WO2012119615A1 - Polymères de silsesquioxane - Google Patents

Polymères de silsesquioxane Download PDF

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WO2012119615A1
WO2012119615A1 PCT/EP2011/001160 EP2011001160W WO2012119615A1 WO 2012119615 A1 WO2012119615 A1 WO 2012119615A1 EP 2011001160 W EP2011001160 W EP 2011001160W WO 2012119615 A1 WO2012119615 A1 WO 2012119615A1
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formula
rsi0
types
silsesquioxane
group
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PCT/EP2011/001160
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Ian P. Teasdale
Antonia PRUAS
Ivo Nischang
Oliver BRÜGGEMANN
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Johannes Kepler Universität Linz
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Priority to PCT/EP2011/001160 priority Critical patent/WO2012119615A1/fr
Publication of WO2012119615A1 publication Critical patent/WO2012119615A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

  • the present invention relates in general to the fields of polymers and porous adsorbents.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the present invention relates to a method for producing a preferably porous polymer (radical polymerisation method), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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 -
  • silsesquioxane monomer comprises n R residues, n Si atoms and 1 ,5 times n O atoms.
  • 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.
  • the methods for producing a polymer according to the present invention 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.
  • n may be 6, 8, 10, or 12
  • the monomers differ in terms of n, but not in terms of R.
  • R decavinyl silsesquioxane monomers
  • 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.
  • 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*).
  • silsesquioxane monomers of the formula (RSi0 3/2 ) n 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).
  • 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.
  • R is a substituent, preferably an organic substituent, or hydrogen.
  • 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).
  • n 12: (R 1 Si0 3/2 )(R 2 Si0 3/2 )(R 3 Si0 3/2 )(R4Si0 3/2 )(R 5 Si0 3Q )(R 6 Si0 3/2 )(R 7 Si0 3/2 ) n (R 8 Si0 3 ⁇ )(R 9 Si0 3/2 )
  • each R of R, to R 12 is selected individually and independently of any other R (which does not rule out as mentioned above that certain Rs are nevertheless identical).
  • each R of R, to R 12 of a first type of monomer may as mentioned above be selected individually and independently of any other R, to R 12 of potential further types of silsesquioxane monomers of the formula (RSi0 3 2 )n provided to the reaction mixture.
  • more than one or even all R in a given monomer of the formula (RSi0 3 2 ) n are identical.
  • reactive group refers in particular to:
  • 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.
  • R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (Q to C 100 )-alkyl, (C, to C 100 )-alkenyl, (C, to C 100 )-alkinyl, (C, to C 100 )-alkoxy, (Q to C 100 )-alkenoxy, (C, to C 100 )-acyl, (Q to C 100 )-cycloacyl (C, to C 100 )-cycloalkenyl, (C, to C 100 )-aryl, (C, to C 100 )-arylalkyl, (Q to C 100 )-arylalkenyl, (C, to C 100 )-heteroalkyl, (C, to C 100 )-heteroalkenyl, (C, to C 100 )-heteroalkinyl, (C, to C 100 )-heteroalkoxy, (C, to C 100 )-
  • R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (C, to C 40 )-alkyl, (C, to C 40 )-alkenyl, (C, to C 40 )-alkinyl, (C, to C 40 )-alkoxy, (C, to C 40 )-alkenoxy, (C, to C 40 )-acyl, (C, to C 40 )-cycloacyl (C to C 40 )-cycloalkenyl, (C, to C 40 )-aryl, (C, to C 40 )-arylalkyl, (C, to C 40 )-arylalkenyl, (C, to C 40 )-heteroalkyl, (C, to C 40 )-heteroalkenyl, (C, to C 40 )-heteroalkinyl, (C, to C 40 )-heteroalkoxy, (C, to C 40
  • R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C 10 )-alkyl, (C, to C 10 )-alkenyl, (Q to C 10 )-alkinyl, (C, to C 10 )-alkoxy, (C, to C 10 )-alkenoxy, (C, to C 10 )-acyl, (C, to C 10 )-cycloacyl (C, to C 10 )-cycloalkenyl, (C, to C, 0 )-aryl, (C, to C 10 )-arylalkyl, (C, to C 10 )-arylalkenyl, (C, to C 10 )-heteroalkyl, (C, to C 10 )-heteroalkenyl, (C, to C, 0 )-heteroalkinyl, (C, to C 10 )-heteroalkoxy, (
  • alkyl is understood as saturated, linear or branched hydrocarbons, which can occur unsubstituted, mono- or polysubstituted.
  • (C, to C 10 )-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 CHF 2 , CF 3 or CH 2 OH etc.
  • substituted is understood as meaning replacement of at least one hydrogen group by F, CI, Br, I, NH 2 , SH or OH.
  • monosubstituted means the replacement of one hydrogen group by F, CI, Br, I, NH 2 , SH or OH
  • 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 CF 3 , or at different places, as in the case of e.g.
  • At least monosubstituted means either “monosubstituted", “polysubstituted” or - if the option is not fulfilled - "unsubstituted”.
  • 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.
  • (C, to C 10 )-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.
  • 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.
  • (C, to C 10 )-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.
  • alkoxy and alkenoxy refers to an alkyl and alkenyl, respectively, as defined above, which is linked to oxygen and which can be unsubstituted, mono- or polysubstituted.
  • (CI to C10)- alkoxy represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- alkoxy.
  • (C1 to C10)- alkenoxy represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- alkenoxy.
  • 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.
  • R is an alkyl, alkenyl, alkinyl, cycloalkyl or cycloalkenyl as defined herein which can be unsubstituted, mono- or polysubstituted.
  • (C1 to C10)- acyl represents C1 -, C2-, C3-, C4-, C5-, C6-, C7-, C8-, C9- or C10- acyl.
  • Examples of "acyl” are methanoyl-, acetoyl-,
  • 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.
  • cycloalkyl or “cycloalkenyl” typically refers to C 3 , Q, C 5 , C 6 , C 7 , C 8 , C 9 or C 10 cycloalkyl or cycloalkenyl, preferably refers to Q, C 5 , C 6 , C 7 , or C 8 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
  • 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, isothi
  • 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 substitu
  • 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).
  • 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
  • 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.
  • z may be in principle any length as long as the rigidity of the final polymer is still in the desired range.
  • 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.
  • 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.
  • 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 -CHCH 2 ).
  • octavinyl silsesquioxane i.e. n is 8
  • all 8 R within the formula (RSi0 3/2 ) 8 are -CHCH 2
  • an approximately even mixture of octavinyl silsesquioxane, decavinyl silsesquioxane and dodecavinyl silsesquioxane 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.
  • 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.
  • 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.
  • 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.
  • the polymerisation method of the present invention may be conducted in presence of an initiator of polymerisation.
  • an initiator of polymerisation A person skilled in the art will be readily aware of initiators most suitable for the desired type of polymerisation.
  • 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.
  • 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.
  • any other radical initiator is possible.
  • 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.
  • 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.
  • solvent or solvent mixture various solvents as well as mixtures of solvents may be used.
  • 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.
  • 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.
  • 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).
  • DCM dichloromethane
  • MMF dimethylformamide
  • MeCN acetonitrile
  • DMSO dimethyl sulfoxide
  • dioxane propanol, butanediol, cyclohexanol, dodecanol, toluene, polyethyleneglycol (PEG; only in combination with other solvents.
  • polymerisation rate affects the porous
  • 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.
  • 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.
  • 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.
  • 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 (RSi0 3 2) n and resulting polymers like polyethyleneglycol or dodecanol induces earlier phase separation and therefore larger pores accessible for flow through ( vide infra).
  • 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.
  • a particularly preferred solvent mixture for polymerisation e.g. of octavinyl si lsesquioxane, is tetrahydrofuran (THF) and polyethyleneglycol.
  • 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.
  • 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).
  • any of the polymerisation methods of the present invention 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.
  • 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;
  • R is a substituent or hydrogen
  • each R of the n R within the formula (RSiO 3/2 ) n may be the same or different, and
  • 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 particularly preferred mode of modification is thiol-ene-click chemistry, but other modes may be contemplated as well, for example methathesis, halogenation and hydrogenation.
  • 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.
  • each (RSiO 3/2 ) n within the m (RSiO 3 2 ) n in such oligomer may be the same or different.
  • 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 .
  • the inventors of the present invention provide in addition to the radical polymerisation method further methods for producing silsesquioxane polymers.
  • the inventors propose the direct formation of a silsesquioxane polymer via thiol-ene click chemistry.
  • the present invention relates in a further aspect to a method for producing a polymer (thiol- ene method 1 ), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (thiol- ene method 2), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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 thiol groups; or at least 2 R of the n R within the formula (RSi0 3/2 ) n comprise at least one thiol group;
  • the present invention relates in a further aspect to a method for producing a polymer (thiol-ene method 3), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • the present invention relates in a further aspect to a method for producing a polymer (thiol-ene method 4), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R' is a substituent or hydrogen
  • each R' of the n R' within the formula (R'Si0 3/2 ) n may be the same or different,
  • At least 1 R' of the n R 1 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;
  • 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.
  • R and R' may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.
  • 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.
  • the present invention relates also to further methods of producing a silsesquioxane polymer, such as by means of azide-alkyne cycloadditions.
  • the present invention relates in a further aspect to a method for producing a polymer (alkyne method 1 ), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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 (RSi0 3 2) n comprise at least one polymerizable (e.g. terminal or ring strained) C ⁇ C bond;
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (alkyne method 2), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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;
  • linker compounds each comprising at least two (e.g. terminal or ring strained) C ⁇ C bonds
  • the present invention relates in a further aspect to a method for producing a polymer (alkyne method 3), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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;
  • 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
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (alkyne method 4), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • each R of the n R within the formula (RSi0 3 2) n may be the same or different
  • 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;
  • n comprise at least one polymerizable (e.g. terminal or ring strained) C ⁇ C bond;
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R 1 is a substituent or hydrogen
  • each R' of the n R' within the formula (R'Si0 3 2) n may be the same or different,
  • 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;
  • 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
  • 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.
  • 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.
  • R and R' may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (Diels Alder method 1 ), wherein the method comprises:
  • n may be 6, 8, 1 0, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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;
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (Diels- Alder method 2), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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;
  • the present invention relates in a further aspect to a method for producing a polymer (Diels-Alder method 3), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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
  • 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.
  • the present invention relates in a further aspect to a method for producing a polymer (Diels-Alder method 4), wherein the method comprises:
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R is a substituent or hydrogen
  • 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
  • At least 2 R of the n R within the formula (RSi0 3/2 ) n comprise at least one diene group
  • n may be 6, 8, 10, 12 or a mixture thereof;
  • R' is a substituent or hydrogen
  • each R 1 of the n R' within the formula (R'Si0 3/2 )n may be the same or different,
  • 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;
  • 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
  • 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.
  • 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.
  • R and R 1 may be selected (independently of each other) from the same group of compounds/substituents as specified above for R.
  • 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.
  • Diels-Alder methods 1 , 2, 3, 4 it is a particularly preferred object of the present invention to obtain porous, three dimensionally adhered polymers. For this purpose branched molecules are preferred.
  • 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.
  • 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.
  • 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.
  • 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.
  • dienophilic groups for R (or R 1 ) are 1 ,2 dicyanoethene groups, dimethyl-cis-2- butenedioate, dimethyl-trans-2-butenedioate, 2-butene-diacid anhydride, dimethyl-butyne- anhydride, propenal, etc.
  • 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.
  • 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;
  • R is a substituent or hydrogen
  • each R of the n R within the formula (RSi0 3 2 ) n may be the same or different, and
  • 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:
  • diene -X- dienophile (formula llli).
  • said linker compounds may comprise more than the specified two reactive groups.
  • 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.
  • 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.
  • 1 ,1 propane dithiol is encompassed by this formula as is 1 ,3 propane dithiol.
  • 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.
  • R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C 100 )-alkyl, (C, to C 10 o)-alkenyl, (Q to C 100 )-alkinyl, (C, to C, 00 )-alkoxy, (C, to C 100 )-alkenoxy, (C, to C 100 )-acyl, (Q to C 100 )-cycloacyl (C, to C 100 )-cycloalkenyl, (C, to C 100 )-aryl, (C, to C 100 )-arylalkyl, (C, to Cioo)-arylalkenyl, (C, to C 100 )-heteroalkyl, (C, to C 100 )-heteroalkenyl, (C, to C, 00 )-heteroalkinyl, (C, to C 100 )-heteroalkoxy, (C,
  • R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (Q to C 40 )-alkyl, (C, to C 40 )-alkenyl, (C, to C 40 )-alkinyl, (C, to C 40 )-alkoxy, (C, to C 40 )-alkenoxy, (C, to C 40 )-acyl, (C, to C 40 )-cycloacyl (C, to C 40 )-cycloalkenyl, (C, to C 40 )-aryl, (C, to C 40 )-arylalkyl, (C, to C 40 )-arylalkenyl, (C, to C 40 )-heteroalkyl, (C, to C 40 )-heteroalkenyl, (C, to C 40 )-heteroalkinyl, (C, to C 40 )-heteroalkoxy, (Q to C 40
  • R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C 10 )-alkyl, (C, to C 10 )-alkenyl, (C, to C 10 )-alkinyl, (C, to C 10 )-alkoxy, (C, to C 10 )-alkenoxy, (C, to C 10 )-acyl, (C, to C 10 )-cycloacyl (C, to C 10 )-cycloalkenyl, (Q to C 10 )-aryl, (C, to C 10 )-arylalkyl, (C, to C 10 )-arylalkenyl, (C, to C 10 )-heteroalkyl, (C, to C 10 )-heteroalkenyl, (C, to C 10 )-heteroalkinyl, (Q to C 10 )-heteroalkoxy, (C, to C 10 )-
  • 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.
  • (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.
  • 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.
  • the present invention relates to the polymers themselves.
  • 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:
  • n may be 6, 8, 10 or 12 or a mixture thereof;
  • R is a substituent, or hydrogen
  • 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).
  • 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.
  • two silsesquioxane units of the formula SI0 3/2 are not linked via -CH 2 - CH 2 -, - O - Si(CH 3 ) 2 - CH 2 - CH 2 or - O - Si(CH 3 ) 2 - CH 2 - CH 2 - Si(CH 3 ) 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:
  • n may be 6, 8, 10 or 12 or a mixture thereof;
  • R is a substituent, or hydrogen
  • 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.
  • 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-
  • 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
  • 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.).
  • 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.
  • 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:
  • 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.
  • R may be chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (Q to C 100 )-alkyl, (Q to C 100 )-alkenyl, (C, to C 100 )-alkinyl, (Q to C 100 )-alkoxy, (Q to C 100 )-alkenoxy, (C, to C 100 )-acyl, (C, to C 100 )-cycloacyl (C, to C 100 )-cycloalkenyl, (C, to C 100 )-aryl, (C, to C 100 )-arylalkyl, (Q to C 100 )-arylalkenyl, (Q to C 100 )-heteroalkyl, (C, to C 100 )-heteroalkenyl, (C, to C 100 )-heteroalkinyl, (C, to C 00 )-heteroalkoxy, (C, to C 100 )-he
  • R may be chosen for example from the group consisting of branched and/or linear, substituted and/or non-substituted (C, to C 40 )-alkyl, (Q to C 40 )-alkenyl, (C, to C 40 )-alkinyl, (C, to C 40 )-alkoxy, (C, to C 40 )-alkenoxy, (C, to C 40 )-acyl, (Q to C 40 )-cycloacyl (C, to C 40 )-cycloalkenyl, (C, to C 40 )-aryl, (C, to C 40 )-arylalkyl, (C, to C 40 )-arylalkenyl, (C, to C 40 )-heteroalkyl, (C, to C 40 )-heteroalkenyl, (C, to C 40 )-heteroalkinyl, (Q to C 40 )-heteroalkoxy, (C, to C 40 )
  • R is chosen from the group consisting of branched and/or linear, substituted and/or non-substituted: (C, to C, 0 )-alkyl, (C, to C 10 )-alkenyl, (C, to C 10 )-alkinyl, (C, to C 10 )-alkoxy, (C, to C 10 )-alkenoxy, (C, to C 10 )-acyl, (C, to C 10 )-cycloacyl (C, to C 10 )-cycloalkenyl, (C, to C 10 )-aryl, (Q to C 10 )-arylalkyl, (Q to C 10 )-arylalkenyl, (C, to C 10 )-heteroalkyl, (C, to C 10 )-heteroalkenyl, (C, to C 10 )-heteroalkinyl, (Q to Ci 0 )-heteroalkoxy, (C, to Ci 0
  • C C bond but may comprise more of them.
  • said reactive groups 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.
  • z may be in principle any length as long as the rigidity of the polymer is in the desired range.
  • 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.
  • 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.
  • 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.
  • 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.
  • the present invention also relates to polymers obtainable or obtained by a polymerisation method according to the present invention.
  • 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..
  • 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.
  • 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.
  • 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).
  • the adsorbent material according to the present invention exhibits preferably a BET surface of about 300 to about 1200 m 2 g " ⁇
  • the adsorbent material according to the present invention comprises preferably pores in the range of 0,1 - 50 nm.
  • 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.
  • 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 alumina
  • agents useful to modify the polymers of the present invention 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.
  • 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.
  • C ⁇ C triple bonds may provide the functions set out herein, e.g. serve as basis for radical polymerisation or site of functional modification.
  • 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.
  • laboratory functions may include immunoassays, PCRs, biochemical assays such as binding assays etc.
  • 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.
  • 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).
  • SEM scanning electron microscopy
  • 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.
  • 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.
  • the polymers resulted from polymerization of a mixture of octavinyl, decavinyl, and dodecavinyl silsesquioxanes.
  • Fig. 7 Plot of pressure with a 100 ⁇ 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.
  • Fig. 9 29 Si CP-MAS NMR of i) octavinyl silsesquioxane (monomer), ii) Polymer 4 and iii) Polymer 4b modified with thioglycolic acid.
  • Fig.10 FTIR spectra of (i) octavinylsilsesquioxane (monomer), (ii) Polymer 4 (see Fig. 8) and (iii) polymer 4modified with thioglycolic acid (polymer 4b).
  • R' as used in this figure corresponds to X as used above in formula III.
  • 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.
  • bulk polymers e.g. Figure 3
  • the bulk polymer may be grounded for example by means of a ball mill and fractioned.
  • 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
  • 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.
  • 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.
  • 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.
  • thiol-ene click chemistry 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.
  • 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 29 Si CP-MAS NMR spectroscopy for the bulk samples (Fig. 9).
  • thioglycolic acid 0.g, 7.6mmol
  • 2,2dimethoxy-2-phenylacetophenone 1 %wt
  • 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.
  • thioglycolic acid 0.g, 7.6mmol
  • AIBN 1 %wt
  • Polymer 4 0.2g was suspended in the solution and the suspension heated for 6h at 80°C.
  • reaction solution was allowed to flow through the column for half an hour at a flow rate of ⁇ ⁇ /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, H 2 0 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.
  • 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).

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Abstract

Cette invention concerne les domaines des polymères et des absorbants poreux. En particulier, cette invention concerne des polymères constitués de motifs silsesquioxane réticulés de formule (RSiO3/2)n où n peut valoir 6, 8, 10 ou 12 ou un mélange de ceux-ci ; R est un substituant, tous les R des n R dans la formule (RSiO3/2)n pouvant être identiques ou différents. Cette invention concerne également des procédés de production desdits polymères, par ex., par polymérisation radicalaire. Pour finir, des matériaux adsorbants contenant lesdits polymères et l'application technique desdits polymères et matériaux adsorbants à des fins techniques différentes telles que des applications en flux continu, des applications microfluidiques, le stockage/la séparation de gaz, l'extraction en phase solide, ou la catalyse sont également décrits.
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