WO2009103757A1 - Polyorganosilane hydrophobe microporeux, procédé de fabrication et utilisation - Google Patents

Polyorganosilane hydrophobe microporeux, procédé de fabrication et utilisation Download PDF

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WO2009103757A1
WO2009103757A1 PCT/EP2009/051965 EP2009051965W WO2009103757A1 WO 2009103757 A1 WO2009103757 A1 WO 2009103757A1 EP 2009051965 W EP2009051965 W EP 2009051965W WO 2009103757 A1 WO2009103757 A1 WO 2009103757A1
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compound
polymer according
silane
substituted
formula
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Stefan Kaskel
Marcus Rose
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Technische Universität Dresden
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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
    • C08G77/60—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • B01J20/267—Cross-linked polymers
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin

Definitions

  • Microporous hydrophobic polyorganosilane method of preparation and use
  • the invention relates to a microporous hydrophobic polyorganosilane, a process for its preparation and its use.
  • the invention is particularly suitable for use in gas storage, air purification, fuel recovery, odor minimization.
  • microporous materials The range of microporous materials is very extensive.
  • Activated carbons have been known for a long time and offer a variety of possible applications, above all as adsorbents in the fields of chemistry, medicine, water and wastewater treatment, etc.
  • Zeolites Another very large and long-known class are the zeolites, crystalline aluminosilicates with micropores and great structural diversity. Zeolites are used commercially as molecular sieves for gas separation and as solid catalysts in heterogeneous catalysis.
  • MOF organometallic coordination compound
  • MOFs are quite dense due to the content of metal ions. Due to the content of polar and ionic groups, they are also hygroscopic. A large proportion of the known MOFs are therefore extremely unstable to moisture, which is a great disadvantage for various applications. In addition, depending on the metal used, there may be a high toxicity. This is the case, for example, with chromium-containing MOFs. In 2005, Cote et al.
  • Covalent-Organic Frameworks are the first porous, covalent organic network compounds that are ordered and microporous and have a high specific surface area, similar to the MOFs COFs have only covalent bonds, leading to a number of new properties, and no metal-based toxic properties are expected, as the COFs are metal-free
  • a very new class of microporous compounds is the so-called PIMs (Polymers of Intrinsic Microporosity) These have interesting properties, such as low intrinsic density, and are composed of light elements such as C, H, O, and N, which is a great advantage over the metal atom-containing MOFs, which are chemically homogeneous, which is superior to activated carbons has high thermal and chemical stability and is synthetically reproducible PIMs on attractive materials for the gas storage of eg hydrogen.
  • Trip-PIM (BET surface: 1064 m 2 g "1 ) adsorbs 1.65% by weight at a pressure of 1 bar and a temperature of 77 K and 2.71% by weight of hydrogen at 10 bar and 77 K (Ghanem et al., Chem. Commun., 2007, 67-69).
  • the object underlying the present invention is to provide a new porous material which is particularly suitable as an adsorption material. Furthermore, the material should have a high thermal and chemical stability, a good gas storage capacity and a lower specific density.
  • the object is achieved by a crosslinked, porous polymer containing silicon atoms which are covalently linked together by four organic linker molecules L, wherein L is a substituted or unsubstituted, acyclic or preferably cyclic alkyl radical having 5 to 50 carbon atoms or a substituted or unsubstituted aryl radical having 5 to 50 C atoms, wherein the aryl radical preferably contains at least one phenyl group.
  • the individual radicals L are selected independently of one another.
  • the polymer according to the invention thus preferably contains structural units according to the general formula 1
  • the polymer according to the invention preferably contains structural units of the formula 1 ', formula 1 "and / or formula 1"':
  • the linker molecules L are preferably with n-1 further silicon atoms or optionally also heteroatoms such. Boron, nitrogen, phosphorus, n is preferably an integer from 2 to 6, preferably 2, 3 or 4.
  • the linker molecules L therefore have n (at least 2) binding sites, which allow the covalent linkage with silicon atoms and optionally also the above-mentioned heteroatoms.
  • Preferred radicals Li are selected from acyclic alkyl radicals having 1 to 5 carbon atoms, preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl.
  • the individual radicals Li are selected independently of one another.
  • the polymer according to the invention preferably contains structural units according to the general formula 2, 2 ', 2 ", 3, 3' and / or formula 3":
  • the silicon atoms are each in turn connected to 4 organic linkers L (or two to three L and one to two Li).
  • the optionally present boron, nitrogen, tin, germanium or phosphorus atoms are respectively connected to 3 organic linkers L (or two L and one Li).
  • B in formulas 3, 3 'and 3 "represents boron, nitrogen, germanium, tin or phosphorus, unless otherwise stated, B represents boron.
  • At least 60%, preferably 80%, more preferably over 95% or even 100% of the silicon atoms contained in the polymer according to the invention are L with at least two organic linker molecules, preferably as in formula 1, formula 1 ', formula 1 "and / or formula 1 "', covalently bonded. More preferably, at least 60%, preferably 80%, more preferably more than 95% or even 100% of the polymer in the invention contained silicon atoms are each covalently linked to four organic linker molecules L as in Formula 1.
  • At least 60%, preferably 80%, more preferably more than 95% or even 100% of the linker molecules L present in the inventive polymer are covalently bonded to at least two silicon atoms, preferably as in formula 2, 2 'and / or 2 " At least 60%, preferably 80%, more preferably more than 95% or even 100% of the linker molecules L present in the inventive polymer are covalently bonded to 4 silicon atoms, preferably as in formula 2.
  • the silicon atoms are preferably covalently bonded to oxygen or aliphatic groups (such as butyl). Due to the manufacturing method, the polymer preferably contains no or almost no Si-Si bonds.
  • the Si-Si bond fraction is preferably 0% to 5%, preferably less than 1%. Due to the method of preparation, the polymer preferably contains no or virtually no Si-H bonds.
  • the Si-H bond fraction is preferably 0% to 5%, preferably less than 1%.
  • the proportion of silicon is preferably 2.5 to 25%, particularly preferably more than 5% and more preferably less than 20%.
  • the proportion of carbon is preferably between 60% by weight and 95% by weight, more preferably above 65% by weight and more preferably below 85% by weight.
  • the proportion of hydrogen is preferably between 2% by weight and 10% by weight, more preferably above 4% by weight and more preferably below 6% by weight. These proportions are dependent in particular on the size of the linker L.
  • further atoms in particular boron, nitrogen, tin, germanium and phosphorus can be contained.
  • the proportion of further atoms is preferably between 0% and 50% by weight, more preferably above 0% by weight and more preferably below 10% by weight.
  • the silicon atoms are ideally each of four substituents (linkers L or optionally with Li) tetrahedrally surrounded (similar to a diamond structure).
  • the distance between the silicon atoms and thus also the pore size of the polymer according to the invention is increased.
  • the selection and combination of the central structural units listed in formulas 1, V, 1 ", 2, 2 ', 2", 3, 3' and 3 "and the organic linkers L and / or Li can therefore be used in a similar manner as in the case of Mentioned MOFs and COFs according to the "modular principle" different structures together.
  • the linkers L are preferably substituted or unsubstituted cyclic alkyl radicals having 5 to 24 carbon atoms or substituted or unsubstituted aryl radical having 6 to 24 carbon atoms, wherein the aryl radical preferably contains at least one substituted or unsubstituted phenyl group, which may also be part of a larger ring system ,
  • L is selected from substituted or unsubstituted aryl radicals containing from 1 to 8 aromatic or heteroaromatic rings.
  • the linker molecules L have n (at least 2) binding sites which allow the covalent linkage with silicon atoms and optionally also the above-mentioned heteroatoms, tin and / or germanium.
  • organic linkers L which have 2 bonding sites for Si (or also the abovementioned heteroatoms, such as, for example, boron) selected from:
  • each X is independently selected from hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy having preferably up to 4 C-atoms, more preferably 1, 2 or 3 C-atoms.
  • Preferred binding sites for Si (or also B) are indicated in each case by the vertical lines. Individual positions marked X may also represent additional or alternative binding sites for Si (or B). Preference is given to organic linkers L which have 3 bonding sites for Si (or else heteroatoms such as B) selected from:
  • X is selected as above.
  • Preferred binding sites for Si (or B) are again indicated by the vertical bars. Individual positions marked X may also represent additional or alternative binding sites for Si (or B).
  • binding sites for Si are again indicated by the vertical bars. Individual positions marked X may also represent additional or alternative binding sites for Si (or B).
  • linkers L are heteroaromatic compounds which correspond to those mentioned above, in which, however, in at least one ring 1 to 4 carbon atoms are replaced by N, such as. B .:
  • the polymer according to the invention has a high porosity and is in principle microporous (preferably d ⁇ 2 nm). It has a relatively large external surface due to very small particles or by the presence of macropores. In addition, the polymer shows a hysteresis over the entire pressure range, which indicates a swelling behavior.
  • the polymer according to the invention preferably has a specific surface area (BET) of more than 500 m 2 g -1 and preferably up to 3000 more preferably from 700 to 2000 more preferably over 750 m 2 g "1 .
  • BET specific surface area
  • the average pore size of the polymer according to the invention is preferably less than 2 nm and preferably greater than 0.1 nm, particularly preferably from 0.5 to 1.5 nm.
  • the polymer according to the invention preferably has a micropore volume of 0.2 to
  • the polymer of the invention is further advantageous air and water stable and chemically stable. In addition, it shows high thermal stability up to about 350 0 C.
  • the polymer according to the invention is preferably amorphous, strongly hydrophobic (comparable to the hydrophobicity of activated carbons).
  • the hydrophobicity can preferably be reduced by the attachment of polar substituents (eg, -OH, -NH 2 ) to the alkyl or aryl radicals.
  • polar substituents eg, -OH, -NH 2
  • the water vapor physisorption is very low in the range of low relative pressure (up to 0.5) (preferably below 200 cm 3 g -1 ), so that hardly any adsorption takes place Even at high pressures, the water vapor physisorption is preferably below 500 cm 3 g -1 . These values are also dependent on the pore size and specific surface area.
  • the hydrophobicity is even more pronounced for poly (4,4'-biphenylene) silane, ie even higher than for activated carbon.
  • a significant adsorption of water begins only at a relative pressure of about 0.6 and thus corresponds approximately to the behavior of most activated carbons.
  • the polymer according to the invention advantageously has a good and above all reversible storage capacity for gases, in particular methane and hydrogen.
  • the hydrogen storage capacities of the polymer of the invention is preferably at least 1 wt .-% hydrogen at 1 bar, with increasing tendency with increasing pressure.
  • the methane storage capacities preferably reach values of at least 4% by weight at pressures of from 50 bar to 100 bar.
  • the polymers of the invention prove to be extremely stable to water. Since no heavy metals are present in the polymers according to the invention, resulting toxic properties can be ruled out.
  • the properties of the polymer according to the invention are comparable to the properties of activated carbon.
  • the polymer according to the invention is advantageously colorless or white and advantageously has a clearly defined chemical composition.
  • by the size and the chemical properties of the linker L can be advantageously set important properties such as porosity, hydrophobicity and gas storage capacity.
  • the optimum synthesis temperature is about -10 0 C, preferably between 0 0 C and -20 0 C. At lower temperatures were the spec. Surfaces lower.
  • the polymer according to the invention is very light (low density), chemically and thermally stable, not sensitive to hydrolysis and non-toxic. This is different from many COFs and MOFs.
  • the invention also relates to a process for the preparation of the polymer according to the invention by reacting
  • L is preferably selected from the abovementioned aryl radicals.
  • Halogen is preferably chlorine, bromine, fluorine or iodine.
  • the alkoxy radical is preferably selected from radicals having 1 to 5 C atoms, such as. For example, methoxy, ethoxy, isopropoxy, n-propoxy.
  • the organometallic is preferably a lithium organic compound of the general formula Li-R, with R selected from alkyl, dialkylamino, alkoxy, allyl or aryl. R is particularly preferably selected from n-, sec- or te / t-butyl lithium (BuLi). Alternatively, organomagnesium compounds such as Grignard reagents are used.
  • step (i) compounds of the LiX type are used in step (i).
  • the compound LiX is only monohalogenated and therefore allows only a linkage with a silicon atom (or boron atom). Li is selected as listed above.
  • step (i) additional compounds of the formulas Si (L 1 ) 2 (LX n-1 ) 2 or Si (Li) (LX n _i) 3 are used, where LX n _i as above for a (nl) - halogenated aryl radical L is.
  • n is also selected as above, that is the aryl compound is preferably di-, tri- or tetra-halogenated. Accordingly, the aryl radicals in the silane compound are preferably mono-, di-, or tri-halogenated to permit attachment to n-1 other silicon or heteroatoms (such as boron).
  • the dihalogenated aryl compound after reaction with an organic alkali metal compound, is reacted directly with a silane compound SiX 4 to give the polymer according to the invention.
  • the starting materials are preferably all in exactly or approximately stoichiometric
  • Metal compound 1: 4 (n-1) ⁇ 20%, preferably ⁇ 10%.
  • Ie. per mole of halogen in the halogenated aryl compound or silane compound preferably 1 ⁇ 20%, preferably ⁇ 10% mol of organic metal compound is used.
  • the concentration of the n-fold halogenated aryl compound is preferably 0.01 to 0.2 mol / l, more preferably 0.02 to 0.1 mol / l.
  • a silane compound SiX 4 is added to achieve further crosslinking to the polymer of the invention.
  • the starting materials are preferably all used in exactly or approximately stoichiometric ratios:
  • silane compound SiX 4 1: 1 ⁇ 20%, preferably ⁇ 10%.
  • the concentration of the (nl) -fine halogenated silane compound is preferably 0.005 to 0.1 mol / l, more preferably 0.01 to 0.5 mol / l.
  • concentrations and molar ratios are basically chosen as above.
  • the ratio of the silane compound of the formula Si (LX n-1 ) 4 to the borane compound B (LX n _i) 3 is preferably 3: 4 ⁇ 20%, preferably ⁇ 10%.
  • the concentration of the borane compound of the formula B (LX n _i) 3 is preferably 0.005 to 0.1 mol / l, particularly preferably 0.01 to 0.5 mol / l.
  • the inventive method is preferably carried out at temperatures below 100 0 C, preferably between +25 0 C and -150 0 C, more preferably below -5 0 C and more preferably above 100 0 C.
  • the solvent used is preferably an aprotic solvent for the reaction.
  • Preferred aprotic solvents are ethers having linear alkyl radicals or cyclic ethers, preferably having 1 to 8 C atoms and 1 oxygen atom.
  • the ether is particularly preferably selected from dimethyl ether, diethyl ether, methoxypropane, tetrahydrofuran, oxacyclohexane (tetrahydropyran).
  • the solvent is a mixture of ether and another apolar solvent, such as.
  • the ether content in such a mixture is over 20%, more preferably over 30%.
  • poly (l, 4-phenylene) silane is carried out in 2 steps: Starting from the tetrahedral molecule tetrakis (4-bromophenyl) silane, a network is generated by a four-fold lithiation with butyllithium and subsequent linking of the tetrahedral unit with silicon.
  • Equation 1 Lithiation of tetrakis (4-bromophenyl) silane
  • Equation 2 Linkage of the tetrahedral scaffold units 0.5 g (0.77 mmol) of tetrakis (4-bromophenylsilane) are introduced into the reaction vessel under an argon atmosphere and dissolved in 50 ml of dried THF. The mixture is cooled in an ice water bath with freeze-salt mixture to -10 0 C and treated dropwise with 1.23 ml (3.07 mmol) of butyllithium. After 10 min stirring at -10 0 C 0.17 ml (0.77 mmol) of tetraethylorthosilicate (TEOS) are added dropwise. The mixture is stirred until it has warmed to room temperature. Following the reaction by adding 40 ml of dist.
  • TEOS tetraethylorthosilicate
  • a relatively narrow peak of high intensity is at a chemical shift of -17.9 ppm. This is attributed to the tetrahedral with phenylene substituted silicon atoms, which make up the bulk of the polymeric compound. From the comparison of the smaller chemical shift in tetrakis (4-bromophenyl) silane of -13.4 ppm with the present of -17.9 ppm, it can be concluded that the type of substituent on the phenylene ring, despite the relatively large distance (4 C atoms) still has a strong influence on the chemical shift of the para-position to sitting silicon atom. This influence is additionally dependent on the nature of the substituent. Furthermore, the spectrum has a very broad peak in the range of -33 to -43 ppm. This is another indication of aliphatic radicals on a part of the silicon atoms and confirms the assumption that by side reactions such were incorporated into the network.
  • Fig. 3 shows the IR spectrum (upper line) and the complementary Raman spectrum (lower line) of poly (1,4-phenylene) silane.
  • thermogravimetric analysis TG was carried out in conjunction with a differential thermal analysis (DTA) of poly (l, 4-phenylene) silane.
  • DTA differential thermal analysis
  • the diagram can be seen in FIG. 4.
  • the maximum of the exothermic signal of the DTA curve is at a temperature of 582 ° C.
  • the signal is due to the decomposition of the compound, which begins slowly between 300 and 400 0 C and then increases rapidly above 500 0 C.
  • the compound is therefore stable up to temperatures of 300 ° C. Elemental analysis
  • Hysteresis occurs in all measured samples because the desorption curve does not close to the adsorption curve down to very small relative pressures. This behavior is typical of amorphous porous polymers (e.g., Trip-PIM (Ghanem et al., Chem. Commun., 2007, 67-69)).
  • the H2-physisorption isotherm of poly (1,4-phenylene) silane shown in FIG. 6 shows a completely reversible storage of hydrogen at 77 K.
  • the characterization of the expected hydrophobic properties was carried out by measuring the water vapor physisorption.
  • the IHbO-physisorption of Po Iy (1, 4- phenylene) silane at 25 0 C are shown in Fig. 7.
  • Fig. 8 shows the Gibbs excess adsorption isotherm (CH 4 ) of poly (1, 4-phenylene) silane at 30 0 C. From the isotherm ( Figure 12), as in H 2 physisorption, a fully reversible adsorption is seen.
  • the present Gibbs excess adsorption isotherm shows a maximum at a pressure of 50 bar, are adsorbed at the 4.8 wt .-% methane.
  • Equation 3 Lithiation of 4,4'-dibromobiphenyl
  • Equation 4 Linkage of the linear linker with the tetrahedral connector 0.78 g (2.5 mmol) of 4,4'-dibromobiphenyl are introduced into the reaction vessel under argon gas atmosphere and dissolved in 50 ml of dried THF. The mixture is cooled in an ice water bath with freezing salt mixture to -10 0 C and treated dropwise with 2.0 ml (5.0 mmol) of butyllithium. After 10 min stirring at -10 0 C 0.28 ml (1.25 mmol) of tetraethylorthosilicate (TEOS) are added dropwise. The mixture is stirred until it has warmed to room temperature. Following the reaction by adding 40 ml of dist. Water stopped. The resulting precipitate is centrifuged off and washed twice with THF, water and ethanol. The product is dried in a drying oven at 100 ° C. for at least six hours.
  • TEOS tetraethylorthosilicate
  • the 13 C CP MAS NMR spectrum of poly (4,4'-biphenylene) silane shows three distinct chemical shift peaks of 139.1, 131.9 and 122.8 ppm , These are assigned to the 4,4'-disubstituted biphenylene units, which are linked via Si atoms. If other substituted biphenylene units were present (eg with unreacted Br residues), further signals would appear with slightly different chemical shifts. Since this is not the case, it can be assumed that within the detection limits of solid-state NMR spectroscopy, all biphenylene linkers have a linking function in the network.
  • Fig. 11 shows the IR spectrum (upper line) and the complementary Raman spectrum (lower line) of poly (4,4'-biphenylene) silane.
  • the diagram of the thermal analysis of poly (4,4'-biphenylene) silane is shown in FIG. In the TG curve, a mass loss of 1.7% can be seen at temperatures up to 100 ° C., whereby it is assumed that these are residues of solvents.
  • the decomposition of the poly (4,4'-biphenylene) silane begins only above a temperature of about 350 0 C. After the DTA exothermic process this signal consists of two clearly separate stages that their maxima at 413 and 564 0 C. exhibit. If one considers the 1.7% as not belonging to the actual compound, a mass loss of 81.6% is observed.
  • N 2 physisorption isotherm of poly (4,4'-biphenylene) silane at 77 K shows that the poly (4,4'-biphenylene) silane produced is a highly porous material.
  • the isotherm was also evaluated according to the t method according to de Boer. The t-plot can be found in Appendix A7.
  • a microporous volume 0.45 cm 3 g "1 .
  • the specific micropore surface is 845 m 2 g "1 and the external surface is 201 m 2 g " 1 .
  • the micropore volume has increased from the phenylene to the biphenylene group due to the linker enlargement.
  • the H2-physisorption isotherm of poly (4,4'-biphenylene) silane shown in Figure 15 shows a fully reversible adsorption of hydrogen at 77K.
  • the compound In comparison with other microporous materials (eg, zeolites, MOFs), the compound has hydrophobic properties similar to those of activated carbons. For many activated carbons, the adsorption of water vapor clearly begins only at a relative pressure greater than 0.5. Zeolites, on the other hand, show strongly hydrophilic properties due to their material composition, whereby most adsorb even at a relative pressure of less than 0.2 and therefore also exhibit type I isotherms in the case of water adsorption in micropores. Methane storage
  • Fig. 17 shows the Gibbs adsorption isotherm Excess (CH 4) poly (4,4'-biphenylene) silane at 30 0 C.
  • the measurement of the methane storage capacity at high pressure has in comparison to the isotherm of poly (1,4-phenylene) silane has a hysteresis which extends over the entire pressure range as in the N 2 physisorption measurement. It can be assumed that the swelling behavior of poly (4,4'-biphenylene) silane is responsible for this.
  • the maximum Gibbs excess adsorption is at a pressure of 85 bar, where the compound adsorbs 6.2 wt .-% of methane. At 50 bar, the capacity is still 5.7% by weight and is thus 0.9 wt .-% greater than for poly (l, 4-phenylene) silane.
  • Embodiment 3 Boron-linked polyphenylene silane
  • Equation 5 Synthesis of boron-linked polyphenylene silane from tetrakis (4-bromophenyl) silane 3.2 Characterization of the compound
  • the porosity and BET surface area of the resulting boron-containing materials is significantly lower than the boron-free materials of the other embodiments.
  • FIG. 24 shows the IR spectrum (upper line) and the complementary Raman spectrum (lower line) of the weakly porous boron-linked polyphenylene silane.
  • the measured spectra of the compound do not contain any information about the chemical environment of the boron atoms. For this reason, reference is made to the IR and Raman spectra of the two polyphenylene silanes presented (Examples 1 and 2) for a further evaluation.
  • the most meaningful bands with the clearly assignable groups are summarized in the following table:
  • the N 2 physisorption isotherm in Fig. 22 was measured at 77K.
  • the compound has a BET specific surface area of 314 m 2 g -1 .
  • the catalytic activity of the compound was used in the model reaction of cyanosilylation of

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Abstract

L'invention concerne un polyorganosilane hydrophobe microporeux, un procédé pour sa fabrication et son utilisation. L’invention convient notamment pour des applications dans le stockage de gaz, l’épuration de l’air, le recyclage de carburant, la minimisation des odeurs, ainsi que comme matériau support pour des composés à action catalytique, comme catalyseur hétérogène, et pour la séparation de matières. Le polymère poreux réticulé selon l'invention, avec un volume de micropores de 0,2 à 1,5 cm3g-1, contient des atomes de silicium qui sont respectivement liés entre eux de manière covalente par quatre molécules de liaison organiques L, sachant que L est un radical alkyle substitué ou non substitué, de préférence cyclique, avec 5 à 50 atomes de carbone, ou un radical aryle substitué ou non substitué avec 5 à 50 atomes de carbone. Les propriétés du polymère selon l'invention sont globalement comparables aux propriétés du charbon actif. Le polymère selon l'invention n’en est pas moins avantageusement incolore ou blanc, et possède avantageusement une composition chimique définie de manière univoque. En particulier, la taille et les propriétés chimiques du lieur L permettent de régler avantageusement des propriétés importantes comme la porosité, l’hydrophobicité et la capacité de stockage de gaz.
PCT/EP2009/051965 2008-02-20 2009-02-19 Polyorganosilane hydrophobe microporeux, procédé de fabrication et utilisation WO2009103757A1 (fr)

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US8697322B2 (en) 2010-07-28 2014-04-15 Xerox Corporation Imaging members comprising structured organic films
US8318892B2 (en) 2010-07-28 2012-11-27 Xerox Corporation Capped structured organic film compositions
US8257889B2 (en) 2010-07-28 2012-09-04 Xerox Corporation Imaging members comprising capped structured organic film compositions
US8759473B2 (en) 2011-03-08 2014-06-24 Xerox Corporation High mobility periodic structured organic films
US8353574B1 (en) 2011-06-30 2013-01-15 Xerox Corporation Ink jet faceplate coatings comprising structured organic films
US8410016B2 (en) 2011-07-13 2013-04-02 Xerox Corporation Application of porous structured organic films for gas storage
US8313560B1 (en) * 2011-07-13 2012-11-20 Xerox Corporation Application of porous structured organic films for gas separation
US8377999B2 (en) 2011-07-13 2013-02-19 Xerox Corporation Porous structured organic film compositions
US8460844B2 (en) 2011-09-27 2013-06-11 Xerox Corporation Robust photoreceptor surface layer
US8372566B1 (en) 2011-09-27 2013-02-12 Xerox Corporation Fluorinated structured organic film photoreceptor layers
US8529997B2 (en) 2012-01-17 2013-09-10 Xerox Corporation Methods for preparing structured organic film micro-features by inkjet printing
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