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WO2009127166A1 - 电纺丝纤维管状材料及其制备方法 - Google Patents

电纺丝纤维管状材料及其制备方法 Download PDF

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Publication number
WO2009127166A1
WO2009127166A1 PCT/CN2009/071348 CN2009071348W WO2009127166A1 WO 2009127166 A1 WO2009127166 A1 WO 2009127166A1 CN 2009071348 W CN2009071348 W CN 2009071348W WO 2009127166 A1 WO2009127166 A1 WO 2009127166A1
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WO
WIPO (PCT)
Prior art keywords
template
tubular material
metal rod
fiber tubular
electrospun fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2009/071348
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English (en)
French (fr)
Inventor
常江
张大明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN2009801145039A priority Critical patent/CN102084042B/zh
Priority to US12/988,449 priority patent/US20110039101A1/en
Publication of WO2009127166A1 publication Critical patent/WO2009127166A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular

Definitions

  • Electrospun fiber fiber tubular material and preparation method thereof are Electrospun fiber fiber tubular material and preparation method thereof.
  • the invention relates to a method for preparing an electrospun fiber tubular material, in particular to a method for preparing an electrospun fiber tubular material by using an electrospinning technique and a specific collecting template, and an electrospun fiber tubular material prepared by the method, belonging to electricity Spinning fiber tubular material field. Background technique
  • Electrospinning is a simple and effective method for preparing nano/microscale fiber materials. It has been widely used in biomedical materials, tissue engineering, photovoltaic materials, filter materials and sensors.
  • the electrospinning technology is a solution or melt of a polymer or other material that forms a jet under the action of a high-voltage electric field force to eject a solution storage device. At the same time, the solvent evaporates and solidifies during the spraying process, and finally falls on the receiving device. A nano/micro scale fiber aggregate material is formed.
  • Tubular fiber materials are widely used in biomedicine and certain industrial fields, and have broad development prospects. Especially in tissue engineering such as blood vessels and nerves, tubular fiber materials play a vital role as tissue engineering scaffold materials. In use, tissue engineering has certain requirements on the macro configuration and microscopic morphology of three-dimensional tubular fiber materials. For example, for different organs or tissues, tissue engineering requires certain tubular fiber materials with specific macro configuration sizes.
  • tubular fiber materials with specific microscopic morphology To meet the matching of the shape of the same organ; in order to promote the attachment and differentiation of specific cells, tissue engineering requires certain tubular fiber materials with specific microscopic morphology; for different organs or tissues, vascular tissue engineering needs to have connectivity
  • tubular fiber material can be collected by electrospinning technology and a roller device, but there are certain limitations regardless of the macro configuration or the microscopic shape, for example, the limitation of the roller device, the tubular fiber material.
  • the size, tube end closure, etc. can not achieve macroscopic configuration controllable; microscopically, the fibers generally appear disorderly or only have a certain orientation in the circumferential direction, but can not control the generation of complex and controllable microtopography;
  • the traditional method is limited to the preparation of a single pipe structure, and it is impossible to produce an electrospun fiber material having a complicated connected pipe structure, let alone controllable the complicated pipe structure. Therefore, the current use of electrospinning to prepare three-dimensional tubular fiber materials with controlled macro configuration and micro-morphology is still a blank. Summary of the invention
  • the object of the present invention is to provide a method for preparing an electrospun fiber tubular material and an electrospun fiber tubular material prepared by the method.
  • the specific steps of the method are as follows:
  • Liquids or melts are known to those skilled in the art.
  • the preparation method may be a conventionally reported electrospinning process, and the material used for formulating the solution or the melt may be a polymer material, an inorganic material or a composite material; the material is not particularly limited as long as the invention of the present invention is not The purpose is to generate a limit.
  • the mounting method of the collecting device can be in accordance with a conventional method in the field of electrospinning.
  • the object of the present invention can also be attained by using only the template without providing a flat auxiliary substrate.
  • the template can be solid or hollow. If the template is hollow, its shape and size are not limited as long as the outer wall of the template can be kept intact.
  • controlling the flow rate of the electrospinning solution or the melt is 0.1-300 ml/h ; controlling the distance between the electrospinning spinneret as the high-pressure end and the collecting device is 1 to 100 cm; controlling the high-voltage generator in the electricity The voltage supplied during the spinning process is 1 to 80 kV.
  • An electrospun fiber tubular material is collected in a template of a metal rod or a metal rod combination and taken off.
  • the electrospinning supply device (including the spinneret therein), the high voltage generator, and the low voltage terminal are disposed in accordance with a conventional method in the field of electrospinning.
  • the template of the above metal rod or metal rod combination includes:
  • a two-dimensional or three-dimensional metal rod-shaped composite template having a cross structure is combined by a single metal rod-shaped template.
  • the angle of intersection is between 10° and 90°; a single metal rod template is combined in more than two pieces.
  • the above two-dimensional or three-dimensional metal rod-shaped combination template can be designed as a removable or non-removable collection template.
  • the loading and unloading single metal rod template surface can be designed with holes matching the size of its secondary movable template.
  • the holes can be cross-connected holes or closed holes at one end.
  • a single metal bar template can be cross-combined from different directions.
  • the single metal rod template described above including a single metal rod template in a two-dimensional or three-dimensional metal rod combination template, may be characterized by the following:
  • the metal material used for the single metal rod template may be a conductive metal material and a conductive metal alloy material including copper, iron, aluminum, and alloys thereof.
  • the shape of the single metal rod-shaped template may be a cylindrical or non-cylindrical or a combination of a cylindrical shape and a non-cylindrical shape, such as a tapered shape, a cylindrical combination of different sizes, a tapered cylindrical combination, and the like.
  • the length of the single metal rod-shaped template can be adjusted between 0. 5cm-50cm.
  • a person skilled in the art can adjust accordingly according to the actual situation, for example, the template is also allowed between 0. 05cm-0. 5cm.
  • the preferred length range is between 0.5 cm and 30 cm.
  • the cross-sectional shape of a single metal rod template may be any regular or irregular pattern, such as a triangle, Squares, rectangles, pentagrams, circles, etc.
  • the cross-sectional dimension of the single metal rod-shaped template may be between 0.005 cm and 30 cm, based on the diameter of the circumscribed circle of each section.
  • the surface of the single metal rod-shaped template may be a smooth plane or a surface having a specific patterned microstructure, which is a mesh collection structure or a convex collection structure.
  • the mesh collecting structure is made by using different radial size grid lines and weaving by different weaving methods.
  • the radial dimension of the grid lines is between 0.1 and 5; the spacing between the grid lines is between ⁇ — ⁇ .
  • the weaving of the grid can be a series of different weaving methods such as single knitting and double knitting.
  • the convex portion is convex on the surface of the single metal rod-shaped template, and the height of the convex portion can be adjusted between ⁇ 500 (m), and the convex portion can be designed as a point-like convex collecting template
  • the protrusions are composed of a combination of different shapes such as a square, a rectangle, a circle, and a star.
  • the linear protrusion collection template (the protrusion is a line, that is, a combination of a straight line, an arc, and a line segment) and a combination of a dotted line
  • the stencil is collected (the bulge is a point of different shapes, and the lines are combined with each other).
  • the non-raised portion may be electrically conductive or insulated.
  • Two-dimensional or three-dimensional fiber tubular materials having interconnected cross-pipe structures having interconnected cross-pipe structures.
  • the angle of intersection is between 10° and 90°.
  • the connecting structure of the fiber aggregate pipe may be completely connected, such as a cross and an "X" type structure, or may be closed at one end and connected at one end, such as a "D" shape and a " ⁇ " type structure; the fiber tubular material may be in different amounts. Combine to form different 2D and 3D network structures.
  • the single fiber tubular material described above including a single fiber tubular material having a cross-over pipe structure in a two-dimensional or three-dimensional fiber tubular material, may have one of the following characteristics or a combination thereof:
  • the material of the single fiber tubular material is a polymer material, an inorganic material or a composite material.
  • the shape of the single-fiber tubular material may be a cylindrical pipe or a non-columnar pipe, or a combination of a cylindrical and a non-columnar pipe, such as a cone, a combination of different sizes of cylinders, and a cone.
  • Three-dimensional pipe configuration such as a cylindrical combination;
  • the length of the single-fiber tubular material may be between 0.5 C m-50 cm; the length of the single-fiber tubular material depends on the length of the template. It is also allowed between 0. 05cm-0. 5cm. 5 ⁇ -30 ⁇ The preferred range of length between 0. 5cm-30cm.
  • the cross-sectional shape of the single-fiber tubular material may be any regular or irregular pattern such as a triangle, a square, a rectangle, a pentagram, a circle, or the like.
  • the cross-sectional dimension of the single-fiber tubular material may be between 0. 005 C m-30cm.
  • the surface morphology of a single-fiber tubular material may be a disordered nonwoven structure or a specific patterned microstructure.
  • the present invention is obtained by designing and applying the above-mentioned collection template, compared with the conventional electrospinning collection method.
  • Unexpected results can be explained by the following mechanism.
  • the fiber is operated toward the receiving template under the action of the high-voltage electric field force.
  • the direction of the electric field force changes to point to the surface of the three-dimensional collecting template.
  • the fibers are deposited from different directions onto the surface of the collection template to form a tubular fiber material rather than a conventional electrospinning process that deposits only on a planar template to form a two-dimensional film.
  • the invention simultaneously introduces a flat auxiliary substrate and a rod-shaped auxiliary template (especially a rod-shaped auxiliary template), thereby successfully avoiding the phenomenon that the fibers are mainly deposited on the top of the three-dimensional collecting template by dispersing the deposition path of the electrospun fiber, and is also effective
  • the fiber suspension from the three-dimensional collection of the roots of the template is avoided, which effectively improves the structural integrity and uniformity of the three-dimensional tubular fiber material (Fig. 1) ; when the fiber travels to the vicinity of the receiving template under the electric field force
  • the static charge on the surface of the fiber induces the opposite polarity of the receiving template.
  • the opposite charges attract each other to produce Coulomb gravity.
  • the three-dimensional configuration of the fiber material can be controlled by the macroscopic configuration of a single three-dimensional collection template.
  • the fiber is mainly deposited on the surface of the three-dimensional collection template, and the macroscopic configuration of the tubular fiber material is very similar to the peripheral configuration of the three-dimensional collection template, and It is mainly determined by it.
  • the position and arrangement of the fibers can be controlled by collecting the micro-patterned structure on the surface of the template.
  • the fibers are mainly deposited on the protrusions, and the suspended fibers between the protrusions exhibit a good alignment.
  • the three-dimensional communication pipeline structure of the fiber material can be controlled by the combination of the removable three-dimensional collection template and the network cross structure: the fiber is mainly deposited on the surface of the removable combined three-dimensional collection template, and the connected pipeline structure of the fiber material is the same as the three-dimensional collection template.
  • the network cross structure is very similar and is largely determined by it.
  • the invention adopts the conventional electrospinning technology and the applicable raw materials and processes thereof, and prepares the tubular electrospun fiber with controllable macro configuration and microscopic morphology by designing a collection template using a controllable macro configuration and a microscopic morphology.
  • the material, and the structural morphology of the tubular material can be controlled by designing the macro configuration and microscopic pattern structure of the template, which is the practical application of electrospinning, especially in biomedical materials, tissue engineering, photovoltaic materials, filter materials and sensors. Areas with high requirements for material morphology offer a broader perspective. BRIEF abstract
  • 1 is a schematic view of the working principle of the electrospinning and the working mechanism of the three-dimensional collecting template, wherein 1 represents a high pressure generator and a high pressure control box, 2 represents a flow control pump, and 3 represents an electrospinning solution or a melt supply.
  • Device 4 denotes an electrospinning spinneret, 5 denotes an electrospun fiber tubular material, 6 denotes a bar-shaped template, and 7 denotes a planar auxiliary substrate;
  • FIG. 2 is a schematic view of a cylindrical collecting template having different three-dimensional configurations
  • Figure 3 is a side view optical photograph of a tubular electrospun fiber material having different diameters obtained in Example 1;
  • Example 4 is a top view optical micrograph of a tubular electrospun fiber material having different diameters obtained in Example 1, and the inset is a magnified electron micrograph of an electrospun fiber tubular material;
  • Figure 5 is an optical photograph of a tubular electrospun fiber material having a longer length obtained in Example 2
  • Figure 6 is an optical photograph of a tubular electrospun fiber material having different cross-sectional shapes obtained in Example 3;
  • Figure 7 is an optical photograph of a tubular electrospun fiber material having an end closure structure obtained in Example 4.
  • Figure 8 is a schematic illustration of a non-columnar collection template having different three-dimensional configurations
  • Figure 9 is an optical photograph of a tubular electrospun fiber material having different configurations obtained in Example 5;
  • Figure 10 is a schematic view of a three-dimensional collection template having a microscopic pattern structure on the surface;
  • Figure 11 is an optical photograph of a tubular electrospun fiber material of a microscopic pattern morphology obtained in Example 6;
  • Figure 12 is an electron micrograph of a tubular electrospun fiber material of a microscopic pattern morphology obtained in Example 6;
  • Figure 13 is an optical photograph of a three-dimensional tubular electrospun fiber material having two different microscopic pattern topography obtained in Example 7;
  • Figure 14 is an optical photograph of a microscopic pattern topography in the three-dimensional tubular electrospun fiber material obtained in Example 7;
  • Figure 15 is an electron micrograph of another microscopic pattern topography of the three-dimensional tubular electrospun fiber material obtained in Example ;
  • Figure 16 is a schematic illustration of a three-dimensional collection template having four microscopic pattern structures on the surface
  • Figure 17 is an optical photograph of a three-dimensional tubular electrospun fiber material having four different microscopic pattern topography obtained in Example 8;
  • Figure 18 is an expanded tiled optical photograph of a three-dimensional tubular electrospun fiber material having four different microscopic pattern topography obtained in Example 8.
  • 19 is a schematic view showing a specific experimental operation procedure for preparing a three-dimensional electrospun fiber material having a connected pipe structure by using an electrospinning technique and a removable combination three-dimensional collection template;
  • FIG. 20 is a schematic diagram of a detachable combined three-dimensional collection template having different cross structures according to Embodiments 9-12;
  • Figure 21 is an optical photograph of a three-dimensional electrospun fiber material having a cross-connected pipe structure obtained in Example 9;
  • Figure 22 is an optical photograph of a three-dimensional electrospun fiber material having a "T" shaped cross-pipe structure obtained in Example 10;
  • Figure 23 is an optical photograph of a three-dimensional electrospun fiber material having an "X"-shaped cross-pipe structure obtained in Example 11;
  • Figure 24 is an optical photograph of a three-dimensional electrospun fiber material having a "Y" shaped cross-pipe structure obtained in Example 12;
  • Figure 25 is a schematic view showing a detachable combined three-dimensional collecting template having a plurality of different intersecting structures according to Embodiment 13;
  • Figure 26 is a schematic view showing a three-dimensional electrospun fiber material having two different configurations of pipe bifurcations on the same main pipe obtained in Example 13;
  • Figure 27 is a schematic diagram of a removable combined three-dimensional collection template having a complex cross-network structure according to Embodiment 14;
  • Figure 28 is a schematic view showing a three-dimensional electrospun fiber material having a complex pipe network structure obtained in Example 14;
  • Figure 29 is an optical photograph of the mass-produced three-dimensional tubular electrospun fiber material obtained in Example 15 together with a collecting template;
  • Figure 30 is an optical photograph of a mass-produced three-dimensional tubular electrospun fiber material obtained in Example 15;
  • Figure 31 is a schematic view showing the mass production of a three-dimensional tubular electrospun fiber material according to Example 16.
  • Figure 32 is a schematic illustration of a three-dimensional tubular electrospun fiber material template according to Example 17.
  • Figure 33 is a schematic view showing a Y-shaped three-dimensional tubular electrospun fiber material sheet according to Example 18.
  • Figure 34 is a schematic illustration of the mass produced three-dimensional tubular electrospun fiber material obtained in Example 20, together with a collecting template.
  • a cylindrical copper rod having different diameters was prepared as a three-dimensional template, and the diameter of the copper rods was 0.18 mm, 0.50 mm, 1.36 mm, and 3.28, and the set of column templates was selected as the electrospinning substrate.
  • the solution supply flow rate was controlled by a flow pump at 0.5 ml/h, the applied voltage was 10 kV, and the distance between the high pressure end and the collecting device was 10 cm.
  • a three-dimensional tubular electrospun fiber material having a different diameter is similar to that of the substrate (Fig. 2 - 4), and the diameter of the tube is 0. 18 mm, 0. 50 mm, 1. 36 mm, and 3. 28 mm, respectively.
  • the length is lcm, 1. 3cm, 1. 5cm, and 1. 3cm.
  • a cylindrical copper wire having a long length was prepared as a three-dimensional template.
  • the diameter of the copper wire was 0.50 mm and the length was 15 cm, and the remaining parameters were selected as in Example 1.
  • a three-dimensional tubular electrospun fiber material having a long length similar to that of the substrate is collected (Fig. 2, 5), and the diameter of the tube is 0.50, and the length is 15 cm.
  • Example 3
  • a columnar copper rod having an arc-shaped structure at one end is prepared as a three-dimensional template.
  • the cross section of the copper rod is square, and the side length is 2 mm.
  • the column template is selected as the electrospinning collecting substrate, the arc end is facing upward, and the spinneret is close to the spinneret.
  • Example 1 After the spinning is completed, the collecting copper rod is taken out from the non-arc end, and the fiber-concentrating structure at the end of the arc is not broken. Through this process, a three-dimensional tubular electrospun fiber material having a one-end sealing structure similar to that of the substrate structure was collected (Fig. 7). The length of the tube is 1. 5 cm, and 2 cm.
  • a non-columnar copper rod having different configurations is prepared as a three-dimensional template, the copper rods are cones having different taper shapes, or cylindrical assemblies having different diameters at different positions, and the remaining parameters are selected as in the first embodiment.
  • the collecting copper rod is taken out from the non-arc end, without damaging the gathered structure at the curved end.
  • a three-dimensional tubular electrospun fiber material having different cross-sectional dimensions at different positions similar to the substrate structure was collected (Figs. 8, 9). The length of the tube is 2 cm.
  • the columnar template is selected as the electrospinning collection substrate.
  • the columnar copper rod having a circular line-like convex microscopic pattern structure is prepared as a three-dimensional template.
  • DMF N,N-dimethylformamide
  • THF tetrahydrofuran
  • the solution is placed in a syringe, and a high voltage power source is connected to the syringe needle as a high pressure end.
  • the solution supply flow rate was controlled by a flow pump at 0.5 ml/h, the applied voltage was 10 kV, and the distance between the high pressure end and the collecting device was 10 cm.
  • a cylindrical copper rod having two different microscopic pattern structures on the surface was prepared as a three-dimensional template. 1 ⁇ , The pitch is 0. 14mm, the pitch is 0. 14mm, the pitch is 0. 14mm, the pitch is 0. 14mm, the pitch is 0. 14mm, the pitch is 0. 14mm, the pitch is 0. 14mm, the cross section of the copper rod is circular and the diameter is 5 mm.
  • the columnar template is selected as the electrospinning collecting substrate, and the other parameters are selected as in the first embodiment. Through this process, a three-dimensional tubular electrospun fiber material having two microscopic pattern structures similar to the substrate structure is collected (Fig. 13 - 15). The length of the tube is 1. 5 cm.
  • a cylindrical copper rod having four different microscopic pattern structures on the surface was prepared as a three-dimensional template.
  • the second microscopic pattern is a smooth flat plate structure;
  • the second microscopic pattern is a regularly arranged square dot-like convex structure, the convex side length is 0. 2 let, the convex pitch is 0. 2mm ;
  • the third microscopic pattern is a straight line a convex structure having a convex width of 0. 2 let, a convex pitch of 0. 2 mm, a line-like convex parallel to the axial direction of the three-dimensional cylindrical template;
  • the fourth microscopic pattern is a linear strip-shaped convex structure, the convex width is 0 2mm, the protrusion pitch is 0.
  • the line-like protrusion is perpendicular to the axial direction of the three-dimensional column template.
  • the cross section of the copper rod is square and the diameter is 3 mm.
  • the column template is selected as the electrospinning collecting substrate, and the other parameters are selected as in the first embodiment.
  • Example 11 Prepare a cylindrical copper rod with a closed hole at one end (matching the size of the above template) as a fixed collection template with a template diameter of 4 mm;
  • the cross-combination forms a removable combined three-dimensional collection template, and the set of templates is selected as an electrospinning collection substrate, and the remaining parameters are selected as in the first embodiment.
  • the procedure for removing the specific electrospun fiber tubular material is the same as in Example 9. Through this process, a three-dimensional electrospun fiber material having a "T" shaped cross-pipe structure similar to that of the substrate structure was collected (Figs. 20, 22).
  • Example 11 Example 10
  • Example 12 Prepare a complete cylindrical copper rod as a movable three-dimensional collection template with a template diameter of 3 mm; prepare a cylindrical copper rod with a continuous hole (matching the size of the above template) as a fixed collection template with a template diameter of 4 mm; ° Cross combination to form a removable combined three-dimensional collection template, which is selected as the electrospinning collection substrate, and the remaining parameters are selected as in the first embodiment.
  • the procedure for removing the specific electrospun fiber tubular material is the same as in Example 9. Through this process, a three-dimensional electrospun fiber material having an "X"-shaped cross-pipe structure similar to that of the substrate structure was collected (Figs. 20, 23).
  • Example 12 Example 10
  • the solution supply flow rate was controlled by a flow pump at 5.0 ml/h, the applied voltage was 60 kV, and the distance between the high pressure end and the collecting device was 25 cm.
  • the specific operation steps of the electrospinning fiber tubular material are the same as the implementation Example 9. Through this process, a three-dimensional electrospun fiber material having a structure similar to that of the substrate and having bifurcations of two different configurations on the same main pipe was collected (Fig. 25, 26).
  • Cylindrical copper rods of different sizes were prepared as a single collection template, and vertically cross-combined with each other to form a detachable combined three-dimensional collection template, which was selected as an electrospinning collection substrate.
  • 48 ⁇ Adding a solution of 0. 5g lmol / 1 hydrochloric acid to 50ml of absolute ethanol, and then adding 6. 7g of tetraethyl orthosilicate (TE0S), 0. 58g of triethyl phosphate (TEP) and 1. 48g four Water calcium nitrate.
  • the solution is placed in a syringe, and a high voltage power source is connected to the syringe needle as a high pressure end.
  • the solution supply flow rate is controlled by a flow pump at 0. lml/h, the applied voltage is 5 kv, and the distance between the high pressure end and the collecting device is 2. 5 cm.
  • the procedure for removing the specific electrospun fiber tubular material is the same as in Example 9. Through this process, a three-dimensional electrospun fiber material having a complex pipe network structure similar to that of the substrate structure is collected, and then the product is sintered to obtain an inorganic bioglass tubular fiber material (Fig. 27, 28).
  • Example 15 Example 15
  • Example 16 Prepare a three-dimensional combined collection template for mass production, the individual template is a cylindrical three-dimensional template, the diameter is 0. 5mm, the height is 2cm, and the nine identical individual templates are fixed on an insulating board, the spacing between each other is 4cm, and other parameters The same as Example 1 was selected. Through this process, nine three-dimensional tubular electrospun fiber materials similar in structure to the substrate were collected simultaneously (Fig. 29, 30). The diameter of the tube is 0.5, and the length is 1. 5 cm. Example 16
  • the individual templates are a single collection template with different macroscopic structures and microscopic features, and a removable collection template with intersecting structures.
  • the nine individual templates are fixed on an insulating plate, spaced apart from each other. It is 4cm.
  • the organic-inorganic composite solution is placed in a syringe, and a high-voltage power source is connected to the syringe needle as a high-pressure end.
  • the solution supply flow rate was controlled by a flow pump at 25.0 ml/h, the applied voltage was 75 kV, and the high pressure end was 60 cm from the collection device.
  • a hollow cylindrical copper rod with different cross-sectional shapes was prepared as a three-dimensional template.
  • the cross-sectional shape of the hollow copper rod was triangular, square, and cylindrical (Fig. 32).
  • the column template was selected as the electrospinning collection substrate, and other parameters were implemented. example 1.
  • a three-dimensional tubular electrospun fiber material having a different cross-sectional shape similar to that of the substrate structure was collected.
  • the length of the tube is 2 cm.
  • a hollow cylindrical copper rod as a movable three-dimensional collection template
  • the template diameter is 3mm
  • the tube thickness is lmm
  • the two templates were cross-combined into 30° to form a removable combined three-dimensional collection template.
  • the set of templates was selected as the electrospinning collection substrate, and the remaining parameters were selected as in Example 1.
  • the procedure for removing the specific electrospun fiber tube material is the same as in Example 9. Through this process, a "Y" shape similar to that of the substrate is collected (Fig. 33).
  • the three-dimensional hollow composite collection template for mass production is prepared.
  • the individual template is a hollow cylindrical three-dimensional template having a diameter of 0. 5 mm, a tube thickness of 0.2 mm, a height of 2 cm, and fixing 9 identical individual templates on an insulating plate.
  • the distance between each other is 4 cm, and the remaining parameters are the same as in the first embodiment.
  • nine three-dimensional tubular electrospun fiber materials similar in structure to the substrate were collected at the same time.
  • the tube has a diameter of 0.5 mm and a length of 1. 5 cm.
  • the individual templates are a single collection template having different macroscopic structures and microscopic appearances, and a removable collection template having a cross structure, and the nine individual templates are fixed on an insulating plate, and each other
  • the pitch was 4 cm, and the remaining parameters were selected as in Example 16.
  • nine organic-inorganic composite tubular fiber materials similar in structure to the individual substrates were collected (Fig. 34).
  • the diameter of the single tube (circumscribed circle diameter) was 10 cm and the length was 20 cm.

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Description

电纺^纤维管状材料及其制备方法 技术领域
本发明涉及一种电纺丝纤维管状材料的制备方法， 具体涉及利用电纺丝技术和 特定收集模板制备电纺丝纤维管状材料的方法以及采用该方法制备的电纺丝纤维 管状材料， 属于电纺丝纤维管状材料领域。 背景技术
随着工业的发展和科技的进步， 电纺丝技术受到了越来越多的关注。 电纺丝是 一种制备纳米 /微米尺度纤维材料的简单有效的方法， 在生物医用材料、 组织工程、 光电材料、 过滤材料以及传感器等方面已经得到了广泛的应用。 电纺丝技术是聚合 物或者其它材料的溶液或者熔体在高压电场力的作用下， 形成射流， 喷射出溶液存 储装置， 同时， 射流在喷射过程中溶剂挥发、 固化， 最终落在接收装置上形成纳米 /微米尺度的纤维聚集体材料。
管状纤维材料在生物医用以及某些工业领域中应用广泛， 具有广阔的发展前 景， 尤其在血管、 神经等组织工程中， 管状纤维材料作为组织工程支架材料， 发挥 着至关重要的作用。 在使用中， 组织工程对三维管状纤维材料的宏观构型和微观形 貌都具有一定的要求， 比如说， 用于不同器官或者组织， 组织工程需要某些具有特 定宏观构型尺寸的管状纤维材料， 以满足其同器官组织外形的匹配； 为了促进特定 细胞的贴壁和分化， 组织工程需要某些具有特定微观形貌的管状纤维材料； 用于不 同器官或者组织中， 血管组织工程需要具有连通管道结构的管状纤维材料网络， 同 时对管道分叉的角度、 数量、 尺寸等都根据实际需求的不同而有所改变。 所以， 制 备具有可控宏观构型和微观形貌的管状纤维材料在生物组织工程以及许多工业应 用中都具有深远的意义。 通常来说， 利用电纺丝技术和滚轮装置可以收集到一定尺 寸的管状纤维材料， 但是无论宏观构型还是微观形貌都具有一定的限制， 比如说， 受到滚轮装置的局限性， 管状纤维材料的尺寸、 管端封闭性等都不能实现宏观构型 可控； 在微观上， 纤维一般呈现杂乱无章排列或者只能沿圆周方向有一定取向性， 但无法控制生成复杂可控微观形貌；另外，传统方法仅仅限于单一管道结构的制备， 不能生产具有复杂连通管道结构的电纺丝纤维材料， 更谈不上对复杂管道结构的可 控。 因此， 目前利用电纺丝来制备具有可控宏观构型和微观形貌的三维管状纤维材 料还是一项空白。 发明内容
本发明的目的在于提出一种电纺丝纤维管状材料的制备方法和由该方法制备 的电纺丝纤维管状材料， 该方法的具体步骤如下：
( 1 )配制适合电纺丝工艺的溶液或者熔体。 其中， 所述适合电纺丝工艺的溶 液或者熔体是本领域技术人员已知的。 具体地， 其配制方法可采用传统报道的电纺 丝工艺方法， 配制溶液或熔体所用的材料可以为聚合物材料、 无机材料或者复合材 料； 所述材料没有具体限制， 只要不对本发明的发明目的产生限制即可。
( 2 )将上述溶液或者熔体装入电纺丝液供给装置。 其中， 所述溶液或者熔体 也可以直接在电纺丝液供给装置中进行配制， 这对于本领域技术人员是已知的。
( 3 )将一个或多个金属棒状模板或金属棒状组合模板固定在平板辅助基板上 作为收集装置， 平板辅助基板同低压接地端相连。 其中， 所述收集装置的安装方法 可按照电纺丝领域的常规方法。 在不设置平板辅助基板的情况下， 仅采用所述模板 也可以达到本发明的发明目的。 所述模板可以为实心或空心。 若模板为空心， 其形 状和尺寸不限， 只要能保持所述模板的外壁完整即可。
( 4 )控制电纺丝溶液或者熔体的流量为 0. l - 300ml/h;控制电纺丝喷丝头作 为高压端同收集装置之间的距离为 1一 100cm;控制高压发生器在电纺丝过程中提供 的电压为 1一 80kv。
( 5 )在金属棒状或金属棒状组合的模板收集得到电纺丝纤维管状材料并取下 得到。
所述的电纺丝供给装置 (包括其中的喷丝头）、 高压发生器、 低压接电端按照 电纺丝领域常规的方法进行设置。
以上所述金属棒状或金属棒状组合的模板， 包括：
( 1 ) 单一金属棒状模板。
( 2 ) 由单一金属棒状模板组合具有交叉结构的二维或三维金属棒状组合模 板。交叉的夹角在 10° — 90° 之间；单一金属棒状模板以两件以上的数量进行组合。
上述二维或三维金属棒状组合模板可设计成装卸式或不可装卸式的收集模 板。
装卸式的单一金属棒状模板表面可以设计有同其次级可移动模板尺寸匹配的 孔洞， 孔洞可以为交叉连通孔洞， 也可以为一端封闭的孔洞， 单一金属棒状模板可 以从不同方向进行交叉组合。
上述所述的单一金属棒状模板， 包括二维或三维金属棒状组合模板中的单一 金属棒状模板的特点可以为以下各项或各项的组合：
( 1 ) 单一金属棒状模板所用的金属材料可以为导电金属材料和导电金属合金 材料， 包括铜、 铁、 铝和它们的合金。
( 2 ) 单一金属棒状模板的形状可以为柱形或非柱形或柱形与非柱形的结合， 如锥形、 不同尺寸的柱形的结合体、 锥形柱形结合体等。
( 3 )单一金属棒状模板的长度可以在 0. 5cm-50cm之间调控。本领域技术人员 可以根据实际情况进行相应调整， 例如模板在 0. 05cm-0. 5cm之间也是允许的。 优 选长度的范围在 0. 5cm-30cm之间。
( 4 )单一金属棒状模板的截面形状可以为任何规则或不规则图形， 如三角形、 正方形、 长方形、 五角星形、 圆形等。
( 5 ) 单一金属棒状模板的截面尺寸以各截面外接圆直径为准计可以在 0. 005cm- 30cm之间。
( 6 ) 单一金属棒状模板的表面可以为光滑平面， 也可以为具有特定图案化微 观结构的表面， 所述特定图案化微观结构为网格收集结构或者凸起收集结构。
所述的网格收集结构是利用不同径向尺寸的网格线，通过不同的编织方法编织 而成。 网格线的径向尺寸在 0. 1讓 5讓之间； 网格线间的间距为 Ιθμηι— ΙΟΟΟμηι之 间.网格的编织可以采用单编、 双编等一系列不同的编织方式。
所述的凸起收集结构中， 凸起部分是在单一金属棒状模板的表面凸起， 凸起 的高度可以在 Ιθμηι 500( m之间调控，凸起部分可以设计为点状凸起收集模板（其 凸起为正方形、长方形、 圆形、星形等不同形状组合构成）、线状凸起收集模板（其 凸起为线状， 即直线、 弧线、 线段组合构成） 以及点线凸起组合收集模板 （其凸起 为不同形状的点、 线相互组合构成） 。 非凸起部分可以导电， 也可以绝缘。
通过本发明工艺并利用上述金属棒状或金属棒状组合的模板， 能够成功制备 出一系列具有可控宏观构型和微观形貌的纳米 /微米尺度纤维的管状材料， 包括：
( 1 ) 单一纤维管状材料。
( 2 )具有连通交叉管道结构的二维或三维纤维管状材料。交叉角度在 10° — 90° 之间。 纤维聚集体管道的连通结构可以为完全连通， 如十字交叉和 "X"型结 构， 也可以为一端连通一端封闭， 如 "丁"字型和 "Υ"型结构； 纤维管状材料可 以以不同数量进行组合形成不同的二维和三维网络结构。
上述单一纤维管状材料， 包括的具有连通交叉管道结构的二维或三维纤维管 状材料中的单一纤维管状材料可以具备下述特点之一或者它们的组合：
( 1 ) 单一纤维管状材料的材质为聚合物材料、 无机材料或者复合材料。
( 2 ) 单一纤维管状材料的形状可以为柱形管道， 也可以为非柱形管道， 也可 以是柱形和非柱形管道的结合， 如锥形、 不同尺寸的柱形的结合体、 锥形柱形结合 体等三维管道构型；
( 3 )单一纤维管状材料的长度可以在 0. 5Cm-50cm之间； 所述单一纤维管状材 料的长度根据模板的长度而定。 也即在 0. 05cm-0. 5cm之间也是允许的。 优选长度 的范围在 0. 5cm-30cm之间。
(4)单一纤维管状材料的截面形状可以为任何规则或不规则图形， 如三角形、 正方形、 长方形、 五角星形、 圆形等。
( 5 )单一纤维管状材料的截面尺寸以外接圆直径计， 可以在 0. 005Cm-30cm之 间。
( 6 ) 单一纤维管状材料的表面形貌可以为杂乱无章的无纺结构， 也可以具有 特定的图案化微观形貌。
本发明通过设计应用上述收集模板， 相比较于传统的电纺丝收集方法， 获得 了意想不到的结果， 其原因可以解释为如下机理。 在电纺丝过程中， 纤维在高压电 场力的作用下朝接收模板运行， 当接收模板结构发生变化时， 电场力作用方向发生 变化而指向三维收集模板的表面， 在此种变形电场作用下， 纤维从不同方向沉积到 收集模板的表面， 形成管状纤维材料， 而不是如传统电纺丝工艺仅仅沉积到平面模 板上， 形成一张二维薄膜。
本发明同时引入了一块平板辅助基板和棒状辅助模板（特别是棒状辅助模 板）， 从而通过分散电纺丝纤维的沉积路径， 成功的避免了纤维主要沉积在三维收 集模板顶端的现象， 同时也有效避免了纤维从三维收集模板根部悬浮搭联现象的产 生， 从了有效的提高了三维管状纤维材料结构的完整性和均匀性 （图 1 ) ; 当纤维 在电场力作用下行进至接收模板附近时， 纤维表面的静电荷会诱导接收模板出现极 性相反的电荷， 异性电荷相互吸引产生库伦引力， 库仑引力同电荷距离的平方成反 比 （F=kqQ/r2， 其中 F为库仑引力， r为异性电荷间距， 即纤维同收集模板之间的 间距） ， 由于纤维片断同邻近凸起的间距小于模板其它区域， 所以纤维在较大库仑 引力的作用下优先沉积在凸起上； 由于纤维不同片断可能受到不同凸起的吸引， 从 而沉积在不同凸起上， 进而在凸起之间形成了悬浮纤维， 悬浮纤维在不同方向库仑 引力的托拽作用下在凸起间呈定向排列。
本发明的特点在于：
( 1 )通过单一三维收集模板的宏观构型可以控制纤维材料的三维构型， 纤维 主要沉积在三维收集模板的表面， 管状纤维材料的宏观构型同三维收集模板的外围 构型非常相似， 并主要由它决定。
( 2 )通过收集模板表面的微观图案化结构可以控制纤维的沉积位置和排列方 式， 纤维主要沉积在凸起上， 凸起之间的悬浮纤维呈现很好的定向排列性。
( 3 )通过可装卸三维收集模板的组合方式和网络交叉结构可以控制纤维材料 的三维连通管道结构： 纤维主要沉积在可装卸组合三维收集模板的表面， 纤维材料 的连通管道结构同三维收集模板的网络交叉结构非常相似， 并主要由它决定。
(4)通过批量生产组合模板可以同时制备数个具有相同或者不同宏观构型和 微观图案结构的电纺丝纤维管状材料。
本发明采用常规电纺丝技术及其所适用的原料和工艺， 通过设计利用可控宏 观构型和微观形貌的收集模板制备出具有可控宏观构型和微观形貌的管状电纺丝 纤维材料， 而且管状材料的结构形貌可以通过设计模板的宏观构型和微观图案结构 来实现调控， 为电纺丝的实际应用， 尤其在生物医用材料、 组织工程、 光电材料、 过滤材料以及传感器等对材料形貌有较高要求的领域提供了更为广阔的前景。 附图概述
图 1 为本发明涉及电纺丝工作原理及三维收集模板工作机理示意图， 其中 1 表示高压发生器和高压控制箱， 2表示流量控制泵， 3表示电纺丝溶液或熔体供给 装置， 4表示电纺丝喷丝头， 5表示电纺丝纤维管状材料， 6表示棒状模板， 7表示 平面辅助基板；
图 2为具有不同三维构型的柱形收集模板的示意图；
图 3为实施例 1所获得的具有不同直径的管状电纺丝纤维材料的侧视光学照 片；
图 4为实施例 1所获得的具有不同直径的管状电纺丝纤维材料的俯视光学显 微镜照片， 插入图为电纺丝纤维管状材料的放大倍数电镜照片；
图 5为实施例 2所获得的具有较长长度的管状电纺丝纤维材料的光学照片； 图 6为实施例 3所获得的具有不同截面形状的管状电纺丝纤维材料的光学照 片；
图 7为实施例 4所获得的具有一端封口结构的管状电纺丝纤维材料的光学照 片；
图 8为具有不同三维构型的非柱形收集模板的示意图；
图 9为实施例 5所获得的具有不同构型的管状电纺丝纤维材料的光学照片； 图 10为表面具有一种微观图案结构的三维收集模板的示意图；
图 11为实施例 6所获得的一种微观图案形貌的管状电纺丝纤维材料的光学照 片；
图 12为实施例 6所获得的一种微观图案形貌的管状电纺丝纤维材料的电镜照 片；
图 13为实施例 7所获得的具有两种不同微观图案形貌的三维管状电纺丝纤维 材料的光学照片；
图 14为实施例 7所获得的三维管状电纺丝纤维材料中一种微观图案形貌的光 学照片；
图 15为实施例 Ί所获得的三维管状电纺丝纤维材料中另外一种微观图案形貌 的电镜照片；
图 16为表面具有四种微观图案结构的三维收集模板的示意图；
图 17为实施例 8所获得的具有四种不同微观图案形貌的三维管状电纺丝纤维 材料的光学照片；
图 18为实施例 8所获得的具有四种不同微观图案形貌的三维管状电纺丝纤维 材料的展开平铺后光学照片
图 19为利用电纺丝技术和可装卸组合三维收集模板制备具有连通管道结构的 三维电纺丝纤维材料的具体实验操作步骤的示意图；
图 20为实施例 9一 12所涉及的具有不同交叉结构的可装卸组合三维收集模板 的示意图；
图 21为实施例 9所获得的具有十字交叉连通管道结构的三维电纺丝纤维材料 的光学照片； 图 22为实施例 10所获得的具有 "T"形交叉管道结构的三维电纺丝纤维材料 的光学照片；
图 23为实施例 11所获得的具有 "X"形交叉管道结构的三维电纺丝纤维材料 的光学照片；
图 24为实施例 12所获得的具有 "Y"形交叉管道结构的三维电纺丝纤维材料 的光学照片；
图 25为实施例 13所涉及的具有多项不同交叉结构的可装卸组合三维收集模 板的示意图；
图 26为实施例 13所获得的在同一主管道上有两种不同构型管道分叉的三维 电纺丝纤维材料的示意图；
图 27为实施例 14所涉及的具有复杂交叉网络结构的可装卸组合三维收集模 板的示意图；
图 28为实施例 14所获得的具有复杂管道网络结构的三维电纺丝纤维材料的 示意图；
图 29为实施例 15所获得的批量生产的三维管状电纺丝纤维材料连同收集模 板的光学照片；
图 30为实施例 15所获得的批量生产的三维管状电纺丝纤维材料的光学照片； 图 31为实施例 16所涉及的批量生产三维管状电纺丝纤维材料的示意图。
图 32为实施例 17所涉及的三维管状电纺丝纤维材料模板的示意图。
图 33为实施例 18所涉及的 Y形三维管状电纺丝纤维材料薄板的示意图。
图 34为实施例 20所获得的批量生产的三维管状电纺丝纤维材料连同收集模 板的示意图。 本发明的最佳实施方案
以下以实施例的方式说明本发明， 但并非仅限于实施例。
实施例 1
制备具有不同直径的圆柱状铜棒作为三维模板， 铜棒的直径依次为 0. 18mm, 0. 50mm, 1. 36mm, 和 3. 28讓， 选取此组柱状模板作为电纺丝收集基板。 将 2g聚己 内酯（PCL， Mw=5w)溶解于 6ml N， N—二甲基甲酰胺（DMF)和 4ml四氢呋喃（THF) 当中， 室温下搅拌形成均一稳定的溶液。 将该溶液放入到注射器当中， 注射器针头 处连接高压电源作为高压端。 溶液供给流量通过流量泵控制在 0. 5ml/h， 施加的电 压为 10kv， 高压端同收集装置的距离为 10cm。 通过此过程， 收集到同基板结构相 似的具有不同直径的三维管状电纺丝纤维材料（图 2— 4)，管子的直径分别为 0. 18mm, 0. 50mm, 1. 36mm, 和 3. 28mm, 长度分别为 lcm， 1. 3cm, 1. 5cm, 和 1. 3cm。 实施例 2
制备具有较长长度的圆柱状铜线作为三维模板，铜线的直径为 0. 50mm,长度为 15cm, 其余参数选择同实施例 1。 通过此过程， 收集到同基板结构相似的具有较长 长度的三维管状电纺丝纤维材料 （图 2、 5 ) ， 管子的直径为 0. 50讓， 长度为 15cm。 实施例 3
制备具有不同截面形状的柱状铜棒作为三维模板， 铜棒的截面形状依次为三 角形， 正方形， 和圆柱形， 选取此组柱状模板作为电纺丝收集基板， 其余参数选择 同实施例 1。 通过此过程， 收集到同基板结构相似的具有不同截面形状的三维管状 电纺丝纤维材料 （图 2、 6) 。 管子的长度为 2cm。 实施例 4
制备一端具有弧状结构的柱状铜棒作为三维模板， 铜棒的截面为正方形， 边 长为 2mm， 选取此柱状模板作为电纺丝收集基板， 弧状端朝上， 接近喷丝头， 其余 参数选择同实施例 1。 喷丝结束后， 将收集铜棒从非弧状一端取出， 不破坏弧状一 端的纤维聚集结构。 通过此过程， 收集到同基板结构相似的具有一端封口结构的三 维管状电纺丝纤维材料 （图 7 ) 。 管子的长度为 1. 5cm， 和 2cm。 实施例 5
制备具有不同构型的非柱状铜棒作为三维模板， 铜棒为具有不同锥度的锥形 体， 或者不同位置具有不同直径的圆柱结合体， 其余参数选择同实施例 1。 喷丝结 束后， 将收集铜棒从非弧状一端取出， 不破坏弧状一端的聚集结构。 通过此过程， 收集到同基板结构相似的不同位置截面尺寸不同的三维管状电纺丝纤维材料（图 8、 9 ) 。 管子的长度分别为 2cm。 实施例 6
制备表面具有环形线条状凸起微观图案结构的柱状铜棒作为三维模板， 铜棒 的截面为圆形， 直径为 5mm， 凸起间距为 0. 5mm，选取此柱状模板作为电纺丝收集基 板。将 0. 275g聚乳酸（PDLLA， Mw=45 kDa)溶解于 8ml N， N—二甲基甲酰胺（DMF) 和 2ml 四氢呋喃 （THF) 当中， 室温下搅拌形成均一稳定的溶液。 将该溶液放入到 注射器当中， 注射器针头处连接高压电源作为高压端。 溶液供给流量通过流量泵控 制在 0. 5ml/h，施加的电压为 10kv，高压端同收集装置的距离为 10cm。通过此过程， 收集到同基板结构相似的具有一种微观图案结构的三维管状电纺丝纤维材料（图 10 - 12 ) 。 管子的直径为 4讓， 长度为 5cm。 实施例 7
制备表面具有两种不同微观图案结构的柱状铜棒作为三维模板。 一种微观图 案为环形线条状凸起结构， 环形线条状凸起间距为 0. 5mm; 另一种微观图案为网格 编织结构，网格线的直径为 0. lmm,间距为 0. 14mm,铜棒的截面为圆形， 直径为 5mm， 选取此柱状模板作为电纺丝收集基板， 其余参数选择同实施例 1。 通过此过程， 收 集到同基板结构相似的具有两种微观图案结构的三维管状电纺丝纤维材料 （图 13 - 15 ) 。 管子的长度为 1. 5cm。 实施例 8
制备表面具有四种不同微观图案结构的柱状铜棒作为三维模板。 第一种微观 图案为光滑平板结构； 第二种微观图案为规则排列的正方形点状凸起结构， 凸起边 长 0. 2讓，凸起间距 0. 2mm;第三种微观图案为直线条状凸起结构， 凸起宽度 0. 2讓， 凸起间距 0. 2mm， 线条状凸起同三维柱状模板的轴向平行； 第四种微观图案为直线 条状凸起结构， 凸起宽度 0. 2mm， 凸起间距 0. 2mm， 线条状凸起同三维柱状模板的 轴向垂直。 铜棒的截面为正方形， 直径为 3mm， 选取此柱状模板作为电纺丝收集基 板， 其余参数选择同实施例 1。 通过此过程， 收集到同基板结构相似的具有四种微 观图案结构的三维管状电纺丝纤维材料 （图 16— 18 ) 。 实施例 9
制备完整圆柱形铜棒作为可移动三维收集模板，模板直径为 3mm; 制备具有连 通孔洞（尺寸同上述模板匹配） 的圆柱形铜棒作为固定收集模板， 模板直径为 4mm; 将两种模板垂直交叉组合形成可装卸组合三维收集模板， 选取此组模板作为电纺丝 收集基板， 其余参数选择同实施例 1。 具体实验操作步骤如下 （图 19 ) ： ①在电纺 丝收集前将两种个体模板组装形成可装卸组合三维收集模板， ②在电纺丝过程中， 纤维沉积在模板表面， 形成同模板结构相似的管道垂直连通的电纺丝纤维材料， ③ 收集完毕后， 首先将可移动模板取出， ④然后将三维电纺丝纤维材料从固定模板上 取下。 通过此过程， 收集到同基板结构相似的具有十字交叉连通管道结构的三维电 纺丝纤维材料 （图 20、 21 ) 。 制备完整圆柱形铜棒作为可移动三维收集模板，模板直径为 3mm; 制备具有一 端封闭孔洞 （尺寸同上述模板匹配） 的圆柱形铜棒作为固定收集模板， 模板直径为 4mm; 将两种模板垂直交叉组合形成可装卸组合三维收集模板， 选取此组模板作为 电纺丝收集基板， 其余参数选择同实施例 1。 具体电纺丝纤维管状材料的移取操作 步骤同实施例 9。 通过此过程， 收集到同基板结构相似的具有" T"形交叉管道结构 的三维电纺丝纤维材料 （图 20、 22 ) 。 实施例 11
制备完整圆柱形铜棒作为可移动三维收集模板，模板直径为 3mm; 制备具有连 通孔洞（尺寸同上述模板匹配） 的圆柱形铜棒作为固定收集模板， 模板直径为 4mm; 将两种模板成 30° 交叉组合形成可装卸组合三维收集模板，选取此组模板作为电纺 丝收集基板， 其余参数选择同实施例 1。 具体电纺丝纤维管状材料的移取操作步骤 同实施例 9。 通过此过程， 收集到同基板结构相似的具有" X"形交叉管道结构的三 维电纺丝纤维材料 （图 20、 23 ) 。 实施例 12
制备完整圆柱形铜棒作为可移动三维收集模板，模板直径为 3mm; 制备具有一 端封闭孔洞 （尺寸同上述模板匹配） 的圆柱形铜棒作为固定收集模板， 模板直径为 4mm; 将两种模板成 30° 交叉组合形成可装卸组合三维收集模板， 选取此组模板作 为电纺丝收集基板， 其余参数选择同实施例 1。 具体电纺丝纤维管状材料的移取操 作步骤同实施例 9。 通过此过程， 收集到同基板结构相似的具有" Y"形交叉管道结 构的三维电纺丝纤维材料 （图 20、 24) 。 实施例 13
制备完整三棱形铜棒和圆锥形铜棒作为可移动三维收集模板； 制备同时具有 一端封闭孔洞和连通孔洞的正方四棱柱铜棒作为固定收集模板；将三者别成 30° 和 垂直交叉组合形成可装卸组合三维收集模板， 选取此组模板作为电纺丝收集基板。 将 l. lg 聚琥珀酸酯 （PBSu， Mw=30w) 溶解于 10ml 三氯甲烷 （CHC13 ) 当中， 室 温下搅拌形成均一稳定的溶液。 将该溶液放入到注射器当中， 注射器针头处连接高 压电源作为高压端。溶液供给流量通过流量泵控制在 5. 0ml/h，施加的电压为 60kv， 高压端同收集装置的距离为 25cm。具体电纺丝纤维管状材料的移取操作步骤同实施 例 9。 通过此过程， 收集到同基板结构相似的， 在同一主管道上有两种不同构型管 道分叉的三维电纺丝纤维材料 （图 25、 26) 。 实施例 14
制备不同尺寸的圆柱形铜棒作为单一收集模板， 彼此垂直交叉组合形成可装 卸组合三维收集模板， 选取此组模板作为电纺丝收集基板。 将 0. 5ml lmol/1 盐酸 溶液加到 50ml无水乙醇中， 然后再往溶液中加入 6. 7g正硅酸乙酯（TE0S ) 、 0. 58g 磷酸三乙酯 (TEP)和 1. 48g四水硝酸钙。 搅拌 2小时后， 将 5ml以上溶胶加到 5ml 含有 lg聚乙烯吡咯烷酮 （PVP， Mw=3w) 和 0. 4gP123的乙醇溶液中， 搅拌 2小时 后待用。 将该溶液放入到注射器当中， 注射器针头处连接高压电源作为高压端。 溶 液供给流量通过流量泵控制在 0. lml/h， 施加的电压为 5kv， 高压端同收集装置的 距离为 2. 5cm。 具体电纺丝纤维管状材料的移取操作步骤同实施例 9。 通过此过程， 收集到同基板结构相似的， 具有复杂管道网络结构的三维电纺丝纤维材料， 然后将 此产物烧结， 即可获得无机生物玻璃管状纤维材料 （图 27、 28 ) 。 实施例 15
制备用于批量生产的三维组合收集模板， 个体模板为圆柱状三维模板， 直径 为 0. 5mm， 高度为 2cm， 将 9个相同的单独模板固定在一块绝缘板上， 彼此间距为 4cm, 其余参数选择同实施例 1。 通过此过程， 同时收集到 9个同基板结构相似的三 维管状电纺丝纤维材料 （图 29、 30) 。 管子的直径为 0. 5讓， 长度为 1. 5cm。 实施例 16
制备用于批量生产的三维组合收集模板， 个体模板分别为具有不同宏观结构 和微观相貌的单一收集模板和具有交叉结构的可装卸收集模板， 将 9个单独模板固 定在一块绝缘板上，彼此间距为 4cm。首先将 0. lg硅灰石纳米晶须（wollastonite ) 溶解于 10ml 三氯甲烷 （CHC13) ， 超声分散均匀， 再在其中加入 l. lg 聚琥珀酸酯 (PBSu， Mw=30w) ， 室温下搅拌形成均一稳定的溶液。 将有机无机复合溶液放入 到注射器当中， 注射器针头处连接高压电源作为高压端。 溶液供给流量通过流量泵 控制在 25. 0ml/h， 施加的电压为 75kv， 高压端同收集装置的距离为 60cm。 通过此 过程，同时收集到 9个同个体基板结构相似的有机无机复合管状纤维材料（图 31 ) ， 单管的直径 （外接圆直径） 为 10cm， 长度为 20cm。 实施例 17
制备具有不同截面形状的空心柱状铜棒作为三维模板， 空心铜棒的截面形状 依次为三角形， 正方形， 和圆柱形 （图 32 ) ， 选取此组柱状模板作为电纺丝收集基 板， 其余参数同实施例 1。 通过此过程， 收集到同基板结构相似的具有不同截面形 状的三维管状电纺丝纤维材料。 管子的长度为 2cm。 实施例 18
制备空心圆柱形铜棒作为可移动三维收集模板， 模板直径为 3mm， 管厚 lmm; 制备具有一端封闭孔洞 （尺寸同上述模板匹配） 的空心圆柱形铜棒作为固定收集模 板， 模板直径为 4mm; 将两种模板成 30° 交叉组合形成可装卸组合三维收集模板， 选取此组模板作为电纺丝收集基板， 其余参数选择同实施例 1。 具体电纺丝纤维管 状材料的移取操作步骤同实施例 9。通过此过程， 收集到同基板结构相似的具有" Y "形 （图 33 ) 。 实施例 19
制备用于批量生产的三维空心组合收集模板， 个体模板为空心圆柱状三维模 板， 直径为 0. 5mm， 管厚 0. 2mm， 高度为 2cm， 将 9个相同的单独模板固定在一块绝 缘板上， 彼此间距为 4cm， 其余参数选择同实施例 1。 通过此过程， 同时收集到 9 个同基板结构相似的三维管状电纺丝纤维材料。管子的直径为 0. 5mm，长度为 1. 5cm。 实施例 20
制备用于批量生产的三维空心组合收集模板， 个体模板分别为具有不同宏观 结构和微观相貌的单一收集模板和具有交叉结构的可装卸收集模板， 将 9个单独模 板固定在一块绝缘板上， 彼此间距为 4cm，其余参数选择同实施例 16。通过此过程， 同时收集到 9个同个体基板结构相似的有机无机复合管状纤维材料 （图 34 ) ，单管 的直径 （外接圆直径） 为 10cm， 长度为 20cm。

Claims

权 利 要 求
1、 一种电纺丝纤维管状材料的制备方法， 包括下述步骤：
( 1 ) 配制适合电纺丝工艺的溶液或者熔体；
( 2 ) 将上述溶液或者熔体装入电纺丝液供给装置；
( 3 )将一个或多个金属棒状模板或金属棒状组合模板固定在平板辅助基板上 作为收集装置； 或者， 将一个或多个金属棒状模板或金属棒状组合模板直接作为收 集装置；
( 4 )控制所述溶液或者熔体的流量为 0. l - 300ml/h;控制电纺丝喷丝头作为 高压端同收集装置之间的距离为 1一 100cm;控制高压发生器在电纺丝过程中提供的 电压为 1一 80kv;
( 5 ) 在步骤 (3)的金属棒状或金属棒状组合的模板收集得到电纺丝纤维管状 材料并取下得到。
2、 按权利要求 1所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 金属棒状模板或金属棒状组合模板为单一金属棒状模板或由单一金属棒状模板组 合具有交叉结构的二维或三维金属棒状组合模板。
3、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述交 叉结构的交叉夹角在 10° — 90° 之间，单一金属棒状模板以两件以上的数量进行组 合。
4、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板所用的金属材料为铜或铁或铝或铜、 铁、 铝的合金。
5、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的形状为柱形或非柱形或柱形与非柱形的结合。
6、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的长度在 0. 5cm-50cm之间。
7、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的截面形状为任何规则或不规则图形。
8、 按权利要求 7所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的截面形状为三角形、 正方形、 长方形、 五角星形、 或圆形。
9、 按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板为空心或实心结构。
10、按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的截面尺寸以各截面外接圆直径计， 在 0. 005cm-30cm之间。
11、按权利要求 2所述的电纺丝纤维管状材料的制备方法， 其特征在于所述的 单一金属棒状模板的表面为网格收集结构或者凸起收集结构。
12、 按权利要求 11所述的电纺丝纤维管状材料的制备方法， 其特征在于所述 的网格收集结构是利用不同径向尺寸的网格线， 通过不同的编织方法编织而成， 网 格线的径向尺寸在 0. lmm— 5mm之间， 网格线间的间距为 ΙΟμηι— ΙΟΟΟμηι之间， 网格 的编织采用单编、 或双编的编织方式。
13、 按权利要求 11所述的电纺丝纤维管状材料的制备方法， 其特征在于所述 的凸起收集结构中凸起部分是在单一金属棒状模板的表面凸起，凸起的高度在 Ιθμηι 一 500( m之间。
14、 按权利要求 13所述的电纺丝纤维管状材料的制备方法， 其特征在于所述 的凸起部分为点状凸起收集模板、 线状凸起收集模板或点线凸起组合收集模板。
15、 一种按权利要求 1所述的电纺丝纤维管状材料的制备方法制备得到的电 纺丝纤维管状材料， 其特征在于其外形为单一纤维管状材料或具有连通交叉管道结 构的二维或三维纤维管状材料。
16、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于交叉角度在 10 90。 之间。
17、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于所述的单一纤维 管状材料的材质为聚合物材料或无机材料或复合材料。
18、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于所述的单一纤维 管状材料的形状为柱形管道或为非柱形管道或柱形和非柱形管道的结合
19、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于所述的单一纤维 管状材料的长度在 0. 5cm-50cm
20、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于所述的单一纤维 管状材料的截面形状为任何规则或不规则图形。
21、 按权利要求 15所述的电纺丝纤维管状材料， 其特征在于所述的单一纤维 管状材料的表面形貌为杂乱无章的无纺结构或特定的图案化微观形貌。
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