Technical field of the I nvention

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.

Several documents are cited throughout the text of this specification. Each of the documents herein (including any manufacturer's specifications, instructions etc.) are hereby incorporated by reference; however, there is no admission that any document cited is indeed prior art of the present invention.

Background of the invention

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. Only one silicate hydrate with a double six-ring silicate unit has been described in K. Benner et al., Angew. Chem. Int. Ed. Engl., 36 (1997) 743-745, a silicate hydrate based on alfa-cyclodextrine, which includes alpha-cyclodextrine. Potassium or sodium cations are necessary to compensate the charge of the cyclosilicate units. In the crystal structure layers of double six rings are sandwiched between double layers of alpha- Cyclodextrine molecules. A potassium cation resides in the center of each of the hexagonal silicate faces and other potassium cations reside between the hexagonal silicate prisms. Each of the terminal oxygen atoms of a silicate unit participates in three hydrogen bonds. Most of the hydrogen bonds engage the alpha-cyclodextrine molecules and on average only 1.3 hydrogen bonds per terminal oxygen atom engage a water molecule (see K. Benner et al., Angew. Chem. Int. Ed. Engl., 36 (1997) 743-745). Three groups of silicate hydrate structures types having silicate units that are directly connected to each other through hydrogen bonds have been described in P.L.H. Verlooy et al. Micropor. Mesopor. Mater., 130 (2010) 14-20. Furthermore it is found that in some if not all silicate hydrate materials a large fraction (if not all) of the crystal water can be removed while retaining specific silicate oligomers inside the structure. A range of silicate oligomers exists, but only a limited number of different semi-ridged silicate oligomers can be synthesized in relatively large quantity, the cyclosilicate oligomers.

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 denotes a hydrogen atom or an alkenyl group which may be equal to or different from each other).

There is a strong need in the art for highly reactive, semi-rigid compounds that could find many applications in for example enforcing polymers, fire retardation, cross linking polymers, mechanically resistant hydrophobic, thermally and chemically stable coatings, hierarchical materials etc. As additives in polymer, or in the application of coatings or for in the synthesis of hierarchical materials, a dispersion or suspension of highly reactive nanoparticles or oligomers may be used. For the same applications larger particles, gel like materials or polymers may also be used. A good dispersion or suspension of nanoparticles or oligomers is however preferred to obtain homogeneity and a better mixing. Moreover both in polymers and coatings the curing time is extremely important. 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).

SUMMARY OF I NVENTI ON

It is an object of the present invention to provide novel highly reactive oligosiloxysilanes and a new synthesis procedure therefor.

An advantage of the present invention is that the group of highly reactive oligosiloxysilane compounds (HROSiSil) can be among other applications be used in (A) Polymers, (B) in coatings, (C) as building block for hierarchical materials, such as in paint, varnish or inorganic glue.

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. In such coatings 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.

According to the present invention a silicate oligomer is reacted with a reactive silane with multiple reactive leaving groups.

According to a first aspect according to the present invention a method for the preparation of a highly reactive silica-based oligosiloxysilane compound is provided 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 said dried cyclosilicate oligomer; optional a removal of a cyclosilicate hydrate or cyclosilicate amine template if present either prior to or after the reaction of said cyclosilicate hydrate or cyclosilicate amine crystals with said one or more preferably predried silanes; optional removal of the solvent or solvent mixture if present; and optional removal or excess of said one or more preferably predried highly reactive silanes if present.

According to a second aspect of the present invention a highly reactive oligosiloxysilane compound is provided obtainable by the method of the first embodiment of the present invention.

According to a third aspect 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.

According to a fourth spect of the present invention, 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.

According to a fifth aspect of the present invention, a polymer is provided comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.

According to a sixth aspect of the present invention, a coating is provided comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.

According to a seventh aspect of the present invention, a hierarchical material is provided comprising the silica-based highly reactive oligosiloxysilane of the second, third or fourth aspects of the present invention.

According to an eighth aspect 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.

According to a ninth aspect of the present invention, 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.

According to a tenth aspect 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.

According to an eleventh aspect 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. According to a twelfth aspect 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.

According to a thirtheenth aspect 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.

According to a fourteenth aspect 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.

Particular and preferred aspects of the invention are set out in the accompanying independent and dependent claims. Features from the dependent claims may be combined with features of the independent claims and with features of other dependent claims as appropriate and not merely as explicitly set out in the claims.

The above and other characteristics, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. This description is given for the sake of example only, without limiting the scope of the invention.

Brief description of the drawings:

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.

Schematical representation of a highly reactive oligosiloxysilane compound with a core (X) (inside red circle) constructed from a double four ring silicate octamer with chemical formulae Si ₈ O ₂₀ , and whereby the shell (S) (between the two black circles) contains eight reactive -SiRR'A groups with A a reactive leaving group (-CI or - OC(0)CH ₃ ) and R and R' independently chosen among organic groups or reactive leaving groups (CI, -OC(0)CH ₃ , OH, H, Br, OR").

Different N-containing template molecules used to synthesise silicate hydrate crystals. A) Quaternary methylammonia: a)Tetramethylammonium (TMA), b) phenyltrimethylammonium (NPhTMA), c) benzyltrimethylammonium (NBzTMA), d) 1 , 1 -dim ethyl- piperidinium , e) 1 ,1 ,4,4-tetramethylpiperazinium (TMPA) f) 1,4- dimethyl-1 ,4-diazoniabicyclo[2.2.2]octane (DDBO) g) Ν,Ν,Ν,Ν'Ν',Ν'- hexamethyl[1 ,1 '-biphenyl]-4,4'dimethanaminium h) Ν,Ν,Ν,Ν'Ν',Ν'- hexamethyl[1 ,1 '-biphenyl]-2,2'dimethanaminium i) 2,3,4,5,6,7,8,9- octahydro-2,2,5,5,8,8-hexamethyl-1 H-benzo [1,2-c: 3,4-c': 5,6c"] tripyrrolium (HMBPT) B) other quaternary ammonia: j) tetraethyl- ammonium (TEA), k) tetrabuthylammonium C) Metal-ethylene- diamine (en) complexes: l)Cu(en) ₂ ²⁺ m), Co(en) ₃ ³⁺ n) Ni(en) ₃ ³⁺ D) Templates capable of synthesizing silicate hydrate crystals of unknown structure: o) triethyl-(2-hydroxyethyl)am monium , p) diethyl-di(2-hydroxyethyl)am monium , q) tetra(2-hydroxyethyl)- ammonium r) triethyl-(2-hydroxypropyl)ammonium , s)pyridine t) N- (2-hydroxyethyl)pyridinium , u) N-(2-hydroxypropyl)pyridinium and v) guanidine.

Schematic representation of a possible reaction product for the reaction between two silanols of two silicate oligomers or between a the silanols of a silicate oligomer and a silanol on the core of the highly reactive oligosiloxy silane or between two silanols on the core of two highly reactive oligosiloxy silanes

Schematic representation or a possible reaction product for the reaction between a silanol group on the silicate oligomer or on the core of a highly reactive oligosiloxy silane and a silicon atom on the shell of a highly reactive oligosiloxy silane. Schematic representation or a possible reaction product for the reaction between two highly reactive silicons on two highly reactive oligosiloxysilane compounds

Schematic representation of the reaction product of a a highly reactive oligosiloxysilane after reaction with a water molecule.

Schematic representation of the reaction product of a highly reactive oligosiloxysilane whereby one silanol did not react with a highly reactive silane.

Schematic representation of the core-shell principle on highly reactive oligosiloxysilanes compounds whereby silicate cores are connected through siloxane bonds or through siloxane bridges.

X-ray diffractogram of HMI-CySH crystals.

X-ray diffractogram of TBA-CySH (NH ₃ ) crystals.

X-ray diffractogram of TBA-CySH (TEA) crystals.

²⁹ Si-NMR of highly reactive oligosiloxysilane compounds synthesized with Dimethyldichlorosilane (Me ₂ CI ₂ Si) , providing evidence for the presence of excess unreacted dichlorodimethylsilane, the presence of a silane dimer (1,2, dichloro-1 ,1 ,2,2 tetramethyl disiloxane) and the desired highly reactive oligosiloxysilane compound [Si ₈ 0 ₂ o][Si(CH ₃ ) ₂ CI] ₈ .

²⁹ Si-NMR of highly reactive oligosiloxysilane compounds synthesized with Dimethyldichlorosilane (Me ₂ CI ₂ Si) whereby the solvent was removed and the particles are redispersed in an organic solvent measured directly after redispersion, providing evidence for the presence of especially the desired highly reactive oligosiloxysilane compound [Si ₈ O ₂₀ ][Si(CH ₃ ) ₂ CI] ₈ .

²⁹ Si-NMR of highly reactive oligosiloxysilane compounds synthesized with Dimethyldichlorosilane (Me ₂ CI ₂ Si) whereby the solvent was removed and the particles are redispersed in an organic solvent measured several hours after redispersion, providing evidence for the presence of the desired highly reactive oligosiloxysilane compound [Si ₈ O ₂₀ ][Si(CH ₃ ) ₂ CI] ₈ , silane oligomers, and highly reactive oligosiloxysilane compound interconnected to each other by siloxane bonds.

²⁹ Si-NMR of highly reactive oligosiloxysilane compounds synthesized with Dimethyldiacetoxysilane providing evidence for the presence of especially the desired highly reactive oligosiloxysilane compound [Si ₈ 0 ₂ o][Si(CH3) ₂ (OC(0)CH ₃ )] ₈ and the unreacted dimethyldiacetoxysilane.

²⁹ Si-NMR of an organic suspension of silicate oligomers, providing evidence for the presence of silicate oligomeric cubes in the suspension.

²⁹ Si-NMR of highly reactive oligosiloxysilane compounds synthesized with Dimethyldichlorosilane (Me ₂ CI ₂ Si) without the addition of a HCI solution, whereby the solvent was removed and the particles are redispersed in an organic solvent providing evidence for the presence of excess unreacted dichlorodimethylsilane, the presence of a silane dimer (1,2, dichloro-1 ,1 ,2,2 tetramethyl disiloxane) and the desired highly reactive oligosiloxysilane compound [Si ₈ 0 ₂ o][Si(CH ₃ ) ₂ CI]8. Description of illustrative embodiments

The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn on scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to actual reductions to practice of the invention.

Furthermore, the terms "first", "second", "third" and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequence, either temporally, spatially, in ranking or in any other manner. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

It is to be noticed that the term "comprising", used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression "a device comprising means A and B" should not be limited to devices consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the device are A and B.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

Similarly it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

The following terms are provided solely to aid in the understanding of the invention. Definitions

A "silicate oligomer" as used herein refers to silicon containing oligomer or polymer whereby every silicon atom is bound to four oxygen atoms. In a silicate oligomer no direct Si-H bonds, no direct Si-C and no direct Si-Si bonds are present. For every set of three orthogonal axes through the center of the silicate oligomer, the dimensions of the silicate oligomer in minimum two orthogonal axes are smaller than 2 nm .

The term "highly reactive silane" as used herein 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.

The term "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.

The term "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.

The terms "core", "shell" and "core-shell" 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).

The term "saturated organic moiety" means an organic moiety without carbon-carbon double or triple bonds and without an aromatic ring structure.

The term "unsaturated organic moiety" means an organic moiety with a carbon-carbon double or triple bond. The term "aromatic organic moiety" means an organic moiety with an aromatic ring structure and no carbon-carbon double or triple bonds.

The term "organic group" encompasses saturated organic moieties unsaturated organic moieties and aromatic organic moieties.

The term "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.

The term "hierarchical structure", as used in disclosing the present invention, means a material containing structural elements which themselves have structure.

The term "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).

Throughout this document many chemical formulae for silicate oligomers, highly reactive silanes and highly reactive oligosiloxysilanes are shown. Since 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.

The abbreviation CySH stands for cyclosilicate hydrate, the abbreviation CySA stands for cyclosilicate amine.

Cyclosilicate oligomers

The cyclosilicate oligomers are double ring silicate oligomers, which are silicate polyhedral with a general formula of [Si0 ₃ / ₂ ] _n [OH] _n * with n = 6, 8, 10 or 12. An example of a silicate octameric cube is shown in figure 2. Furthermore it is also possible to obtain 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.

According to a preferred embodiment of the present invention, the silicate oligomer is a silicate polyhedra of formula [Si0 _3/2 ] _n [OH] _n ^* with n = 6, 8, 10 or 12, with a silicate octameric cube with formula [Si ₈ O ₂₀ ] H _m ^m"8 with m = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 being preferred.

According to another preferred embodiment of present invention, the silicate oligomers are silicate polyhedrals 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 and without missing corner whereby n = 6, 8, 10 or 12 more preferably n = 8.

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 hydrates

Silicate hydrate materials and silicate amines can be obtained from a variety of silicate suspensions. For example: double four ring silicate hydrate crystals can be formed in an aqueous suspension of (excess) hexamethyleneimine and a silica source.

The present inventors have recently discovered that many 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. In many cases the silicate oligomers in those materials are interconnected through a network of hydrogen bonds. Silicate hydrates are positioned between zeolites and clathrate hydrates. In 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. 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. 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). In TBA- silicate hydrates 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. 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). Adding diethylentriamine (di-en), triethylenetetramine (tri-en), 1 ,4- Diazabicyclo[2.2.2]octane (triethylenediamine; di-tri), hexamethylenetetramine (hex-tetra) or para-xylenediamine (p-Xyl-di) to the starting clear solution resulted in a structure similar to the TBA-silicate hydrate in which it is expected that part or all the water is replaced by en, di-en, tri-en, di-tri, hex-tetra or p-Xyl-di molecules. 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. The use of hexamethyleneimine (HMI) as a template give rise to yet another different silicate hydrate structure (HMI-CySH). 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. All terminal oxygen atoms (O _term ) are engaged in hydrogen bonds with the O _term of the neighboring silicate cube, either as donor (O _term H) or as acceptor (O _term ). Due to the short distance between the silicate cubes within a column, it is probable that the hydrogen atoms on the terminal oxygen atoms are flipping from one silicate cube to the other, spreading the net negative charge over the whole of the silicate column.

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.

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.

It is to be expected that many other templates can be used to synthesise silicate hydrate materials. Especially but not exclusively water soluble amines with some degree of restrained flexibility (ring structures, high degree of branching, multiple charge centres) and quaternary methyl amines are interesting candidates as (co-)template in the synthesis of (new) silicate hydrate materials. Silicate hydrates containing ethylenediamine metal-complexes

A silicate hydrate containing isolated cubes was formed in presence of Cu(en) ₂ . In this structure 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.

In the case of 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.

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.

Some more silicate hydrates are formed using ethylendiamine complexes of zinc and palladium. The crystal structure of these silicate hydrates has not been reported so far.

Highly reactive silanes

Among the 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. Moreover 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.

According to the present invention 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. Although 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.

According to a preferred embodiment of the first aspect according to the present invention, 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.

According to the preferred embodiment of the present invention, 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.

In present invention highly reactive leaving groups on said highly reactive silane molecules and on said highly reactive oligosiloxysilane compounds can be Chlorine or Acetoxy groups. In present invention 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.

Silica-based oligosiloxysilane compounds

According to a third aspect of the present invention, 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. According to a preferred embodiment of the third aspect of the present invention, the oligosiloxysilane compound has the formula [Si ₈ 0 ₂ o][SiRR'A] ₈ .

According to another preferred embodiment of the third aspect of the present invention, 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.

According to another preferred embodiment of the third aspect of the present invention, 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.

According to a preferred embodiment of the third aspect of the present invention, wherein a is a chorine atom.

According to a preferred embodiment of the third aspect of the present invention, wherein A is an acetoxy group (-OC(0)CH ₃ ).

According to a preferred embodiment of the fourth aspect of the present invention, 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.

According to a preferred embodiment of the third aspect of the present invention, 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. According to another preferred embodiment of the third aspect of the present invention, R, R' are independently selected among the fluorinated hydrocarbons. According to another preferred embodiment of the fourth aspect of the present invention, R, R' are independently selected among the fluorinated hydrocarbons.

According to another preferred embodiment of the third aspect of the present invention, 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.

According to another preferred embodiment of the third aspect of the present invention, said highly reactive oligosiloxysilane is capable of being dissolved in a dry alcohol-free solvent or solvent mixture.

According to a fifteenth aspect of present invention a method is provided 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.

According to sixteenth aspect of present invention a method is provided 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.

According to seventeenth aspect of present invention a method is provided 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.

According to an eighteenth aspect of present invention a method is provided 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. According to an embodiment of the present invention a highly reactive oligosiloxysilane compound is provided obtainable by one of the methods of fifteenth, sixteenth, seventeenth or eighteenth aspect of the present invention.

According to another preferred embodiment of the third aspect of the present invention, wherein said highly reactive oligosiloxysilane is capable of being suspended in a dry alcohol-free solvent or solvent mixture.

According to another preferred embodiment of the third aspect of the present invention, wherein highly reactive oligosiloxysilane comprises a silica core and a highly reactive silane shell.

According to an embodiment according to the present invention, 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.

According to another embodiment according to the present invention, 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.

According to another embodiment according to the present invention, 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.

According to another embodiment according to the present invention, 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.

According to another embodiment according to the present invention, 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.

According to another embodiment according to the present invention, two or more highly reactive oligosiloxysilanes can be connected through one or more direct siloxane bonds. According to another embodiment according to the present invention, two or more highly reactive oligosiloxysilanes can be connected through one or more siloxane bridges.

According to another embodiment according to the present invention, two or more highly reactive oligosiloxysilanes can be connected and can contain one or more silanols.

According to another embodiment according to the present invention, 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.

According to another embodiment according to the present invention, 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.

In an embodiment of present invention the core part of the highly reactive oligosiloxysilane compounds (HROSiSil) of present invention consist of a double four ring silicate octamer. In the highly reactive oligosiloxysilane compounds of present invention, 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.

In another embodiment of present invention we claim materials as shown in figure 4 whereby a 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. Method of preparation of a silica-based highly reactive oligosiloxysilane

In a typical synthesis of highly reactive oligosiloxysilane compounds, according to the present invention, a source of silicate oligomers (X, X', X",...) is brought into contact with highly reactive silane molecules (Y, Υ', Υ', ...) with minimum two reactive (-CI and/or -OC(0)CH ₃ ) leaving groups.

It is a specific embodiment of present invention to synthesize highly reactive oligosiloxysilane compounds with silicate oligomers in the absence of water and alcohol and to have highly reactive silane molecules can come into contact with the silicate oligomers. 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.

Next to the water also the presence of alcohols should be avoided. 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.

The here above described or 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.

In order to have a good contact between the silicate oligomers and the highly reactive silanes there are three main possible pathways: or 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.

Specific embodiments of present invention can each follow one of the above described pathways.

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.

During the reaction between the silicate oligomers and the silane molecules some side reactions could occur. Instead of the desired reaction between silicate oligomers and highly reactive silane molecules also reactions between silicate oligomers (X, X',...) or between highly reactive silane molecules (y(rlg), y'(rlg), y"(rlg),...) could occur. Through the reaction of the highly reactive silanes with the silicate oligomers a core shell particle is formed: a highly reactive oligosiloxysilane with a Silica core (X) and a highly reactive silane shell (S). Side reactions between the silicate oligomers or between the highly reactive silane molecules are not desired, so some precautions should be taken. 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. 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. Another method to stabilize silicate oligomers is by using a solvent with a high ionic nature. 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. 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.

Prior and during to the synthesis of highly reactive oligosiloxysilane compounds the 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.

During the synthesis of highly reactive oligosiloxysilane compounds 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. To prevent this type of reaction it is important to work as dry as possible Especially in the case of acetoxy-based silanes 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. If during or after the synthesis of the highly reactive oligosiloxysilane, 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).

Furthermore if 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.

According to the present invention 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:

a) 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.

b) Drying silicate oligomers etc.

When reacting the silicate oligomers with highly reactive silanes, the presence of water is dendrimerical. Also after the formation of highly reactive oligosiloxysilane compounds water is not wanted. Therefor all reagents should preferentially be dryed. Drying of silicate oligomers can be performed though storage in dry environment, though the use of a dry gas stream, through washing with dry solvents, through the use of drying agents, the addition of heat or the application of vacuum or a combination of one or more of the previous drying options. Highly reactive silane and the eventually used solvents or mixtures of solvents should also preferentially be dried as much as reasonably possible.

c) Suspension 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.

e) Silane in a solvent

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.

f) Distillation of silane

In order to purify highly reactive silanes, those silanes can be distilled. In this way 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.

g) Distillation of solvent

A solvent or mixture of solvent can be distilled in order to reduce the water content in this solvent or this mixture of solvents. To obtain even dryer 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. Furthermore 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.

h) Formation of the highly reactive oligosiloxysilane compounds

Once the silicate oligomers are brought into contact with the highly reactive silanes, the highly reactive oligosiloxysilane compounds can be formed.

i) Removal of template

Silicate oligomers often come together with some kind of template. 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. Also if 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,

j) Removing of solvent

If at any time prior, during or after the reaction between the silicate oligomers with the highly reactive silane molecules a solvent or mixture of solvents is used, 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.

k) Removing excess silane

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.

It is clear that highly reactive 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..

I) Re-dissoving the highly reactive oligosiloxysilane compounds

If for any reason the highly reactive oligosiloxysilane compounds are not or no longer in a solvent, 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. It is clear that the solvent or mixture of solvents preferentially contains as little as possible water and preferentially contains as little as possible alcohol.

m) Use of the highly reactive oligosiloxysilane compounds as additive or crosslinker in polymers, for the formation of coatings for building hierarchical materials, as glue, paint or varnish, as a component in glue, as a component in paint or as a compont in varnish.

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. In this case 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. However 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.

According to a preferred embodiment of the first aspect of the present invention, said cyclosilicate oligomer is a double four ring silicate octamer.

According to another preferred embodiment of the first aspect of the present invention, said cyclosilicate oligomer is dissolved or suspended in a solvent or mixture of solvents, which are preferably dry and alcohol-free.

According to a preferred embodiment of the first aspect of the present invention, said cyclosilicate hydrate or cyclosilicate amine is a D4R cyclosilicate hydrate. According to another preferred embodiment of the first aspect of the present invention, said cyclosilicate hydrate or cyclosilicate amine is a D4R cyclosilicate amine.

According to another preferred embodiment of the first aspect of the present invention, 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.

According to another preferred embodiment of the first aspect of the present invention, 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.

According to another preferred embodiment of the second aspect of the present invention, the highly reactive oligosiloxysilane comprises highly reactive leaving groups said CI or acetoxy groups directly bound to a silicon atom.

According to another preferred embodiment of the first aspect of the present invention, 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.

According to another preferred embodiment of the first aspect of the present invention, said highly reactive silane is selected from the group consisting of dichlorodimethylsilane and diacetoxydimethylsilane.

According to another preferred embodiment of the first aspect of the present invention, 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.

According to another preferred embodiment of the present invention, 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.

According to an embodiment of the present invention 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 ,

wherein n = 6, 8, 10 or 12, with n = 8 being preferred, and m = 1, 2, ..n, with 2 < m < n being preferred, n/2 < m < n being particularly preferred and m = n being especially preferred;

wherein A is a reactive leaving group, with chlorine or an acetoxy group being preferred and chlorine being particularly preferred;

wherein 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;

and wherein 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.

According to another embodiment of the present invention 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 ;

wherein n = 6, 8, 10 or 12, with n = 8 being preferred, and m = 1, 2, ...,n, with 2 < m < n, being preferred, n/2 < m < n being particularly preferred and m = n being especially particularly preferred;

wherein 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;

wherein 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;

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 preferably a saturated or aromatic moiety and particularly prefaerably a saturated organic moiety.

According to a still further embodiment of present invention, 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;

n = 6, 8, 10 or 12, with n = 8 being preferred and wherein m = 1, 2, .., (2n+2), with 2 < m < 2n+2 being preferred and n/2 < m < 2n+2 being particularly preferred;

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; wherein 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;

and wherein 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.

According to a still further embodiment of present invention 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 ₍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 ;

wherein n = 6, 8, 10 or 12, with n = 8 being preferred, and wherein m = 1, 2, ... (,2n+2), with 2 < m < 2n+2 being preferred and n/2 < m < 2n+2 being particularly preferred;

wherein 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;

wherein 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 preferably a saturated or aromatic organic moiety and particularly preferably a saturated organic moiety.

Solvents

In the present invention highly reactive oligosiloxysilane compounds can be obtained through the reaction of silicate oligomers with highly reactive silanes. During this reaction 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.

In order to obtain highly reactive oligosiloxysilane compounds through the reaction of silicate oligomers with highly reactive silanes a solvent 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. Also any combination of the above solvents together with an acid (HCI, HN0 ₃ , H ₂ S0 ₄ , etc.) 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). Use of a silica-based highly reactive oligosiloxysilane compound

According to a preferred embodiment of the eighth aspect of the present invention 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.

According to another preferred embodiment of the eighth aspect of the present invention, 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.

According to another preferred embodiment of the eighth aspect of the present invention, 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.

According to a preferred embodiment of the eighth aspect of the present invention 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.

According to a preferred embodiment of the eighth aspect of the present invention 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.

According to a preferred embodiment of the eighth aspect of the present invention 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. EXAMPLES

EXAMPLE 1 Synthesis of HMI -CySH crystals

20 ml Hexamethyleneimine (HMI) was added to a 250 ml polypropylene containing 60 ml of deionized water. To this stirred aqueous mixture, 20 ml tetraethyl orthosilicate (TEOS) was added over a period of 60 minutes. This mixture was stirred continuously until crystals were formed. After 3 additional days of stirring, the mixture was filtered. A white/yellowish powder is obtained, HMI-CySH crystals. The structure of the silicate hydrate material was confirmed using X-ray diffraction (XRD) (see Figure 12).

EXAMPLE 2 Synthesis of TBA-CySH (NH ₃ ) crystals

20 ml Tetrabutylammonium hydroxide 40% (TBAOH) and 20 ml of Ammonia 25% (NH ₃ ) was added to a 250 ml polypropylene containing 40 ml of deionized water. To this stirred aqueous mixture, 20 ml tetraethyl orthosilicate (TEOS) was added over a period of 60 minutes. This mixture was stirred continuously until crystals were formed. After 1 additional day of stirring, the mixture was filtered. A white powder is obtained, TBA-CySH (NH ₃ ) crystals. The structure of the silicate hydrate material was confirmed using X-ray diffraction (XRD) (see Figure 13). EXAMPLE 3 Synthesis of TBA-CySH (TEA) crystals

20 ml Tetrabutylammonium hydroxide 40% (TBAOH) and 20 ml of Triethylamine (TEA) was added to a 250 ml polypropylene containing 20 ml of deionized water. To this stirred aqueous mixture, 20 ml tetraethyl orthosilicate (TEOS) was added over a period of 60 minutes. This mixture was stirred continuously until crystals were formed. After 7 additional days of stirring, the mixture was filtered. A white/yellowish powder is obtained, TBA-CySH (TEA) crystals. The structure of the silicate hydrate material was confirmed using X-ray diffraction (XRD) (see Figure 14). EXAMPLE 4 Highly reactive oligosiloxysilane compounds with Dimethyl- dichlorosilane (Me ₂ CI ₂ Si)

2 grams of 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 μητι Teflon filter and characterized using ²⁹ Si NMR. ²⁹ Si-NMR showed four clear signals, providing evidence for the presence of excess unreacted dichlorodimethylsilane, the presence of a silane dimer (1,2, dichloro-1 ,1 ,2,2 tetramethyl disiloxane) and the desired highly reactive oligosiloxysilane compound [Si ₈ 0 ₂ o][Si(CH ₃ ) ₂ CI]8 (see Figure 15).

EXAMPLE 5 Highly reactive oligosiloxysilane compounds with Dimethyl- dichlorosilane ( Me ₂ CI ₂ Si) redispersed in organic solvent

2 grams of 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. To this dry powder 15 ml of dry deuterated Chloroform (CHCI ₃ ) was added. This solution was filtered through a 0.2 μηι Teflon filter to remove remaining particles and characterized using ²⁹ Si NMR. ²⁹ Si-NMR clearly showed two sharp signals, providing evidence for the desired highly reactive oligosiloxysilane compound [Si ₈ 02o][Si(CH ₃ ) ₂ CI] ₈ (see Figure 16a and 16b).

EXAMPLE 6 Highly reactive oligosiloxysilane compounds with Diacetoxy- dimethylsilane ( Ac ₂ Me ₂ Si)

2 grams of 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. ²⁹ Si-NMR showed four clear signals, providing evidence for the presence of excess unreacted diacetoxydimethylsilane, the presence of a silane dimer (1,2, diacetoxy-1 ,1 ,2,2 tetramethyl disiloxane) and the desired highly reactive oligosiloxysilane compound [Si ₈ 0 ₂ o][Si(CH ₃ ) ₂ (OC(0)CH ₃ )] ₈ (see Figure 17). EXAMPLE 7 Organic suspension of silicate oligomers

0,8 grams of 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 μιη 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

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 μιη 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).

EXAMPLE 9 Highly reactive oligosiloxysilane compounds with Dimethyl- dichlorosilane (Me ₂ CI ₂ Si) redispersed in organic solvent and without the addition of a HCI solution

2 grams of 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 μηι Teflon filter and characterized using ²⁹ Si NMR. ²⁹ Si-NMR showed four clear signals, providing evidence for the presence of excess unreacted dichlorodimethylsilane, the presence of a silane dimer (1,2, dichloro-1 ,1 ,2,2 tetramethyl disiloxane) and the desired highly reactive oligosiloxysilane compound [Si ₈ O2 ₀ ][Si(CH ₃ ) ₂ CI] ₈ (see Figure 19).