WO2005063365A1 - Procede pour la preparation de membranes autoportantes - Google Patents

Procede pour la preparation de membranes autoportantes Download PDF

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WO2005063365A1
WO2005063365A1 PCT/IN2003/000430 IN0300430W WO2005063365A1 WO 2005063365 A1 WO2005063365 A1 WO 2005063365A1 IN 0300430 W IN0300430 W IN 0300430W WO 2005063365 A1 WO2005063365 A1 WO 2005063365A1
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membrane
membranes
polymer
monomer
free standing
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PCT/IN2003/000430
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English (en)
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Pandian Senthil Kumar
Periasamy Selva Kannan
Arvind More
Rahul Shingte
Prakash Wadgaonkar
Murali Sastry
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Council Of Scientific And Industrial Research
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Priority to PCT/IN2003/000430 priority Critical patent/WO2005063365A1/fr
Priority to AU2003296868A priority patent/AU2003296868A1/en
Publication of WO2005063365A1 publication Critical patent/WO2005063365A1/fr

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    • 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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • 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
    • 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
    • B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D69/08—Hollow fibre membranes
    • 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
    • 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
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/18—Pore-control agents or pore formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/28—Degradation or stability over time
    • 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
    • B01D71/02—Inorganic material
    • B01D71/022—Metals

Definitions

  • the present invention relates to a novel process for the preparation of gold nanoparticles incorporated freqstanding membranes. These membranes can be used in simple membrane permeation experiments to cleanly separate small molecules on the basis of molecular size.
  • membrane based enzyme separations can in principle scaled up for large-scale use in commercial production.
  • Gold nanotubule membranes are ideal model systems to explore how pore size affects the rate and selectivity of protein transport in synthetic membranes. These membranes can also act as extraordinary molecular' sieves.
  • Membranes are widely used in separation techniques. The transport of fluids through membranes takes place by means of different mechanisms, which depend on the structure and nature of the membrane. The most widely used membranes are formed from synthetic or natural organic polymers. Porous membranes contain voids, which are large compared with the size of the molecules transported. In these membranes, the pores are interconnected and the solid materials represent only a small percentage of the total volume of the membrane.
  • the porous membranes available commercially have a pore size of between 0.005 micron and 20 micron. They are made from a great variety of polymers so as to obtain a wide range of rigidities and mechanical strengths.
  • hydrophilic membranes or hydrophobic membranes are used, according to the experimental conditions (pH, oxidizing medium), but also according to the type of molecules to be separated.
  • molecules of the hydrophobic type will tend to be adsorbed more, on a hydrophobic support.
  • the surface of the hydrophobic support can be modified by incorporating a hydrophilic group or by means of a fine surface deposition of a hydrophilic polymer.
  • Porous membranes are used as separation membranes in various industrial fields.
  • the membranes are widely used for the preparation of ultra pure water in the field of semiconductor production, the removal of a very small amount of iron contained in cooling water at power plants and filtration or the removal of microorganisms in medical appliances and in the pharmaceutical and food industries.
  • the current trend is one of continuing expansion in the range and volume of the application and use of such membranes.
  • the demand for porous membranes excellent in heat and chemical resistance is oft the increase. Therefore, porous membranes are in demand from which ion fractions, organic substances or the like are eluted in small quantities at high temperatures arid which are excellent in heat and chemical resistance.
  • block copolymer membranes are two to three times thicker than conventional lipid bilayers they can be regarded as a mimetic of biological membranes and can be used as a matrix for membrane spanning proteins. Surprisingly the proteins remain functional despite the extreme thickness of the membranes and even after polymerization of the reactive block copolymers.
  • the unique combination of block copolymers with membrane proteins allows the preparation of mechanically stable, defect-free membranes and nanocapsules that have highly selective permeability and/or specific recognition sites.
  • Conventional methods for producing microporous membranes are classified into a wet method and dry method. These methods utilize fillers or wax with a solvent-as-in_wet- method, or without the solvent as in dry method, to produce a precursor film.
  • a resulting microporous membrane is obtained by forming micro-pores in the precursor film.
  • micro-pores there are numerous methods of forming micro-pores, such as in cold, and hot stretching methods the precursor. film is subjected to a stretching process, and in an extraction method low molecular weight particles are extracted from the precursor film which has been subjected to a biaxial stretching (alternatively, biaxial stretching process can be implemented after the extraction method) to form micro-pores on the precursor film.
  • the precursor film can be subjected to a corona discharge method followed by a stretching, or it can be etched after being irradiated with high-energy ion-beams as in a track-etching method to obtain microporous membrane.
  • the dry process has an advantage in that it does not utilize environmental hazardous solvents, and hence the method is referred to as a clean process and is widely used in the industry.
  • microporous membranes produced by the dry process have pores with undesirable small sizes, and presents the difficulties of adjusting and increasing shape and size of the pores. Further, there is a drawback in that during stretching, maintaining shape of the pores becomes difficult as stretch ratio increases.
  • the conventional methods for producing microporous membranes utilize polyolefin resin because of its cost and chemical and physical property.
  • hydrophilic property to polyolefin resin membranes.
  • the method described by Hoechst Celenese processes the surface of the polyolefin resin membrane with surfactants, and other methods described by U.S.
  • Pat. Nos. 3,231,530; 3,853,601; 3,951,815; 4,039,440; and 4,340,482 integrates monomers having high hydrophilic property or processes the polyolefin resin membranes with chemicals. However, because of simultaneously occurring chemical reactions, the molecular weight of polymer decreases and the structural integrity of the polyolefin membrane weakens. Further, due to the complexity of the processes involved, it is difficult to mass-produce the polyolefin membranes having hydrophilic property. Other methods for integrating hydrophilic property to the polyolefin membranes are further described by U.S. Pat. Nos. 4,346,142; 5,085,775 and 5,294,346. These. mfifl ⁇ sjiafi...
  • the polyaniline class of conducting polymers has been shown to be. one of the most promising and most suited conducting polymers for a broad range of commercial applications.
  • the polymer has excellent environmental stability and offers a- simple, one- step synthesis.
  • the processability of this class of polymers requires improvement.
  • polyaniline is a soluble polymer, it has been noted that the solutions tend to be unstable with time. (E. J. OH et al, Synth. Met., 1993, 55-57, 977). Solutions of for example the polyaniline in the non-doped form tend to gel upon standing. Solutions greater than 5% solids concentration tends to gel within hours limiting the applicability of the polymer. It is desirable to devise methods of increasing the electrical conductivity of the doped polyaniline and to enhance the processability of these systems to allow broader applicability.
  • asymmetrical polymer materials obtained from mixtures of monomers exist. Their functioning is described, for example, in Chapter I, entitled “Physical Chemistry of . Membranes", page 19 of Membrane Science and Technology, edited by Y. Osada and T. Nakagawa. "The hydrophobic domain prevails on one side of the membrane, where in contact with the hydrophobic substrate, and the hydrophilic domain prevails on the other side of the membrane. A flow reversal effect has been observed for such asymmetric membranes when the concentration dependence of the diffusion coefficient through a hydrophilic membrane is marked. A high permeability coefficient is obtained when the hydrophilic penetrant permeates the membrane from the hydrophilic side of the asymmetric membrane.
  • the permeability coefficient is low when the hydrophilic penetrant permeates from the hydrophobic domain side.
  • Hydrophobic porous membranes are highly resistant to chemical substances and do not swell in water. On the .other hand, they function only under pressure, and even under these conditions they do not allow the water to pass sufficiently. It is therefore necessary to treat these membranes in order for their pores to have a hydrophilic surface. Numerous known methods for making the surface of hydrophobic membranes hydrophilic are described in "Synthetic Polymeric Membranes, a Structural Perspective", Second Edition, by Robert E Kesting, published by Wiley- erscience (New York, 1985). For example, U.S. Pat. No. 5,098,569 describes a membrane support with a modified surface, in which a monomolecular layer of a hydrophilic polymer derived from cellulose is grafted onto a porous hydrophobic membrane. The membrane obtained is stable in ethanol.
  • Polyacrylonitrile membranes are naturally rather hydrophobic but are not lipophobic. For certain specific applications, it is necessary to increase their lipophobia so as to avoid clogging by organic compounds. They are electrostatically neutral and possess higher physical resistance to alkalis than cellulose and its derivatives.
  • a microporous, hollow fiber is a polymeric capillary tube having an outside diameter of less than or equal to 1 mm, and whose wall functions as a semi permeable membrane.
  • the fibers are . useful in separation processes involving transport mainly through sorption and diffusion. Such processes include dialysis, hemodialysis, ultrafiltration, hemofiltration, plasma filtration;, blood separation drug release in artificial organs and water filtration where ultra-pure water is needed such as in the electronic and pharmaceutical industries. Each of these applications has various requirements including pore size, strength, biocompatibility, cost and speed ofproduction and reproducibility.
  • the hollow fiber membrane have as little leachable impurities as possible in water, blood, from 0% to saturated solutions of NaCl in water, and other similar type of aqueous solutions.
  • the membranes be easily or immediately wettable by water, blood and other types of aqueous solutions without the need for costly polymer additives, post fiber-formation treatments with wetting agents or both, hi other applications, it would be highly desirable for these membranes to remove endotoxin from the solution to be filtered, h still other applications, it may be desirable to be able to repeatedly autoc laved without the loss of the rewetting characteristic.
  • U.S. Pat. No. 4,051,300 discloses a process for the preparation of hollow microporous fibers capable of withstanding from 600 psi to 2000. psi applied pressure without collapse.
  • the fibers are prepared by a solution spinning process. This process comprises extruding a polymer solution of a first fiber forming polymer and a second, hydrophilic polymer through the outer annulus of a coextrusion die, providing a precipitating liquid miscible with the polymer solvent through an inner or center orifice in the coextrusion die.
  • the precipitating liquid forms an inner liquid core surrounded by the polymer solution.
  • the precipitation liquid causes the annular polymer solution to precipitate into a hollow fiber.
  • the fiber is washed free of the residual solvents and nonsolvents.
  • U.S. Patent No. 4,432,875 to Wrasidlo et al. discloses reverse osmosis fiber membranes made from specific polyimide structures. Baked onto the membrane is a polymeric, high molecular weight surfactant. The polymeric surfactant apparently takes the place of the hydrophilic polymer Heilmann reference and is used to increase the wettability of the resultant fiber membrane.
  • the fiber produced using the Wrasidlo process is limited to sheet membranes that have a porosity significantly different than microporous hollow fiber membranes.
  • U.S. Patent No. 3,719,640 to Le et al. discloses linear polymers of polyamide-imides having a specific formulation-containing a quaternizable nitrogen atom. When-nitrogen is quaternized, the polymer becomes hygroscopic and may be used as separatory membranes in such processes as desalination.
  • U.S. Patent No. 4,900,449 to Kraus et al. discloses the use of polyimide polymers for pleated flat sheet type membranes.
  • the membranes and process described are limited in use to flat sheet membranes for water filtration applications. Such membranes have less than one-half the surface area available for filtration as the filter membranes of the present invention.
  • a hollow fiber membrane that could be applied across a wide range of applications would provide a decided advantage over early hollow fiber membranes.
  • a new and useful hollow fiber membrane is needed that incorporates a low molecular weight surfactant which does not require the use of high temperatures to ensure the incorporation of the surfactant into and/or onto the membrane resulting in a membrane that can be autoclaved repeatedly without the loss of the rewetting characteristic and one which does not rely on glycerol for rewettability.
  • a new and useful membrane is needed that is chemically inert to blood and water solutions, or both, within the normal blood pH range of 7.35-7.45 and also be rewettable after repeated sterilizations.
  • leachable additives such as surfactants and/or hydrophilic polymers are completely absent from the resultant fiber because residual toxic substances are a major concern.
  • the membrane In cases where the membrane will be in contact with human blood, it is also highly desirable that the membrane be biocompatible in that it will not activate complement and that it have high sieving coefficients for middle molecules (5,000 daltons to 25,000 daltons molecular weight) such as beta. Sub.2 microglobulin and myoglobin.
  • Inorganic-organic hybrid materials have also been prepared by dispersing powdered or particulate forms of inorganic materials within various polymeric matrices. Although the inorganic - organic hybrid materials are homogeneously mixed, they contain separate inorganic and organic phases on a macromolecular scale. These separate phases frequently give rise to the inorganic material's migration within and/or leaching out of the polymeric matrix. Furthermore, the inorganic phases of these inorganic-organic hybrid materials can be separated from the polymer matrix by simple mechanical processes or by solvent extraction of the polymer. Consequently, upon exposure to certain temperatures or solvents, the inorganic phases of these hybrids can migrate and dissipate out of or accumulate in various regions within the polymeric matrix, reducing its useful life.
  • each of the above inorganic-organic hybrid materials were made either (1) by melting and then mixing the inorganic and organic phases into a homogeneous mixture which was then cured, extracted, or dried or (2) by dissolving the polymer and inorganic material together in a solvent in which both materials were miscible, mixing to produce a homogeneous solution, and then evaporating the solvent to extract the hybrid material.
  • the resulting inorganic-organic hybrid materials are essentially homogeneous macromolecular blends, which have separate inorganic and organic domains, which range from nanometers to tens of micrometers in size.
  • inorganic materials typically naturally occurring minerals, which are in thermodynamically stable metallic forms, such as metal oxides, metal nitrides, and zero-valent metals.
  • inorganic-organic hybrid materials suffer from a number of drawbacks, which limit their utility.
  • the size of the domain that the inorganic materials assume within the hybrid depends on the particle size of the inorganic material particulate or fibre used in making the hybrid.
  • the homogeneity of the inorganic-organic hybrid material largely depends on either the solubility of the inorganic material in the polymeric melt or on the solubility of the inorganic material in the solvent used to solubilize the polymeric material.
  • hybrid materials containing inorganic phases having greater stability have been developed. These materials rely on physically entrapping large interpenetrating macromolecular networks of inorganic materials in the polymeric chains of the organic material.
  • the present invention is the first of its kind that involves a simple synthesis procedure for the formation of free standing membranes incorporated in situ with gold nanoparticles, the advantage of which lies in its exciting applications.
  • the present invention is directed towards the formation of freestanding gold membranes consisting of Au nanoparticles surrounded by the network of polymer.
  • Composites consisting of a polymer matrix filled with nanosized particles are of particular interest because of their long-term stability and they offer new routes to influencing the interactions that may take place between the matrix and the gold nanoparticle.
  • the main object of this invention to prepare in situ the freestanding polymer membranes incorporated with gold nanoparticles.
  • Yet another object of this invention to produce gold nanoparticles as well as the polymer membrane in-situ without any further processing..
  • Another object of this invention to prepare gold nanoparticles of various concentrations 1 incorporated in situ in these freestanding membranes.
  • the initial monomer dianiline molecule is oxidatively polymerized to polyaniline by in situ reduction with acidic pH aqueous chloroaureate ions which themselves reduced form to gold nanoparticles.
  • the gold ions dissolved in aqueous solution at a pH of 3 is mixed under static ambient conditions with the organically dissolved monomer dianiline.
  • the freestanding polymer membrane forms at the liquid-liquid interface of the two solutions within 3 hours under ambient conditions.
  • thickness of the as-formed membranes controlled by mixing equimolar concentrations of acidic pH aqueous tetrachloroauric acid solution and the organically dissolved dianiline solution.
  • the membranes are thicker as well as flexible for higher concentrations of gold nanoparticles.
  • the as-prepared membranes are stable for long-term use.
  • Yet another object of this invention to prepare porous flexible freestanding membranes.
  • a further object of this invention to leach out the gold nanoparticles from the membrane using iodine treatment. .
  • gold nanoparticles could be leached out thoroughly using iodine solution within 4-5 hours.
  • polymer hollow structures or capsules are formed when the gold nanoparticles are leached out.
  • these polymer hollow structures are bioc ⁇ mpatible; thereby proteins and enzymes could well be immobilized.
  • the invention discloses-a -novel method for synthesizing freestanding-gold-nanoparticles encapsulated polymer membranes.
  • the freestanding nature and the long-term stability of this polymer covered gold nanoparticles membrane makes it viable for many practical applications such as protein separation and drug delivery.
  • Hollow structured membranes could as well be prepared simply by leaching out the Au nanoparticles using iodine treatment.
  • the hollow pore size distribution corresponds to the dimensions of the Au nanoclusters initially present in the membrane.
  • the present invention provides a new process for the preparation of hollow structured freestanding membrane having pore size of in the range of 2 to 200 nm for use in protein/enzyme immobilization and drug delivery, said process comprises the steps: (a) mixing a monomer with aqueous chloroaurate ions in an organic solvent; (b) polymerizing the mixture of step (a) for a time period in the range of 3 to 5 hours to obtain gold nanoparticles encapsulated free standing membrane, (c) treating the free standing membrane of step (c) with iodine solution for a time period in the range of 3 to 7 hours to leach out the gold nano particles thereby obtaining the hollow structured free standing membrane.
  • the monomer is diamine having ethereal linkages.
  • the diamine used is 2-bis (4- aminophenoxy) diethyl ether.
  • the solubility of monomer in the organic solvent is in the range of 10 _1 M to 10 "5 M.
  • the organic solvent used is hydrocarbons or substituted hydrocarbons.
  • the hydrocarbon is selected from hexane or benzene.
  • the substituted hydrocarbon is toluene.
  • the pH value of the mixture of step (a) is not greater than 3.
  • the concentration of chloroaurate ions and the monomer is greater than 10 " M. In another embodiment of the present invention the concentration of chloroaurate ions is almost equal to the concentration of the monomer.
  • the polymerisation of the monomer is carried out at liquid-liquid interface of organic and aqueous phases.
  • the membrane has uniform pore size in the range of 2 to 200 nm.
  • the as-prepared freestanding membranes is stable for a period of about one year.
  • said freestanding membrane contains polyaniline which is formed by cross linking of diamine monomers.
  • leaching of gold nano particles is performed by using iodine-iodide solution.
  • the iodine-iodide solution is prepared by dissolving iodine in potassium iodide solution.
  • the leaching of gold nanoparticles is performed by floating thoroughly washed free standing membrane in the iodine-iodide solution to obtain hollow structured membrane. Yet in another embodiment of the present invention the gold nanoparticles are leached out in a time period in the range of 4-5 hours.
  • the present invention provides a new synthesis procedure for the preparation of free standing gold membranes encapsulated in a polymer matrix. Preliminary experiments of the present invention using the solutions of tetrachloroauric acid (HAuCl 4 ) and an . aromatic diamine have demonstrated the in . situ formation of polyaniline and Au nanoparticles.
  • a simple organic/aqueous liquid-liquid interface has been utilized to synthesize as well as cast Au nanocrystals into a polymer • membrane in situ.
  • This invention is clearly distinguished from others where the metal nanocrystals synthesized ex situ are obtained in the form of films at the air-liquid or liquid- liquid interfaces.
  • two immiscible liquids like, water and an organic solvent are brought into contact, without any additional input of energy i.e. under static conditions; an interface is formed between the phases. If the two phases are initially not in equilibrium with each other, mass transfer will take place across the interface forming thin film like structures.
  • Nanometer and micrometer sized particles adsorbed at these interfaces are ubiquitous in technological applications ? _as well as in biological constructs (Zhang et al Environ. Sci. Technol, 2003, 37, 1663; Gittins and Caruso J. Phys. Chem. B., 2001, 105, 6846). Furthermore, nanocrystals anchored to surfaces in the form of a film are considered to be important because of their potential use in nanodevices (Khomutov et al Microelect. Engn. , 2003).
  • aqueous chloroauric acid is mixed with the aromatic diamine in chloroform. Due to the acidic pH of the mixture, the aniline group in the diamine molecule points towards the aqueous phase i.e. interface of both liquids while its hydrocarbon part points towards the organic phase like a surfactant. Due to the electrostatic interaction between chloroaurate ions and aniline group in the diamine molecule, chloroaurate ions tend to move towards the aqueous/organic interface, where the density of amine functional groups is more. Thus, at the aqueous/organic interface, the respective reduction of both chloroaurate and the aromatic diamine molecule takes place, leading to the formation of Au and polyaniline.
  • polymer means an organic material consisting of repeated chemical units joined together, usually in a line, like beads on a string.
  • monomers like the above said aromatic diamines, are the basic building blocks of polymers. These monomers by the so-called oxidative polymerisation get transformed into composite polymer membranes.
  • Chemical oxidative polymerization of aniline in micellar system also lead to an acceleration of polymerization rate and enabled the resulted polyaniline soluble in water or organic solvents (Kuramoto, Japanese Patent, 1998; Kuramoto and Genies Synthetic Metals, 1994, 68, 191; Shigehito Sagisaka et al, Thin Solid Films, 1995, 271, 138).
  • a cross-linked polymer could only form with the availability of more than one functional group of monomers.
  • the diamine molecule necessarily satisfies this general criterion of having two terminal aniline groups, polyaniline
  • the cross-linked polymer forms capping around the as-formed gold nanoparticles, thus forming the resultant freestanding ' membrane.
  • the encapsulation of gold nanoparticles into the polymer network makes the membrane more stable and stretchable to an extent. The whole process for the formation of this membrane is completed within 3 hours. After 3 hours, a homogeneously formed dark purple colored freestanding membrane is clearly at the aqueous/organic interface, indicating-the-completion of the reaction.
  • the stability of the membrane is more than 1 year.
  • Example 1 This example illustrates the process for the preparation of large area freestanding polymer membranes incorporated in situ with gold nanoparticles.
  • a 100 mL aqueous solution of 10 "3 M chloro auric acid was added with 10 "3 M aromatic diamine dissolved in chloroform under static ambient experimental conditions. This mixture is left static for 3-5 hours. After 5 hours, a freestanding polymer membrane is formed at the liquid-liquid interface between the organic and aqueous phases. The dark purple color of the membrane itself indicates that the gold nanoparticles are incorporated into them.
  • the as-formed membrane is transformed to Si (III) and glass substrates for further characterization.
  • Example 2 This example illustrates the process for the preparation of large area freestanding polymer membranes incorporated in situ with gold nanoparticles. A 100 mL aqueous solution of 10 "2 M chloroauric acid was added with 10 "2 M aromatic diamine dissolved in chloroform under static ambient experimental conditions. This mixture is left static for 3-5 hours.
  • Example 3 This example illustrates the process for the preparation of large area freestanding polymer membranes incorporated in situ with gold nanoparticles.
  • a 100 mL aqueous solution of 10 " M chloroauric acid was added with 10 " M 2-bis (4-aminophenoxy) diethylether dissolved in chloroform under static ambient experimental conditions. This mixture is left static for 3-5 hours. After 5 hours, a freestanding thicker polymer membrane is formed at the liquid-liquid interface between the organic and aqueous phases. The dark purple color of the membrane itself indicates that the gold nanoparticles are incorporated into them.
  • the as-formed membrane is transformed to Si (111) and glass substrates for further characterization.
  • Example 4 This example illustrates the process for the preparation of large area freestanding polymer membranes incorporated in situ with gold nanoparticles. A 100 mL aqueous solution of 10 "3 M chloroauric acid was added with 10 "3 M 2-bis (4-aminophenoxy) diethylether dissolved in chloroform under static ambient experimental conditions. This mixture is left static for 3-5 hours.
  • This example illustrates the leaching of gold nanoparticles from he_as:prepared large area freestanding polymer membranes.
  • the preparation procedure of the polymer membranes is the same as illustrated in examples 1 and 2.
  • This polymer membrane is carefully removed from the liquid-liquid interface and washed thoroughly for 4-5 times with distilled water. This is to be done to remove the surface impurities present in the as- formed membrane.
  • the iodine solution is prepared by mixing small amount of iodine in aqueous potassium iodide solution. The thoroughly washed membrane is made to float on this iodine solution for 4-5 hours. After 5 hours, the membrane becomes stiffer indicating the complete removal of gold nanoparticles.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Cette invention se rapporte à un procédé servant à synthétiser des membranes autoportantes structurées creuses ayant une porométrie comprise entre 2 et 200 nm, qui se caractérisent par une stabilité à long terme les rendant viables pour un grand nombre d'applications pratiques, tels que la séparation de protéines et l'apport de médicaments.
PCT/IN2003/000430 2003-12-31 2003-12-31 Procede pour la preparation de membranes autoportantes WO2005063365A1 (fr)

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CN103088011A (zh) * 2013-02-06 2013-05-08 扬州大学 一种反应-吸附耦合固定化脂肪酶的制备方法
CN103103178A (zh) * 2013-02-06 2013-05-15 扬州大学 一种反应-吸附耦联固定化蛋白酶的制备方法
CN103103177A (zh) * 2013-02-06 2013-05-15 扬州大学 一种反应-吸附耦合固定化氧化还原酶的制备方法
US20160075976A1 (en) * 2013-05-03 2016-03-17 Novozymes A/S Microencapsulation of Detergent Enzymes
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US9764292B2 (en) 2014-02-28 2017-09-19 Pall Corporation Porous polymeric membrane with high void volume
US9776142B2 (en) 2014-02-28 2017-10-03 Pall Corporation Porous polymeric membrane with high void volume
US9808770B2 (en) 2013-05-14 2017-11-07 Pall Corporation High throughput membrane with channels

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9499773B2 (en) 2007-01-11 2016-11-22 Novozymes A/S Enzyme particles comprising a vinyl pyrrolidone/vinyl acetate copolymer
DE102007029444A1 (de) 2007-06-22 2008-12-24 Goedel, Werner A., Dr. Poröse Membran mit asymmetrischer Struktur und das Verfahren zu ihrer Herstellung
CN103088011A (zh) * 2013-02-06 2013-05-08 扬州大学 一种反应-吸附耦合固定化脂肪酶的制备方法
CN103103178A (zh) * 2013-02-06 2013-05-15 扬州大学 一种反应-吸附耦联固定化蛋白酶的制备方法
CN103103177A (zh) * 2013-02-06 2013-05-15 扬州大学 一种反应-吸附耦合固定化氧化还原酶的制备方法
US20160075976A1 (en) * 2013-05-03 2016-03-17 Novozymes A/S Microencapsulation of Detergent Enzymes
US9808770B2 (en) 2013-05-14 2017-11-07 Pall Corporation High throughput membrane with channels
US9309126B2 (en) 2014-02-28 2016-04-12 Pall Corporation Rapidly dissolvable nanoparticles
US9561473B2 (en) 2014-02-28 2017-02-07 Pall Corporation Charged hollow fiber membrane having hexagonal voids
US9610548B2 (en) 2014-02-28 2017-04-04 Pall Corporation Composite porous polymeric membrane with high void volume
US9737860B2 (en) 2014-02-28 2017-08-22 Pall Corporation Hollow fiber membrane having hexagonal voids
US9764292B2 (en) 2014-02-28 2017-09-19 Pall Corporation Porous polymeric membrane with high void volume
US9776142B2 (en) 2014-02-28 2017-10-03 Pall Corporation Porous polymeric membrane with high void volume
US9302228B2 (en) 2014-02-28 2016-04-05 Pall Corporation Charged porous polymeric membrane with high void volume

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