CN102586929B - Preparation method for interface targeted film and interface targeted fiber - Google Patents
Preparation method for interface targeted film and interface targeted fiber Download PDFInfo
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Abstract
The invention discloses a preparation method for an interface targeted film and an interface targeted fiber. A hydrophobic macromoleclar polymer serves as a raw material, a nano fiber film is prepared by an electrostatic spinning method, the film is subjected to hydrophilic modification through the absorbing or coupling effect of a protein on the fiber film, and the fiber film which is spontaneously distributed at a plurality of oil and water two-phase interfaces is obtained by adjusting a contact angle between the film and water and the water content in the film; and the interface targeted fiber can be prepared by a freezing slice method. The preparation process is simple and convenient, and easy to amplify. The prepared interface targeted film and the prepared interface targeted fiber are high in mechanical strength, and can be widely applied to fields of biological catalysis, oil and water separating, emulsion stabilizing and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of interface target film and interface target fiber, belong to technical field of function materials.Be specifically related to a kind ofly take the hydrophobic polymer polymer and prepare the method for interface target film and interface target fiber as raw material, prepared film or the spontaneous oil-water two-phase interfaces that is distributed to of fiber energy, can be widely used in the fields such as living things catalysis, water-oil separating and stable emulsion.
Background technology
As far back as 1907, just Pickering has set forth the adsorbable phenomenon to oil-water two-phase interfaces of colloidal particle, and if point out colloidal solid is added in oil hydrosol, self assembly can be played the function of stable droplet at the particle at two-phase interface place.Since then, the spontaneous distribution in the interface of particle and interface self assembly gradually become study hotspot.Known so far, no matter the size of particle belongs to Nano grade or micron level, also tube particle is not made by inorganic material or organic material, as long as it has suitable hydrophilic and hydrophobic, there is sufficiently high Interfacial Adsorption energy, get final product spontaneous oil-water interfaces (Soft Matter, 2007 of being distributed to, 3,1231-1248).The interface self assembly behavior that comprises silica, ferric oxide particles, hydrocarbon black powder etc. all is proved (Langmuir, 2004,20,11821-11823), U.S. Pat 7470840 B2 also disclose the regulate and control method of nano particle in interface self assembly behavior.
To 1991, Nobel Laureate De Gennes proposed the concept of Janus particle, and from chemical terms, two hemisphere of this particle have diverse surface nature.If two hemispheres surface is tool hydrophily and hydrophobicity respectively, with homogeneous particle, compare, this Janus particle more easily be adsorbed and stable existence in oil-water interfaces (Langmuir, 2004,20,11821-11823; Langmuir, 2001,17,4708-4710).As U.S. Pat, 7875654 B2 are described, the most ripe Janus preparation method of granules is that nanometer or the micron particles to homogeneous carries out the local surfaces modification, thereby obtain polystyrene/polymethyl granulates, silica/polyacrylic acid granules (J.Am.Chem.Soc., 2003,125,3260-3267) etc.In addition, utilize the cross-linking reaction between the particle functional group also can obtain unique interfacial film.
Separately have a kind of at the oil-water interfaces place generated in-situ Janus inoranic membrane, possess equally the spontaneous function that is distributed in interface.The presoma for preparing inorganic oxide or sulfide is dissolved in to organic phase, the substance dissolves of catalyst precursor hydrolysis and polycondensation is at water, two-phase can generate inorganic thin film in interface reaction original position after mixing, after the film drying, show distinctive amphipathic, this method is suitable for preparing the interfacial film (J.Mater.Chem. such as silica, titanium oxide, zirconia, cadmium sulfide, zinc sulphide and copper sulfide, 2008,18,1021-1028; J.Colloid Interf.Sci., 2009,333,404-410).
The Application Areas of boundary particle and interfacial film is extensive, Janus particle and homogeneous particle all can be used as the graininess surfactant for stable emulsion (US 2010/0305219 A1), and the boundary particle of carried metal or biocatalyst also demonstrates efficient effect in this field of catalysis profit two phase reaction.Janus cross linking membrane or inoranic membrane water-oil separating and micro-fluidic field tool preferably application prospect (J.Mater.Chem., 2008,18,1021-1028).But existing boundary particle or by the crosslinked interfacial film formed of particle, its preparation process complexity, preparative-scale be difficult to amplify (J.Mater.Chem., 2005,15,3745-3760).There is again bad mechanical strength in inorganic Janus film, the preparation and dry run in very easily the breakage problem, apply also limited thus.Visible, be necessary to develop a kind of novel and easy interface material producing method.
Electrostatic spinning is a kind of easy and efficient nanofiber preparation method, and the gained fibrous material is the pattern of film on macroscopic view, and thickness can freely regulate and control in micron level, due to fibre diameter, at Nano grade, often has the incomparable peculiar property of normal film material.Although nano fibrous membrane has been used to air filtration and sensor field, have no the report that utilizes the electrostatic spinning nano fiber to prepare interfacial film.
Summary of the invention
Loaded down with trivial details for existing interfacial film preparation process, the problem of inorganic world facial mask bad mechanical strength, the invention provides the preparation method of a kind of interface target film, take the hydrophobicity organic high molecular polymer as raw material, method by electrostatic spinning and hydrophilic modifying prepares interface target film, also can be further by the method acquisition interface target fiber of freezing microtome section.
The preparation method of a kind of interface target film and interface target fiber specifically comprises the following steps:
(1) prepare the hydrophobic nano tunica fibrosa: the hydrophobic polymer polymer is dissolved in to organic solvent and is mixed with electrospinning liquid, utilizing method of electrostatic spinning to prepare film thickness is 20～200 μ m, average fibre diameter is between the film of 100～1000nm, the electrospinning time is 1～10h, treats volatilize the fully contact angle of caudacoria and water>110 ° of solvent;
(2) hydrophilic modifying of hydrophobic nano tunica fibrosa: nano fibrous membrane is soaked in water, methanol solution or ethanolic solution, makes the film complete wetting, then remove alcoholic solution residual on striping by washing; Film is transferred in the protein solution that concentration is 0.5～10mg/mL, and the 0.5～24h that vibrates makes the protein coupling or is adsorbed on film, and fully wash and remove the protein be not bonded on film with deionized water, after the film drying, with the contact angle of water, be 70～100 °;
(3) regulation and control that membrane interface distributes: the nano fibrous membrane of getting after hydrophilic modifying is infiltrated in water again, then absorb moisture on film, until moisture content of drying base is between 50～2000%, film is dropped in the profit two-phase system that interfacial tension is 6.8～51.1mN/m, and tunica fibrosa can spontaneously be distributed in two-phase interface;
(4) prepare the interface fiber by interfacial film: the hydrophilic modifying nano fibrous membrane repeatedly prepared in cutting step (2) along two vertical direction of transverse and longitudinal with freezing-microtome, it is 1～15 μ m that slice thickness is set, the gained fiber is infiltrated in water, heating makes moisture evaporation on fiber, until moisture content of drying base is between 50～2000%, fiber is dropped in the two-phase system that interfacial tension is 6.8～51.1mN/m, stir and make it form emulsion, fiber can spontaneously be distributed in the surface of emulsion droplet.
Described hydrophobic polymer polymer is one or both the mixture in polyurethane and styrene-maleic anhydride copolymer, and wherein, the molecular weight of styrene-maleic anhydride copolymer is 120000～224000, and anhydride content is 7～18% (w/v).Described protein is the mixture of a kind of in ovalbumin, bovine serum albumin(BSA) and gelatin or any two kinds.
The present invention compares with existing interfacial film technology of preparing, and advantage is that the preparation method is easy, is easy to amplify, gained film mechanical strength is high, in addition, also provides a kind of target fiber preparation method of interface efficiently.
The accompanying drawing explanation
The polyurethane nanofiber film that Fig. 1 is embodiment 2 preparations, the stereoscan photograph that wherein (a) is fiber, (b) be the diameter distribution map of fiber.
Fig. 2 is the contact angle that embodiment 2 prepares tunica fibrosa and water, and the contact angle that wherein (a) is unmodified polyurethane nanofiber film and water is 110 °, is (b) polyurethane nanofiber film after the ovalbumin modification and the contact angle of water, is 88 °.
Fig. 3 is the photo that in embodiment 4, the polyurethane interface target film after the bovine serum albumin(BSA) modification distributes in n-hexyl alcohol/water termination, and wherein (a) is front view, is (b) top view, and the part of drawing a circle in figure is the polyurethane interface film.
Fig. 4 prepares the stereoscan photograph of tunica fibrosa in embodiment 6, the stereoscan photograph that wherein (a) is unmodified polyurethane nanofiber film section, the tunica fibrosa integral thickness is about 29 μ m, (b) be the stereoscan photograph that after the ovalbumin modification, the polyurethane nanofiber membrane interface distributes, film thickness in water is about 12 μ m, adopts the method for two-phase gel embedding to characterize (Langmuir, 2003,19,7970-7976).
The styrene-maleic anhydride copolymer nano fibrous membrane that Fig. 5 is embodiment 10 preparations, the stereoscan photograph that wherein (a) is fiber, (b) be the diameter distribution map of fiber.
Fig. 6 prepares the photo that polystyrene-maleic anhydride copolymer interface target film distributes in butyl acetate/water termination in embodiment 10.
The styrene-maleic anhydride copolymer interface target fiber that Fig. 7 is preparation in embodiment 15 drips the microphoto of surface distributed at n-hexyl alcohol/water and milk.
The specific embodiment
Embodiment 1: the polyurethane nanofiber film of ovalbumin modification is in the spontaneous distribution of n-hexyl alcohol/water termination
Polyurethane is dissolved in DMA, and being mixed with concentration is the electrospinning liquid of 25% (w/v), with the syringe needle of internal diameter 0.5mm, carries out electrostatic spinning, electrospinning flow quantity 100 μ L/h, voltage 25kV, receiving range 25cm, time of reception 1h.Gained polyurethane nanofiber film thickness 20 μ m, the about 500nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 112 °.
5mg polyurethane nanofiber film is fully infiltrated in water, absorb moisture on film with filter paper after taking out film, in the ovalbumin solution that to drop into 1mL concentration be 10mg/mL again, room temperature vibration 24h, taking out the tunica fibrosa water fully washs, recording the load capacity of ovalbumin on tunica fibrosa and can reach 110mg protein/g film, is 70 ° with the contact angle of water after the film drying.
By the polyurethane nanofiber film that has adsorbed ovalbumin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 13 μ m, the film thickness that is distributed in water is 7 μ m.
Embodiment 2: the polyurethane nanofiber film of ovalbumin modification is in the spontaneous distribution of n-hexyl alcohol/water termination
Polyurethane is dissolved in DMA, and being mixed with concentration is the electrospinning liquid of 30% (w/v), with the syringe needle of internal diameter 0.5mm, carries out electrostatic spinning, electrospinning flow quantity 500 μ L/h, voltage 30kV, receiving range 20cm, time of reception 4h.Gained polyurethane nanofiber film thickness 100 μ m, the about 925nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 110 °.
5mg polyurethane nanofiber film is fully infiltrated in water, absorb moisture on film with filter paper after taking out film, in the ovalbumin solution that to drop into 1mL concentration be 5mg/mL again, room temperature vibration 3h, taking out the tunica fibrosa water fully washs, the load capacity of protein on tunica fibrosa can reach 60mg protein/g film, after the film drying, with the contact angle of water, is 88 °.
By the polyurethane nanofiber film that has adsorbed ovalbumin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 75 μ m, the film thickness that is distributed in water is 25 μ m.
Embodiment 3: the polyurethane nanofiber film of ovalbumin modification is in the spontaneous distribution of n-hexyl alcohol/water termination
Polyurethane is dissolved in DMA, and being mixed with concentration is the electrospinning liquid of 25% (w/v), with the syringe needle of internal diameter 0.5mm, carries out electrostatic spinning, electrospinning flow quantity 100 μ L/h, voltage 25kV, receiving range 25cm, time of reception 1.5h.Gained polyurethane nanofiber film thickness 29 μ m, the about 500nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 112 °.
5mg polyurethane nanofiber film is fully infiltrated in water, absorb moisture on film with filter paper after taking out film, in the ovalbumin solution that to drop into 1mL concentration be 8mg/mL again, room temperature vibration 12h, taking out the tunica fibrosa water fully washs, recording the load capacity of ovalbumin on tunica fibrosa and can reach 95mg protein/g film, is 74 ° with the contact angle of water after the film drying.
By the polyurethane nanofiber film that has adsorbed ovalbumin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 20 μ m, the film thickness that is distributed in water is 9 μ m.
Embodiment 4: the polyurethane nanofiber film of bovine serum albumin(BSA) modification is in the spontaneous distribution of n-hexyl alcohol/water termination
Prepare thickness 20 μ m according to method shown in embodiment 1, the polyurethane nanofiber film of the about 500nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 112 °.
5mg polyurethane nanofiber film is fully infiltrated in water, absorb moisture on film with filter paper after taking out film, in the bovine serum albumin solution that to drop into 1mL concentration be 0.5mg/mL again, room temperature vibration 0.5h, taking out the tunica fibrosa water fully washs, the load capacity of protein on tunica fibrosa can reach 12mg protein/g film, after the film drying, with the contact angle of water, is 100 °.
By the polyurethane nanofiber film that has adsorbed bovine serum albumin(BSA), again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 18 μ m, the film thickness that is distributed in water is 2 μ m.
Embodiment 5: gelatin modified polyurethane nanofiber film is in the spontaneous distribution of n-hexyl alcohol/water termination
Prepare thickness 100 μ m according to method shown in embodiment 2, the polyurethane nanofiber film of the about 925nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 110 °.
5mg polyurethane nanofiber film is fully infiltrated in water, absorb moisture on film with filter paper after taking out film, in the gelatin solution that to drop into 1mL concentration be 1mg/mL again, room temperature vibration 5h, taking out the tunica fibrosa water fully washs, the load capacity of protein on tunica fibrosa can reach 34mg protein/g film, after the film drying, with the contact angle of water, is 96 °.
By the polyurethane nanofiber film that has adsorbed gelatin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 84 μ m, the film thickness that is distributed in water is 16 μ m.
Embodiment 6: polyurethane interface target film is in the spontaneous distribution of n-hexyl alcohol/water termination
Prepare the polyurethane nanofiber film according to method shown in embodiment 3, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.
The polyurethane nanofiber film that has adsorbed ovalbumin is infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 1430%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 17 μ m, the film thickness that is distributed in water is 12 μ m.
Embodiment 7: polyurethane interface target film is in the spontaneous distribution of n-hexyl alcohol/water termination
Prepare the polyurethane nanofiber film according to method shown in embodiment 3, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.
The polyurethane nanofiber film that has adsorbed ovalbumin is infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 2000%, film is dropped in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexanol phase is 13 μ m, the film thickness that is distributed in water is 16 μ m.
Embodiment 8: polyurethane interface target film is in the spontaneous distribution of benzene/water termination
Prepare the polyurethane nanofiber film according to method shown in embodiment 3, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.
By the polyurethane nanofiber film that has adsorbed ovalbumin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the benzene that interfacial tension is 35mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the benzene phase is 10 μ m, the film thickness that is distributed in water is 19 μ m.
Embodiment 9: polyurethane interface target film is in the spontaneous distribution of n-hexane/water termination
Prepare the polyurethane nanofiber film according to method shown in embodiment 3, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.
By the polyurethane nanofiber film that has adsorbed ovalbumin, again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 50%, film is dropped in the n-hexane that interfacial tension is 51.1mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the hexane phase is 2 μ m, the film thickness that is distributed in water is 27 μ m.
Embodiment 10: the styrene-maleic anhydride copolymer nano fibrous membrane of ovalbumin modification is in the spontaneous distribution of butyl acetate/water termination
By molecular weight be 120000, the styrene-maleic anhydride copolymer of anhydride content 18% is dissolved in N, in the N-dimethylacetylamide, being made into concentration is the electrospinning liquid of 50% (w/v), carry out electrostatic spinning with the syringe needle of internal diameter 0.5mm, electrospinning flow quantity 200 μ L/h, voltage 24kV, receiving range 25cm, time of reception 10h.Gained nanofiber film thickness 200 μ m, the about 425nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 118 °.
1mg styrene-maleic anhydride copolymer nano fibrous membrane is fully infiltrated in the ethanol water of 50% (v/v), after taking out film, water fully washes away ethanol, absorb moisture on film with filter paper again, drop in the ovalbumin solution that 1mL concentration is 0.5mg/mL, room temperature vibration 0.5h, take out the tunica fibrosa water and fully wash, the load capacity of ovalbumin on tunica fibrosa is 18mg protein/g film, after the film drying, with the contact angle of water, is 100 °.
By coupling the styrene-maleic anhydride copolymer nano fibrous membrane of ovalbumin again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 630%, film is dropped in the butyl acetate that interfacial tension is 14.5mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the butyl acetate phase is 136 μ m, the film thickness that is distributed in water is 64 μ m.
Embodiment 11: gelatin modified styrene-maleic anhydride copolymer nano fibrous membrane is in the spontaneous distribution of chlorobutane/water termination
By molecular weight be 224000, the styrene-maleic anhydride copolymer of anhydride content 7% is dissolved in N, in the N-dimethylacetylamide, being made into concentration is the electrospinning liquid of 35% (w/v), carry out electrostatic spinning with the syringe needle of internal diameter 0.5mm, electrospinning flow quantity 250 μ L/h, voltage 21kV, receiving range 25cm, time of reception 0.5h.Gained nanofiber film thickness 80 μ m, the about 300nm of average fibre diameter, after solvent volatilizees fully, the contact angle of film and water is 120 °.
1mg styrene-maleic anhydride copolymer nano fibrous membrane is fully infiltrated in the methanol aqueous solution of 20% (v/v), after taking out film, water fully washes away methyl alcohol, absorb moisture on film with filter paper again, drop in the gelatin solution that 1mL concentration is 5mg/mL, room temperature vibration 8h, take out the tunica fibrosa water and fully wash, the load capacity of protein on tunica fibrosa is 27mg protein/g film, after the film drying, with the contact angle of water, is 90 °.
By coupling the styrene-maleic anhydride copolymer nano fibrous membrane of gelatin again be infiltrated in water, absorb moisture on film with filter paper after taking out film, until moisture content of drying base is 1086%, film is dropped in the chlorobutane that interfacial tension is 23mN/m/water two-phase system, the spontaneous two-phase interface that is distributed in of tunica fibrosa, and the film thickness that is distributed in the chlorobutane phase is 43 μ m, the film thickness that is distributed in water is 37 μ m.
Embodiment 12: polyurethane nanofiber is in the spontaneous distribution of butyl acetate/water termination
Prepare the polyurethane nanofiber film according to method shown in embodiment 1, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.
Get the polyurethane nanofiber film of ovalbumin modification, repeatedly cut dry polyurethane interface film with freezing-microtome along both direction in length and breadth, it is 1 μ m that slice thickness is set, the gained fiber is infiltrated in water, heating makes moisture evaporation on fiber, until moisture content of drying base is 1750%, the gained fiber drops in the butyl acetate that interfacial tension is 14.5mN/m/water two-phase system, and fiber can spontaneously be distributed to two-phase interface.
Embodiment 13: the styrene-maleic anhydride copolymer nanofiber is in the spontaneous distribution of n-hexyl alcohol/water termination
Prepare the styrene-maleic anhydride copolymer nano fibrous membrane according to method shown in embodiment 11, and utilize gelatin to carry out hydrophilic modifying to tunica fibrosa.
Get gelatin modified styrene-maleic anhydride copolymer nano fibrous membrane, repeatedly cut dry interfacial film with freezing-microtome along both direction in length and breadth, it is 15 μ m that slice thickness is set, the gained fiber is infiltrated in water, heating makes moisture evaporation on fiber, until moisture content of drying base is 312%, the gained fiber drops in the n-hexyl alcohol that interfacial tension is 6.8mN/m/water two-phase system, and fiber can spontaneously be distributed to two-phase interface.
Embodiment 14: polyurethane interface target film transforms for the two-phase system enzymatic
Prepare the polyurethane nanofiber film according to method shown in embodiment 1, and utilize ovalbumin to carry out hydrophilic modifying to tunica fibrosa.Tunica fibrosa after modification is dropped in the beta-D-galactosidase solution of 1mg/mL, and utilize 1.0% (w/v) glutaraldehyde that enzyme is cross-linked on film, the enzyme load capacity is 5mg protein/g film.
The polyurethane nanofiber film that carries enzyme drops in the two-phase system of 5mL n-hexyl alcohol and 5mL water composition, and dissolve the 50mmol/L lactose in water, now, but turn the glucosides reaction between lactose in n-hexyl alcohol and water in crosslinked beta-D-galactosidase selectivity catalysis organic phase on the polyurethane interface film, at hexanol, the concentration in mutually can reach 8.1mmol/L to 24h afterproduct hexyl galactoside.
If free beta-D-galactosidase is dropped in n-hexyl alcohol/lactose reaction system, be dissolved in enzyme in water can only the catalysis water in the hydrolysis of lactose, generate galactolipin and glucose.
Embodiment 15: styrene-maleic anhydride copolymer interface target fiber is for stable emulsion
Prepare styrene-maleic anhydride copolymer interface target fiber according to method shown in embodiment 13, and fiber is dropped in n-hexyl alcohol/water two-phase system, fiber can spontaneously be distributed in two-phase interface.And then two-phase system is carried out to high-speed stirred, and forming n-hexyl alcohol/aqueous emulsion, nanofiber can spontaneously be distributed in the surface of drop, and can make emulsion-stabilizing have 21 days.
Claims (5)
1. the preparation method of an interface target film is characterized in that comprising the following steps:
(1) prepare the hydrophobic nano tunica fibrosa:
The hydrophobic polymer polymer is dissolved in to organic solvent and is mixed with electrospinning liquid, utilizing method of electrostatic spinning to prepare film thickness is 20～200 μ m, average fibre diameter is between the film of 100～1000nm, and the electrospinning time is 1～10h, treats volatilize the fully contact angle of caudacoria and water of solvent > 110 °;
(2) hydrophilic modifying of hydrophobic nano tunica fibrosa:
Nano fibrous membrane is soaked in water, methanol solution or ethanolic solution, makes the film complete wetting, then remove alcoholic solution residual on striping by washing; Film is transferred in the protein solution that concentration is 0.5～10mg/mL, and the 0.5～24h that vibrates makes the protein coupling or is adsorbed on film, and fully wash and remove the protein be not bonded on film with deionized water, after the film drying, with the contact angle of water, be 70～100 °;
(3) regulation and control that membrane interface distributes:
The nano fibrous membrane of getting after hydrophilic modifying is infiltrated in water again, then absorb moisture on film, until moisture content of drying base, between 50～2000%, drops into film in the profit two-phase system that interfacial tension is 6.8～51.1mN/m, tunica fibrosa can spontaneously be distributed in two-phase interface.
2. the preparation method of an interface target fiber is characterized in that comprising the following steps:
(1) prepare the hydrophobic nano tunica fibrosa:
The hydrophobic polymer polymer is dissolved in to organic solvent and is mixed with electrospinning liquid, utilizing method of electrostatic spinning to prepare film thickness is 20～200 μ m, average fibre diameter is between the film of 100～1000nm, and the electrospinning time is 1～10h, treats volatilize the fully contact angle of caudacoria and water of solvent > 110 °;
(2) hydrophilic modifying of hydrophobic nano tunica fibrosa:
Nano fibrous membrane is soaked in water, methanol solution or ethanolic solution, makes the film complete wetting, then remove alcoholic solution residual on striping by washing; Film is transferred in the protein solution that concentration is 0.5～10mg/mL, and the 0.5～24h that vibrates makes the protein coupling or is adsorbed on film, and fully wash and remove the protein be not bonded on film with deionized water, after the film drying, with the contact angle of water, be 70～100 °;
(3) prepare the interface fiber by interfacial film:
With freezing-microtome along two vertical direction of transverse and longitudinal hydrophilic modifying nano fibrous membrane of preparation in cutting step (2) repeatedly, it is 1～15 μ m that slice thickness is set, the gained fiber is infiltrated in water, heating makes moisture evaporation on fiber, until moisture content of drying base is between 50～2000%, fiber is dropped in the two-phase system that interfacial tension is 6.8～51.1mN/m, stir and make it form emulsion, fiber can spontaneously be distributed in the surface of emulsion droplet.
3. preparation method as claimed in claim 1 or 2, is characterized in that hydrophobic polymer polymer in described step (1) is one or both the mixture in polyurethane and styrene-maleic anhydride copolymer.
4. preparation method as claimed in claim 3, the molecular weight that it is characterized in that described styrene-maleic anhydride copolymer is 120000～224000, anhydride content is 7～18%w/v.
5. preparation method as claimed in claim 1 or 2, is characterized in that protein in described step (2) is the mixture of a kind of in ovalbumin, bovine serum albumin(BSA) and gelatin or any two kinds.
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| US7470840B2 (en) * | 2003-01-08 | 2008-12-30 | University Of Massachusetts | Liquid-liquid interfacial nanoparticle assemblies |
| US7875654B2 (en) * | 2007-03-23 | 2011-01-25 | The Board Of Trustees Of The University Of Illinois | System for forming janus particles |
| US20100305219A1 (en) * | 2009-06-02 | 2010-12-02 | The Board Of Trustees Of The University Of Illinois | Emulsions and foams using patchy particles |
| CN102336916B (en) * | 2011-09-13 | 2012-12-19 | 福建师范大学 | Method for preparing modified bipolar membrane taking poly(vinyl alcohol)-chitosan as interface layer |
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