formed through reaction of a highly reactive silane with more then one silicate oligomer.
  • two or more highly reactive oligosiloxysilanes can be connected through one or more direct siloxane bonds.
  • two or more highly reactive oligosiloxysilanes can be connected through one or more siloxane bridges.
  • two or more highly reactive oligosiloxysilanes can be connected and can contain one or more silanols.
  • two or more highly reactive oligosiloxysilane compounds can be connected and can contain one or more silanols, wherein the highly reactive oligosiloxysilane compound still comprises one or more highly reactive leaving groups in the form of a CI atom or an acetoxy group directly bound to one or more silicon atoms of the compound.
  • two or more highly reactive oligosiloxysilanes can be connected and can contain one or more silanols characterized in that the compound still comprises one or more highly reactive leaving groups in the form of a CI atom or an acetoxy group directly bound to one or more silicon atoms of the compound on more than 5% of the silicon atoms of the compound, with on more than 10% of the silicon atoms of the compound being preferred, more than 25% of the silicon atoms of the compound being particularly preferred, more then 35% of the silicon atoms of the compound being especially preferred and on between 40% and 50% of the silicon atoms of the compound being especially particularly preferred.
  • the core part of the highly reactive oligosiloxysilane compounds (HROSiSil) of present invention consist of a double four ring silicate octamer.
  • HROSiSil highly reactive oligosiloxysilane compounds
  • a double ring silicate octamer is further connected through siloxane bonds to up to eight highly reactive silane molecules whereby each of those up to eight highly reactive silane molecules is connected through exactly one siloxane bond with exactly one of the eight corners of the double four ring silicate octamer.
  • silica core consisting of up to 8 silicon atoms and 20 oxygen atoms is surrounded by and connected with a shell of eight reactive silane molecules each consisting of one silicon atom connected to the core structure and connected to minimum one highly reactive leaving group in the form of a Chlorine atom or an acetoxy group.
  • a source of silicate oligomers (X, X', X",...) is brought into contact with highly reactive silane molecules (Y, ⁇ ', ⁇ ', 7) with minimum two reactive (-CI and/or -OC(0)CH 3 ) leaving groups.
  • Best synthesis of highly reactive oligosiloxysilane compounds are obtained from silicate oligomers in the absence of water and alcohol and when the highly reactive silane molecules can come into contact with the silicate oligomers for optimal reaction.
  • Optimal results are obtainable when the silicate oligomers are stable enough in order not to break any of the Si-O-Si bond of the silicate oligomer.
  • Alcohols can react with silicate oligomers and therefor reduce the reaction rate and or the reaction equilibrium when the silicate oligomers come into contact with the highly reactive silane molecules. Moreover alcohols can react with the highly reactive silane molecules through an exchange reaction whereby the highly reactive leaving group is exchanged by a less reactive alcoxy group. Furthermore alcohols can react with the highly reactive oligosiloxysilane compounds thereby exchanging the highly reactive leaving groups with less reactive alkoxy-groups. The reactivity of the alcohols in this exchange reaction depends strongly on the acidity of the alcohol and the sterical hindrance of the alcohol group whereby the alcohols whereby the alcohol group is shielded are less reactive. All of those reactions with alcohols are undesired side reactions and therefor the presence of especially not sterically hindered alcohols should preferentially be avoided.
  • silicate hydrate structures that are for instance synthesized by a selection of the organic templates shown in Figure 5, mentioned in the above text are suitable for the production of the silicate oligomers used in the synthesis of the silica based oligomers of present invention.
  • the silicate oligomers are dispersed or even better suspended in a solvent so the highly reactive silane can easily diffuse towards the silicate oligomer, or the silicate oligomers are in a (semi) solid matrix with enough flexibility to allow the silane molecules to diffuse towards the different silicate oligomers, or the silicate oligomers are in a solid matrix and the solid matrix partially or completely disaggregates during the reaction between the silicate oligomer and the highly reactive silane molecules.
  • the silicate oligomers also can be in a suspension or solution.
  • the solvent of combination of solvents used for this suspension should preferably contain as little as possible water and preferably do not contain any alcohols.
  • the solvent or combination of solvents preferably stabilizes the silicate oligomers in order to reduce the reaction between the silicate oligomers with each other.
  • a good dispersion of silicate oligomers in a dry and alcohol free organic solvent or combination of solvent is not easy to achieve. Moreover a relative stable or stable suspension of silicate oligomers in a dry and alcohol free organic solvent or combination of solvent is even more difficult to obtain. Moreover, diffusion of highly reactive silanes through a solid material containing silicate oligomers or even though a solid material build from silicate oligomers is not known in literature. Synthesis of highly reactive oligosiloxysilane compounds provides evidence that this diffusion of highly reactive silanes through a solid material containing or build from silicate oligomers is however possible.
  • the highly reactive silanes can be added to the silicate oligomers or the silicate oligomers can be added to the highly reactive silanes.
  • the highly reactive silanes can be added through the gas phase, through the liquid phase or as a solid.
  • the highly reactive silanes could be suspended in a solvent or combination of solvents prior to the addition to the silicate oligomers. If a solvent is used this solvent should preferentially contain as little as possible water and should preferentially contain as little as possible alcohol.
  • silicate oligomers During the reaction between the silicate oligomers and the highly reactive silanes, water and even traces of water should be avoided in order to reduce the formation of silane oligomers and in order to reduce the hydrolysis of the highly reactive groups on the highly reactive silanes and on the highly reactive oligosiloxysilane compounds.
  • the silicate oligomers Prior and during the reaction of silicate oligomers with the highly reactive silanes, the silicate oligomers should best be stabilized to some extend in order to limit the reaction of the silicate oligomers amongst each other.
  • a possible method to stabilize the silicate oligomers is to work in a strong acidic environment or though addition of a Lewis acid or through the addition of a bronsted acid or through a combination of different acids.
  • silicate oligomers can also be stabilized by solvent stabilization, for example by using solvents with a high dielectrical constant or using solvents capable of forming hydrogen bonds with the terminal oxygens and/or silanols on the silicate oligomers.
  • solvent stabilization for example by using solvents with a high dielectrical constant or using solvents capable of forming hydrogen bonds with the terminal oxygens and/or silanols on the silicate oligomers.
  • Another method of stabilizing silicate oligomers is to work in a viscous medium thereby reducing the mobility of the silicate oligomers.
  • Silicate oligomers can also be stabilized by working at a low or reduced temperature and by working with diluted solutions or suspensions.
  • silanols of a silicate oligomers or the silanols on the core of the highly reactive oligosiloxy silane can still react with each other leading to a type of side reaction as shown in Figure 6.
  • the formed connection between the two particles is a siloxane bond.
  • a low temperature, a good stabilization and high concentrations of highly reactive silanes are some of the ways of reducing this type of side reaction.
  • a silanol group on the silicate oligomer or on the core of a highly reactive oligosiloxy silane can react with a silicon atom on the shell of a highly reactive oligosiloxy silane compound leading to a type of side reaction as shown in Figure 7.
  • the formed connection between the two particles is a siloxane bridge.
  • This type of side-reaction is hard to prevent, but working with a high excess of highly reactive silane is one way of reducing this side reaction.
  • Another way to reduce this side reaction is reducing the mobility of the silicate oligomers and the highly reactive oligosiloxysilanes.
  • Reaction between two highly reactive silanes, between a highly reactive silane and a highly reactive silicon on a highly reactive oligosiloxysilane compound or between two highly reactive silicons on two highly reactive oligosiloxysilane compounds can also occur (see Figure 8).
  • the formed connection between for example the two higly reactive oligosiloxysilanes is a siloxane bridge.
  • this side-reaction can occur also partially in the absence of water but in this case this reaction can also be reduced by reducing the temperature or in general by reducing the formation of acetic acid anhydride.
  • the environment is not dry enough, it is possible that the one or more of the highly reactive leaving groups on the highly reactive oligosiloxysilane are replaced by a silanol (see Figure 9).
  • the highly reactive silanes are present in too low concentration, the highly reactive silane contains a bulky R group, the silicate oligomer contains sterically hindered silanols, the silicate oligomer contains a hydroxyl nest or the reaction conditions are not optimal then it is possible that not all silanols of the silicate oligomer will react with the highly reactive silanes.
  • the highly reactive oligosiloxysilane formed will in this case still contain one or more silanol groups (see Figure 10). The effect of the side reactions on the concept of core-shell particles is shown in Figure 11.
  • highly reactive oligosiloxysilane compounds are synthesized using solid materials or suspension containing especially double four ring silicate octamers. It is however important that the silica oligomer containing material or suspensions used in the synthesis of the highly reactive oligosiloxysilane compounds does not contain water and does not contain alcohol since alcohol and water will lead to the formation of often undesired side product.
  • Highly reactive oligosiloxysilane compounds can be obtained through the reaction of silicate oligomers with highly reactive silanes.
  • Synthesis of oligosiloxysilanes involves in principle the reaction of a source of silicate oligomers with highly reactive silanes. Without intention of being limited to a certain process for obtaining the materials of present invention a general synthesis procedure for the synthesis of members of this new family of silica based polymers - the HROSiSils - is hereby provided. In comprises the following steps a- m, whereby not all steps a-m are necessary; whereby the order of the steps a-m can be altered and whereby anyone or more of the steps a-m can be repeated one or more times:
  • Silicate oligomers A typical source of cyclosilicate oligomers are cyclosilicate hydrates or cylcosilicate amine crystals. Next to and not limited to solid or even crystalline forms of cyclosilicate oligomers also suspensions or dispersions of silicate oligomers could be used as a source of silicate oligomers.
  • Silicate oligomers could be suspended in a solvent. Special care should preferentially be taken to avoid the presence of water and alcohol. Additionally special care could be taken to stabilize the silicate oligomers to some extent, d) Addition of silane
  • Highly reactive silane can be brought into contact with the silicate oligomers or silicate oligomers can be brought into contact with the highly reactive silane.
  • the highly reactive silane can be used as such, can be distilled or can be dissolved in a solvent or mixture of solvents.
  • the silicate oligomers can be in a solid phase or suspended or dissolved in a solvent or mixture of solvents.
  • One or more highly reactive silanes can be used as such or one or more highly reactive silanes can be used in a solvent or mixture of solvents.
  • silane oligomers will be separated from the silane monomers. If needed a distillation could also be used to separate HCI, acetic acid and/or acetic anhydride from the highly reactive silanes and the (highly reactive) silane oligomers.
  • a solvent or mixture of solvent can be distilled in order to reduce the water content in this solvent or this mixture of solvents.
  • the distillation of a solvent or mixture of solvents can be done over a conventional drying agent like Na, K, NaOH, LiOH, Li, MgS0 4 , Zeolite 3A, Zeolite 4A, Zeolite 5A, silica gel, etc.
  • a distillation of a solvent or a mixture of solvents with silanes can also be used in order to dry the solvent or mixture of solvents.
  • the distillation of highly reactive silanes in combination with a solvent or mixture of solvent can serve both in purifying the silane and in drying the solvent.
  • the highly reactive oligosiloxysilane compounds can be formed.
  • Silicate oligomers often come together with some kind of template.
  • the silicate oligomers When the silicate oligomers are dissolved, suspended or dispersed in a solvent or mixture of solvents, it is possible that some of the organic or inorganic template(s) are not well dissolved.
  • the silicate oligomers, highly reactive silanes and optionally one or more solvents are mixed it is possible that some of the organic or inorganic template molecules are not well dissolved. If desired, part or all of the not well dissolved templates could be removed from the solvent or solvent mixture. This removal can be done prior to the reaction of the silicate oligomers with the highly reactive silanes or after this reaction.
  • the removal of the template molecules can be done using filtration or centrifugation techniques or using UV radiation or calcination techniques or using phase separation or by the use of (re)crystallization techniques or through the use of immiscible solvents,
  • this solvent or mixture of solvents can optionally be removed.
  • Some of the possible methods to remove the solvent or mixture of solvents are amongst other: distillation, filtration, centrifugation, evaporation, decantation, vacuum-distillation, etc.
  • any excess highly reactive silanes added to the reaction mixture for the reaction between the silicate oligomers with the highly reactive silane molecules can optionally be removed.
  • Some of the possible methods to remove the solvent or mixture of solvents are amongst other: distillation, filtration, centrifugation, evaporation, decantation, vacuum-distillation, etc.
  • Next to the highly reactive silane monomers also small (highly reactive) silane oligomers can be removed using methods similar to the methods used for removing of excess highly reactive silanes.
  • silanes, silane oligomers, solvent or mixtures of solvents and even some template molecules can be optionally removed during the same or similar chemical processes like for example: distillation, filtration, centrifugation, evaporation, decantation, vacuum-distillation, etc..
  • the highly reactive oligosiloxysilane compounds can be (re)dissolved in a solvent or mixture of solvents in order to obtain a suspension or solution of highly reactive oligosiloxysilane compounds.
  • the solvent or mixture of solvents preferentially contains as little as possible water and preferentially contains as little as possible alcohol.
  • Highly reactive oligosiloxysilane compounds can be used as precursor, as reagent or as additive in the synthesis of coatings, polymers, hierarchical materials, glue, paint or varnish.
  • the highly reactive oligosiloxysilane compounds are formed prior to the formation of the coating, the polymer the hierarchical material or prior to the application of the glue, paint or varnish.
  • the highly reactive oligosiloxysilane compounds could even be formed prior to the start of the synthesis of the coating, the polymer or the hierarchical material.
  • highly reactive oligosiloxysilane compounds could also be generated during the synthesis process of the coatings, polymers or hierarchical materials or generated during application of the glue, paint or varnish.
  • said cyclosilicate oligomer is a double four ring silicate octamer.
  • said cyclosilicate oligomer is dissolved or suspended in a solvent or mixture of solvents, which are preferably dry and alcohol-free.
  • said cyclosilicate hydrate or cyclosilicate amine is a D4R cyclosilicate hydrate.
  • said cyclosilicate hydrate or cyclosilicate amine is a D4R cyclosilicate amine.
  • said at least partial stabilization of said cyclosilicate hydrate of cyclosilicate amine is realized with a stabilizer selected from the group consisting of Bronsted acids, Lewis acids and solvents with a high ionic nature, said Bronsted acid being preferably selected from the group consisting or hydrochloric, nitric, sulphuric and acetic acids.
  • said at least partial stabilization of said cyclosilicate oligomer is realized with a stabilizer selected from the group consisting of Bronsted acids, Lewis acids and solvents with a high ionic nature and said one or more highly reactive silane as such or in a dry alcohol-free organic solvent or solvent mixture contains a Bronsted acid, with hydrochloric acid being preferred.
  • a stabilizer selected from the group consisting of Bronsted acids, Lewis acids and solvents with a high ionic nature and said one or more highly reactive silane as such or in a dry alcohol-free organic solvent or solvent mixture contains a Bronsted acid, with hydrochloric acid being preferred.
  • the highly reactive oligosiloxysilane comprises highly reactive leaving groups said CI or acetoxy groups directly bound to a silicon atom.
  • said at least partial stabilization of said cyclosilicate hydrate of cyclosilicate amine is realized with a stabilizer selected from the group consisting of Bronsted acids, Lewis acids and solvents with a high ionic nature and said one or more highly reactive silane as such or in a dry alcohol-free organic solvent or solvent mixture contains a Bronsted acid, with hydrochloric acid being preferred.
  • said highly reactive silane is selected from the group consisting of dichlorodimethylsilane and diacetoxydimethylsilane.
  • said dry alcohol-free solvent or solvent mixture is selected from the group consisting of tetrahydrofuran, chloroform, propanone, diethyl ether, toluene, N-methylpyrrolidone, N-methylimidazole, dichloromethane, dimethylsulphoxide, acetonitrile and alkanes.
  • said highly reactive oligosiloxysilane compound synthesized from silicate oligomers and highly reactive silanes comprises at least one highly reactive leaving group in the form of a Chlorine atom or acetoxy group connected directly to a silicon atom, with more than one reactive leaving group being preferred.
  • the silicate oligomers with a polyhedral skeleton are silicate polyhedral with formula [Si0 3/2 ] n [OH] n , whereby this silicate oligomer is reacted with m silane molecules whereby said silane has a chemical formula of the form SiA 2 R 1 R 2 ,
  • A is a reactive leaving group, with chlorine or an acetoxy group being preferred and chlorine being particularly preferred;
  • R 1 is a reactive leaving group, a hydrogen atom or an organic moiety, preferably a chlorine, an acetoxy group, a hydrogen atom or an organic moiety, particularly preferably a chlorine, an acetoxy group or an organic moiety, especially preferably a chlorine or an organic moiety and especially particularly preferably an organic moiety, with the organic moiety being preferably a saturated or aromatic organic moiety, with a saturated organic moiety being particularly preferred;
  • R 2 is a reactive leaving group, a hydrogen atom or an organic moiety, preferably a chlorine, an acetoxy group, a hydrogen atom or an organic moiety, more preferably a chlorine, an acetoxy group or an organic moiety; particularly preferably a chlorine or an organic moiety and particularly preferably an organic moiety, with the organic moiety being preferably a saturated or aromatic organic moiety, with a saturated organic moiety being particularly preferred.
  • the silicate oligomers with a polyhedral skeleton are silicate polyhedral with formula [Si0 3/2 ] n [OH] n whereby this silicate oligomer is reacted with one up to m identical or different silane molecules whereby said silanes have a typical chemical formula of the form SiA 1 2 R 1 R 2 ; SiA 2 2 R 3 R 4 ; SiA 3 2 R 5 R 6 ; SiA 4 2 R 7 R 8 ; ... ;SiA m 2 R 2m 1 R 2m ;
  • a 1 , A 2 , A 3 , A 4 , .., A m are independently from each other a chlorine, an acetoxy group or a reactive leaving group; with a chlorine or an acetoxy group being preferred and a chloring being particularly preferred;
  • R 1 , R 3 , R 5 , R 7 , .., R 2m 1 are independently from each other a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred, a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being preferably being a saturated or an aromatic organic moiety and particularly preferably being a saturated organic moiety;
  • R 2 , R 4 , R 6 , R 8 , .., R 2m is a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred, a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being preferably a saturated or aromatic moiety and particularly prefaerably a saturated organic moiety.
  • the silicate oligomers with a polyhedral skeleton are silicate polyhedral with formula [Si0 3/2 ] n [OH] n , silicate oligomers with a polyhedral skeleton with a missing corner of formula [Sin. ! 0 ( 3n-6)/2] n[OH] n+2 or a combination of both silicate oligomers with polyhedral skeletons with and without missing corner whereby this silicate oligomer with a polyhedral skeleton is reacted with m silane molecules whereby said silane have a typical chemical formula of the form SiA 2 R 1 R 2 wherein;
  • A is chlorine, an acetoxy group or a reactive leaving group, with a chlorine or an acetoxy group being preferred and a chlorine being particularly preferred;
  • R 1 is a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred and a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being preferably a saturated or aromatic organic moiety and particularly preferably a saturated organic moiety;
  • R 2 is a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred, a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being preferably a saturated or aromatic organic moiety and particularly preferably a saturated organic moiety.
  • the silicate oligomers with a polyhedral skeleton are silicate polyhedral with formula [Si0 3/2 ] n [OH] n , silicate oligomers with a polyhedral skeleton with a missing corner of formula [Sin. !
  • silicate oligomers 0 (3 n-6)/2]n[OH] n+2 or a combination of both silicate oligomers with polyhedral skeletons with and without missing corner whereby this silicate oligomer with a polyhedral skeleton is reacted with one up to m equal or different silane molecules whereby said silanes have a typical chemical formula of the form SiA 1 2 R 1 Ft 2 ; SiA 2 2 R 3 R 4 ; SiA 3 2 R 5 R 6 ; SiA 4 2 R 7 R 8 ; SiA m 2 R 2m 1 R 2m ;
  • a 1 , A 2 , A 3 , A 4 , .., A m are independently from each other a chlorine, an acetoxy group or a reactive leaving group, with a chlorine or an acetoxy group being preferred and a chlorine being particularly preferred;
  • R 1 , R 3 , R 5 , R 7 , .., R 2m 1 are independently from each other a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred, a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being preferably a saturated or aromatic organic moiety and particularly preferably a saturated organic moiety; and wherein R 2 , R 4 , R 6 , R 8 , .., R 2m is a reactive leaving group, a hydrogen atom or an organic moiety, with a chlorine, an acetoxy group, a hydrogen atom or an organic moiety being preferred, a chlorine, an acetoxy group or an organic moiety being particularly preferred, a chlorine or an organic moiety being especially preferred and an organic moiety being especially particularly preferred, with the organic moiety being
  • highly reactive oligosiloxysilane compounds can be obtained through the reaction of silicate oligomers with highly reactive silanes.
  • a solvent or combination of solvents can be used.
  • This solvent or combination of solvents can be mixed with the silicate oligomers, with the highly reactive silanes or with the mixture of silicate oligomers and highly reactive silanes.
  • the solvent or combination of solvents preferentially only contain limited amounts of water and preferentially contains only limited amounts of alcohol. This solvent or combination of solvents could also contain some acid.
  • solvents or combination of solvents can be used.
  • This solvent should preferentially contain as little as possible water and should preferentially contain as little as possible alcohol.
  • Some typical solvents or mixtures of solvents are: tetrahyrofuran, chloroform, acetone, diethyl ether, toluene, N-methylpyrrolidone, N-methylimidazole, dichloromethane, dimethylsulfoxide, acetonitrile, alkane, petroleum-ether or any combination of those solvents.
  • any combination of the above solvents together with an acid is a potential good solvent for suspending or dissolving the silicate oligomers, the highly reactive silanes or the highly reactive oligosiloxysilane compounds.
  • Some of the preferred solvents are: tetrahydrofuran, chloroform and acetone or a combination of one of those solvents with a strong acid (especially HCI).
  • said highly reactive oligosiloxysilane compounds are used in coating whereby the coating can comprise the highly reactive oligosiloxysilane compounds, whereby the coating is completely build from highly reactive oligosiloxysilane compounds, whereby the coating is partially build from highly reactive oligosiloxysilane compounds, whereby the coating is partially constructed using highly reactive oligosiloxysilane compounds or whereby the coating is obtained through the use of highly reactive oligosiloxysilane compounds.
  • said highly reactive oligosiloxysilane compounds are used in polymer whereby the polymer can comprise the highly reactive oligosiloxysilane compounds, whereby the polymer is built completely from highly reactive oligosiloxysilane compounds, whereby the polymer is built partially from highly reactive oligosiloxysilane compounds, whereby the polymer is partially constructed using highly reactive oligosiloxysilane compounds or whereby the polymer is obtained through the use of highly reactive oligosiloxysilane compounds.
  • said highly reactive oligosiloxysilane compounds are used in hierarchical materials whereby the hierarchical material can comprise the highly reactive oligosiloxysilane compounds, whereby the hierarchical material are built completely from highly reactive oligosiloxysilane compounds, whereby the hierarchical material are built partially from highly reactive oligosiloxysilane compounds, whereby the hierarchical material are partially constructed using highly reactive oligosiloxysilane compounds or whereby the hierarchical material are obtained through the use of highly reactive oligosiloxysilane compounds.
  • said highly reactive oligosiloxysilane compounds are used in glue whereby the glue can comprise the highly reactive oligosiloxysilane compounds, whereby the glue is completely build from highly reactive oligosiloxysilane compounds, whereby the glue is partially build from highly reactive oligosiloxysilane compounds, whereby the glue is partially constructed using highly reactive oligosiloxysilane compounds or whereby the glue is obtained through the use of highly reactive oligosiloxysilane compounds.
  • said highly reactive oligosiloxysilane compounds are used in paint whereby the paint can comprise the highly reactive oligosiloxysilane compounds, whereby the paint is completely build from highly reactive oligosiloxysilane compounds, whereby the paint is partially build from highly reactive oligosiloxysilane compounds, whereby the paint is partially constructed using highly reactive oligosiloxysilane compounds or whereby the paint is obtained through the use of highly reactive oligosiloxysilane compounds.
  • said highly reactive oligosiloxysilane compounds are used in varnish whereby the varnish can comprise the highly reactive oligosiloxysilane compounds, whereby the varnish is completely build from highly reactive oligosiloxysilane compounds, whereby the varnish is partially build from highly reactive oligosiloxysilane compounds, whereby the varnish is partially constructed using highly reactive oligosiloxysilane compounds or whereby the varnish is obtained through the use of highly reactive oligosiloxysilane compounds.
  • HMI Hexamethyleneimine
  • TEOS tetraethyl orthosilicate
  • TBA-CySH (TEA) crystals of example 3 were dried under vacuum at room temperature for 48 hours.
  • a mixture of 0.6 ml hydrochloric acid 37% (HCI), 8 ml deuterated tetrahydrofuran (THF) , 12 ml tetrahydrofuran (THF) and 9 ml Dimethyldichlorosilane (Me 2 CI 2 Si)) was partially distilled. 25.5 ml of this partially distilled mixture was added to the dried TBA-CySH (TEA) crystals. A white suspension was formed. The suspension was filtered through a 0.2 ⁇ Teflon filter and characterized using 29 Si NMR.
  • TBA-CySH (TEA) crystals of example 3 were dried under vacuum at room temperature for 48 hours.
  • a mixture of 0.6 ml hydrochloric acid 37% (HCI), 8 ml deuterated tetrahydrofuran (THF), 12 ml tetrahydrofuran (THF) and 9 ml Dimethyldichlorosilane (Me 2 CI 2 Si)) was partially distilled. 25.5 ml of this partially distilled mixture was added to the dried TBA-CySH (TEA) crystals. A white suspension was formed. 15ml of the suspension was filtered through a 0.2 Mm Teflon filter and was evaporated under vacuum at 100°C for 24 hours until a dry white powder was formed.
  • TBA-CySH (NH 3 ) (example 2) crystals were dried under vacuum at room temperature for 48 hours. 20 ml of dried tetrahydrofuran (THF) and 5 ml of Diacetoxydimethylsilane (Ac 2 Me 2 Si) were added to the dried crystals. A white suspension was obtained. The solution was filtered through a 0.2 im Teflon filter and characterized using 9 Si NMR.
  • HMI-CySH crystals (example 1) crystals were dried under vacuum at room temperature for 48 hours. 20 ml of dried tetrahydrofuran (THF) and 5 ml of a 2M HCI in diethylether solution were added to the dried crystals. A white suspension was obtained. The solution was filtered through a 0.2 ⁇ Teflon filter and characterized using 9 Si NMR. 29 Si-NMR showed 1 clear and sharp resonance around -99 - " lOOppm providing evidence for the presence of silicate oligomeric cubes in the suspension. EXAMPLE 8 Organic suspension of silicate oligomers
  • TBA-CySH crystals 1 gram of TBA-CySH crystals (example 2) crystals were dried under vacuum at room temperature for 48 hours. 15 ml of dried tetrahydrofuran (THF) and 5 ml of an aqueous solution (37%) were added to the dried crystals. A white suspension was obtained. The solution was filtered through a 0.2 ⁇ Teflon filter and characterized using 29 Si NMR. 29 Si- NMR showed 1 clear and sharp resonance around -99 -100 ppm providing evidence for the presence of silicate oligomeric cubes in the suspension (see Figure 18).
  • TBA-CySH (NH 3 ) (example 2) crystals were dried under vacuum at room temperature for 48 hours. 20 ml of dried tetrahydrofuran (THF) and 8 ml of Dichlorodimethylsilane (CI 2 Me 2 Si) were added to the dried crystals. A white suspension was obtained. The solution was filtered through a 0.2 ⁇ Teflon filter and characterized using 29 Si NMR.

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Abstract

La présente invention concerne une nouvelle technique de synthèse destinée à une famille de matériaux polymères à base de silice synthétisés par le biais de la réaction d'oligomères de silicate avec des silanes hautement réactifs. A l'aide de cette synthèse, il est possible de produire de nouveaux composés oligosiloxysilane hautement réactifs. La présente invention concerne donc également les éléments de ce groupe de composés oligosiloxysilane hautement réactifs, les oligomères de silicate étant mis en réaction avec des silanes hautement réactifs pour former ce que l'on appelle une structure cœur-écorce. Les composés oligosiloxysilane hautement réactifs de formules empiriques Xy8, dans lesquelles X représente un octamère de silicate à double cycle à quatre chaînons, y représente un silane hautement réactif relié avec une liaison siloxane au double cycle à quatre chaînons.
PCT/EP2015/054212 2014-02-28 2015-02-27 Composé oligosiloxysilane hautement réactif WO2015128496A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018184395A (ja) * 2017-04-24 2018-11-22 国立研究開発法人産業技術総合研究所 シロキサン化合物の製造方法、新規なシロキサン化合物、およびそれらの用途
WO2021085482A1 (fr) * 2019-10-31 2021-05-06 国立研究開発法人産業技術総合研究所 Composé et son procédé de production
CN113195801A (zh) * 2018-10-24 2021-07-30 国立研究开发法人产业技术综合研究所 晶体、晶体的制造方法、以及使硅烷醇化合物自组装化的方法
JP2021127345A (ja) * 2017-04-20 2021-09-02 国立研究開発法人産業技術総合研究所 シラノール化合物及びシラノール化合物の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173760A (ja) 2008-01-23 2009-08-06 Kaneka Corp 液状多面体構造ポリシロキサン系化合物および該化合物を用いた組成物と硬化物。
WO2013026106A2 (fr) * 2011-08-19 2013-02-28 Katholieke Universiteit Leuven Polyoligosiloxysilane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173760A (ja) 2008-01-23 2009-08-06 Kaneka Corp 液状多面体構造ポリシロキサン系化合物および該化合物を用いた組成物と硬化物。
WO2013026106A2 (fr) * 2011-08-19 2013-02-28 Katholieke Universiteit Leuven Polyoligosiloxysilane

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
C.A. CROCK; A.R. ROGENSUES; W. SHAN; V.V. TARABARA, NANOTECHNOLOGY FOR WATER AND WASTEWATER TREATMENT., vol. 12, 2013, pages 3984 - 3996
K. BENNER ET AL., ANGEW. CHEM. INT. ED. ENGL., vol. 36, 1997, pages 743 - 745
P.L.H. VERLOOY ET AL., MICROPOR. AND MESOPOR. MATER., vol. 130, 2010, pages 14 - 20
P.L.H. VERLOOY ET AL., MICROPOR. MESOPOR. MATER., vol. 130, 2010, pages 14 - 20

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021127345A (ja) * 2017-04-20 2021-09-02 国立研究開発法人産業技術総合研究所 シラノール化合物及びシラノール化合物の製造方法
JP7198523B2 (ja) 2017-04-20 2023-01-04 国立研究開発法人産業技術総合研究所 シラノール化合物及びシラノール化合物の製造方法
JP2018184395A (ja) * 2017-04-24 2018-11-22 国立研究開発法人産業技術総合研究所 シロキサン化合物の製造方法、新規なシロキサン化合物、およびそれらの用途
JP7157998B2 (ja) 2017-04-24 2022-10-21 国立研究開発法人産業技術総合研究所 シロキサン化合物の製造方法、新規なシロキサン化合物、およびそれらの用途
CN113195801A (zh) * 2018-10-24 2021-07-30 国立研究开发法人产业技术综合研究所 晶体、晶体的制造方法、以及使硅烷醇化合物自组装化的方法
WO2021085482A1 (fr) * 2019-10-31 2021-05-06 国立研究開発法人産業技術総合研究所 Composé et son procédé de production

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