WO2012119615A1

WO2012119615A1 - Silsesquioxane polymers

Info

Publication number: WO2012119615A1
Application number: PCT/EP2011/001160
Authority: WO
Inventors: Ian P. Teasdale; Antonia PRUAS; Ivo Nischang; Oliver BRÜGGEMANN
Original assignee: Johannes Kepler Universität Linz
Priority date: 2011-03-09
Filing date: 2011-03-09
Publication date: 2012-09-13

Abstract

The present invention relates to the fields of polymers and porous adsorbents. In particular the present invention relates to polymers of crosslinked silsesquioxane units of the formula (RSi0_3/2)_n wherein n may be 6, 8, 10 or 12 or a mixture thereof; R is a substituent, each R of the n R within the formula (RSi0_3/2)_n may be the same or different. The present invention relates also to methods of producing said polymers, e.g. by way of radical polymerisation. Finally, the present invention relates to adsorbent materials comprising said polymers and the technical application of said polymers and adsorbent materials for different technical purposes such as flow-through applications, micro-fluidic applications, gas storage/separation, solid phase extraction, or catalysis.

Description

Silsesquioxane polymers

The present invention relates in general to the fields of polymers and porous adsorbents. In particular the present invention relates to polymers of crosslinked silsesquioxane units of the formula (RSi0_3/2)_n wherein n may be 6, 8, 10 or 12 or a mixture thereof; R is a substituent, and each R of the n R within the formula (RSi0_{3 2})_n may be the same or different. The present invention relates also to methods of producing said polymers, e.g. by way of radical polymerisation. Finally, the present invention relates to adsorbent materials comprising said polymers and the technical application of said polymers and adsorbent materials for different technical purposes such as flow- through applications, micro-fluidic applications, gas storage, or catalysis.

High surface area, (nano)porous adsorbents have a wide variety of applications including hydrogen storage, catalysis, as selectively permeable membranes, as adsorbents for solid phase extractions, as well as in liquid chromatographic separations in a wide variety of modes. The rapidly developing field of microfluidics, in particular dealing with lab-on-a-chip technologies, demands an increase in surface-to-volume ratios of open channel systems in order to increase loading, provide selectivity and excellent flow through properties at decent backpressures. Porous, monolithic materials for such applications demand facile, repeatable and relative ease of preparation, alongside reasonable mass transfer rates important for the performance of such devices. For flow through applications, both in mircofluidic and in larger dimensions, hierarchically-structured silica monoliths offer a number of advantages considering high permeability to flow achieved by the presence of micrometer-sized through-pores in which convective mass transfer prevails together with a mesoporous pore space in the silica skeleton providing surface area and high density of interacting functionality.

Cubic polyhedral silsesquioxanes (POSS) (for review see Gnanasekaran D et al. (Journal of Scientific industrial Research, 2009, 68, p. 437-464)), with the basic structure (RSi0_3/2 )_n, are nanometer-sized inorganic/organic hybrid building blocks of interest in many areas and for applications ranging from dendrimer synthesis to the reinforcement of high performance polymer materials. Furthermore, the hybrid nature and absence of silanol groups leads to an improved pH tolerance for cage-like silsesquioxanes. Microporous materials (pore size < 2nm) based on POSS precursors have been prepared using sol-gel chemical routes (K. Nakanishi & K. Kanamori, Journal of Materials Chemistry, 2005, 15, p. 3776-3786) as well as by hydrosilation reactions (Zhang CX et al., J. Am. Chem. Soc, 1998,120,8380-8391 ) to yield materials with surface areas of approximately 500 m²g^"\

Nakanishi and Kanamori synthesized siloxane-based organic-inorganic hybrid monoliths with well-defined macropores and/or mesopores by a sol-gel process, accompanied by polymerisation- induced phase separation. Using aklyltrialkoxysilanes and alkylene-bridged alkoxysilanes, two different categories of organosiloxane networks were characterized in view of macroporosity (based on phase separation) and mesoporosity (supramolecularly templated by surfactants).

Zhang CX et al. 0· Am. Chem. Soc, 1998,120,8380-8391 ) describe preparations of copolymers of octahydridosilsesquioxanes, and octavinylsilsesquioxanes in presence of platinum divinyltetramethyldisiloxane as catalyst (hydrosilation method). The resulting polymers exhibit pores in the interior of about 0,3 nm in diameter, and 1 to 50 nm in diameter between the cubes.

However, the multi-step processes used in the prior art for preparation of these monoliths, in particular via sol-gel synthetic routes, tends to be highly sensitive to operational variables and are known to be difficult to realize, particularly in microfluidic devices resulting in their limited availability to a broad audience.

Therefore, the object of the present invention was to provide novel adsorbent polymers and materials, which may be prepared easily, preferably in many types of formats.

This object is solved by the present invention, in particular by means as set forth in the appended set of claims and as illustrated in the following.

The inventors of the present invention discovered that it is possible to create by means of e.g. radical polymerisation of silsesquioxane monomers versatile, high surface area, hierarchically- structured adsorbent materials. The simple, single step polymerization reaction under e.g. mild conditions can be used to prepare materials in almost any format, for example as (porous) particulate, columnar (tubular) porous format and in any spatial confinement as well as thin sheet. In a first aspect the present invention relates to a method for producing a preferably porous polymer (radical polymerisation method), wherein the method comprises:

- providing one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n (formula I) wherein:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one polymerizable C=C bond, in particular a non-aromatic C=C bond; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n by means of radical polymerisation, preferably in solution.

The molecular building blocks of the polymers according to the present invention are preferably predominantly or even exclusively silsesquioxane monomers of the formula (RSi0_{3 2})_n- A person skilled in the art will understand that such silsesquioxane monomer comprises n R residues, n Si atoms and 1 ,5 times n O atoms.

Predominantly in the context of the radical polymerisation method mentioned above means that the fraction of said silsesquioxane monomers in the polymerisation reaction constitutes preferably stoichiometrically at least 50% or more than 50% of the monomers to be polymerized, preferably more than 55%, even more preferably more than 60%, even more preferably more than 65%, even more preferably more than 70%, even more preferably more than 75%, even more preferably more than 80%, even more preferably more than 85%, even more preferably more than 90%, even more preferably more than 95%, even more preferably more than 98%, most preferably 100% (ignoring any potential initiators) of the monomers provided. In other words, in particular embodiments it may be advantageous or at least not disadvantageous to create (hetero-)polymers not only comprising the silsesquioxane monomers of the formula (RSi0_{3 2})_n but also to a lesser extent other monomers which may be included in the polymerisation process. However, particularly preferred is the use of only silsesquioxane monomers of the formula (RSi0_{3 2})_n as building blocks of the polymer according to the invention.

As mentioned above, the methods for producing a polymer according to the present invention (radical polymerisation method above as well as thiol-ene, alkyne and Diels Alder methods below) are based on monomeric building blocks which consist of one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n. The various types of silsesquioxane monomers of the formula (RSi0_3/2)n can differ from each other in terms of n and/or R and/or position of substituents. With regard to n: Since n may be 6, 8, 10, or 12, it is within the scope of the present invention to polymerize for example a mixture of octavinyl silsesquioxane monomers and decavinyl silsesquioxane monomers (i.e. the monomers differ in terms of n, but not in terms of R). It is not even unlikely that for example commercially available silsesquioxanes are inherently heterogenic with regard to n as a consequence of the production process. This concept, that the individual monomers may vary with regard to n, is herein further highlighted by the term "or a mixture thereof". Likewise, the monomers for use as starting material for the polymerisation reactions of the present invention may vary with regard to R. For example, the first type of monomer may be octavinyl silsesquioxane while another type of monomer is octapropenyl silsesquioxane (i.e. the monomers differ in terms of R, but not in terms of n). The monomers may also differ in terms of R and n, for example a combination of octavinyl silsesquioxane monomers and decapropenyl silsesquioxane. Likewise the monomers may neither differ in n nor (at least in principle) in R, but only in terms of position of the substituent (for example in divinylhexaisobutyl silsesquioxane the two vinyl substituents (*) may be on adjacent Si atoms (Si*-0-Si*) or may be on non-adjacent Si atoms (Si*-O-Si-O-Si*). In addition, it will be understood by a person skilled in the art that there may not only be two types of silsesquioxane monomers of the formula (RSi0_3/2)_n (as in the examples given above), but that more than two types of silsesquioxane monomers of the formula (RSi0_3/2)n can be used in the polymerisation methods of the present invention. This may for example apply if some of the monomers are modified before the actual polymerisation (vide infra). In a particular embodiment of the invention three types of silsesquioxane monomers of the formula (RSi0_{3 2})n are used as building block of the polymers according to the present invention. In an example given below for instance a mixture of silsesquioxane monomers of the formula (RSi0_{3 2})_n with n=8, 10 and 12 is shown.

R is a substituent, preferably an organic substituent, or hydrogen. In addition, each R of the n R within the formula (RSi0_3/2)_n of a given monomer may be the same or different. This includes for example that all R within a given monomer may be identical (e.g. octavinyl silsesquioxane, in which all 8 R are vinyl), that all R are within a given monomer are entirely different from each other or that 2, 3, 4, 5, 6, or (if applicable, depending on n) 7, 8, 9, 10, or 1 1 Rs of the n Rs within a given monomer are identical (e.g. vinyl heptaisobutyl silsesquioxane, wherein 7 of 8 Rs are identical). Of course there may be also groups of identical Rs (e.g. tetravinyl tetraisobutyl silsesquioxane, where two times 4 Rs are identical). In principle the formula (RSiO_3/2)_n may thus also be understood to cover the following subformulas: n=6: (R₁SiO_3/2)(R₂SiO_3/2)(R₃SiO_M)(R₄SiO_3/2)(R₅SiO_3/2)(R₆SiO_3/2) (subformula la)

n=8: (R,SiO_M)(R₂SiO_3/2)(R₃SiO_3/2)(R4SiO_3/2)(R5SiO_3/2)(R₆SiO_3/2)(R₇SiO_3/2)_n(R₈SiO_3/2) (subformula lb) n=10: (R₁Si0_3/2)(R₂Si0_3/2)(R3Si03_/2)(R₄Si03_/2)(R₅Si0_3/2)(R₆Si0_3/2)(R₇Si0_3/2)_n(R₈Si03_/2)(R₉Si0_3/2)

(R₁₀SiO_3/2) (subformula lc), and

n=12: (R₁Si0_3/2)(R₂Si0_3/2)(R₃Si0_3/2)(R4Si0_3/2)(R₅Si0_3Q)(R₆Si0_3/2)(R₇Si0_3/2)_n(R₈Si0₃^)(R₉Si0_3/2)

(R₁₀SiO_3/2) (R„SiO_M) (R₁₂Si0_3/2) (subformula Id), wherein each R of R, to R₁₂ is selected individually and independently of any other R (which does not rule out as mentioned above that certain Rs are nevertheless identical). And each R of R, to R₁₂ of a first type of monomer may as mentioned above be selected individually and independently of any other R, to R₁₂ of potential further types of silsesquioxane monomers of the formula (RSi0_{3 2})n provided to the reaction mixture. In a particular embodiment of the invention more than one or even all R in a given monomer of the formula (RSi0_{3 2})_n are identical.

A person skilled in the art will understand in view of the description of the invention provided herein and in view of his common general knowledge about polymerisation that the precise chemical nature of R is in principle entirely irrelevant. For the radical polymerisation method disclosed above (but as well for the thiol-ene, alkyne and Diels Alder reactions below) this applies in particular to those Rs which do not comprise the reactive group, e.g. the polymerizable C=C bond. For example, in view of the cage like structure of the silsesquioxane monomers these other substituents do not interfere with the polymerisation reaction. Likewise, even the nature of the substituent comprising the reactive group, e.g. the polymerizable C=C bond is in principle irrelevant for the polymerisation reactions of the present invention (e.g. the radical polymerisation method) as long as the reactive group, e.g. the C=C bond, is polymerizable (which is usually the case and may easily be tested). A person skilled in the art will readily understand that a polymerizable C=C-bond is preferably a C=C bond which is susceptible to radical polymerisation or thiol-ene click reactions (e.g. non-aromatic C=C bonds such as in alkenyls). Ideally the polymerizable C=C bond is positioned at a periphery of the substituent making polymerisation more easily possible.

The term "reactive group" refers in particular to:

i) C=C bonds and C≡C bonds in the context of the radical polymerisation method of the present invention (see above)

ii) to C=C and thiol groups, respectively, in the context of the thiol-ene polymerisation methods of the present invention (see below);

iii) to alkyne and azide groups, respectively in the context of the alkyne polymerisation methods of the present invention (see below); and iv) to diene and dienophilic groups, respectively, in the context of the Diels-Alder polymerisation methods of the present invention (see below).

A given R in formula (RSi0_3/2)_n as used herein may be for example chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide. In particular R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (Q to C₁₀₀)-alkyl, (C, to C₁₀₀)-alkenyl, (C, to C₁₀₀)-alkinyl, (C, to C₁₀₀)-alkoxy, (Q to C₁₀₀)-alkenoxy, (C, to C₁₀₀)-acyl, (Q to C₁₀₀)-cycloacyl (C, to C₁₀₀)-cycloalkenyl, (C, to C₁₀₀)-aryl, (C, to C₁₀₀)-arylalkyl, (Q to C₁₀₀)-arylalkenyl, (C, to C₁₀₀)-heteroalkyl, (C, to C₁₀₀)-heteroalkenyl, (C, to C₁₀₀)-heteroalkinyl, (C, to C₁₀₀)-heteroalkoxy, (C, to C₁₀₀)-heteroalkenoxy, (C, to C₁₀₀)-heteroacyl, (Q to C₁₀₀)-heterocycloalkyl, (C, to C₁₀₀)-heterocycloalkenyl, (C, to C₁₀₀)-heteroaryl, (C, to C₁₀₀)-heteroarykalkenyl, (C, to C₁₀₀)-heteroarylalkyls, and polyethylene oxide. R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (C, to C₄₀)-alkyl, (C, to C₄₀)-alkenyl, (C, to C₄₀)-alkinyl, (C, to C₄₀)-alkoxy, (C, to C₄₀)-alkenoxy, (C, to C₄₀)-acyl, (C, to C₄₀)-cycloacyl (C to C₄₀)-cycloalkenyl, (C, to C₄₀)-aryl, (C, to C₄₀)-arylalkyl, (C, to C₄₀)-arylalkenyl, (C, to C₄₀)-heteroalkyl, (C, to C₄₀)-heteroalkenyl, (C, to C₄₀)-heteroalkinyl, (C, to C₄₀)-heteroalkoxy, (C, to C₄₀)-heteroalkenoxy, (C, to C₄₀)-heteroacyl, (C, to C₄₀)-heterocycloalkyl, (C, to C₄₀)-heterocycloalkenyl, (C, to C₄₀)-heteroaryl, (C, to C₄₀)-heteroarykalkenyl, (C, to C₄₀)-heteroarylalkyls, and polyethylene oxide. Preferably, R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀)-alkyl, (C, to C₁₀)-alkenyl, (Q to C₁₀)-alkinyl, (C, to C₁₀)-alkoxy, (C, to C₁₀)-alkenoxy, (C, to C₁₀)-acyl, (C, to C₁₀)-cycloacyl (C, to C₁₀)-cycloalkenyl, (C, to C,₀)-aryl, (C, to C₁₀)-arylalkyl, (C, to C₁₀)-arylalkenyl, (C, to C₁₀)-heteroalkyl, (C, to C₁₀)-heteroalkenyl, (C, to C,₀)-heteroalkinyl, (C, to C₁₀)-heteroalkoxy, (C, to C,₀)-heteroalkenoxy, (C, to C₁₀)-heteroacyl, (CT to C₁₀)-heterocycloalkyl, (C, to C,₀)-heterocycloalkenyl, (C, to C₁₀)-heteroaryl, (CT to C₁₀)-heteroarykalkenyl, (C, to C₁₀)-heteroarylalkyls, and polyethylene oxide. Preferably, R does not comprise any Si atom.

In the context of this invention, the term "alkyl" is understood as saturated, linear or branched hydrocarbons, which can occur unsubstituted, mono- or polysubstituted. In this respect, (C, to C₁₀)-alkyl represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or Cl O-alkyl. Alkyls of the present invention are, for example, methyl, ethyl, propyl, isopropyl, methylethyl, butyl, tert-butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 ,1 -dimethylpropyl, 1 ,2- dimethylpropyl, 2,2-dimethylpropyl, 1 -methylpentyl, if substituted also CHF₂, CF₃ or CH₂OH etc. In connection with the present invention - unless defined otherwise - the term "substituted" is understood as meaning replacement of at least one hydrogen group by F, CI, Br, I, NH₂, SH or OH. In this respect "monosubstituted" means the replacement of one hydrogen group by F, CI, Br, I, NH₂, SH or OH, wherein "polysubstituted" (more than once substituted) means that the replacement takes effect both on different and on the same atoms several times, e.g. at least two times, with the same or different substituents, for example three times on the same C atom, as in the case of CF₃, or at different places, as in the case of e.g. -CH(OH)-CH=CH-CHCl₂. Optionally at least monosubstituted" means either "monosubstituted", "polysubstituted" or - if the option is not fulfilled - "unsubstituted".

The term "alkenyl" as used herein is understood as unsaturated, linear or branched hydrocarbons containing at least one double bond, which can be unsubstituted, mono- or polysubstituted. In this respect, (C, to C₁₀)-alkenyl represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10-alkenyl. "Alkenyls" of the present invention are, for example, methenyl, ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, octenyl, butadienyl, and allenyl groups.

The term "alkinyl" as used herein is understood as unsaturated, linear or branched hydrocarbons containing at least one triple bond, which can be unsubstituted, mono- or polysubstituted. In this respect, (C, to C₁₀)-alkinyl represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10-alkenyl. "Alkinyls" of the present invention are, for example, methinyl, ethinyl, propinyl, isopropinyl, butinyl, isobutinyl, tert-butinyl, pentinyl, hexinyl, octinyl, and allinyl groups.

The terms "alkoxy" and "alkenoxy" as used herein refers to an alkyl and alkenyl, respectively, as defined above, which is linked to oxygen and which can be unsubstituted, mono- or polysubstituted. In this respect, (CI to C10)- alkoxy represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- alkoxy. In addition, (C1 to C10)- alkenoxy represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- alkenoxy. Examples of "alkoxy" and "alkenoxy" of the present invention are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octoxy,groups, methenoxy, ethenoxy, propenoxy, butenoxy, pentenoxy, hexenoxy, octenoxy groups, etc.

The term "acyl" as used herein refers a functional group of R-(C=O)-, wherein R is an alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkenyl as defined herein which can be unsubstituted, mono- or polysubstituted. Thus, the term "acyl" comprises linear, branched, cyclic, saturated or unstaturated hydrocarbons containing the functional group R-(C=O)-. In this respect, (C1 to C10)- acyl represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- acyl. Examples of "acyl" are methanoyl-, acetoyl-, ethanoyl-, propanoyl-, butanoyl-, malonyl-, benzoyl-groups, etc.

The term "cycloalkyl" or "cycloalkenyl" as used herein is a subdefinition of "alkyl" or "alkenyl" as defined above and is a carbon ring which can be unsubstituted, mono- or polysubstituted. The term "cycloalkyl" or "cycloalkenyl" typically refers to C₃, Q, C₅, C₆, C₇, C₈, C₉ or C₁₀ cycloalkyl or cycloalkenyl, preferably refers to Q, C₅, C₆, C₇, or C₈ cycloalkyl or cycloalkenyl and may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and cyclooctenyl groups.

A "heteroalkyl", "heteroalkenyl", "heteroalkinyl", "heteroyalkoxy", "heteroalkenoxy", "heteroacyl", "heterocycloalkyl", "heterocycloalkenyl", "heteroaryl", "heteroarylalkenyl", or a "heteroarylalkyls" are defined as an alkyl, an alkenyls an alkinyl, an alkoxy, an alkenoxy, an acyl, a cycloalkyl, a cycloalkenyl, an aryl, an arylalkenyl or an arylalkyl, as defined above, wherein said structures contain 0-7 heteroatoms selected from O, N or S, which replace at least one carbon atom in the alkyl, an alkenyls an alkinyl, an alkoxy, an alkenoxy, an acyl, a cycloalkyl or a cycloalkenyl as defined above.

The term "aryl" or "heteroaryl" as used herein refers to a 5- or 6-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from O, N or S, a bicyclic 9- or 10-membered aromatic or heteroaromatic ring system ring containing 0-5 heteroatoms selected from O, N or S, or a tricyclic 13- or 14 membered aromatic or heteroaromatic ring system containing 0-7 heteroatoms selected from O, N or S and which can be unsubstituted, mono- or polysubstituted. The aromatic 6- to 14-membered ring systems include e.g. phenyl, naphthalene, indane, tetraline, and fluorene and the 5- to 10-membered aromatic heterocycloc ringsystems include e.g. imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furane, benzimidazole, chinolin, isochinoline, chinoxaline, pyrimidine, pyrazine, tetrazole, pyrazole, pyrrole, imidazole, pyridazine, indolizine, isoindole, indole, indazole, purine, quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, phenanthroline, isothiazole, phenazine, isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline, piperidine, piperazine, and indoline.

Arylalkyl, arylalkenyls, heteroarylalkyl, heteroalkylalkenyl, heterocycloalkyl, heterocycloalkenyl moieties are each defined as their corresponding basic structures alkyl, alkenyl, aryl, heteroaryl, heteroalkyl, or heterocycloalkyl. Any of the above alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, arylalkenyls, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkenyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarylalkyl groups may either be unsubstituted or (mono- or poly-) substituted with one or more non- interfering substituents, e.g., halogen, alkoxy, acyloxy, hydroxy, mercapto, carboxy, benzyloxy, phenyl, benzyl, or other functionality which may or has been suitably blocked with a protecting group so as to render the functionality non-interfering. Each substituent may be optionally substituted with additional non-interfering substituents. The term "non-interfering" characterizes the substituents as not adversely affecting any reactions to be performed in accordance with the methods of the present invention.

A limitation for the selection of silsesquioxane monomers of the formula (RSi0_{3 2})_n in the radical polymerisation reaction is, that at least 1 R of the n R within the formula (RSi0_3/2)_n must comprise at least one polymerizable C=C bond, in particular most commonly a non-aromatic C=C bond. The reason for this will be readily apparent to a person skilled in the art, because this first method of producing a polymer according to the present invention is based on radical polymerisation via C=C groups. Furthermore, it is even preferred, if the silsesquioxane monomers comprise more than the single minimally required C=C bond. This is because under the minimal requirements most likely "only" linear polymers will be yielded. However, it is a particularly preferred object of the present invention to obtain porous, three dimensionally adhered polymers. For this purpose branched molecules are preferred. Thus, it is preferred if at least 1 R of the n R within the formula (RSi03/2)n comprises at least two polymerizable C=C bonds, in particular non-aromatic C=C bonds; or at least 2 R of the n R within the formula (RSi03/2)n comprise at least one polymerizable C=C bond, in particular a non-aromatic C=C bond.

Moreover, since the gist of present invention lies on the one hand in polymerisation of of silsesquioxane monomers of the formula (RSi0_3/2)_n but also in the (e.g. subsequent) modification of the resulting polymers,, of the n R within the formula (RSi0_3/2)_n preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs comprise reactive group(s). For example, in case of the radical polymerisation method of the present invention of the n R within the formula (RSi0_3/2)_n preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs comprise at least one polymerizable, preferably non-aromatic C=C bond. This will ensure on the one hand efficient polymerisation and on the other a sufficient number of C=C bonds remaining which are accessible for e.g. post-polymerisation modification and detailing interface chemistry.

Preferably, a given reactive group is positioned in R distal to the respective Si atom, at the least distal end of R, in between on any branching unit or most distal. Wherever a C=C bond is the reactive moiety (e.g. the radical polymerisation method of the present invention, the thiol-ene methods, etc.) said (e.g. non-aromatic) C=C bond is positioned in R distal to the respective Si atom, at the least distal end of R preferably in between on any branching unit or most distal. By this means the C=C bond will be sterically readily accessible for (e.g. radical) polymerisation. Preferred examples for C=C bonds, positioned for example in R distal to the respective Si atom, are selected from any (polymerizable) ethenyl (vinyl) group, methacrylate group, acrylate group, norbornenyl group and maleimide groups, e.g.:

wherein z may be in principle any length as long as the rigidity of the final polymer is still in the desired range. Preferabyl, z is in the range of 0-100, more preferably 0-50, even more preferably 0-40, even more preferably 0-25, 0-1 0, or 0-5. Z may for example be 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 1 0. If z=0 then the at least one R simply comprises as polymerizable C=C bond or simply is vinyl, propenyl, methacrylate, acrylate, norbornenyl or maleimide, respectively.

Silsesquioxane monomers are known in the art for many decades now. The silsesquioxane monomers of the formula (RSi0_3/2)_n for use in the methods of producing a polymer according to the present invention may for example either be obtained commercially (e.g. from Hybrid Plastics; 55 W.L. Runnels Industrial Drive, Hattiesburg, MS 39401 , USA) or may be synthesized according to techniques well established in the art, e.g. see D. B. Cordes, P. D. Lickiss, F. Rataboul, Chemical Reviews, 2010, 1 10, 2081 -21 73 and references cited therein, all of which are incorporated herein by reference.

In a particularly preferred embodiment according to the present invention only one type of silsesquioxane monomers of the formula (RSi0_3/2)_n is provided for (e.g. radical) polymerisation, e.g. octavinyl silsesquioxane (i.e. n is 8, and all 8 R within the formula (RSi0_3/2)₈ are -CHCH₂). In another particularly preferred embodiment an approximately even mixture of octavinyl silsesquioxane, decavinyl silsesquioxane and dodecavinyl silsesquioxane (n is a mixture of 8, 10, 12; Rs are vinyl) is provided for (e.g. radical) polymerisation.

The polymerisation processes of the present invention can be carried out according to established principles in the art for polymeriosation, e.g. radical polymerisation. The polymerisation may be initiated for example thermally or photochemical ly.

Thermal polymerisation is well known in the art. A person skilled in the art will thus easily find the most appropriate conditions for his specific polymerisation of interest. Exemplary reaction conditions are ranging from 0°C temperature to 1 00°C while usually the boiling point of the solvent/solvent mixture determines the upper limit. Alternatively, the thermal stabi lity of the resulting polymer may determine the upper limit. The thermal stability of polymers according to the present invention is usually, but not limited thereto, about 400°C at 95 % weight loss and a heating rate of 1 0°C in thermogravi metric analysis. In contrast to other methods known from the prior art for achieving (related) polymeric adsorbent materials, the present invention allows polymerisation even at mild conditions. While mild and easily realizable conditions are sufficient for the preparation of the polymers according to the present invention (e.g. low temperature), the polymers would also easily withstand operating or polymerisation at harsh conditions as encountered typically in polymerisation reactions of typical polymeric materials. Mi ld conditions as used herein are considered to range for example from about 0°C to about 1 00°C. Particularly preferred conditions for thermal polymerisation at mild polymerisation conditions in the current invention are within a range selected from the group consisting of: about 0°C to about 80°C, about room temperature to about 80°C, about room temperature to about 70°C; about room temperature to about 60°C, about 30°C to about 80°C, about 30°C to about 60°C, about 40°C to about 60°C, even more preferably in the range of 50 to 60°C; for e.g. 24 hours. The polymerisation time span will be chosen by the skilled person in the art considering the correlation between temperature and initiation rate, consequently reaction rate and therefore desired polymerisation grade and/or conversion. In a simple sense this may imply that phase separation is observed and a three- dimensionally adhered material is obtained, while complete conversion is not yet achieved.

As mentioned above, the polymerisations of the present invention, e.g. the radical polymerisation can, as generally known in the art for such type of reactions, also be carried out by photochemical means. For example, the polymerisation reaction may be initiated by means of UV radiation or visible light irradiation (e.g. by light emitting diodes), by any ionizing radiation, e.g. gamma x-ray radiation or by redox initiation providing a trigger for polymerisation. It is understood that a combination of methods thereof may likewise easily be realized by a person skilled in the art.

Certainly, and preferably, the polymerisation method of the present invention may be conducted in presence of an initiator of polymerisation. A person skilled in the art will be readily aware of initiators most suitable for the desired type of polymerisation. In particular, initiators may be selected from the group consisting of: AIBN, ABCN, chlorine, and organic peroxides such as di- t(tertiary)-butylperoxide (tBuOOtBu), benzoyl peroxide ((PhCOO)₂) methyl ethyl ketone peroxide and acetone peroxide. Particularly AIBN is preferred as initiator in the polymerisation method of the present invention since it enables photo- as well as thermal initiation and is the most widely used, accessible, and well-understood initiator. However, for radical polymerisation any other radical initiator is possible. Ideally, but not necessarily, such initiator is present in the monomeric precursor mixture in a ratio of about 0.1 to about 40 wt% with respect to the monomeric precursors.

The polymerisations of the present invention are preferably wet polymerisations, i.e. are carried out in solution/liquid physical state. Preferably the one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n will thus be provided dissolved or dispersed in a solvent or solvent mixture. For this purposes various solvents as well as mixtures of solvents may be used. In principle any solvent or solvent mixture that is able to dissolve/disperse the specific monomeric silsesquioxane precursors is suitable. In that respect a range of nonpolar and polar solvents and mixtures thereof are most suitable. Preferably the solvent/solvent mixture is chosen so that the resulting polymer is sooner or later immiscible with the solvent/solvent mixture. This process is generally known as "polymerisation induced phase separation" ("PIPS"). PIPS is a widely existing process where an initially miscible, single-phase mixture undergoes phase decomposition during the polymerisation of one component (here the polymerisation of the silsesquioxane monomers), and finally transforms to a phase separated material. The solvent/solvent mixture acts then as porogen (herein also termed porogenic solvent), because the separated solvent phases form for example droplets in the polymeric phase and thus lead to pores in the resulting polymer eventually. Good solvents yield thus small pores in the polymer, worse solvents yield large(r) pores in the polymer. Solvents suitable for putting the present invention in practice may be selected for example from the group consisting of: tetrahydrofuran, dichloromethane (DCM), chloroform, ethyl acetate, acetone, dimethylformamide (DMF), acetonitrile (MeCN), dimethyl sulfoxide (DMSO), dioxane, propanol, butanediol, cyclohexanol, dodecanol, toluene, polyethyleneglycol (PEG; only in combination with other solvents). Likewise, polymerisation rate affects the porous properties as does the choice of solvent, i.e. choosing one solvent can result in different porous properties depending for example on solubility criteria of polymerized material at varying temperature and mobility and stability of the radicals.

In view of what has been said above regarding PIPS the inventors contemplate as well that additional solvents may be added to the polymerisation mixture in the course of the polymerisation. If desired, one, two or more additional solvents can be provided. They may be added as mixture or individually in subsequent steps. This approach improves the possibilities of tailoring the desired pore sizes in the resulting polymer and contributes in achieving hierarchically-structured adsorbent materials which exhibit various pore sizes, which can for example vary in single factors of size up to at least one order of magnitude. Examples for solvents which may be added in course of the polymerisation are for example THF, toluene, chloroform, dioxane, dodecanol, propanol, butanediol, cyclohexanol, PEG (e.g. PEG 200) and mixtures thereof. Surfactants such as ionic surfactants (e.g. cationic surfactants such as benzalkonium chloride), hybrid (amphoteric) surfactants (e.g cocamidopropyl betain), or nonionic surfactants (e.g. cetyl alcohol) may also act as porogen and their use in a polymerisation method of the present invention is contemplated by the inventors of the present invention as embodiment as well.

In view of the foregoing, a particularly preferred embodiment according to the present invention is a (e.g. radical) polymerisation method as defined herein, wherein the silsesquioxane monomers of the formula (RSi0_3/2)_n comprise octavinyl silsesquioxane, decavinyl silsesquioxane and dodecasilsesquioxane and wherein THF and/or mixtures of THF and PEG are used as solvents. The composition of a single phase polymerisation mixture for monolith preparation allows introduction of a hierarchy in pore space with convectively accessible flow through pores and smal l pores containing the majority of interacting or reactive functionality. Particularly preferred is any solvent mixture allowing on the one hand dissolution of monomeric precursor while being a worse solvent for the formed polymer on the other hand. In such scenario loss of solubility of the polymer formed during polymerisation leads to phase separation. The optimal choice of porogenic solvent mixtures depends on the type of monomeric precursors selected and a person skilled in the art will readily be able to choose an appropriate solvent mixture. Preferred solvent mixtures comprise for example THF/PEG; toluene/dodecanol; dioxane/PEG; THF/dodecanol; THF/toluene/PEG; THF/toluene/dodecanol; THF/dioxane/PEG; THF/dioxane/dodecanol; etc.. A "worse" solvent for silsesquioxane monomers of the formula (RSi0₃ 2)_n and resulting polymers like polyethyleneglycol or dodecanol induces earlier phase separation and therefore larger pores accessible for flow through ( vide infra).

For example, for octavinyl silsesquioxane polymerisation tetrahydrofuran is a good solvent for the monomer leading to a porous entity with preliminary mesopores (pore size > 2 but < 50 nm) and inherently existing nanopores from the building blocks cal led micropores (pore size < 2 nm). Addition of polar solvents like polyethyleneglycol allows introduction of larger pores called macropores (pore size > 50 nm) over at least an order of magnitude ( vide infra), i.e. to dimensions of several micrometers. Thus, a particularly preferred solvent mixture for polymerisation, e.g. of octavinyl si lsesquioxane, is tetrahydrofuran (THF) and polyethyleneglycol.

Furthermore, a person ski lled in the art may certainly fine-tune the characteristics of the solvent mixture by varying the ratio of the solvents involved. In the context of a mixed polymer comprising octavinyl, decavinyl and dodecavinyl silsesquioxane the inventors have illustrated the impact of such varying ratios with regard to PEG THF mixtures (PEG/THF in ratio 0/80, 1 0/70, 20/60, 30/50, and 40/40 of total wt % (see Fig. 8).

Although the inventors of the present invention contemplate in particular post-polymerisation modification of the polymers according to the present invention (vide infra), it is of course also possible in some instances to modify at least some of the monomeric bui lding blocks in advance and polymerize in a subsequent step. Thus, in one embodiment any of the polymerisation methods of the present invention (radical polymerisation, thiol-ene polymerisation; alkyne polymerisation, Diels Alder polymerisation) may comprises the intermediate step of : modifying at least partially the provided one or more types of silsesquioxane monomers with at least one type of functional moiety.

For the radical polymerisation method of the present invention and the thiol-ene methods 1 , 3 and 4 that implies that the polymerisation method may for example comprises the intermediate step of: modifying at least partially the provided one or more types of silsesquioxane monomers as defined herein, i.e. silsesquioxane monomers of the formula (RSiO_3/2)_n (formula I) wherein: a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSiO_3/2)_n may be the same or different, and

d) at least 1 R of the n R within the formula (RSiO_3/2)_n comprises at least one (e.g. non-aromatic) C=C bond;

with at least one type of functional moiety.

In one embodiment the modification is introduced via the C=C bonds, for instance via thiol-ene click chemistry.

Other modification reactions of silsesquioxane monomers for use in the present invention will be described further down below, as are functional moieties defined further below. A person skilled in the art will understand that the above mentioned modification preferably remains on a level which still leaves some of the reactive groups, e.g. the C=C bonds available for (e.g. radical) polymerisation and post-polymerization modification. A particularly preferred mode of modification is thiol-ene-click chemistry, but other modes may be contemplated as well, for example methathesis, halogenation and hydrogenation.

It will also be understood by a person skilled in the art that for the polymerisation reactions described herein (above as well as below) it is not critical to start from actual monomers. The inventors of the present invention also contemplate for example to use instead of or in addition to the mentioned silsesquioxane monomers silsesquioxane oligomers. It is of course possible to initiate the reactions of the invention also with such preformed oligomers. Such oligomers can have the formula [(RSiO_3/2)_n]_m (formula II) (or[(R'SiO_3/2)_n]_m; formula Mb), wherein (RSiO_{3 2})_n (or (R'SiO_3/2)n ) is as defined above (below) and wherein m may be in the range of preferably 2 -50, 2- 40, 2-30 and/or 2- 20. Most preferably m is < 20, e.g. is 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 1 5, 16, 1 7, 18, 19, 20. As before, each (RSiO_3/2)_n within the m (RSiO_{3 2})_n in such oligomer may be the same or different. Moreover, certainly more than one type of oligomer may be used, i.e. the oligomers employed need not be (but may be) identical. They oligomers may vary for example with regard to R, n, and/or m. The same criteria apply for [(R'Si0_3/2)_n]_m. Besides, a person skilled in the art will also understand from the above that if herein reference is made to a silsesquioxane "polymer", then this terminology is intended to imply that the molecule comprises preferably more than 50 silsesquioxane units.

As mentioned already above, the inventors of the present invention provide in addition to the radical polymerisation method further methods for producing silsesquioxane polymers. In one embodiment the inventors propose the direct formation of a silsesquioxane polymer via thiol-ene click chemistry.

Thus, the present invention relates in a further aspect to a method for producing a polymer (thiol- ene method 1 ), wherein the method comprises:

- providing one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n wherein:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})n may be the same or different, d) at least 1 R of the n R within the formula (RSi0₃ 2)_n comprises at least two polymerizable C=C bonds, in particular non-aromatic C=C bonds; or at least 2 R of the n R within the formula (RSi0_{3 2})_n comprise at least one polymerizable C=C bond, in particular a non-aromatic C=C bond;

- providing one or more types of linker compounds each comprising at least two thiol groups; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n and the one or more types of linker compounds by means of thiol-ene reaction, preferably in solution.

In a particularly preferred embodiment of the above mentioned thiol-ene method 1 the silsesquioxane monomers are octavinyl silsesquioxane monomers or a mixture of octa-, deca-, and dodecavinyl silsesquioxane and the linker compound is 1 ,2 ethanedithiol, 1 ,3 propanedithiol or 1 ,4 butanedithiol. Particularly preferred is 1 ,2 ethanedithiol.

In a similar manner the "opposite" constellation of the thiol-ene reaction may be used, i.e. the thiol residues are present on the silsesquioxane monomers while the C=C bonds are present on the linker compound. Thus, the present invention relates in a further aspect to a method for producing a polymer (thiol- ene method 2), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0₃ 2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two polymerizable thiol groups; or at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one thiol group;

- providing one or more types of linker compounds each comprising at least two polymerizable (e.g. non-aromatic) C=C bonds; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of thiol-ene reaction, preferably in solution.

In similar manner a mixed constellation of the thiol-ene reaction may be used, i.e. at least one thiol residue and at least one C=C bond are present on the silsesquioxane monomer and optionally as well on the linker compound. Thus, the present invention relates in a further aspect to a method for producing a polymer (thiol-ene method 3), wherein the method comprises:

- providing one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n wherein:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least one polymerizable thiol group and at least one polymerizable C=C bond; and/or at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one thiol group; while at least one other R of the n R within formula (RSi0_3/2)_n comprises at least one polymerizable C=C bond

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two thiol groups, compounds comprising at least two polymerizable (e.g. non-aromatic) C=C bonds and compounds comprising on the one hand at least one thiol group and on the other hand at least one polymerizable (e.g. non-aromatic) C=C bond, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the optional one or more types of linker compounds by means of thiol-ene reaction, preferably in solution. In such scenario the linker compounds are optional because the silsesquioxane monomers may react with each other directly due to the presence of at least one thiol group and at least one C=C bond on each monomer.

In an even further variation of this invention of this thiol-ene reaction scenario, which is however nothing but an embodiment of the thiol-ene methods 1 and 2, the present invention relates in a further aspect to a method for producing a polymer (thiol-ene method 4), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0₃ 2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})n comprises at least two polymerizable C=C bonds, in particular non-aromatic C=C bonds; and/or at least 2 R of the n R within the formula (RSi0₃ 2)_n comprise at least one polymerizable C=C bond, in particular a non-aromatic C=C bond;

- providing one or more types of silsesquioxane monomers of the formula (R'Si0_{3 2})_n wherein:

a') n may be 6, 8, 10, 12 or a mixture thereof;

b') R' is a substituent or hydrogen,

c') each R' of the n R' within the formula (R'Si0_3/2)_n may be the same or different,

d') at least 1 R' of the n R¹ within the formula (R'Si0_3/2)_n comprises at least two polymerizable thiol groups; or at least 2 R' of the n R' within the formula (R'Si0_3/2)_n comprise at least one thiol group;

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)n and optionally the one or more types of linker compounds by means of thiol-ene reaction, preferably in solution. Thiol group carrying silsesquioxane monomers may for example be generated if the above described vinyl silsesquioxane monomers of the formula (RSi0_3/2)_n are modified via thiol-ene click chemistry with dithiol compounds. In thiol-ene method 4 the linker compounds are again entirely optional, because the silsesquioxane monomers of the formula (RSi0_3/2)n and of the formula (R'Si0_3/2)_n can directly react with each other. Apart of the features set out in d) and d') above, R and R' may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.

For all the above mentioned thiol-ene reactions (1 , 2, 3, 4) it is preferred, if the silsesquioxane monomers and/or the potential linker compounds comprise more than the minimally required thiol groups and C=C bonds. This is because under the minimal requirements for thiol groups and C=C bonds given for these methods above (thiol-ene reactions 1 , 2, 3, 4) "only" linear polymers will be yielded. However, it is a particularly preferred object of the present invention to obtain porous, three dimensional ly adhered polymers. For this purpose branched molecules are preferred. Thus, in particular if a highly porous polymer shall be produced, the term " at least one" used above for describing the thiol-ene reactions 1 , 2, 3, and 4 may be replaced with "at least to 2", "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 10", "at least 1 1 ", or "at least 12" etc., and/or the term " at least two" used above for describing the thiol- ene reactions 1 , 2, 3, 4 may be replaced with "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 10", "at least 1 1 ", or "at least 12" etc.

In other words of the n R within the formula (RSi0_3/2)_n in thiol-ene reactions 1 , 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs comprise at least one polymerizable, preferably non-aromatic C=C bond. In turn, of the n R within the formula (RSi0_3/2)_n (and/or of the n R' within the formula (R'Si0_3/2)_n ) in thiol-ene reactions 2, 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs (and/or R's) comprise at least one thiol group. This will ensure on the one hand efficient polymerisation and on the other a sufficient number of C=C bonds and/or thiol groups remaining which are accessible for e.g. post- polymerisation modification and detailing interface chemistry.

The present invention relates also to further methods of producing a silsesquioxane polymer, such as by means of azide-alkyne cycloadditions. Thus, the present invention relates in a further aspect to a method for producing a polymer (alkyne method 1 ), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two polymerizable (e.g. terminal or ring strained) C≡C bonds; or at least 2 R of the n R within the formula (RSi0₃ 2)_n comprise at least one polymerizable (e.g. terminal or ring strained) C≡C bond;

- providing one or more types of linker compounds each comprising at least two azide groups; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of azide-alkyne (e.g. Huisgen) cycloaddition, preferably in solution.

In a similar manner the "opposite" constellation of the azide-alkyne cycloaddition reaction may be used, i.e. the azide residues are present on the silsesquioxane monomers while the C≡C bonds are present on the linker compound.

Thus, the present invention relates in a further aspect to a method for producing a polymer (alkyne method 2), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least two azide groups; or at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one azide group;

- providing one or more types of linker compounds each comprising at least two (e.g. terminal or ring strained) C≡C bonds; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of azide-alkyne cycloaddition reaction, preferably in solution. In similar manner a mixed constellation of the azide-alkyne cycloaddition reaction may be used, i.e. at least one azide residue and at least one C≡C bond are present on the silsesquioxane monomers and optionally as well on the linker compound. Thus, the present invention relates in a further aspect to a method for producing a polymer (alkyne method 3), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one polymerizable azide group and at least one polymerizable (e.g. terminal or ring strained) C≡C bond; and/or

at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least one azide group; while at least one other R of the n R within formula (RSi0_3/2)_n comprises at least one polymerizable (e.g. terminal or ring strained) G≡C bond;

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two azide groups, compounds comprising at least two polymerizable (e.g. terminal or ring strained) C≡C bonds and compounds comprising on the one hand at least one azide group and on the other hand at least one polymerizable (e.g. terminal or ring strained) C≡C bond, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the optional one or more types of linker compounds by means of azide-alkyne cycloaddition reaction, preferably in solution.

In such scenario the linker compounds are optional because the silsesquioxane monomers may react with each other directly due to the presence of at least one azide group and at least one C≡C bond on each monomer.

In an even further variation of this invention of this alkyne reaction scenario, which is however nothing but an embodiment of the alkyne methods 1 and 2, the present invention relates in a further aspect to a method for producing a polymer (alkyne method 4), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen, c) each R of the n R within the formula (RSi0₃ 2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two polymerizable (e.g. terminal or ring strained) C≡C bonds; and/or

at least 2 R of the n R within the formula (RSi0₃/2)_n comprise at least one polymerizable (e.g. terminal or ring strained) C≡C bond;

- providing one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)_n wherein:

a') n may be 6, 8, 10, 12 or a mixture thereof;

b') R¹ is a substituent or hydrogen,

c') each R' of the n R' within the formula (R'Si0₃ 2)_n may be the same or different,

d') at least 1 R' of the n R' within the formula (R'Si0_3/2)_n comprises at least two polymerizable azide groups; or at least 2 R' of the n R' within the formula (R'Si0_3/2)n comprise at least one azide group;

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two azide groups, compounds comprising at least two polymerizable (e.g. terminal or ring strained) C≡C bonds and compounds comprising on the one hand at least one azide group and on the other hand at least one polymerizable (e.g. terminal or ring strained) G≡C bond, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of silsesquioxane monomers of the formula (R'Si0_{3 2})n and optionally the one or more types of linker compounds by means of azide-alkyne cycloaddition reaction, preferably in solution.

Azide group or alkyne group carrying silsesquioxane monomers may for example be generated if the above described vinyl silsesquioxane monomers of the formula (RSi0_3/2)_n are modified via thiol-ene click chemistry with compounds carrying azide/alkyne groups and thiol groups. In alkyne method 4 the linker compounds are again entirely optional, because the silsesquioxane monomers of the formula (RSi0_3/2)_n and of the formula (R'Si0_3/2)_n can directly react with each other. Apart of the features set out in d) and d') above, R and R' may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.

For all the above mentioned alkyne methods 1 , 2, 3, 4 it is preferred, if the silsesquioxane monomers and/or the potential linker compounds comprise more than the minimally required azide groups and C≡C bonds. This is because under the minimal requirements for azide groups and C≡C bonds given for these methods above (alkyne methods 1 , 2, 3, 4) "only" linear polymers will be yielded. However, it is a particularly preferred object of the present invention to obtain porous, three dimensionally adhered polymers. For this purpose branched molecules are preferred. Thus, in particular if a highly porous polymer shall be produced, the term " at least one" used above for describing the alkyne methods 1 , 2, 3, and 4 may be replaced with "at least to 2", "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 10", "at least 1 1 ", or "at least 1 2" etc., and/or the term " at least two" used above for describing the alkyne methods 1 , 2, 3, 4 may be replaced with "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 1 0", "at least 1 1 ", or "at least 12" etc.

In other words of the n R within the formula (RSi0_3/2)_n in alkyne methods 1 , 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 1 0, > 1 1 or 1 2 or n-2, n-1 or n Rs comprise at least one polymerizable, preferably non-aromatic C≡C bond. In turn, of the n R within the formula (RSi0_3/2)_n (and/or of the n R' within the formula (R'Si0_3/2)n) in alkyne methods 2, 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 1 0, > 1 1 or 1 2 or n-2, n-1 or n Rs (and/or n R') comprise at least one azide group. This will ensure on the one hand efficient polymerisation and on the other a sufficient number of C≡C bonds and/or azide groups remaining which are accessible for e.g. post- polymerisation modification and detailing interface chemistry.

The present invention relates also to further methods of producing a silsesquioxane polymer, such as by means of Diels-Alder reaction.

Thus, the present invention relates in a further aspect to a method for producing a polymer (Diels Alder method 1 ), wherein the method comprises:

- providing one or more types of si lsesquioxane monomers of the formula (RSi0_3/2)_n wherein:

a) n may be 6, 8, 1 0, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least two diene groups; or at least 2 R of the n R within the formula (RSi0_{3 2})_n comprise at least one diene group;

- providing one or more types of linker compounds each comprising at least two dienophilic groups; and - polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

In a similar manner the "opposite" constellation of the Diels-Alder reaction may be used, i.e. the dienophilic residues are present on the silsesquioxane monomers while the dienes are present on the linker compound.

Thus, the present invention relates in a further aspect to a method for producing a polymer (Diels- Alder method 2), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two dienophilic groups; or at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one dienophilic group;

- providing one or more types of linker compounds each comprising at least two diene groups; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

In similar manner a mixed constellation of the Diels-Alder reaction may be used, i.e. at least one diene group and at least one dienophilic group are present on the silsesquioxane monomers and optionally as well on the linker compound. Thus, the present invention relates in a further aspect to a method for producing a polymer (Diels-Alder method 3), wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})n comprises at least one diene group and at least one dienophilic group; and/or at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one diene group; while at least one other R of the n R within formula (RSi0_3/2)_n comprises at least one dienophilic group; - optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two diene groups, compounds comprising at least two dienophilic groups and compounds comprising on the one hand at least one diene group and on the other hand at least one dienophilic group, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the optional one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

In such scenario the linker compounds are optional because the silsesquioxane monomers may react with each other directly due to the presence of at least one diene group and at least one dienophilic group on each monomer.

In an even further variation of this invention of this alkyne reaction scenario, which is however nothing but an embodiment of the Diels-Alder methods 1 and 2, the present invention relates in a further aspect to a method for producing a polymer (Diels-Alder method 4), wherein the method comprises:

- providing one or more types of silsesquioxane monomers of the formula (RSi0₃ 2)_n wherein:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0₃/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two diene groups; and/or

at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one diene group;

a') n may be 6, 8, 10, 12 or a mixture thereof;

b¹) R' is a substituent or hydrogen,

c') each R¹ of the n R' within the formula (R'Si0_3/2)n may be the same or different,

d') at least 1 R' of the n R' within the formula (R'Si0_3/2)_n comprises at least two dienophilic groups; or at least 2 R' of the n R' within the formula (R'Si0_3/2)_n comprise at least one dienophilic group;

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two diene groups, compounds comprising at least two dienophilic groups and compounds comprising on the one hand at least one diene group and on the other hand at least one dienophilic group, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)n and optionally the one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

Diene group or dienophilic group carrying silsesquioxane monomers may for example be generated if the above described vinyl silsesquioxane monomers of the formula (RSi0_{3 2})_n are modified via thiol-ene click chemistry with diene/dienophilic group carrying compounds. In Diels- Alder method 4 the linker compounds are again entirely optional, because the silsesquioxane monomers of the formula (RSi0_3/2)n and of the formula (R'Si0_3/2)n can directly react with each other. Apart of the features set out in d) and d') above, R and R¹ may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.

For all the above mentioned Diels Alder methods 1 , 2, 3, 4 it is preferred, if the silsesquioxane monomers and/or the potential linker compounds comprise more than the minimally required diene and dienophilic groups. This is because under the minimal requirements for diene groups and dienophilic groups given for these methods above (Diels-Alder methods 1 , 2, 3, 4) "only" linear polymers will be yielded. However, it is a particularly preferred object of the present invention to obtain porous, three dimensionally adhered polymers. For this purpose branched molecules are preferred. Thus, in particular if a highly porous polymer shall be produced, the term " at least one" used above for describing the Diels-Alder methods 1 , 2, 3, and 4 may be replaced with "at least to 2", "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 10", "at least 1 1 ", or "at least 12" etc., and/or the term " at least two" used above for describing the Diels-Alder methods 1 , 2, 3, 4 may be replaced with "at least 3", "at least 4", "at least 5", "at least 6", "at least 7", "at least 8", "at least 9", "at least 10", "at least 1 1 ", or "at least 12" etc.

In other words of the n R within the formula (RSi0_3/2)_n in Diels-Alder methods 1 , 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs comprise at least one diene group. In turn, of the n R within the formula (RSi0_3/2)_n (and/or of the n R' within the formula (R'Si0_3/2)_n) in Diels Alder methods 2, 3 and 4 preferably at least two, even more preferably > 3, even more preferably > 4, > 5, >6, or (if applicable, depending on n) > 7, > 8, >9, > 10, > 1 1 or 12 or n-2, n-1 or n Rs (or R's) comprise at least one dienophilic group. This will ensure on the one hand efficient polymerisation and on the other a sufficient number of dienes and/or dienophiles remaining which are accessible for e.g. post-polymerisation modification and detailing interface chemistry.

Examples for diene groups which may be present in a given R are 1 ,3 butadiene groups, 2,3 dimethylbutadiene groups, 2,4 hexadien groups, 1 ,3 cyclopentadien groups, 1 ,3 cyclohexadien groups, 5 methylen 1 ,3 cyclopentadien groups, 1 ,2 dimethylene cyclohexane groups etc.. Examples for dienophilic groups for R (or R¹) are 1 ,2 dicyanoethene groups, dimethyl-cis-2- butenedioate, dimethyl-trans-2-butenedioate, 2-butene-diacid anhydride, dimethyl-butyne- anhydride, propenal, etc.

As described above, the silsesquioxane monomers for use in the methods of the present invention may be modified also before polymerisation. It is of course also possible if desired to modify the monomeric building blocks in advance and polymerize in a subsequent step via the thiol-ene, alkyne or Diels Alder methods.

For the polymerisation methods of the present invention that implies that the polymerisation method may for example comprises the intermediate step of: modifying at least partially the provided one or more types of silsesquioxane monomers as defined herein, i.e. silsesquioxane monomers of the formula (RSi0_{3 2})_n (formula I) wherein: a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})_n may be the same or different, and

d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least one C=C bond, thiol group, azide group; C≡C bond, diene and/or dienophile with at least one type of functional moiety.

The modification may for example be introduced exactly via some of the C=C bonds, thiol groups, azide groups; C≡C bonds, dienes and/or dienophiles.

The linker compounds described above for the thiol-ene methods 1 , 2, 3 and 4, for the alkyne methods 1 , 2, 3, 4 as well as for the Diels Alder methods 1 ,2 , 3 and 4 may for example (but not limited thereto) be represented by the general formula:

Reactive group (1 ) -X- Reactive group (2) (formula III) wherein the reactive groups are as specified in the individual methods (thiol groups, C=C bonds, azide groups, C≡C bonds, diene, dienophile). Examples of subformulae of this formula III are thus:

HS - X - SH (subformula Ilia)

C=C - X - C=C (formula 1Mb)

C=C -X- SH (formula lllc)

N≡N⁺-N^" -X- N -N⁺≡N (formula llld)

C≡C -X- C≡C (formula llle)

N≡N⁺-N- - X- C≡C (formula lllf)

diene -X- diene (formula lllg)

dienophile -X- dienophile (formula lllh)

diene -X- dienophile (formula llli).

Certainly, said linker compounds may comprise more than the specified two reactive groups. For example, they may comprise at least 2, at least 3, at least 4, at least 5, at least 6, at least 8, at least 10, at least 12 etc. reactive groups. Again, a multitude of reactive groups will facilitate generation of branched polymers and will increase the number of unreacted groups in the final polymer which are then still available for postpolymerization modification. The "linear" presentation of the formula Reactive group (1 ) -X- Reactive group (2) need not imply that the reactive residues are positioned diametrically opposed. For example 1 ,1 propane dithiol is encompassed by this formula as is 1 ,3 propane dithiol.

In view of the fact that the decisive moieties for the polymer formation are in principle the reactive groups, X in above formula III and subformulas llla-llli may in principle be any type of molecule. A given X in above formula III and subformulas llla-llli as used herein may be for example chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide. In particular R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀₀)-alkyl, (C, to C₁₀o)-alkenyl, (Q to C₁₀₀)-alkinyl, (C, to C,₀₀)-alkoxy, (C, to C₁₀₀)-alkenoxy, (C, to C₁₀₀)-acyl, (Q to C₁₀₀)-cycloacyl (C, to C₁₀₀)-cycloalkenyl, (C, to C₁₀₀)-aryl, (C, to C₁₀₀)-arylalkyl, (C, to Cioo)-arylalkenyl, (C, to C₁₀₀)-heteroalkyl, (C, to C₁₀₀)-heteroalkenyl, (C, to C,₀₀)-heteroalkinyl, (C, to C₁₀₀)-heteroalkoxy, (C, to C₁₀₀)-heteroalkenoxy, (C, to C₁₀₀)-heteroacyl, (C, to C₁₀₀)-heterocycloalkyl, (d to C₁₀₀)-heterocycloalkenyl, (C, to C₁₀₀)-heteroaryl, (C, to C₁₀₀)-heteroarykalkenyl, (C, to Cioo)-heteroarylalkyls, and polyethylene oxide. R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (Q to C₄₀)-alkyl, (C, to C₄₀)-alkenyl, (C, to C₄₀)-alkinyl, (C, to C₄₀)-alkoxy, (C, to C₄₀)-alkenoxy, (C, to C₄₀)-acyl, (C, to C₄₀)-cycloacyl (C, to C₄₀)-cycloalkenyl, (C, to C₄₀)-aryl, (C, to C₄₀)-arylalkyl, (C, to C₄₀)-arylalkenyl, (C, to C₄₀)-heteroalkyl, (C, to C₄₀)-heteroalkenyl, (C, to C₄₀)-heteroalkinyl, (C, to C₄₀)-heteroalkoxy, (Q to C₄₀)-heteroalkenoxy, (C, to C₄₀)-heteroacyl, (C, to C₄₀)-heterocycloalkyl, (C, to C₄₀)-heterocycloalkenyl, (C, to C₄₀)-heteroaryl, (C, to C₄₀)-heteroarykalkenyl, (C, to C₄₀)-heteroarylalkyls, and polyethylene oxide. Preferably, R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀)-alkyl, (C, to C₁₀)-alkenyl, (C, to C₁₀)-alkinyl, (C, to C₁₀)-alkoxy, (C, to C₁₀)-alkenoxy, (C, to C₁₀)-acyl, (C, to C₁₀)-cycloacyl (C, to C₁₀)-cycloalkenyl, (Q to C₁₀)-aryl, (C, to C₁₀)-arylalkyl, (C, to C₁₀)-arylalkenyl, (C, to C₁₀)-heteroalkyl, (C, to C₁₀)-heteroalkenyl, (C, to C₁₀)-heteroalkinyl, (Q to C₁₀)-heteroalkoxy, (C, to C₁₀)-heteroalkenoxy, (C, to C₁₀)-heteroacyl, (C, to C₁₀)-heterocycloalkyl, (C, to C₁₀)-heterocycloalkenyl, (C, to C₁₀)-heteroaryl, (C, to C₁₀)-heteroarykalkenyl, (C, to C₁₀)-heteroarylalkyls, and polyethylene oxide. Preferably, X does not comprise any Si atoms.

Reaction conditions and catalysts useful in thiol-ene, azide alkyne reactions and Diels Alder reactions are well known in the art. They may be realized initiator-free under UV-light or visible light and also under thermal conditions. It is understood, that for example for the thiol-ene methods the reaction will proceed already under daylight conditions. Addition of initiator accelerates the polymerization. A useful catalyst for the azide alkyne reaction is for example Cu.

The molecular building blocks of the polymers according to the present invention are preferably predominantly or even exclusively silsesquioxane monomers of the formula (RSi0_3/2)_n. Predominantly in the context of the thiol-ene, alkyne and Diels Alder methods mentioned above means that the combined fraction of said silsesquioxane monomers and linker compounds in the polymerisation reaction constitutes stoichiometrically preferably at least 50% or more than 50% of the monomers to be polymerized, preferably more than 55%, even more preferably more than 60%, even more preferably more than 65%, even more preferably more than 70%, even more preferably more than 75%, even more preferably more than 80%, even more preferably more than 85%, even more preferably more than 90%, even more preferably more than 95%, even more preferably more than 98%, most preferably 100% (ignoring any potential initiators) of the monomers provided. In other words, in particular embodiments it may be advantageous or at least not disadvantageous to create (hetero-)polymers not only comprising the silsesquioxane monomers and respective linker compounds of the formula (RSi0_3/2)_n but also to a lesser extent other monomers which may be included in the polymerisation process. However, particularly preferred is the use of only silsesquioxane monomers of the formula (RSi0_3/2)_n and the respective linker compounds as building blocks of the polymer according to the invention. The stoichiometrical ratio between linker compounds and silsesquioxane monomers may be for example in the range of 90:10 to 50:50.

In a further aspect the present invention relates to the polymers themselves. Thus, the present invention relates also to a polymer consisting predominantly of or consisting of one or more types of crosslinked silsesquioxane units of the formula (RSi0_{3 2})_n wherein:

a) n may be 6, 8, 10 or 12 or a mixture thereof;

b) R is a substituent, or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least one R of the n R within the formula (RSi0_3/2)_n of a first given silsesquioxane unit shares at least one chemical bond with at least one R of the n R within the formula (RSi0_3/2)_n of one or more further silsesquioxane unit(s).

Preferably, a given silsesquioxane unit shares chemical bonds with at least two, preferably at least three further silsesquioxane units (i.e. is crosslinked with at least two or three further silsesquioxane units). Such polymers are for example obtainable or obtained with the radical polymerisation method of the present invention. Preferably, two silsesquioxane units of the formula SI0_3/2 are not linked via -CH₂ - CH₂-, - O - Si(CH₃)₂ - CH₂ - CH₂ or - O - Si(CH₃)₂ - CH₂ - CH₂ - Si(CH₃)₂ - O.

The present invention relates also to a polymer obtainable or obtained with the thiol-ene methods 1 , 2, 3 or 4, the alkyne methods 1 , 2, 3, or 4, or the Diels Alder methods 1 , 2, 3 or 4. Such polymers preferably consist predominantly of or consist of one or more types of crosslinked silsesquioxane units of the formula (RSi0_3/2)_n wherein:

a) n may be 6, 8, 10 or 12 or a mixture thereof;

b) R is a substituent, or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least one R of the n R within the formula (RSi0_3/2)_n of a first given silsesquioxane unit is crosslinked with at least one R of the n R within the formula (RSi0_3/2)_n of one or more further silsesquioxane unit(s) via a thioether group; a cyclohexene group or a triazole group.

Again, a given silsesquioxane unit is preferably crosslinked with at least two, preferably at least three further silsesquioxane units. The monomeric building blocks of such polymers are, as mentioned and defined above, preferably predominantly or even exclusively silsesquioxane monomers of the formula (RSi0_{3 2})n- Predominantly in this context means again that the fraction of said silsesquioxane monomer units (radical polymerisation method) or the combined fraction of silsesquioxane monomers and linker compounds (thiol-ene, alkyne and Diels Alder methods) in the polymer constitute stoichiometrically 50% or more than 50% of the monomeric repeat units, preferably more than 55%, even more preferably more than 60%, even more preferably more than 65%, even more preferably more than 70%, even more preferably more than 75%, even more preferably more than 80%, even more preferably more than 85%, even more preferably more than 90%, even more preferably more than 95%, even more preferably more than 98%, most preferably 100% (ignoring any potential initiators) of the monomeric units in the polymer. In other words, in particular embodiments it may be advantageous or at least not disadvantageous to create (hetero-)polymers not only comprising the silsesquioxane monomers of the formula (RSi0_3/2)_n but also to lesser extent other monomers. However, particularly preferred are "homopolymers" of only silsesquioxane monomeric units of the formula (RSi0_3/2)_n. With regard to the possible heterogeneity of silsesquioxane monomers of the formula (RSi0_3/2)_n within the polymer see above (i.e. monomeric units differ in terms of n, but not R; monomeric units differ in terms of R but not in terms of n; monomeric units differ in terms of n and R; monomeric units do not differ in terms of n and R but in terms of position of the substituent etc.). Likewise a given monomeric unit within the polymer may exhibit different Rs. This applies for the polymer even the more so, because in course of the polymerisation reaction some substituents of a given monomeric repeat unit may have reacted, while others have not (see for example intermediate product in Fig. 1 ), or have reacted in a different manner.

With regard to the nature of R the situation in the polymer is more complex than for the monomers, because there are at least 3 possible situations for a given R:

a) R has not reacted during polymerisation (either because the specific R was not reactive per se or because it simply did not participate in the polymerisation reaction),

b) R has reacted with another R (R ) in the course of the polymerisation,

c) R has been modified, e.g. by means of thiol-ene-click chemistry (see below).

A given substituent R (in particular for situation a) in the polymer may still be for example chosen from the group as mentioned above, e.g. chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide. In particular R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (Q to C₁₀₀)-alkyl, (Q to C₁₀₀)-alkenyl, (C, to C₁₀₀)-alkinyl, (Q to C₁₀₀)-alkoxy, (Q to C₁₀₀)-alkenoxy, (C, to C₁₀₀)-acyl, (C, to C₁₀₀)-cycloacyl (C, to C₁₀₀)-cycloalkenyl, (C, to C₁₀₀)-aryl, (C, to C₁₀₀)-arylalkyl, (Q to C₁₀₀)-arylalkenyl, (Q to C₁₀₀)-heteroalkyl, (C, to C₁₀₀)-heteroalkenyl, (C, to C₁₀₀)-heteroalkinyl, (C, to C ₀₀)-heteroalkoxy, (C, to C₁₀₀)-heteroalkenoxy, (C, to C₁₀₀)-heteroacyl, (Q to C₁₀₀)-heterocycloalkyl, (C, to C,oo)-heterocycloalkenyl, (C, to C₁₀₀)-heteroaryl, (C, to C₁₀o)-heteroarykalkenyl, (C, to C₁₀₀)-heteroarylalkyls, and polyethylene oxide. R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (C, to C₄₀)-alkyl, (Q to C₄₀)-alkenyl, (C, to C₄₀)-alkinyl, (C, to C₄₀)-alkoxy, (C, to C₄₀)-alkenoxy, (C, to C₄₀)-acyl, (Q to C₄₀)-cycloacyl (C, to C₄₀)-cycloalkenyl, (C, to C₄₀)-aryl, (C, to C₄₀)-arylalkyl, (C, to C₄₀)-arylalkenyl, (C, to C₄₀)-heteroalkyl, (C, to C₄₀)-heteroalkenyl, (C, to C₄₀)-heteroalkinyl, (Q to C₄₀)-heteroalkoxy, (C, to C₄₀)-heteroalkenoxy, (C, to C₄₀)-heteroacyl, (C, to C₄₀)-heterocycloalkyl, (C, to C₄₀)-heterocycloalkenyl, (C, to C₄₀)-heteroaryl, (C, to C₄₀)-heteroarykalkenyl, (Q to C₄₀)-heteroarylalkyls, and polyethylene oxide. Preferably, R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C,₀)-alkyl, (C, to C₁₀)-alkenyl, (C, to C₁₀)-alkinyl, (C, to C₁₀)-alkoxy, (C, to C₁₀)-alkenoxy, (C, to C₁₀)-acyl, (C, to C₁₀)-cycloacyl (C, to C₁₀)-cycloalkenyl, (C, to C₁₀)-aryl, (Q to C₁₀)-arylalkyl, (Q to C₁₀)-arylalkenyl, (C, to C₁₀)-heteroalkyl, (C, to C₁₀)-heteroalkenyl, (C, to C₁₀)-heteroalkinyl, (Q to Ci₀)-heteroalkoxy, (C, to C₁₀)-heteroalkenoxy, (C, to C₁₀)-heteroacyl, (C, to C₁₀)-heterocycloalkyl, (C, to C₁₀)-heterocycloalkenyl, (C, to C₁₀)-heteroaryl, (C, to C₁₀)-heteroarykalkenyl, (C, to C₁₀)-heteroarylalkyls, and polyethylene oxide.

If the resulting polymer shall be further modified, the polymer preferably still comprises reactive groups, e.g. polymerizable (non-aromatic) C=C bonds. Even more preferably the polymer comprises on average about at least one, at least 2, at least 3, at least 4, at least 5, or (if applicable, depending on n) at least 6, at least 7, at least 8, at least 9, at least 10, or 1 1 or more reactive groups, e.g. C=C bonds per monomeric silsesquioxane repeat unit in the polymer. Despite n is limited to be at most 12, the number of reactive groups, e.g. C=C bonds can nevertheless exceed 12, even after polymerisation, because a given R of the monomeric precursors needs not necessarily contain only one reactive group, e.g. C=C bond but may comprise more of them. The number of reactive groups, e.g. C=C bonds, available in the polymer for further modification can be influenced for example by the choice of the appropriate monomers (e.g. by choosing Rs that comprise one or more reactive groups, e.g. polymerizable C=C bonds) as well as careful choice of the initiator (less initiator = less consumption of reactive groups, e.g. C=C bonds and less termination by initiator or other existent radicals), as well as by the stoichiometrical ratio of silsesquioxane monomer to linker compound.

Preferably, said reactive groups, e.g. polymerizable (non-aromatic) C=C bonds, are positioned in R distal to the respective Si atom, at the least distal end of R, in between on any branching unit or most distal. By this means the reactive group, e.g. C=C bond will be sterically readily accessible for (e.g. radical) polymerisation. Whether or not such reactive group, e.g. C=C bonds, are positioned distal to the Si atom depends essentially on the choice of respective monomeric precursors. Preferred examples for C=C bonds positioned in R distal to the respective Si atom are selected from any (polymerizable) ethenyl (vinyl) group, methacrylate group, acrylate group, norbornenyl group and maleimide groups, i.e.

wherein z may be in principle any length as long as the rigidity of the polymer is in the desired range. Preferably, z is in the range of 0-100, more preferably 0-50, even more preferably 0-40, even more preferably 0-25, 0-10 or 0-5. Z may for example be 0, 1 , 2, 3, 4, 5, 6, 7, 8 , 9 or 10. If z=0 then the R simply comprises as C=C bond or simply is vinyl, propenyl, methacrylate, acrylate, norbornenyl or maleimide, respectively.

As set out above, in contrast to the description above for the monomeric precursors, the resulting polymer does not necessarily still comprise reactive groups such as C=C bonds. However, since (e.g. post-polymerisation) modification is desirable, the polymer of the present invention comprises preferably still reactive groups, in particular C=C bonds. In other words, the polymer comprises preferably crosslinked silsesquioxane repeat units of the formula (RSi0_3/2)_n, of which at least 1 R of the n R within the formula (RSi0_3/2)_n comprises in turn at least one reactive group such as a polymerizable (non-aromatic) C=C bond. Particularly preferred are reactive groups, e.g. polymerizable (non-aromatic) C=C bonds, positioned in R distal to the respective Si atom (see above).

In a preferred embodiment on average at least 1 R of the n R within the formula (RSi0_{3 2})_n of each silsesquioxane unit within the polymer comprises at least one reactive group, such as a poylmerizable C=C bond.

As mentioned above, the polymers obtained with the polymerisation methods of the present invention may easily be functionalised, e.g. by thiol-ene-click chemistry, methathesis, halogenation or hydrogenation. Thus, in a further embodiment the present invention relates to a polymer as defined herein, wherein said polymer exhibits modifications at at least some R substituents with a functional moiety. Such functional moieties provide the polymer with properties which are desirable for a given application. Such functional moieties may be for example hydrophilic moieties, hydrophobic moieties; ionic moieties, ligands, antibodies, receptors, proteins, peptides, nucleic acids; linker molecules, etc.. Examples of functional moieties include carboxylic acids, acid halides, carboxylic esters, carboxylic salts, carboxylic anhydrides, aldehydes and their chalcogen analogues, alcohols and phenols, ethers, peroxides and hydroperoxides, carboxylic amides, hydrazides and imides, amidines and other nitrogen analogues of amides, nitriles, amines and imines, azo, nitro, other nitrogen compounds, sulfur acids, selenium acids, thiols, sulfides, sulfoxides, sulfones, sulfonates, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, and aluminates.

Hence, the present invention also relates to a polymer of the present invention as defined above, wherein at least some silsesquioxane units of the formula (RSi0_3/2)_n within the polymer are modified at at least one R with a functional moiety. In a further embodiment, the present invention also relates to polymers obtainable or obtained by a polymerisation method according to the present invention.

In a further aspect the present invention relates to an adsorbent material comprising a polymer according to the present invention. Said adsorbent material may consist exclusively of the polymer according to the present invention, but may just as well comprise other compounds and materials, e.g. coatings, support materials, carriers, etc.. In this respect the material may be used for example as a precursor for other technological applications after chemical modification, coating or surface decoration, or as template for otherwise derived materials.

In a preferred embodiment the adsorbent material is - at least in the portion of the adsorbent material comprising the polymer of the present invention - hierarchically structured, e.g. exhibits pores ranging from micropores to macropores. Micropores as used herein are understood to have pore sizes in the range of about 0,1 nm to < 2 nm, mesopores are understood to have pore sizes of >2 nm to < 50 nm and macropores are pores with a pore size of > 50 nm, for example up to <10 pm. Thus, preferably the adsorbent material comprises micropores, micropores and mesopores, micropores and macropores and/or micropores, mesopores and macropores. It is understood by those skilled in the art that exclusively micropores can be present, if a good solvent is used for polymerisation (influencing phase separation behaviour).

In a further embodiment the adsorbent material according to the present invention exhibits preferably a BET surface of about 300 to about 1200 m²g^"\

In a further embodiment the adsorbent material according to the present invention comprises preferably pores in the range of 0,1 - 50 nm.

In a particular embodiment of the present invention the adsorbent material according to the present invention comprises pores in the range of about 50 - to about 10000 nm accessible for example for fluid flow.

In some embodiment the adsorbent material according to the present invention comprises reactive groups, e.g. C=C bonds. Usually these C=C bonds will be present on the polymer of the invention and allow modification of the material with functional moieties.

Thus, in a further aspect the present invention relates also to a method of modifying a polymer or adsorbent material according to the present invention, the method comprising the following steps: - providing a polymer or adsorbent material according to the present invention, wherein the polymer/adsorbent material comprises C=C bonds; and

- modifying said polymer with at least one type of functional moiety of interest at said C=C bond, preferably by means of thiol-ene click mechanism (hydrothiolation of C=C bond), methathesis, halogenation or hydrogenation.

Thiol-ene-click chemistry is well known in the art (see for example A. B. Lowe, Polymer Chemistry, 2010,1 ,1 7-36; Click Chemistry for Biotechnology and Materials Science; Wiley; Ed. Joerg Lahann, 2009; incorporated herein by way of reference).

Functional moieties may be for example hydrophilic moieties, hydrophobic moieties; ligands, antibodies, receptors, proteins, peptides, nucleic acids; linker molecules, etc. They include carboxylic acids, acid halides, carboxylic esters, carboxylic salts, carboxylic anhydrides, aldehydes and their chalcogen analogues, alcohols and phenols, ethers, peroxides and hydroperoxides, carboxylic amides, hydrazides and imides, amidines and other nitrogen analogues of amides, nitriles, amines and imines, azos, nitros, other nitrogen compounds, sulfur acids, selenium acids, thiols, sulfides, sulfoxides, sulfones, sulfonates, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, and aluminates.

Specific examples for agents useful to modify the polymers of the present invention and disclosed herein are 2,2'-(ethylenedioxy)diethanethiol and thioglycolic acid.

A polymer particularly contemplated for further modification is a polymer of octavinylsilsesquioxane monomers produced as disclosed herein.

A person skilled in the art will understand that the actual modification is not a critical technical element of the present invention. The present invention provides a versatile polymer which may be modified by simple means such as thiol-ene-click chemistry to any desired and technically possible extent according to the state of the art.

Furthermore, it will be readily apparent to a person skilled in the art that instead of (or in addition to) the (e.g. polymerizable) C=C bond referred herein, also C≡C triple bonds may provide the functions set out herein, e.g. serve as basis for radical polymerisation or site of functional modification. Thus, in further embodiments the inventors contemplate the very same embodiments disclosed herein for C=C bonds but with C≡C triple bonds.

The present invention relates in a further aspect to the use of a polymer according to the present invention or an adsorbent material according to the present invention in solid phase extraction processes, flow-through applications, micro-fluidic applications, gas storage, enzymatic digestions, extractions, or catalysis as well as open tubular formats for the aforementioned applications, e.g. as monolithic entity.

Flow through applications may in particular be selected from liquid and/or gas chromatography in ion-exchange, reversed phase, hydrophilic interaction mode, hydrophobic interaction mode, enzymatic reactors, enrichment/extraction units, and preparative chromatography.

Micro-fluidic applications may in particular be flow through applications as before or other embodiments selected from inkjet printheads, selectively permeable membranes, chips for biological applications/studies, and lab-on-a-chip technologies.

Lab-on-a-chip technologies is understood here as involving an device that integrates one or more laboratory functions on a single chip of only micrometers to a few square centimeters in size. Such laboratory functions may include immunoassays, PCRs, biochemical assays such as binding assays etc.

In the following a brief description of the appended figures will be given. The figures are intended to illustrate the present invention in more detail. However, they are not intended to limit the overall scope of the invention.

Fig. 1 Scheme illustrating exemplary a two step method in which (i) first the polymer according to the invention is polymerized and (ii) second the polymer is modified with R-SH via thiol- ene click reaction. Reaction conditions may for example be: step (i): AIBN (1 6% w/w), THF (0-80% w/w), PEG (0-40% w/w), 24 hours, 60°C. Step (ii): DM PA (1 % w/w), chloroform, R-SH, hv, 10mins.

Fig. 2 a) Nitrogen adsorption/desorption isotherms and b) pore size distribution curves according to Barrett-Joyner-Halenda (BJH). Symbols: Polymer 1 (solid); Polymer 2 (semi-filled); Polymer 3 (open). The isotherm with pure THF as solvent/porogen shows no hysteresis, increasing amounts of PEG200 at the cost of THF show a pronounced hysteresis loop at relative pressures p/p° of 0.6-0.9 indicating a mesoporous structure (Polymer 3). The polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.

Fig. 3 Silsesquioxanes according to the present invention bulk-polymerized in solvents of increasing hydrophilicity from (i-iii) with (i) Polymer 1 and (ii) Polymer 3 and (iii) Polymer 4 (see Fig. 8 for details). The polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.

Fig. 4 Scanning electron microscopy (SEM) of bulk samples (a) Polymer 1 ; (b) Polymer 2; (c) Polymer 3; (d) polymer 4; (e) polymer 5 (see Fig. 8). An increasing amount of PEG 200 at the cost of THF is provided which leads to an increase in pore sizes up to several micrometers (from a to e). Magnification: top, 250x; middle, 2000x; bottom, 25000x. The polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.

Fig. 5 Scanning electron microscopy images of Polymer 4 (see Fig. 8) prepared in situ in a 100 pm ID-sized fused-silica mold; left, cross-section; middle, bulk region; right, wall region. The polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.

Fig 6 Plot of retention of a homologous series of alkylbenzenes ranging from benzene (n=0) to pentylbenzene (n=5) on Polymer 4 (closed circles) in a 100 μιτι ID-sized mold and the scaffold modified in situ via UV-initiated thiol-ene click chemistry with dithiol 2,2'- (ethylenedioxy)diethanethiol (polymer 4a, open circles). The mobile phase comprised a mixture of acetonitrile and water (80/20). The decrease in retention, and consequently the number of interactive hydrophobic vinyl sites is significantly reduced indicating existence of the hydrophilic dithiol moiety. Remaining retention mostly stems from alkyl chains between building precursors (Fig. 1 ). The polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.

Fig. 7 Plot of pressure with a 100 μιη ID fused-silica capillary containing polymer 4 against applied flow rate, realized after installation in the nano-LC setup.

Fig. 8 Table illustrating the porous properties of polymers according to the invention probed by nitrogen adsorption/desorption. [a] all w/w, (octa/deca/dodeca)vinyl silsesquioxane 20% w/w ; [b] BJH adsorption cumulative pore volume. Fig. 9 ²⁹Si CP-MAS NMR of i) octavinyl silsesquioxane (monomer), ii) Polymer 4 and iii) Polymer 4b modified with thioglycolic acid. The partial transformation of the vinyl groups to alkyl chain groups upon polymerization, followed by a further reduction upon modification, is reflected in the shift of the neighbouring ²⁹Si nuclei. Solid state 29Si CP-MAS NMR spectra were measured on a Bruker MSL300 spectrometer at 59.62 MHz and spun at 12 kHz. A Rayonet Chamber Reactor was used for photochemical reactions.

Fig.10 FTIR spectra of (i) octavinylsilsesquioxane (monomer), (ii) Polymer 4 (see Fig. 8) and (iii) polymer 4modified with thioglycolic acid (polymer 4b). A strong band at 1075 cm^"1 associated with the Si-O-Si stretching vibration is preserved throughout the synthetic procedure, whilst the peaks at 3050, 1 600, 1410 and 1275 cm^"1, associated with -HC=CH₂ groups are seen to decrease in intensity, alongside an increase in CH₃ bands at 2900 cm^"1!. An additional C=0 stretching band at 1 710 cm^"1 is observed for the thioglycolic acid modified polymer.

Fig.1 1 Scheme illustrating exemplary thiol-ene method 1 according to the present invention, i.e. the C=C bonds are present in the silsesquioxane monomers (which are here octavinyl silsesquioxane monomers) and the reactive thiol residues are present on the linker compound. R' as used in this figure corresponds to X as used above in formula III.

EXAMPLES

In the following the concept of the present invention will be illustrated on basis of a polymer derived from a mixture of approximately 33% octavinyl silsesquioxane monomers, approximately 33% decavinyl silsesquioxane monomers and approximately 33% dodecavinyl silsesquioxane monomers. However, a person skilled in the art will readily realize in view of the foregoing description and on basis of general knowledge, that the present invention is not limited to the below examples and that the principles set out below for vinyl silsesquioxanepolymers and modified polymers derived therefrom can be applied to other types of silsesquioxane polymers according to the present invention as well. Example 1 : Polymer synthesis

A mixture of approximately 33% octavinyl silsesquioxane monomers, approximately 33% decavinyl silsesquioxane monomers and approximately 33% dodecavinyl silsesquioxane monomers was dissolved in THF, followed by addition of varying amounts of PEG 200 such that the total wt% of porogens to monomer was maintained at 80 wt % porogen to 20 wt % (octa/deca/dodeca)vinylsilsesquioxane (see Fig. 8) leading to high surface area, high porosity three dimensionally adhered monolithic polymers. The solution was added to 1 6 wt% AIBN (with respect to the monomer mass) and filled in 4mL glass vials. The homogeneous single phase polymerisation mixture was deoxygenated by bubbling through nitrogen for 2-5 min. Thermally initiated polymerisation was then carried out in a water bath thermo-stated at 60°C for 24 hours. After polymerisation, bulk polymers (e.g. Figure 3) were cut into smaller pieces, extracted with THF overnight in a Soxhlet apparatus and dried in a vacuum oven overnight. The bulk polymer may be grounded for example by means of a ball mill and fractioned.

Polymerisation of (octa/deca/dodeca)vinylsilsesquioxane in THF resulted in a transparent, glassy polymer (see scheme in Fig. 1 and Figure 3). BET analysis (Figs. 2 and 8) reveal a nanoporous structure with surface areas of approximately 800 m²g^_1, unprecedented for materials prepared via a single-step vinyl polymerisation. Pore volumes of approximately 0.5 ml/g were provided by micro and mesopores. This high surface area originates from the assembly of the nanometer-sized bulky rigid cages which can only pack with a limited density. The introduction of mesopores and subsequently macropores in the monolithic material could be achieved and tailored through polymerisation in a binary porogenic (THF/PEG 200) solvent in varying ratios (Figs. 2, 3, and 8). This could also be visually observed from bulk polymers, whereby a transition from transparent glassy materials to opaque materials was seen upon increasing the PEG200/THF ratio and hence the fraction of macropore content (Figures 3 and 4). The total surface area of the polymers probed by nitrogen adsorption/desorption changed little upon increasing the macropore fraction of the polymers (always exceeding 600 m²g^_1), thus suggesting that this, as expected, stems mostly from the porous structure between the covalently adhered nanometer-sized building blocks. An inherent consequence of the polymerisation of a multi-functional vinyl monomeric species is the existence of a number of residual functionalities in the form of pendant vinyl groups. The use of an (octa/deca/dodeca)-functional vinyl monomeric pre-cursor mixture is, therefore, expected to result in high residual vinyl group content. Solid state ²⁹Si CP-MAS NMR spectroscopy (Fig. 9) and FTIR spectroscopy (Fig. 10) confirmed partial consumption of vinyl groups. This could be estimated from the reduction in the bands associated with the vinyl groups, with respect to the strong, constant -Si-O-Si- band (~1 1 00 cm^"1) in the FTIR spectra of the polymers. The appearance of new bands associated with the newly formed alkyl groups is also observed in both the ²⁹Si CP-MAS NMR and FTIR spectra. The materials showed good thermal stability (~ 485 °C at 95% mass loss via TGA in N2) in comparison to typical monolithic polymeric materials based on methacrylate and styrene-based chemistry (see Y. Lv, T. C. Hughes, X. Hao, N. K. Hart, S. W. Littler, X. Zhang and T. Tan, Macromolecular Rapid Communications, 31 , 1 785-1 790; L. Chen and M. A. Hillmyer, Macromolecules, 2009, 42, 4237-4243).

In another experiment octavinyl silsesquioxane (Hybrid Plastics, Hattiesburg, MS, USA) was dissolved in THF, followed by addition of varying amounts of PEG 200 such that the total wt% of porogens to monomer was maintained at 80 wt % porogen to 20 wt % octavinylsilsesquioxane leading to high surface area, high porosity three dimensionally adhered monolithic polymers. The solution was added to 16 wt% AIBN (with respect to the monomer mass) and filled in 4mL glass vials. The homogeneous single phase polymerisation mixture was deoxygenated by bubbling through nitrogen for 2-5 min. Thermally initiated polymerisation was then carried out in a water bath thermo-stated at 60°C for 24 hours. After polymerisation, bulk polymers were cut into smaller pieces, extracted with THF overnight in a Soxhlet apparatus and dried in a vacuum oven overnight. The bulk polymer may be grounded for example by means of a ball mill and fractioned.

Example 2: Polymer synthesis in capillary/small conduit

The introduction of macropores to the materials according to the present invention increases hydrodynamic permeability for viscous gas and liquid flow and allows the facile convective transport at reasonable backpressures while maintaining the high surface area inherent to polymers formed from these nanoscale building blocks. This was realized by the polymerisation of vinyl silsesquioxane building blocks in a wall functionalized 100 pm ID conduit.

For molding in 100 μιη ID (inner diameter) capillaries previously vinylized fused-silica capillaries (see for example I. Nischang, F. Svec and J. M. J. Frechet, Analytieal Chemistry, 2009, 81 , 7390- 7396, incorporated herein by reference) were filled with the (octa/deca/dodeca)- vinylsilsesquioxane pre-polymerisation mixture described above using a syringe, sealed with rubber stoppers and immersed in a water bath at 50°C for 24 hours. After monolith preparation, a small piece of capillary at the inlet and outlet end was cut and they were flushed with THF.

The polymer could therefore be covalently bound to pendant vinyl groups stemming from vinylization with 3-(trimethoxysilyl)propyl methacrylate precursor resulting in a single-piece of porous wall-adhered polymer, perceptive to liquid flow. Pressure stability up to 13 MPa was confirmed by the linearity of the slope of backpressure against mobile phase flow rate. The covalent wall anchorage also reduced shrinking and wall gap formation. As may be expected, initial experiments showed a strong correlation between the amount of AIBN used as radical initiator, the residual vinyl group content and consequently the rigidity/pressure stability of the monoliths. An AIBN content of 16% was chosen for the current experiments.

Example 3: Polymer modification

It is clearly desirable to design the surface properties of the high surface area materials according to the present invention (see example 1 ) in order to suit the desired application. For example thiol-ene click chemistry (see for example A. B. Lowe, Polymer Chemistry, 2010,1 ,1 7-36.) provides a simple and effective route to tailor the surface properties of the polymers of the invention via functionalization of e.g. residual vinyl groups. To demonstrate the versatility of the approach, the inventors modified the polymers with the dithiol 2,2'-(ethylenedioxy)diethanethiol (4a) to render it hydrophilic, and with thioglycolic acid (4b). The modification can be done thermally or photochemical ly. Successful modification was confirmed by FTIR spectroscopy (Fig. 10) and ²⁹Si CP-MAS NMR spectroscopy for the bulk samples (Fig. 9).

For Polymer 4a, dithiol 2,2'-(ethylenedioxy)diethanethiol (0.7g) and 2,2-dimethoxy-2- phenylacetophenone (1 %wt) were dissolved in chloroform (1 mL). For bulk modification polymer 4 (0.2g) was suspended in the solution, continuously stirred, and was exposed to UV light for 10 minutes with cooling at 4°C."

For polymer 4b, thioglycolic acid (0.7g, 7.6mmol) and 2,2dimethoxy-2-phenylacetophenone (1 %wt) were dissolved in chloroform (1 mL). Forbulk modification polymer 4 (see Fig. 8) (0.2g) was suspended in the solution and was exposed to UV light for 10 minutes with cooling at 4°C.

In parallel, thioglycolic acid (0.7g, 7.6mmol) and AIBN (1 %wt) were dissolved in toluene (1 mL). Polymer 4 (0.2g) was suspended in the solution and the suspension heated for 6h at 80°C.

For capillary modifications the reaction solution was allowed to flow through the column for half an hour at a flow rate of Ι μΙ/min. Under continuous flow the capillary was irradiated with UV- light at 4°C. After reaction, the functionalized materials were washed repeatedly with chloroform, THF, H₂0 and subsequently MeOH. Bulk polymers were then dried in a vacuum oven at 40°C for at least 24 hours before analysis, whereas capillary-anchored monoliths were dried under a stream of nitrogen for microscopic dry- state analysis (Figs. 4 and 5).

Example 4: Technical application of modified polymer in LC

Viscous flow-through ability is a desirable property of polymers according to the present invention, in particular with respect to their application in microfluidic devices, including desirable interactive properties of the pore confining polymer which would open avenues to a wide variety of applications. For such purpose the octa/deca/dodecavinyl silsesquioxane polymers of the present invention were modified (see Example 3). The inventors rendered the hydrophobic materials more hydrophilic with thiol glycol moieties (Polymer 4a). A simple example from LC of small molecules clearly revealed that the inherent hydrophobicity of the materials containing a multiplicity of pendant vinyls and selectively retaining the alkylbenzenes can be drastically reduced via thiol-ene click chemistry. The retentive property for small hydrophobic alkylbenzenes percolated through the structure was significantly reduced (Fig. 6).

Claims

1 . Method for producing a porous polymer, wherein the method comprises:

a) n is 6, 8, 10, 12, or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)n comprises at least one C=C bond, in particular a non-aromatic C=C bond; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n by means of radical polymerisation in solution.

2. Method according to claim 1 , wherein the n R are chosen individually and independently of each other from the group consisting of branched and/or linear, substituted and/or non- substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide.

3. Method according to claim 2, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀₀)-alkyl, (C, to C₁₀₀)-alkenyl, (C, to C₁₀₀)-a!kinyl, (C, to C₁₀₀)-alkoxy, (C, to C₁₀₀)-alkenoxy, (C, to C₁₀₀)-acyl, (C, to C₁₀₀)-cycloacyl (C, to C₁₀₀)-cycloalkenyl, (C, to C₁₀₀)-aryl, (C, to C₁₀₀)-arylalkyl, (C, to C₁₀₀)-arylalkenyl, (C, to C₁₀₀)-heteroalkyl, (C, to C₁₀₀)-heteroalkenyl, (C, to C₁₀₀)-heteroalkinyl, (C, to C₁₀₀)-heteroalkoxy, (C, to C₁₀₀)-heteroalkenoxy, (C, to C₁₀₀)-heteroacyl, (C, to C₁₀₀)-heterocycloalkyl, (C, to C₁₀₀)-heterocycloalkenyl, (C, to C₁₀₀)-heteroaryl, (C, to C₁₀o)-heteroarykalkenyl, (C, to C₁₀₀)-heteroarylalkyls, and polyethylene oxide.

4. Method according to claim 3, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀)-alkyl, (C, to C₁₀)-alkenyl, (C, to C,₀)-alkinyl, (C, to C₁₀)-alkoxy, (C, to C₁₀)-alkenoxy, (C, to C₁₀)-acyl, (Q to C₁₀)-cycloacyl (C, to C₁₀)-cycloalkenyl, (C, to C₁₀)-aryl, (C, to C₁₀)-arylalkyl, (C, to C₁₀)-arylalkenyl, (C, to C₁₀)-heteroalkyl, (C, to C₁₀)-heteroalkenyl, (C, to C₁₀)-heteroalkinyl, (C, to C₁₀)-heteroalkoxy, (C, to C₁₀)-heteroalkenoxy, (C, to C₁₀)-heteroacyl, (C, to C₁₀)-heterocycloalkyl, (C, to C₁₀)-heterocycloalkenyl, (Q to C₁₀)-heteroaryl, (C, to C₁₀)-heteroarykalkenyl, (C, to C₁₀)-heteroarylalkyls, and polyethylene oxide.

Method according to anyone of claims 1 to 4, wherein said C=C bond is positioned in R distal to the respective Si atom, preferably at the most distal end of R.

Method according to anyone of claims 1 to 5, wherein the at least 1 R of the n R within the selected from the group consisting

wherein z may be 0-100.

7. Method according to claim 6, wherein z is 0.

8. Method according to anyone of claims 1 to 7, wherein at least 2, preferably > 3, R of the n R within the formula (RSi0_3/2)_n comprise at least one C=C bond, in particular a non-aromatic C=C bond.

9. Method according to anyone of claims 1 to 8, wherein all R in a given monomer of the formula (RSi0_3/2)n are identical.

10. Method according to anyone of claims 1 to 9, wherein only one type of silsesquioxane monomer of the formula (RSi0_3/2)_n is provided.

1 1 . Method according to anyone of claims 1 -10, wherein octavinyl silsesquioxane, decavinyl silsesquioxane and/or dodecavinylsilsesquioxane is provided as silsesquioxane monomer.

12. Method according to anyone of claims 1 to 1 1 , wherein the polymerization is done thermally or photochemically.

13. Method according to anyone of claims 1 to 12, wherein the polymerisation is carried out in presence of at least one porogenic solvent such as THF.

14. Method according to anyone of claims 1 to 13, wherein polymerisation is started with an initiator, preferably selected from: AIBN, , ABCN, chlorine, and organic peroxides such as di- t(tertiary)-butylperoxide (tBuOOtBu), benzoyl peroxide ((PhCOO)₂) methyl ethyl ketone peroxide and acetone peroxide

1 5. Method according to claim 14, wherein the initiator of the polymerisation reaction is present in a ratio of about 0.1 to about 40 wt% with respect to the monomers.

16. Method according to anyone of claims 1 to 15, wherein the polymerisation reaction is done in solution comprising a solvent selected from the group consisting of: THF;_dichloromethane (DCM), chloroform, ethyl acetate, acetone, dimethylformamide (DMF), acetonitrile (MeCN), dimethyl sulfoxide (DMSO), dioxane, propanol, butanediol, cyclohexanol, dodecanol toluene.

1 7. Method according to anyone of claims 1 to 1 6, wherein the polymerisation is carried out thermally at mild conditions in a range of about 0°C to about 100°C, such as at 50 to 60°C for 24 hours.

18. Method according to anyone of claims 1 to 1 7, wherein the polymerisation is carried out photochemically by means of UV radiation, visible light irradiation, by any ionizing radiation, e.g. gamma x-ray radiation or by redox initiation providing a trigger for polymerisation.

19. Method according to anyone of claims 1 to 18, wherein a mixture octavinyl silsesquioxane, decavinyl silsesquioxane and dodecavinyl silsesquioxane is provided as silsesquioxane monomers and wherein the solvents used comprise THF and PEG.

20. Method according to anyone of claims 1 to 19, wherein instead of or in addition to the silsesquioxane monomers of the formula (RSi0₃ 2)_n silsesquioxane oligomers of formula [(RSi0_3/2)_n]_m (formula II) are used, wherein (RSi0_3/2)n is as defined in any of the preceding claims and wherein m is 2 - 50.

21 . Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two C=C bonds, in particular non-aromatic C=C bonds; or at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one C=C bond, in particular a non-aromatic C=C bond;

22. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n within the formula (RSi0_3/2)_n comprises at least two thiol groups; or at least 2 R of the n R within the formula (RSi0_{3 2})n comprise at least one thiol group;

- providing one or more types of linker compounds each comprising at least two C=C bonds; and

23. Method for producing a porous polymer, wherein the method comprises:

- providing one or more types of silsesquioxane monomers of the formula ( Si0₃ 2)_n wherein:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least one thiol group and at least one C=C bond; and/or

at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least one thiol group; while at least one other R of the n R within formula (RSi0_{3 2})_n comprises at least one C=C bond

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two thiol groups, compounds comprising at least two C=C bonds and compounds comprising on the one hand at least one thiol group and on the other hand at least one C=C bond, and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n and the optional one or more types of linker compounds by means of thiol-ene reaction, preferably in solution.

24. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two C=C bonds, in particular non-aromatic C=C bonds; and/or

at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one C=C bond, in particular a non-aromatic C=C bond; - providing one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)_n wherein:

a¹) n may be 6, 8, 10, 12 or a mixture thereof;

b') R' is a substituent or hydrogen,

c') each R' of the n R' within the formula (R'Si0_3/2)n may be the same or different,

d') at least 1 R' of the n R' within the formula (R'Si0_3/2)_n comprises at least two thiol groups; or at least 2 R' of the n R¹ within the formula (R'Si0_3/2)_n comprise at least one thiol group;

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)_n and optionally the one or more types of linker compounds by means of thiol-ene reaction, preferably in solution.

25. Method according to anyone of claims 21 , 23 or 24, wherein at least 2, preferably > 3, R of the n R within the formula (RSi0_{3 2})_n comprise at least one C=C bond, in particular a non- aromatic C=C bond.

26. Method according to anyone of claims 22, 23 or 24, wherein at least 2, preferably > 3, R (or R') of the n R (n R') within the formula (RSi0_{3 2})_n (or R' Si0_3/2)_n comprise at least one thiol group.

27. Method according to anyone of claims 21 or 24, wherein octavinyl silsesquioxane, decavinyl silsesquioxane and/or dodecavinylsilsesquioxane is provided as silsesquioxane monomer.

28. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two C≡C bonds; or at least 2 R of the n R within the formula (RSi0_3/2)n comprise at least one C≡C bond;

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)_n and the one or more types of linker compounds by means of azide-alkyne cycloaddition, preferably in solution.

29. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two azide groups; or at least 2 R of the n R within the formula (RSi0_{3 2})_n comprise at least one azide group;

- providing one or more types of linker compounds each comprising at least two C≡C bonds; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n and the one or more types of linker compounds by means of azide-alkyne cycloaddition reaction, preferably in solution.

30. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0₃ 2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)„ comprises at least one azide group and at least one C≡C bond; and/or

at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one azide group; while at least one other R of the n R within formula (RSi0_{3 2})_n comprises at least one C≡C bond;

- optionally providing one or more types of linker compounds selected from the group consisting of compounds comprising at least two azide groups, compounds comprising at least two C≡C bonds and compounds comprising on the one hand at least one azide group and on the other hand at least one C≡C bond, and

31 . Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0₃/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two C≡C bonds; and/or

at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one C≡C bond;

a') n may be 6, 8, 10, 12 or a mixture thereof;

b') R' is a substituent or hydrogen,

d') at least 1 R' of the n R¹ within the formula (R'Si0_3/2)_n comprises at least two azide groups; or at least 2 R' of the n R' within the formula (R'SiO^),, comprise at least one azide group;

32. Method according to anyone of claims 28, 30 or 31 , wherein at least 2, preferably > 3, R of the n R within the formula (RSi0_3/2)_n comprise at least one C≡C bond.

33. Method according to anyone of claims 29, 30 or 31 , wherein at least 2, preferably > 3, R (or R') of the n R (n R') within the formula (RSi0_3/2)n (or R' Si0_3/2)_n comprise at least one azide group.

34. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least two diene groups; or at least 2 R of the n R within the formula (RSi0_3/2)_n comprise at least one diene group;

- providing one or more types of linker compounds each comprising at least two dienophilic groups; and

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_3/2)n and the one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

35. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least two dienophilic groups; or at least 2 R of the n R within the formula (RSi0_{3 2})_n comprise at least one dienophilic group;

36. Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof; b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one diene group and at least one dienophilic group; and/or

at least 1 R of the n R within the formula (RSi0_3/2)_n comprises at least one diene group; while at least one other R of the n R within formula (RSi0_{3 2})_n comprises at least one dienophilic group;

Method for producing a porous polymer, wherein the method comprises:

a) n may be 6, 8, 10, 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})_n may be the same or different, d) at least 1 R of the n R within the formula (RSi0_{3 2})_n comprises at least two diene groups; and/or

- providing one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)n wherein:

a') n may be 6, 8, 10, 12 or a mixture thereof;

b') R' is a substituent or hydrogen,

c') each R' of the n R' within the formula (R'Si0_{3 2})_n may be the same or different,

d') at least 1 R' of the n R¹ within the formula (R'Si0_3/2)_n comprises at least two dienophilic groups; or at least 2 R' of the n R' within the formula (R'SiO^),, comprise at least one dienophilic group;

- polymerizing the one or more types of silsesquioxane monomers of the formula (RSi0_{3 2})_n and the one or more types of silsesquioxane monomers of the formula (R'Si0_3/2)_n and optionally the one or more types of linker compounds by means of Diels-Alder reaction, preferably in solution.

38. Method according to anyone of claims 34, 36 or 37, wherein at least 2, preferably > 3, R of the n R within the formula (RSi0_3/2)_n comprise at least one diene.

39. Method according to anyone of claims 35, 36 or 27, wherein at least 2, preferably > 3, R (or R') of the n R (n R') within the formula (RSi0_3/2)_n (or R' Si0_3/2)_n comprise at least one dienophile.

40. Method according to any of claims 21 to 39, wherein the nR are chosen individually and independently of each other from the group consisting of branched and/or linear, substituted and/or non-substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide.

41 . Method according to claim 40, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C₁₀₀)-alkyl, (C, to C₁₀₀)-alkenyl, (C, to C₁₀₀)-alkinyl, (Q to C₁₀₀)-alkoxy, (C, to C₁₀₀)-alkenoxy, (C, to C₁₀₀)-acyl, (C, to C₁₀₀)-cycloacyl (C, to C₁₀₀)-cycloalkenyl, (C, to C₁₀₀)-aryl, (C, to C₁₀₀)-arylalkyl, (C, to C₁₀₀)-arylalkenyl, (C, to C₁₀₀)-heteroalkyl, (C, to C₁₀₀)-heteroalkenyl, (C, to C₁₀₀)-heteroalkinyl, (C, to C₁₀₀)-heteroalkoxy, (C, to C₁₀₀)-heteroalkenoxy, (C, to C₁₀₀)-heteroacyl, (C, to C₁₀₀)-heterocycloalkyl, (C, to C₁₀₀)-heterocycloalkenyl, (C, to C₁₀₀)-heteroaryl, (C, to C₁₀₀)-heteroarykalkenyl, (C, to C₁₀₀)-heteroarylalkyls, and polyethylene oxide.

42. Method according to anyone of claims 21 to 41 , wherein all R in a given monomer of the formula (RSi0_3/2)_n are identical.

43. Method according to anyone of claims 21 to 42, wherein only one type of silsesquioxane monomer of the formula (RSi0_3/2)_n is provided.

44. Method according to anyone of claims 21 to 42, wherein the polymerisation is done thermally or photochemical ly.

45. Method according to anyone of claims 21 to 43, wherein the polymerisation is carried out in presence of at least one porogenic solvent such as THF.

46. Method according to anyone of claims 21 to 43, wherein polymerisation is started with an initiator, preferably selected from: AIBN, ABCN, chlorine, and organic peroxides such as di- t(tertiary)-butylperoxide (tBuOOtBu), benzoyl peroxide ((PhCOO)₂) methyl ethyl ketone peroxide and acetone peroxide

47. Method according to claim 46, wherein the initiator of the polymerisation reaction is present in a ratio of about 0.1 to about 40 wt% with respect to the monomers.

48. Method according to anyone of claims 21 to 47, wherein the polymerisation reaction is done in solution comprising a solvent selected from the group consisting of: THF;_dichloromethane (DCM), chloroform, ethyl acetate, acetone, dimethylformamide (DMF), acetonitrile (MeCN), dimethyl sulfoxide (DMSO), dioxane, propanol, butanediol, cyclohexanol, dodecanol toluene.

49. Method according to anyone of claims 21 to 48, wherein the polymerisation is carried out thermally at mild conditions in a range of about 0°C to about 100°C, such as at 50 to 60°C for 24 hours.

50. Method according to anyone of claims 21 to 49, wherein the polymerisation is carried out photochemical ly by means of UV radiation, visible light irradiation, by any ionizing radiation, e.g. gamma x-ray radiation or by redox initiation providing a trigger for polymerisation.

51 . Method according to anyone of claims 21 to 50, wherein instead of or in addition to the silsesquioxane monomers of the formula (RSi0_3/2)_n or (R'Si0₃/2)_n silsesquioxane oligomers of formula [(RSi0₃/2)_n] m (formula II) or [(RSi0_3/2)_n]_m (formula Mb) ], respectively, are used, wherein (RSi0_3/2)_n and (R'Si0_3/2)_n are as defined in any of claim 21 to 50 and wherein m is 2 - 50.

52. Polymer obtainable by any one of the methods according to claims 1 to 51 .

53. Polymer consisting essential ly of or consisting of one or more types of crosslinked silsesquioxane units of the formula (RSi0₃ 2)_n wherein:

a) n may be 6, 8, 10 or 12 or a mixture thereof;

b) R is a substituent or hydrogen,

c) each R of the n R within the formula (RSi0_3/2)n may be the same or different, d) at least one R of the n R within the formula (RSi0_3/2)_n of a first silsesquioxane unit shares at least one chemical bond with at least one R of the n R within the formula (RSi0_3/2)n of one or more further silsesquioxane unit(s).

54. Polymer according to claim 53, wherein the polymer comprises crosslinked silsesquioxane units of the formula (RSi0_3/2)_n, of which at least 1 R of the n R within the formula (RSi0_3/2)_n comprises in turn at least one C=C bond.

55. Polymers consisting predominantly of or consisting of one or more types of crosslinked si lsesquioxane units of the formula (RSi0_{3 2})_n wherein:

a) n may be 6, 8, 10 or 12 or a mixture thereof;

b) R is a substituent, or hydrogen,

c) each R of the n R within the formula (RSi0_{3 2})_n may be the same or different, d) at least one R of the n R within the formula (RSi0_{3 2})_n of a first given si lsesquioxane unit is crosslinked with at least one R of the n R within the formula (RSi0_3/2)_n of at least one or more further silsesquioxane unit(s) via a thioether group; a cyclohexene group or a triazole group.

56. Polymer according to any of claims 52 to 55, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: alkyl, alkenyl, alkinyl, alkoxy, alkenoxy, acyl, cycloacyl cycloalkenyl, aryl, arylalkyl, arylalkenyl, heteroalkyl, heteroalkenyl, heteroalkinyl, heteroalkoxy, heteroalkenoxy, heteroacyl, heterocycloalkyl, heterocycloalkenyl, heteroaryl, heteroarykalkenyl, heteroarylalkyls, and polyalkylene oxide.

57. Polymer according toclaim 56, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C1 to C100)-alkyl, (CI to C1 00)-alkenyl, (CI to C100)-alkinyl, (C1 to C100)-alkoxy, (C1 to C1 00)-alkenoxy, (C1 to C1 00)-acyl, (C1 to C1 00)-cycloacyl (C1 to C1 00)-cycloalkenyl, (C1 to C100)-aryl, (C1 to C100)-arylalkyl, (CI to C1 00)-arylalkenyl, (CI to C100)-heteroalkyl, (C1 to Cl 00)-heteroalkenyl, (C1 to C100)-heteroalkinyl, (C1 to C100)-heteroalkoxy, (C1 to

C100)-heteroalkenoxy, (C1 to C100)-heteroacyl, (C1 to C100)-heterocycloalkyl, (C1 to

C100)-heterocycloalkenyl, (CI to C100)-heteroaryl, (C1 to C100)-heteroarykalkenyl, (CI to CI O0)-heteroarylalkyls, and polyethylene oxide.

58. Polymer according to claim 57, wherein R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (CI to C10)-alkyl, (C1 to C10)-alkenyl, (CI to C10)-alkinyl, (C1 to C10)-alkoxy, (C1 to C10)-alkenoxy, (CI to C10)-acyl, (C1 to CI 0)-cycloacyl (C1 to C10)-cycloalkenyl, (C1 to C10)-aryl, (C1 to C10)-arylalkyl, (C1 to C10)-arylalkenyl, (C1 to C10)-heteroalkyl, (C1 to C10)-heteroalkenyl, (CI to C10)-heteroalkinyl, (C1 to C10)-heteroalkoxy, (CI to C10)-heteroalkenoxy, (CI to C10)-heteroacyl, (C1 to C10)-heterocycloalkyl, (C1 to C10)-heterocycloalkenyl, (C1 to C10)-heteroaryl, (C1 to C10)-heteroarykalkenyl, (C1 to C10)-heteroarylalkyls, and polyethylene oxide.

59. Polymer according to any one of claims 52 to 58, wherein the polymer comprises crosslinked silsesquioxane units of the formula (RSi0_{3 2})n, of which at least 1 R of the n R within the formula (RSi0_3/2)_n comprises in turn at least one C=C bond and wherein said C=C bond is preferably positioned in R distal to the respective Si atom, preferably at the most distal end of R.

60. Polymer according to anyone of claims 52 to 59, wherein on average at least 1 R of the n R within the formula (RSi0_3/2)n of a each silsesquioxane unit of the polymer comprises at least one C=C bond.

Polymer according to claim 52 to 60, wherein the at least 1 R comprising at least oneC=C bond is selected from the group consisting of:

wherein z may be 0-100.

62. Polymer according to claim 61 wherein z = 0.

63. Polymer according to anyone of claims 52 to 62, wherein the polymer is further modified with one or more types of functional moieties.

64. Polymer according to claim 63, wherein the one or more types of functional moieties are selected from the group consisting of: a hydrophilic moiety, hydrophobic moieties; ligands, antibodies, receptors, proteins, peptides, nucleic acids; linker molecules .

65. Polymer according to claim 63 or 64, wherein the polymer is modified via click chemistry, in particular via thiol-ene- click chemistry.

66. Polymer according to any of claims 52 - 65, wherein the polymer comprises octavinyl silsesquioxane units, preferably wherein the polymer comprises octavinyl silsesquioxane units, decavinyl silsesquioxane units and dodecavinylsilsesquioxane units.

67. Polymer according to any of claims 52 - 34, wherein the polymer comprises micropores, micropores and mesopores, micropores and macropores, and/or micropores and mesopores and macropores.

68. Adsorbent material comprising the polymer according to anyone of claims 52 to 67.

69. Adsorbent material according to claim 68, wherein the adsorbent material is hierarchically structured.

70. Adsorbent material according to claim 68 or 69 wherein the adsorbent material comprises micropores, micropores and mesopores, micropores and macropores, and/or micropores and mesopores and macropores.

71 . Adsorbent material according to anyone of claims 68 to 70, wherein the adsorbent material comprises C=C bonds.

72. Adsorbent material according to anyone of claims 68 to 71 , wherein the adsorbent material exhibits a BET surface of about 300 to about 1200 m²g^"1 .

73. Adsorbent material according to anyone of claims 68 to 72, wherein the adsorbent material comprises pores in the range of 0,1 - 50 nm.

74. Adsorbent material according to anyone of claims 68 to 73, wherein the adsorbent material comprises pores in the range of 50 - 10000 nm.

75. Method for modifying a polymer according to anyone of claims 52 to 67 or adsorbent material according to anyone of claims 68 to 74; the method comprising the following steps:

- providing a polymer according to claim 52 to 67 or an adsorbent material according to anyone of claims 68 to 74, wherein the polymer comprises C=C bonds; and - modifying said polymer with at least one type of functional moiety of interest at said C=C bonds, preferably by means of thiol-ene click mechanism (hydrothiolation of C=C bond).

76. Use of the polymer according to claims 52 to 67 or the adsorbent material of claims 68 to 74 in solid phase extraction processes, flow-through applications, micro-fluidic applications, gas storage, membrane processes, enzymatic digestions and/or catalysis.

77. Use according to claim 76, wherein the flow through application is selected from liquid and gas chromatography.

78. Use according to claim 76, wherein the micro-fluidic application is selected from inkjet printheads, selectively permeable membranes, chips for biological applications/studies and lab-on-a-chip technologies.