WO2010031877A1 - Hybrid silica -polycarbonate porous membranes and porous polycarbonate replicas obtained thereof - Google Patents

Hybrid silica -polycarbonate porous membranes and porous polycarbonate replicas obtained thereof Download PDF

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Publication number
WO2010031877A1
WO2010031877A1 PCT/EP2009/062283 EP2009062283W WO2010031877A1 WO 2010031877 A1 WO2010031877 A1 WO 2010031877A1 EP 2009062283 W EP2009062283 W EP 2009062283W WO 2010031877 A1 WO2010031877 A1 WO 2010031877A1
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polycarbonate
membrane
hybrid
manufacturing
porous
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PCT/EP2009/062283
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French (fr)
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Alfonso E. Garcia-Bennet
Hernán MÍGUEZ
Mauricio Calvo
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Nanologica Ab
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    • 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
    • C08J9/36—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/50—Polycarbonates
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0047—Preparation of sols containing a metal oxide
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • 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
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention relates to a self-standing polycarbonate and hybrid metal oxide- polycarbonate membranes. These membranes may be of use in different fields such as separation, recognition, and detection of chemical compounds in its various phases. BACKGROUND OF THE INVENTION
  • This invention relates to the field of porous membranes for separation, recognition, and detection of chemical compounds in its various phases.
  • Such membranes are typically porous polymer films, commonly polycarbonate based, and they present good diffusion properties that allow the flow of compounds through them. When adequately functionalized, they can also be used to retain on their pore inner surface a targeted compound from a mixture, letting the rest to flow unaffected and cross the membrane.
  • such membranes present poor transparency due to the existing refractive index contrast between the pore cavities, whose sizes are typically comprised between the several tens to the hundreds of nanometers, and the pore walls, which causes light to be diffusely scattered. This characteristic hinders the possibility to employ these membranes to recognize the presence of compounds within them by direct inspection under an optical microscope. This is one of the issues addressed and solved in the present invention.
  • the hybrid membranes herein reported present enhanced functionality due to the combination of the surface properties of both silica and polycarbonate.
  • One objective of the present invention is a porous hybrid polycarbonate-silica membrane with tailored optical properties and that can be functionalized.
  • the manufacturing process comprises the following steps: a) Preparation of suspensions of metal oxide particles, through a standard technique typically employed in the field, such as hydrolysis of an alkoxide or a salt, or a mild precipitation from solution. Additionally is possible to use these particles as seeds to re-grow bigger particles. Typically the particles are synthesized in the range between 10 and 1000 nanometers. b) Preparation of layers (films) of oxide particles from the suspensions described before.
  • the suspension media is any media in which the particles can be dispersed and the concentration of particles can be between 1% and 99% (solid volume/liquid volume ratio).
  • the particle deposition can be made by spin-coating, dip-coating, doctor-blade.
  • c) Films obtained as in b) are thermally stabilized at temperatures below 200 0 C. Layers can be deposited over any flat substrate such as regular borosilicate glass, conductive glass, quartz slides, silicon wafers, germanium wafers, etc. d) Infiltration of these structures with a carbonate based polymer by techniques such as immersion, dip or spin coating of a carbonate polymer solution or, alternatively, thermal diffusion of a polycarbonate compound. e) Removing of the hybrid membrane from the substrate by mechanic or chemical methods. The membranes can be separated using mechanical traction combined with wetting, or using fluorhydric acid. f) Functionalization of the membranes to different applications. Membranes can be functionalized using the physico-chemical surface properties of both silica particles and polycarbonate.
  • a porous polycarbonate membrane can be prepared by carrying out steps a) to e) and then: g) Removal of the metal oxide template by using the appropriate methods, such as chemical etching; h) Functionalisation of the membranes to different applications.
  • said porous films can be functionalised at different stages in the preparation whereby the hybrid polycarbonate silica film can be functionalised with active moieties, or the final polycarbonate film can be functionalised after, e.g., etching..
  • the metal oxide that forms the layer described in b) can be made of any compounds attainable in the shape of crystallites with sizes between 5 nm and 1000 nm, for example between 50 and 500 nanometers.
  • the compound is selected among the following group: Si ⁇ 2, Ti ⁇ 2, Sn ⁇ 2, ZnO, Nb2 ⁇ 5, Ce ⁇ 2, Fe2 ⁇ 3, Fe3 ⁇ 4, V2O5, Cr2 ⁇ 3, Hft>2, Mn ⁇ 2, Mn2 ⁇ 3, C0304, NiO, AI2O3, In2 ⁇ 3, Sn ⁇ 2- CdS, CdSe, ZnS, ZnSe, Ni. Co, Fe, Ag. Au, Se, Si, and Ge.
  • One implementation comprises the oxide SiO2 chosen due to its particular physico-chemical and packing properties.
  • the deposition techniques to form the particle layers forming the membrane described in b can be any that allows one to attain a layer of particles with thickness comprised between 100 nanometers and 10 micrometers, such as spin-coating, Langmuir- Blodgett or dip-coating.
  • the dispersions or suspensions which are used as precursors to deposit the particle layer that will form the membrane employ as liquid dispersion medium any dispersant of the particles.
  • the liquid medium is volatile.
  • This liquid can be selected among the group of water, alcohols, or alicyclic, aromatic, or aliphatic hydrocarbons, for example water, ethanol, ethyleneglycol and methanol, pure or mixed in any proportion.
  • the polycarbonate solution mentioned in c) can be any carbonate based polymer and copolymer precursor compound.
  • the invention herein reported can be readily extended to any type of polymer capable of infiltrating a layer of packed metal oxide nanoparticles.
  • a highly porous polycarbonate film possessing a degree of surface functionalisation (functional group) above 1 mmol/m 2 , and wherein the functional group is capable of interacting electrostatically or covalently with biomolecules containing proteins, enzymes and/or amino acids.
  • the invention herein reported can be readily include a method for preparation of functionalised hybrid porous polycarbonate-silica thin films where the choice of functional groups is (i) alkoxysilanes of the series ROSi(CH n ) ⁇ Y, and (ii) groups capable of reacting with a silica surface.
  • groups (i) include 3-aminopropyl triethoxysilane.
  • Figure 1 is a scanning electron microscopy image of the cross section of a hybrid silica-polycarbonate film.
  • the polycarbonate network embedding the silica spherical particles can be clearly seen.
  • Figure 2 is a scanning electron microscopy image of the cross section of a highly porous polycarbonate film.
  • the voids in the polycarbonate films have been created by templating with silica nanoparticles.
  • Figure 3 a shows pictures of a standard opaque polycarbonate round membrane (right) and one of the hybrid silica-polycarbonate membranes herein reported (left), both deposited onto a glass slide and this in turn onto a paper sheet.
  • Figure 3b shows pictures of a standard opaque polycarbonate round membrane (right) and one of the hybrid silica-polycarbonate membranes herein reported (left) after soaking them in water.
  • the improved transparency of the hybrid membrane versus that of the standard membrane can be clearly confirmed in both figures 3a and 3b.
  • Figure 4 is a thermogravimetric spectra of functionalised polycarbonate-silica film is shown, where the weight loss owing to decomposition of the aminopropyl moety is indicated by an arrow.
  • SiO 2 particles are synthesised by using a modification of the method reported by St ⁇ ber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide. Cleaning of the particles with ethanol involves several centrifugation stages. Once particles were cleaned, they were re-suspended and dispersed again in a sufficient quantity of ethanol to obtain the desired particle concentration. Particle size and monodispersion are measured by scanning electron microscopy and by photocorrelation spectroscopy.
  • Silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned flat substrates. A certain quantity is dispensed onto the substrate that is rotating at a speed comprised between 1000 rpm (revolutions per minute) and 8000 rpm. The thickness of the deposited packing of SiO 2 particles can be modified changing either particle concentration or spinning velocity.
  • SiO 2 layers are thermally stabilized. After that, samples are cooled down to room temperature and they infiltrated with a solution of carbonate based polymer precursor dissolved in an organic solvent. Infiltration is made by depositing the precursor solution onto the silica particle film and then rotating the substrate at high speed using a spin-coater. After that, the film is heated to remove solvent traces.
  • Silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned flat substrates. A certain quantity is dispensed onto the substrate that is rotating at a speed comprised between 1000 rpm (revolutions per minute) and 8000 rpm. The thickness of the deposited packing of SiO 2 particles can be modified changing either particle concentration or spinning velocity.
  • SiO 2 layers are thermally stabilized. After that, samples are cooled down to room temperature and they infiltrated with a solution of carbonate based polymer precursor dissolved in an organic solvent. Infiltration is made by depositing the precursor solution onto the silica particle film and then rotating the substrate at high speed using a spin-coater. After that, the film is heated to remove solvent traces.
  • a hybrid silica-polycarbonate film is attained.
  • the films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film.
  • membranes can be separated using an aqueous solution of fluorhydric acid in which samples are immersed for one hour to decrease the adherence to the substrate. Then, membranes are then dried. After that, the silica in the membranes can be etched away by immersing them in an aqueous hydrofluoric solution, yielding a highly porous polycarbonate membrane with a structure similar to that shown in Figure 2.
  • SiO 2 particles are synthesised by using a modification of the method reported by St ⁇ ber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide.
  • a pre-thermalized solution at 60 0 C containing 8.9 ml of silicon tetraethoxide (Aldrich) in 70 ml of ethanol (Solution 1) are added vigorously to a mixture of 9.7 ml of ammonium, 41 ml of water and 70 ml of ethanol and maintained at the same temperature than solution 1. The mixture reacts during two hours. Monodisperse silica particles of approximately 130 nm ( ⁇ 5%) are obtained.
  • Cleaning of the particles with ethanol involves three centrifugation stages of 15 minutes at 9000 r.p.m. each one. Once particles are cleaned, they are re-suspended and dispersed again in a sufficient quantity of ethanol to obtain a particle concentration of 25 vol. %.
  • silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned 25 mm X 25 mm flat substrates (standard microscope glass slides). A quantity of 250 micro-litres is dispensed onto the substrate that is rotating at 1200 r.p.m. Rotation of the substrate was maintained for 40 seconds. In this work we build layers from IML to 20ML. Once SiO 2 layers are deposited onto the substrate, they are stabilized at 6O 0 C during 24 hours. After that, samples are cooled down to room temperature and they were infiltrated with a 5% solution of Poly(Bisphenol A carbonate) in methlyene chloride warmed at 4O 0 C.
  • Infiltration was made by depositing the polycarbonate precursor solution onto the nanoparticle packing and then spin-coating at 6000 r.p.m. for 40 seconds.
  • the hybrid silica- polycarbonate films so obtained were heated at 6O 0 C during 2 hours to remove solvent traces.
  • the polycarbonate filled silica particle films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film.
  • SiO 2 particles are synthesised by using a modification of the method reported by St ⁇ ber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide.
  • a pre-thermalized solution at 60 0 C containing 8.9 ml of silicon tetraethoxide (Aldrich) in 70 ml of ethanol (Solution 1) are added vigorously to a mixture of 9.7 ml of ammonium, 41 ml of water and 70 ml of ethanol and maintained at the same temperature than solution 1. The mixture reacts during two hours. Monodisperse silica particles of approximately 130 nm ( ⁇ 5%) are obtained.
  • Cleaning of the particles with ethanol involves three centrifugation stages of 15 minutes at 9000 r.p.m. each one. Once particles are cleaned, they are re-suspended and dispersed again in a sufficient quantity of ethanol to obtain a particle concentration of 25 vol. %.
  • silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned 25 mm X 25 mm flat substrates (standard microscope glass slides). A quantity of 250 micro-litres is dispensed onto the substrate that is rotating at 1200 r.p.m. Rotation of the substrate was maintained for 40 seconds. In this work we build layers from IML to 20ML. Once SiO 2 layers are deposited onto the substrate, they are stabilized at 6O 0 C during 24 hours. After that, samples are cooled down to room temperature and they were infiltrated with a 5% solution of Poly(Bisphenol A carbonate) in methlyene chloride warmed at 4O 0 C.
  • Infiltration was made by depositing the polycarbonate precursor solution onto the nanoparticle packing and then spin-coating at 6000 r.p.m. for 40 seconds.
  • the hybrid silica- polycarbonate films so obtained were heated at 6O 0 C during 2 hours to remove solvent traces.
  • the polycarbonate filled silica particle films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film. After that, the silica in the membranes can be etched away by immersing them in an aqueous hydrofluoric solution, yielding a highly porous polycarbonate membrane.
  • hybrid porous polycarbonate-silica films may be conducted through wetness impregnation of the desired alkoxysilane precursor in water, ethanol or mixtures of the following.
  • the best mode is to utilize water alone, but in this case a longer time is required to achieve high functionalisation loadings.
  • the polycarbonate-silica films is immersed in the desired solution supported between filter papers, and left in the solutions for a period between 10 minutes and 24 hours.
  • the solution is stirred in order and can be heated at temperatures upto 6O 0 C.
  • the best mode of practice is to conduct the immersion at room temperatures and to immerse for a period of 6 hours.
  • the films are then removed from the solutions and slowly dried at room temperature for a period of 24 hours.
  • the aminated hybrid porous film is clearly suitable for direct coupling with bio molecules containing carboxyl groups such as amino acids, proteins and enzymes.
  • Functionalisation of silica-free porous polycarbonate film can be performed by reacting the film with a solution of a strong oxidant such as K 2 S 2 O s for a period 30 minutes in water in order to hydroxylate the films. After washing with water, such a film may be directly reacted with alkoxysilanes as described for the hybrid film.
  • a strong oxidant such as K 2 S 2 O s

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Abstract

The present invention relates to a self-standing membrane made of metal oxide particles and polycarbonate. Said membrane combines the surface properties of porous colloidal metal oxide packings with the mechanical stability and flexibility of polycarbonate. The resulting porous film presents enhanced diffusion properties and, besides, the possibilityto design its optical response. The combination of metal oxide particles, of different and controlled size, and polycarbonate allows tailoring to measure the optical properties of the membrane in order to obtain from transparent to coloured or opaquefilms. On another side of this invention, the metal oxide particles of said hybrid membranes can be etched yielding an even more porous membrane. Furthermore, said porous films can be functionalised at different stages in the preparation wherebythe hybrid polycarbonate metal oxide film can be functionalised with active moieties, or the final polycarbonate film can be functionalised.

Description

HYBRID SILICA -POLYCARBONATE POROUS MEMBRANES AND POROUS POLYCARBONATE REPLICAS OBTAINED THEREOF.
DESCRIPTION FIELD OF THE INVENTION
The present invention relates to a self-standing polycarbonate and hybrid metal oxide- polycarbonate membranes. These membranes may be of use in different fields such as separation, recognition, and detection of chemical compounds in its various phases. BACKGROUND OF THE INVENTION
This invention relates to the field of porous membranes for separation, recognition, and detection of chemical compounds in its various phases. Such membranes are typically porous polymer films, commonly polycarbonate based, and they present good diffusion properties that allow the flow of compounds through them. When adequately functionalized, they can also be used to retain on their pore inner surface a targeted compound from a mixture, letting the rest to flow unaffected and cross the membrane. In general, such membranes present poor transparency due to the existing refractive index contrast between the pore cavities, whose sizes are typically comprised between the several tens to the hundreds of nanometers, and the pore walls, which causes light to be diffusely scattered. This characteristic hinders the possibility to employ these membranes to recognize the presence of compounds within them by direct inspection under an optical microscope. This is one of the issues addressed and solved in the present invention. On a different but related note, the hybrid membranes herein reported present enhanced functionality due to the combination of the surface properties of both silica and polycarbonate. DESCRIPTION OF THE INVENTION
One objective of the present invention is a porous hybrid polycarbonate-silica membrane with tailored optical properties and that can be functionalized.
The manufacturing process comprises the following steps: a) Preparation of suspensions of metal oxide particles, through a standard technique typically employed in the field, such as hydrolysis of an alkoxide or a salt, or a mild precipitation from solution. Additionally is possible to use these particles as seeds to re-grow bigger particles. Typically the particles are synthesized in the range between 10 and 1000 nanometers. b) Preparation of layers (films) of oxide particles from the suspensions described before. The suspension media is any media in which the particles can be dispersed and the concentration of particles can be between 1% and 99% (solid volume/liquid volume ratio). The particle deposition can be made by spin-coating, dip-coating, doctor-blade. c) Films obtained as in b) are thermally stabilized at temperatures below 2000C. Layers can be deposited over any flat substrate such as regular borosilicate glass, conductive glass, quartz slides, silicon wafers, germanium wafers, etc. d) Infiltration of these structures with a carbonate based polymer by techniques such as immersion, dip or spin coating of a carbonate polymer solution or, alternatively, thermal diffusion of a polycarbonate compound. e) Removing of the hybrid membrane from the substrate by mechanic or chemical methods. The membranes can be separated using mechanical traction combined with wetting, or using fluorhydric acid. f) Functionalization of the membranes to different applications. Membranes can be functionalized using the physico-chemical surface properties of both silica particles and polycarbonate.
If desired, a porous polycarbonate membrane can be prepared by carrying out steps a) to e) and then: g) Removal of the metal oxide template by using the appropriate methods, such as chemical etching; h) Functionalisation of the membranes to different applications.
Thus, according to the method of the invention, said porous films can be functionalised at different stages in the preparation whereby the hybrid polycarbonate silica film can be functionalised with active moieties, or the final polycarbonate film can be functionalised after, e.g., etching..
The metal oxide that forms the layer described in b) can be made of any compounds attainable in the shape of crystallites with sizes between 5 nm and 1000 nm, for example between 50 and 500 nanometers. As example the compound is selected among the following group: Siθ2, Tiθ2, Snθ2, ZnO, Nb2θ5, Ceθ2, Fe2θ3, Fe3θ4, V2O5, Cr2θ3, Hft>2, Mnθ2, Mn2θ3, C0304, NiO, AI2O3, In2θ3, Snθ2- CdS, CdSe, ZnS, ZnSe, Ni. Co, Fe, Ag. Au, Se, Si, and Ge. One implementation comprises the oxide SiO2 chosen due to its particular physico-chemical and packing properties.
Regarding the deposition techniques to form the particle layers forming the membrane described in b), it can be any that allows one to attain a layer of particles with thickness comprised between 100 nanometers and 10 micrometers, such as spin-coating, Langmuir- Blodgett or dip-coating. The dispersions or suspensions which are used as precursors to deposit the particle layer that will form the membrane employ as liquid dispersion medium any dispersant of the particles. Preferably, the liquid medium is volatile. This liquid can be selected among the group of water, alcohols, or alicyclic, aromatic, or aliphatic hydrocarbons, for example water, ethanol, ethyleneglycol and methanol, pure or mixed in any proportion.
The polycarbonate solution mentioned in c) can be any carbonate based polymer and copolymer precursor compound.
The invention herein reported can be readily extended to any type of polymer capable of infiltrating a layer of packed metal oxide nanoparticles.
According to the method of the invention, it is possible to obtain a highly porous polycarbonate film possessing a degree of surface functionalisation (functional group) above 1 mmol/m2, and wherein the functional group is capable of interacting electrostatically or covalently with biomolecules containing proteins, enzymes and/or amino acids.
The invention herein reported can be readily include a method for preparation of functionalised hybrid porous polycarbonate-silica thin films where the choice of functional groups is (i) alkoxysilanes of the series ROSi(CHn)χY, and (ii) groups capable of reacting with a silica surface. Examples of group (i) include 3-aminopropyl triethoxysilane. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a scanning electron microscopy image of the cross section of a hybrid silica-polycarbonate film. The polycarbonate network embedding the silica spherical particles can be clearly seen.
Figure 2 is a scanning electron microscopy image of the cross section of a highly porous polycarbonate film. The voids in the polycarbonate films have been created by templating with silica nanoparticles.
Figure 3 a shows pictures of a standard opaque polycarbonate round membrane (right) and one of the hybrid silica-polycarbonate membranes herein reported (left), both deposited onto a glass slide and this in turn onto a paper sheet.
Figure 3b shows pictures of a standard opaque polycarbonate round membrane (right) and one of the hybrid silica-polycarbonate membranes herein reported (left) after soaking them in water. The improved transparency of the hybrid membrane versus that of the standard membrane can be clearly confirmed in both figures 3a and 3b.
Figure 4 is a thermogravimetric spectra of functionalised polycarbonate-silica film is shown, where the weight loss owing to decomposition of the aminopropyl moety is indicated by an arrow.
DETAILED DESCRIPTION OF THE INVENTION
SiO 2 Particles Synthesis
SiO2 particles are synthesised by using a modification of the method reported by Stόber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide. Cleaning of the particles with ethanol involves several centrifugation stages. Once particles were cleaned, they were re-suspended and dispersed again in a sufficient quantity of ethanol to obtain the desired particle concentration. Particle size and monodispersion are measured by scanning electron microscopy and by photocorrelation spectroscopy.
Fabrication of the hybrid silica-polycarbonate membrane
Silicon dioxide particles, synthesised as described above, are deposited from the suspension by spin coating onto previously cleaned flat substrates. A certain quantity is dispensed onto the substrate that is rotating at a speed comprised between 1000 rpm (revolutions per minute) and 8000 rpm. The thickness of the deposited packing of SiO2 particles can be modified changing either particle concentration or spinning velocity. Once SiO2 layers are deposited onto the substrate, they are thermally stabilized. After that, samples are cooled down to room temperature and they infiltrated with a solution of carbonate based polymer precursor dissolved in an organic solvent. Infiltration is made by depositing the precursor solution onto the silica particle film and then rotating the substrate at high speed using a spin-coater. After that, the film is heated to remove solvent traces. By doing so, a hybrid silica-polycarbonate film is attained. In order to get the membranes, the films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film. Also, membranes can be separated using an aqueous solution of fluorhydric acid in which samples are immersed for one hour to decrease the adherence to the substrate. Then, membranes are then dried. An example of the resulting structure attained using this generic procedure is shown in Figure 1.
Fabrication of the highly porous polycarbonate membrane
Silicon dioxide particles, synthesised as described above, are deposited from the suspension by spin coating onto previously cleaned flat substrates. A certain quantity is dispensed onto the substrate that is rotating at a speed comprised between 1000 rpm (revolutions per minute) and 8000 rpm. The thickness of the deposited packing of SiO2 particles can be modified changing either particle concentration or spinning velocity. Once SiO2 layers are deposited onto the substrate, they are thermally stabilized. After that, samples are cooled down to room temperature and they infiltrated with a solution of carbonate based polymer precursor dissolved in an organic solvent. Infiltration is made by depositing the precursor solution onto the silica particle film and then rotating the substrate at high speed using a spin-coater. After that, the film is heated to remove solvent traces. By doing so, a hybrid silica-polycarbonate film is attained. In order to get the membranes, the films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film. Also, membranes can be separated using an aqueous solution of fluorhydric acid in which samples are immersed for one hour to decrease the adherence to the substrate. Then, membranes are then dried. After that, the silica in the membranes can be etched away by immersing them in an aqueous hydrofluoric solution, yielding a highly porous polycarbonate membrane with a structure similar to that shown in Figure 2.
Functionalization
In order to obtain an active surface for application of porous polycarbonate and porous hybrid silica-polycarbonate films as described herein, functionalisation of the surface is necessary. This allows to for example to perform further chemical modification or coupling chemistry, that is coupling different biomolecules, such as fluorescent markers, proteins or antibodies to the polymer surface or to modify its surface behaviour such as to render it hydrophobic or hydrophilic. Functionalisation over silica surfaces is well know to be effective via the use of alkoxysilane precursors of the type ROSi(CHn)χY, where R may be a methyl or ethyl group capable of hydro lysing to the silica surface via its hydroxyl groups, n typically equals 2, x may vary between 2 and 5 and Y may include such active moeities as SH, NH2, Cl, Ph, or COOH. The latter for example may react with EDC, l-Ethyl-3-[3- dimethylaminopropyl]carbodiimide hydrochloride which is a typical coupling agent for primary amines forming amide bonds. EXAMPLES
EXAMPLE 1 : Fabrication of a hybrid silica-polycarbonate porous membrane
SiO2 particles are synthesised by using a modification of the method reported by Stόber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide. In this example, a pre-thermalized solution at 60 0C containing 8.9 ml of silicon tetraethoxide (Aldrich) in 70 ml of ethanol (Solution 1) are added vigorously to a mixture of 9.7 ml of ammonium, 41 ml of water and 70 ml of ethanol and maintained at the same temperature than solution 1. The mixture reacts during two hours. Monodisperse silica particles of approximately 130 nm (±5%) are obtained. Cleaning of the particles with ethanol involves three centrifugation stages of 15 minutes at 9000 r.p.m. each one. Once particles are cleaned, they are re-suspended and dispersed again in a sufficient quantity of ethanol to obtain a particle concentration of 25 vol. %.
Then, silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned 25 mm X 25 mm flat substrates (standard microscope glass slides). A quantity of 250 micro-litres is dispensed onto the substrate that is rotating at 1200 r.p.m. Rotation of the substrate was maintained for 40 seconds. In this work we build layers from IML to 20ML. Once SiO2 layers are deposited onto the substrate, they are stabilized at 6O0C during 24 hours. After that, samples are cooled down to room temperature and they were infiltrated with a 5% solution of Poly(Bisphenol A carbonate) in methlyene chloride warmed at 4O0C. Infiltration was made by depositing the polycarbonate precursor solution onto the nanoparticle packing and then spin-coating at 6000 r.p.m. for 40 seconds. The hybrid silica- polycarbonate films so obtained were heated at 6O0C during 2 hours to remove solvent traces. In order to attain self-standing membranes, the polycarbonate filled silica particle films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film.
EXAMPLE 2: Fabrication of a highly porous polycarbonate membrane
SiO2 particles are synthesised by using a modification of the method reported by Stόber et al, based on the hydrolysis of silicon tetraethoxide in a mixture of ethanol, water and ammonium isopropoxide. In this example, a pre-thermalized solution at 60 0C containing 8.9 ml of silicon tetraethoxide (Aldrich) in 70 ml of ethanol (Solution 1) are added vigorously to a mixture of 9.7 ml of ammonium, 41 ml of water and 70 ml of ethanol and maintained at the same temperature than solution 1. The mixture reacts during two hours. Monodisperse silica particles of approximately 130 nm (±5%) are obtained. Cleaning of the particles with ethanol involves three centrifugation stages of 15 minutes at 9000 r.p.m. each one. Once particles are cleaned, they are re-suspended and dispersed again in a sufficient quantity of ethanol to obtain a particle concentration of 25 vol. %.
Then, silicon dioxide particles are deposited from the suspension by spin coating onto previously cleaned 25 mm X 25 mm flat substrates (standard microscope glass slides). A quantity of 250 micro-litres is dispensed onto the substrate that is rotating at 1200 r.p.m. Rotation of the substrate was maintained for 40 seconds. In this work we build layers from IML to 20ML. Once SiO2 layers are deposited onto the substrate, they are stabilized at 6O0C during 24 hours. After that, samples are cooled down to room temperature and they were infiltrated with a 5% solution of Poly(Bisphenol A carbonate) in methlyene chloride warmed at 4O0C. Infiltration was made by depositing the polycarbonate precursor solution onto the nanoparticle packing and then spin-coating at 6000 r.p.m. for 40 seconds. The hybrid silica- polycarbonate films so obtained were heated at 6O0C during 2 hours to remove solvent traces. In order to attain self-standing membranes, the polycarbonate filled silica particle films were peeled off using mechanical traction from one vertex of the substrate using drops of distilled water in the interstitial space between the membrane and the glass substrate to prevent the cracking of the film. After that, the silica in the membranes can be etched away by immersing them in an aqueous hydrofluoric solution, yielding a highly porous polycarbonate membrane.
Functionalisation of hybrid porous polycarbonate-silica films may be conducted through wetness impregnation of the desired alkoxysilane precursor in water, ethanol or mixtures of the following. The best mode is to utilize water alone, but in this case a longer time is required to achieve high functionalisation loadings. The polycarbonate-silica films is immersed in the desired solution supported between filter papers, and left in the solutions for a period between 10 minutes and 24 hours. The solution is stirred in order and can be heated at temperatures upto 6O0C. The best mode of practice is to conduct the immersion at room temperatures and to immerse for a period of 6 hours. The films are then removed from the solutions and slowly dried at room temperature for a period of 24 hours. The aminated hybrid porous film is clearly suitable for direct coupling with bio molecules containing carboxyl groups such as amino acids, proteins and enzymes.
Functionalisation of silica-free porous polycarbonate film can be performed by reacting the film with a solution of a strong oxidant such as K2S2 O s for a period 30 minutes in water in order to hydroxylate the films. After washing with water, such a film may be directly reacted with alkoxysilanes as described for the hybrid film.

Claims

1. A method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane characterized in that it comprises the following steps: a) Preparation of suspensions of 10 and 1000 nanometer size metal oxide particles; b) Preparation of layers (films) of metal oxide particles from the suspensions described before, being the suspension media any in which the particles can be dispersed and the particle concentration comprised between 0.1% and 99.9% (solid volume/liquid volume ratio), and employing flat substrates of any type; c) Thermal stabilization of layers (films) at temperatures below 200 0C for a period of time comprised between 1 minutes and several days; d) Infiltration of the structures obtained in c) with a carbonate polymer; e) Removal of the hybrid membranes obtained in d) from the substrate; f) Functionalisation of the membranes for different applications using the physico- chemical surface properties of both silica particles and polycarbonate.
2. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in claim 1 , characterized in that the suspension of step a) is prepared using a technique selected from: hydrolysis of an alkoxide or a salt, mild precipitation from solution, or regrowth from previously synthesised particles.
3. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in claim 1 or 2, characterized in that the layers (films) of step b) are prepared using a deposition method selected from: spin-coating, dip-coating, doctor-blade.
4. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in any of the preceding claims, characterized in that said step d) is carried out using a technique selected from: immersion, dip or spin coating of a carbonate polymer solution and thermal diffusion of a polycarbonate compound.
5. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in any of the preceding claims, characterized in that said step e) is carried out using any physical or chemical method.
6. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in any of the preceding claims, characterized in that the metal- oxide particles forming the layer are selected from: SiO2, TiO2, SnO2, ZnO, Nb2Os, CeO2, Fe2O3, Fe3O4, V2O5, Cr2O3, HfO2, MnO2, Mn2O3, Co3O4, NiO, Al2O3, In2O3, SnO2.
7. The method for manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in any of the preceding claims, characterized in that the metal- oxide particles forming the layer are made Of SiO2.
8. A method for manufacturing a porous polycarbonate membrane characterized in that it comprises manufacturing a hybrid metal-oxide particle and polycarbonate membrane as described in steps a) to e) of any of the preceding claims, and in that it further comprises the following step: g) Removal of the metal oxide template; h) Functionalisation of the so obtained membrane for different applications.
9. The method for manufacturing a porous polycarbonate membrane as described in claim 8, characterized in that said step g) is carried out by chemical etching.
10. A hybrid membrane made of metal-oxide particles and a carbonate based polymer prepared as described in any of claims 1-7.
11. A highly porous polycarbonate membrane prepared as described in claims 8 or 9.
12. A highly porous polycarbonate film possessing a degree of surface functionalisation above 1 mmol/m2, wherein said functional group is capable of interacting electrostatically with biomolecules containing proteins, enzymes and/or amino acids.
13. A highly porous polycarbonate film possessing a degree of surface functionalisation above 1 mmol/m2, where said functional group is capable of interacting covalently with biomolecules containing proteins, enzymes and/or amino acids.
PCT/EP2009/062283 2008-09-22 2009-09-22 Hybrid silica -polycarbonate porous membranes and porous polycarbonate replicas obtained thereof WO2010031877A1 (en)

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