WO2007054029A1 - Dispositif et procede de preparation de cables de filaments formes de nanofibres composites - Google Patents

Dispositif et procede de preparation de cables de filaments formes de nanofibres composites Download PDF

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Publication number
WO2007054029A1
WO2007054029A1 PCT/CN2006/003014 CN2006003014W WO2007054029A1 WO 2007054029 A1 WO2007054029 A1 WO 2007054029A1 CN 2006003014 W CN2006003014 W CN 2006003014W WO 2007054029 A1 WO2007054029 A1 WO 2007054029A1
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WIPO (PCT)
Prior art keywords
nozzles
electrospinning
pair
filament bundle
composite nanofiber
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PCT/CN2006/003014
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English (en)
French (fr)
Inventor
Xinsong Li
Chen Yao
Fuqian Sun
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Southeast University
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Application filed by Southeast University filed Critical Southeast University
Priority to US12/084,839 priority Critical patent/US20080265469A1/en
Publication of WO2007054029A1 publication Critical patent/WO2007054029A1/zh

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    • 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
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof

Definitions

  • the invention relates to a method for preparing a composite nanofiber filament bundle, which belongs to the technical field of preparation of special fibers. Background technique
  • Electrospinning is an effective method for producing polymer nanofibers by applying an external electric field to a polymer solution, and has received particular attention in recent years.
  • the low density, high porosity and large specific surface area of electrospun nanofibers can not only produce high-efficiency filter materials, but also have broad application prospects in biomedical materials, chemical sensors, protective materials, nanocomposites and the like.
  • the size of the electrospun nanofibers is on the nanometer or submicron scale.
  • the fibers are repelled by the same kind of charge, and the fibers are randomly distributed to obtain a nanofiber nonwoven fabric. And there are often cases where the fiber is lost, so inevitably unstable conditions will occur.
  • the preparation of oriented nanofiber filament bundles by electrospinning is a challenge.
  • the nanofibers ejected from the electrospinning nozzle are subjected to a high-speed rotating drum to receive a bundle of nanofiber filaments in which a small amount of orientation can be obtained.
  • the nanofibers ejected from the electrospinning nozzle are deposited on the water surface, and are drawn, drawn, and wound to the underwater to obtain an oriented filament bundle.
  • Others have deposited the nanofibers ejected from the electrospinning nozzle onto a stainless steel drum, which is gathered, drawn, and wound to obtain an oriented filament bundle.
  • An object of the present invention is to provide a composite nanofiber filament bundle preparation device and a preparation method thereof, which can produce a composite nanofiber filament bundle simply and efficiently.
  • the composite nanofiber filament tow preparation device of the invention is characterized in that the device comprises a plurality of pairs of spinning nozzles, a pair of guide rollers, a bracket, a fixing rod and a base, and the two pairs of nozzles face opposite pairs of electrospinning The nozzle pair is fixed on the bracket, and each pair of electrospinning nozzles can be on the same horizontal plane or different horizontal planes, and the bracket is connected to the base through the fixing rod of the vertical base, the pair of guide rollers is in the middle of the bracket, the plane of the bracket and the fixed rod An acute angle.
  • the spacing between the electrospinning nozzles of the same row of brackets is 2-50 cm; the distance between the two nozzles of the pair of electrospinning nozzles facing the two rows of nozzles is 10-100 cm.
  • the angle between the plane of the bracket and the fixed rod is 0-90°.
  • Each pair of opposing nozzles ejects oppositely charged nanofibers, and attracts and collides each other in the air to form composite nanofibers, or is deposited as a lower traction along the plane of the bracket between the two nozzles of the pair of electrospinning nozzles. Forming a composite nanofiber filament bundle on the filament of the polymer fiber of the receiving body after being pulled and drawn;
  • the first pair of oppositely placed electrospinning nozzles are formed by spinning the composite nanofiber filament bundles downwardly, and as the acceptor and the second pair of electrospinning nozzles respectively, the oppositely charged and mutually attracted nanofibers Meet in the air, wrapped by the second pair of electrospinning nozzles, and then stretched and stretched to form two layers of composite nanofiber filament bundles;
  • the filament bundle formed by the upper layer is stretched downward and the nanofibers formed by spinning as the acceptor and the lower electrospinning nozzle meet in the air, and are coated by the lower layer electrospinning nozzle for the sprayed nanofibers.
  • a composite nanofiber filament bundle is formed, and finally, a multi-layer composite nanofiber filament bundle is obtained by drawing and stretching by a godet roller pair.
  • the 3KV-200KVo liquid is a polymer solution or a polymer solution containing additives or a mixture system of polymer and inorganic particles.
  • the polymer is polyolefin, polyhalogenated olefin, polysiloxane, polyether, polyamide, polyester, polycarbonate, polyurethane, epoxy resin, polyacrylonitrile, polyacrylic polymer, polyacrylate, poly Phenyl ether, polyanhydride, poly- ⁇ -amino acid, polyphenylene sulfide, or a blend of two or more thereof; or cellulose, cellulose derivative, dextran, silk protein, chitosan , chitosan derivatives, hyaluronic acid, hyaluronic acid derivatives, collagen, carrageenan, sodium alginate, calcium alginate, chondroitin sulfate, gelatin, agar, dextran, fibrin, fibrinogen, One of keratin, casein, albumin, elastin or a derivative thereof, Or a blend of two or more thereof; or a bioabsorbable synthetic polymer poly-L-lactic acid, poly-(D,
  • Additives are antibiotics, immunosuppressants, antibacterial agents, hormones, vitamins, amino acids, peptides, proteins, enzymes, growth factors, antibacterials, anesthetics, hemostatic drugs, hormones, analgesics, antihypertensive drugs, antitumor drugs.
  • the invention has the following advantages:
  • a method for preparing a composite nanofiber filament bundle according to the present invention wherein a reverse polarity DC high voltage is applied to an electrospinning nozzle opposite to the nozzle, and the oppositely charged nanofibers produced by the electrospinning nozzle attract and aggregate in the air. Collision, the charge of the nanofibers is dissipated, effectively avoiding the scattering and loss of nanofibers in the air, improving production efficiency, and eliminating the need for a metal receiver for the grounding wire.
  • the invention can avoid the unstable injection caused by various disturbances by adjusting the angle of the plane of the bracket and the ground, and is convenient to operate, thereby greatly improving the production efficiency.
  • the present invention can easily and efficiently prepare a composite nanofiber filament bundle.
  • the present invention can efficiently produce multi-component composite nanofiber filament bundles by transferring different cerium polymer solutions to the electrospinning nozzles of the nozzles or polymer solutions containing additives.
  • the composite nanofiber filament bundle prepared by using multiple pairs of electrospinning nozzles has the characteristics of fiber composition, nano structure control, coarse tow and good mechanical properties.
  • the oppositely charged nanofiber filament bundles are deposited on the filaments of the polymer fibers which are drawn downward along the plane of the stent between the two nozzles of the pair of electrospinning nozzles, and the nanofibers are not scattered, which can be further improved.
  • the mechanical properties of the filament bundle, the surface layer is a nanofiber layer, and the core layer is a common polymer fiber.
  • the present invention combines an electrospinning nanofiber filament bundle with an electrospray preparation nanoparticle to prepare a composite nanofiber filament bundle containing electrospray nanoparticles.
  • the composite nanofiber filament bundle of the present invention can be used for tissue engineering scaffolds, textiles and the like.
  • Figure 1 is a schematic view of the overall structure of the present invention.
  • Figure 2 is a schematic diagram of the operation of the present invention.
  • Fig. 3 is a photograph showing the appearance of a bundle of PLLA (poly-1-lactic acid) nanofiber filaments of the present invention.
  • Fig. 4 is a photograph showing the appearance of a PLLA (poly-1-lactic acid) composite nanofiber filament bundle of the present invention.
  • Fig. 5 is a scanning electron microscope image of a PLLA (poly-1-lactic acid) composite nanofiber filament bundle of the present invention.
  • Fig. 6 is a scanning electron microscope image of a PU/PVDF (polyurethane/polyvinylidene fluoride) composite nanofiber filament bundle of the present invention.
  • Fig. 7 is a scanning electron microscope image of a PAN (polyacrylonitrile) composite nanofiber filament bundle of the present invention.
  • Fig. 8 is a scanning electron microscope image of a PVDF (polyvinylidene fluoride) composite nanofiber filament bundle of the present invention.
  • the composite nanofiber filament bundle preparation device is composed of a pair of spinning nozzle pair 1, a guide roller pair 2, a bracket 3, a fixing rod 4, and a base 5.
  • the pair of nozzles facing the two pairs of nozzles are fixed to the bracket 3
  • each pair of electrospinning nozzles may be on the same horizontal plane or different horizontal planes, and the bracket 3 is connected to the base 5 through the fixing rod 4 of the vertical base.
  • the pair of guide rollers 2 is in the middle of the lower part of the bracket 3, and the plane and the fixed rod of the bracket 3 4 between the sharp angle.
  • Each pair of opposite nozzles sprays oppositely charged nanofibers, and attracts and collides each other in the air to form composite nanofibers, which are drawn and stretched to form composite nanofiber filament bundles;
  • the first pair of oppositely placed electrospinning nozzles are formed by spinning the composite nanofiber filament bundles downwardly, and as the acceptor and the second pair of electrospinning nozzles respectively, the oppositely charged and mutually attracted nanofibers Meet in the air, wrapped by the second pair of electrospinning nozzles, and then stretched and stretched to form two layers of composite nanofiber filament bundles;
  • the filament bundle formed by the upper layer is stretched downward and the nanofibers formed by spinning as the acceptor and the lower electrospinning nozzle meet in the air, and the nanofiber package is sprayed by the lower electrospinning nozzle. Wrapped, stretched and stretched to form a composite nanofiber filament bundle, and finally drawn and stretched by a godet pair 2 to obtain a multi-layer composite nanofiber filament bundle.
  • the specific steps of the preparation method of the composite nanofiber filament bundle are as follows: 1) conveying the liquid to the electrospinning nozzle pair 1 on the support 3; 2) the opposite polarity of each nozzle of the electrospinning nozzle facing the nozzle 1 DC high voltage; 3) each pair of opposite nozzles ejects oppositely charged nanofibers, and are attracted to each other in the air and deposited in the air between the two nozzles of the electrospinning nozzle pair 1
  • the composite polymer fiber filaments are drawn and stretched to form a composite nanofiber filament bundle.
  • the distance between the two rows of electrospinning nozzles 1 of the brackets is 2 - 50 cm; the distance between the two nozzles of the electrospinning nozzles of the two rows of nozzles is 10 - 100 cm.
  • the angle between the plane of the bracket 3 and the fixed rod 4 is 0-90°.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC ⁇ voltage of opposite polarity.
  • the liquid solution is a polymer solution or a polymer solution containing an additive or a mixture system of cerium molecules and inorganic particles.
  • the polymer is polyolefin, polyhalogenated olefin, polysiloxane, polyether, polyamide, polyester, polycarbonate, polyurethane, epoxy resin, polyacrylonitrile, polyacrylic polymer, polyacrylate, poly Phenyl ether, polyanhydride, poly-a-amino acid, polyphenylene sulfide, or a blend of two or more thereof; or cellulose, cellulose derivative, dextran, silk protein, chitosan , chitosan derivatives, hyaluronic acid, hyaluronic acid derivatives, collagen, carrageenan, sodium alginate, calcium alginate, chondroitin sulfate, gelatin, agar, dextran, fibrin, fibrinogen, a keratin protein, casein, albumin, elastin or a derivative thereof, or a blend of two or more thereof; or a bioabsorbable synthetic polymer poly-L-lactic acid, poly -(
  • Inorganic nanomaterials are nano antibacterial agents, catalysts, and carbon nanotubes.
  • Additives are antibiotics, immunosuppressants, antibacterial agents, hormones, vitamins, amino acids, peptides, proteins, enzymes, growth factors, antibacterials, anesthetics, hemostatic drugs, hormones, analgesics, antihypertensive drugs, antitumor drugs.
  • the composite nanofiber filament bundle of the present invention can be used in many fields such as regenerative medicine, textiles and the like.
  • Example 1
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ral N, N-dimethylformamide in a mixed solvent to prepare solution No. 1, lactide-glycolide copolymer PLGA (wherein Quality group Formulation No. 1 in a mixed solvent of carbamide, lactide-glycolide copolymer PLGA (wherein the mass composition is 50% lactide, 50% of glycolide, viscosity average molecular weight 100,000) 15 g dissolved in 50 ml of acetone Mix solution with 50ml of N, N-dimethylformamide to form solution No. 2, transfer solution No.
  • the spacing between the nozzles and the adjacent rows of adjacent electrospinning nozzles on the support is 15 ctn, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is at an angle of 90° to the fixed rod. 5 ⁇
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied to the opposite polarity of the DC high voltage ⁇ 20kV, the inner diameter of the electrospinning nozzle is 0. 5 ⁇ .
  • the speed of the godet to draw the filament bundle was 8 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA/PLGA two-component three-layer composite nanofiber filament bundle is collected.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare solution No. 1, polycaprolactone PCL (molecular weight 90,000) 10 g dissolved
  • solution No. 2 in 100ml N, N-dimethylformamide, deliver No. 1 solution to the same row of 4 electrospinning nozzles on the support, and deliver No. 2 solution to the other four electrospinning nozzles on the support.
  • the spacing between adjacent electrospinning nozzles in the same column is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is at an angle of 90° to the pole. 5 ⁇
  • the electro-spinning nozzle has an inner diameter of 0.5 ⁇ .
  • the speed of the godet to draw the filament bundle was 8 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA/PCL two-component three-layer composite nanofiber filament bundle is collected.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare solution No. 1, zein ZEIN (molecular weight 35,000) 35 g dissolved 8 ⁇ 2 ⁇ ,
  • the inner diameter of the electrospinning nozzle is 0. 8mm, will be No. 2, in the solution of the first and third electrospinning nozzles.
  • the solution is delivered to another row of three electrospinning nozzles on the support.
  • the inner diameter of the electrospinning nozzle is 1. 2 hidden.
  • the spacing between adjacent electrospinning nozzles in the same column on the bracket is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is at an angle of 90° to the fixed rod.
  • a DC high voltage of 25 kV of opposite polarity is applied to the electrospinning nozzles facing the two nozzles.
  • the speed of the godet to draw the filament bundle was 8 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA/ZEIN two-component three-layer composite nanofiber filament bundle is collected.
  • Polyacrylonitrile PAN (average molecular weight 130,000) 10 g dissolved in 100 ml of N, N-dimethylformamide to form solution No. 1, polyphenylene ether sulfone PPES (melt index 3. 9 g/10 min, 320 ° C) 10 g Dissolve in 100ml dimethyl sulfoxide to form solution No. 2, and deliver solution No. 1 to the same column of four electrospinning nozzles on the support, and deliver the No. 2 solution to the other four electrospinning nozzles on the support, the same column on the support
  • the spacing between adjacent electrospinning nozzles is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is at an angle of 90° to the pole. 5 ⁇
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied with a DC high voltage of the opposite polarity of ⁇ 20kV, the inner diameter of the electrospinning nozzle is 0. 5mm.
  • the speed of the godet to draw the filament bundle was 8 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PAN/PPES two-component three-layer composite nanofiber filament bundle is collected.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare solution No. 1, lactide-glycolide copolymer PLGA (wherein Mass composition 50% lactide, glycolide 50 ° /., viscosity average molecular weight 100,000) 15 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare solution No. 2, polyurethane PU15g dissolved Prepare solution No.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC polarity of 20kv of opposite polarity, the inner diameter of the electrospinning nozzle is 0. 8mm.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the electrospinning nozzle The nanofibers ejected from the top end are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a bundle of four composite nanofiber filaments is collected.
  • Hyaluronic acid (molecular weight 100,000) lg dissolved in 100ml of water to form solution No. 1, chitosan 0. 5g dissolved in lOOmlO. 1M diluted acetic acid in solution No. 2, poly-L-lactic acid PLLA (viscosity average molecular weight 100,000 g 10 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to form solution No.
  • lactide-glycolide copolymer PLGA (wherein the mass composition of lactide 50%, glycolide 50%, viscosity average molecular weight 100,000) 15g dissolved in 50ml of acetone and 50ralN, N-dimethylformamide in a mixed solvent solution No. 4, polyurethane PU15g dissolved in 100ml N, N-dimethylformamide in a solution No. 5, polycaprolactone PCL (molecular weight 9 10,000) lOg is dissolved in 100ml of N, N-dimethylformamide to form solution No. 6, fully dissolved, and then these high polymer solutions are separately delivered to two rows of 6 different electrospinning nozzles on the support (each column 3 An electrospinning nozzle).
  • the spacing between adjacent electrospinning nozzles in each column of the bracket is 10 cm, and the electrospinning nozzles of the two rows of nozzles are opposite each other by 30 cm.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°). 8 ram.
  • the inner diameter of the electrospinning nozzle is 0. 8 ram.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a six-component composite nanofiber filament bundle is collected.
  • Hyaluronic acid (molecular weight 100,000) lg dissolved in 100ml of water to form solution No. 1, poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10g mixed solvent of 50ml of acetone and 50ml of N, dimethylformamide
  • the solution was prepared into solution No. 2, and after fully dissolving, the high polymer solution was separately supplied to two rows of a total of six electrospinning nozzles on the stent (three electrospinning nozzles per column, and the same polymer solution was transported in the same column).
  • the spacing between adjacent electrospinning nozzles in each column of the stent is 10 cm, and the electrospinning nozzles of the two rows of nozzles are 30 cm apart.
  • the plane between the bracket and the fixed rod is parallel (at 0° angle). 8 ⁇
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied with a direct current high voltage of ⁇ 20kv, and the inner diameter of the electrospinning nozzle is 0.8 ⁇ .
  • the godet roller has a speed of pulling the filament bundle of 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward to collect a bundle of two-component composite nanofiber filaments. 'Example 8
  • Hyaluronic acid (molecular weight 100,000) lg and ibuprofen 0.2 g dissolved in 100 ml of water to form solution No. 1, poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ml of N, N-
  • the mixed solvent of dimethylformamide is prepared into solution No. 2, and after fully dissolving, these high polymer solutions are respectively supplied to two rows of electrospinning nozzles in two rows (three electrospinning nozzles per column, the same column) Deliver the same polymer solution).
  • the spacing between adjacent electrospinning nozzles in each column of the stent is lOcm, and the electrospinning nozzles of the two rows of nozzles are opposite each other by 30 cm.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°). 8 ⁇
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied with a direct current high voltage of ⁇ 20kv, the inner diameter of the electrospinning nozzle is 0. 8mm.
  • the speed of the godet to the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls and then formed into a tow and forwarded to obtain a bicomponent composite nanofiber filament bundle containing ibuprofen.
  • Polyacrylonitrile PANlOg is dissolved in 100 ml of N, N-dimethylformamide to form solution No. 1
  • polyurethane PU15g is dissolved in 100 ml of N, N-dimethylformamide to form solution No. 2, and these polymers are fully dissolved.
  • the solution was separately delivered to two rows of electrospinning nozzles in two rows (three electrospinning nozzles per column, the same polymer solution in the same column).
  • the spacing between adjacent electrospinning nozzles in each column of the bracket is 10 cm, and the electrospinning nozzles of the two rows of nozzles are opposite each other by 30 cm.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°).
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 20kv, the inner diameter of the electrospinning nozzle is 0. 8 ⁇ .
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are attracted to each other and deposited on the polyester filament drawn downward in the middle of the stent. After the guide roller pair is pulled, the core layer is polyester filament, and the cortex is PAN/PU composite nanometer. Fiber nanofiber filament bundle.
  • Polyurethane PU15g is dissolved in 100ml N, N-dimethylformamide to form solution No. 1, polycaprolactone PCLlOg is dissolved in lOOmlN, N-dimethylformamide is formulated into solution No. 2, and solutions 1 and 2 are separately transported.
  • the spacing of the electrospinning nozzles in each column is 10cm, and the electrospinning nozzles of the two rows of nozzles are 30cm apart.
  • the plane between the bracket and the pole is at an angle of 45°.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a direct current high voltage of ⁇ 15 kV of opposite polarity, and the inner diameter of the electrospinning nozzle is 1. 2 mm.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a multi-layer composite nanofiber filament bundle is collected.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 20 g dissolved in 100 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare a solution, the solution was separately delivered to the stent on two columns of a total of 4 electrospinning Nozzles (2 electrospinning nozzles per column).
  • the spacing between adjacent electrospinning nozzles in each column of the stent is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°).
  • the electrospinning nozzles facing the two nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 20 kV, and the inner diameter of the electrospinning nozzle is 1. 2 mm.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA one-component composite nanofiber filament bundle is collected.
  • the spacing between the two electrospinning nozzles in each column of the stent was 15 cm, and the electrospinning nozzles of the two rows of nozzles were 30 cm apart.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°). 8 ⁇
  • the electro-spinning nozzles of the two pairs of nozzles are respectively applied to the opposite polarity of the DC high voltage ⁇ 10kv, the inner diameter of the electrospinning nozzle is 0. 8mm.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PCL/PLGA double-layer composite nanofiber filament bundle is collected.
  • Two rows of 20 electrospinning nozzles (10 per column) are arranged on the electrospinning support, poly-L-lactic acid PLLA (viscosity average molecular weight 150,000) 50g is dissolved in 250ml acetone and 250ralN, N-dimethylformamide In the solvent, after fully dissolving, the solution is delivered to 10 electrospinning nozzles on one side of the stent.
  • 5 g of hyaluronic acid (molecular weight 1 million) is dissolved in 500 ml of water, fully dissolved and the solution is delivered to the other side of the stent.
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied with a reverse polarity of DC high voltage ⁇ 50kv, and the inner diameter of the electrospinning nozzle is 0.8 ⁇ .
  • the godet roller has a speed of pulling the filament bundle of 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a composite nanofiber filament bundle is collected, and the tow diameter is about 150 ⁇ m.
  • electrospinning stent On the electrospinning stent, two rows of six electrospinning nozzles (three in each column) are arranged in the opposite direction, and chitosan 0.5 g is dissolved in 100 ml of O. 1 M dilute acetic acid, and the solution is fully dissolved and then transferred to a column of three electric wires.
  • Spinning nozzle, polycaprolactone PCLlOg is dissolved in 100ml N, N-dimethylformamide, fully dissolved and then transferred to the other three electrospinning nozzles on the other side of the stent. 10cm, the electrospinning nozzles of the two rows of nozzles are 20cm apart. The plane between the bracket and the fixed rod is at an angle of 30°.
  • the electro-spinning nozzles of the two pairs of nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 20kv, the inner diameter of the electrospinning nozzle is 0.6 awake.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward to collect a two-component composite nanofiber filament bundle.
  • Polycarbonate PC (average molecular weight 100,000) 10g dissolved in 100ml N, N-dimethylformamide in solution No. 1, polyphenylene ether sulfone PPES (melt index 3.9 g/10 min, 320 ° C) 10 g Dissolve in 100ml dimethyl sulfoxide to form solution No. 2, and deliver solution No. 1 to the same column of 4 electrospinning nozzles on the support, 2 The solution is delivered to another row of 4 electrospinning nozzles on the bracket.
  • the spacing between adjacent electrospinning nozzles in the same row on the bracket is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is at an angle of 90° to the fixed rod. 5 ⁇
  • the electro-spinning nozzle has an inner diameter of 0. 5mm.
  • the speed of the godet to draw the filament bundle was 8 cm/ s .
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PC/PPES two-component three-layer composite nanofiber filament bundle is collected.
  • Polyacrylonitrile PAN (average molecular weight 130,000) 10g dissolved in 100ml N, N-dimethylformamide, and 0.1g of single-walled carbon nanotubes dispersed therein, formulated into solution No. 1, polyphenylene ether sulfone PPES (melt index 3.9 g/10 min, 320 ° C) 10 g dissolved in 100 ml of dimethyl sulfoxide to prepare solution No. 2, the No. 1 solution was delivered to the same column of 4 electrospinning nozzles, the No. 2 solution It is sent to another row of 4 electrospinning nozzles on the bracket.
  • the spacing between adjacent electrospinning nozzles on the bracket is 15cm, and the electrospinning nozzles of the two rows of nozzles are 40cm apart.
  • the plane between the bracket and the fixed rod is at an angle of 30°. 5 ⁇
  • the electro-spinning nozzles of the two rows of nozzles are respectively applied to the opposite polarity of the DC high voltage ⁇ 20kV, the inner diameter of the electrospinning nozzle is 0. 5 ⁇ .
  • the speed of the godet to draw the filament bundle was 8 cm/ s .
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a single-walled carbon nanotube-reinforced PC/PPES two-component composite nanofiber filament bundle is collected.
  • Hyaluronic acid (molecular weight 100,000) lg is dissolved in 100ml of water, and 10mg of bone morphogenetic protein is dispersed therein to form solution No. 1, poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10g dissolved in 50ml of acetone and 50mlN , N-dimethylformamide in a mixed solvent to prepare a solution No. 2, fully dissolved and then transport these high polymer solutions to the two rows of a total of six electrospinning nozzles on the stent (3 electrospinning nozzles per column) , the same column delivers the same polymer solution).
  • PLLA viscosity average molecular weight 100,000
  • the spacing between adjacent electrospinning nozzles in each column of the stent is 10 cm, and the electrospinning nozzles of the two rows of nozzles are 30 cm apart.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°).
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC high voltage of opposite polarity of ⁇ 20 kV, and the inner diameter of the electrospinning nozzle is 0.8.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward to collect a two-component composite nanofiber filament bundle.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 20 g dissolved in 100 ml of acetone and 50 ml of N, N-dimethyl In a mixed solvent of carbamide, 1 g of tricalcium phosphate having a particle diameter of 300 nm was dispersed therein, and a solution was prepared, and the solution was separately supplied to two rows of electrospinning nozzles in two rows (two electrospinning nozzles per column). ).
  • the spacing between adjacent electrospinning nozzles in each row of the bracket is 15 cm, and the electrospinning nozzles of the two rows of nozzles are 40 cm apart.
  • the plane of the bracket is parallel to the fixed rod (at an angle of 0°).
  • the electro-spinning nozzles of the two pairs of nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 50kV, the inner diameter of the electrospinning nozzle is 1. 2 let.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA composite nanofiber filament bundle containing tricalcium phosphate is collected.
  • Two rows of 50 electrospinning nozzles are arranged on the electrospinning support, and poly-L-lactic acid PLLA (viscosity average molecular weight: 150,000) 100g is dissolved in 500ml of acetone and 500ml of N, dimethylformamide. In the solvent, after fully dissolving, the solution is delivered to 25 electrospinning nozzles on one side of the stent. 10 g of hyaluronic acid (molecular weight 1 million) is dissolved in 1000 ml of water, fully dissolved and the solution is delivered to the other side of the stent.
  • poly-L-lactic acid PLLA viscosity average molecular weight: 150,000
  • the distance between adjacent electrospinning nozzles in the same row in the bracket is 2cm, and the electrospinning nozzles of the two rows of nozzles are 40cm apart.
  • the plane of the bracket is parallel to the fixed rod.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with DC high voltage of opposite polarity ⁇ 120 kV, and the inner diameter of the electrospinning nozzle is 1. 2 mm.
  • the godet roller has a speed of 10 cm/s for pulling the filament bundle.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a composite nanofiber filament bundle is collected, and the tow diameter is about 200 ⁇ m.
  • Two rows of 20 electrospinning nozzles (10 in each column) are arranged on the electrospinning support, poly-L-lactic acid PLLA (viscosity average molecular weight 150,000) 50g is dissolved in 250ml acetone and 250ml N, N-dimethylformamide is mixed. In the solvent, after fully dissolving, the solution was delivered to 20 electrospinning nozzles on both sides of the stent. The distance between the adjacent electrospinning nozzles in the same row in the stent was 8 cm, and the electrospinning nozzles of the two rows of nozzles were 40 cm apart. The plane of the bracket is parallel to the fixed rod.
  • the electrospinning nozzles of the two rows of nozzles were respectively applied with a DC high voltage earth of opposite polarity of 80 kV, and the inner diameter of the electrospinning nozzle was 1. 2 mm.
  • the speed of the godet to draw the filament bundle was 5 cm/s.
  • the electrospinning nozzle The nanofibers ejected from the top end are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a bundle of polylactic acid composite nanofiber filaments is collected, and the tow has a diameter of about 100 ⁇ m.
  • Two rows of four electrospinning nozzles are arranged on the electrospinning support, poly-L-lactic acid PLLA (viscosity average molecular weight: 150,000), 10 g of a mixture of 50 ml of acetone and 50 ml of N,N-dimethylformamide In the solvent, after fully dissolving, the solution was delivered to the two electrospinning nozzles on one side of the stent, collagen 1. 5 g dissolved in 30 ml In hexafluoroisopropanol, after fully dissolving, the solution is delivered to the two electrospinning nozzles on the other side of the stent.
  • the distance between the adjacent electrospinning nozzles in the same column is 10 cm, and the two rows of nozzles are electrospun.
  • the nozzles are 30 cm apart.
  • the plane of the bracket is parallel to the fixed rod. 2 ⁇
  • the electro-spinning nozzles of the two pairs of nozzles are respectively applied to the opposite polarity of the DC high voltage ⁇ 30kV, the inner diameter of the electrospinning nozzle is 1. 2mm.
  • the speed of the godet to draw the filament bundle was 3 cm/s.
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by a pair of godet rolls to form a filament bundle and are led forward, and a PLLA/collagen composite nanofiber filament bundle is collected.
  • Two rows of four electrospinning nozzles are arranged on the electrospinning support, and the polyvinylidene fluoride PVDFlOg is dissolved in a mixed solvent of 50 ml of acetone and 50 ml of N,N-dimethylformamide, and the solution is fully dissolved.
  • feeding the spinning head of a bracket in the same column of the distance between adjacent nozzles is electrospun 15 C m, two opposing orifices electrospinning nozzle distance 40cm, the plane of the fixed rod holder angle of 30 degrees.
  • the electro-spinning nozzles of the two pairs of nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 30kV, the inner diameter of the electrospinning nozzle is 1. 2mm.
  • the speed of the godet to the filament bundle is 3 C m/ s .
  • the nanofibers ejected from the tip of the electrospinning nozzle are drawn by the pair of godet rolls to form a filament bundle and are led forward, and the PVDF composite nanofiber filament bundle is collected.
  • Two rows of four electrospinning nozzles (two in each column) are arranged on the electrospinning support, and the polyvinylidene fluoride PVDFlOg is dissolved in a mixed solvent of 50 ml of acetone and 50 ml of N,N-dimethylformamide, and the solution is fully dissolved.
  • the distance between adjacent electrospinning nozzles is 10 cm, and the electrospinning nozzles of the two rows of nozzles are 30 cm apart.
  • the plane of the bracket is parallel to the fixed rod.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC high voltage earth of opposite polarity of 20 kV, and the inner diameter of the electrospinning nozzle is 1. 2 mm.
  • the speed of the godet to draw the filament bundle was 3 cm/s.
  • the electrospinning nozzle The nanofibers ejected from the top end are drawn by a pair of godet rolls to form a filament bundle and are led forward, and the PLLA/PU composite nanofiber filament bundle is collected.
  • Two rows of four electrospinning nozzles are arranged on the electrospinning support, poly-L-lactic acid PLLA (viscosity average molecular weight: 150,000), 10 g of a mixture of 50 ml of acetone and 50 ml of N, dimethylformamide In the solvent, after fully dissolving, the solution is transferred to two electrospinning nozzles on one side of the stent.
  • Polyvinylpyrrolidone PVP K60 product of BASF 10 g is dissolved in 50 ml of acetone, fully dissolved and the solution is transferred to the other on the stent.
  • Poly-L-lactic acid PLLA (viscosity average molecular weight 100,000) 10 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent solution No. 1, lactide-glycolide copolymer PLGA (where Mass composition lactide 50 ° /., glycolide 50%, viscosity average molecular weight 100,000) 15 g dissolved in 50 ml of acetone and 50 ml of N, dimethylformamide in a mixed solvent to prepare solution No. 2, hyaluronic acid (Molecular weight: 100,000) lg dissolved in 100ml of water to form No. 3, chitosan 0. 3g dissolved in lOOmlO.
  • the electrospinning nozzles of the two rows of nozzles are respectively applied with a DC high voltage of opposite polarity ⁇ 15kv, and the inner diameter of the electrospinning nozzle is 0.8 ⁇ . 1.
  • No. 2 sprayed nanofibers attract each other, gather and pull down to obtain a filament bundle, and serve as a carrier for electrospray particle deposition of No. 3 and No. 4 solutions, and a filament bundle with electrospray particles attached to the surface is drawn downward.
  • the nanofibers ejected from the solution No. 6 are continuously deposited on the filament bundles on which the electrospray particles are attached, and the nanofiber filament bundles are drawn by the pair of godet rolls to form a bundle of complex component composite nanofiber filaments.

Description

复合纳米纤维长丝束制备装置及其制备方法 技术领域
本发明涉及一种复合纳米纤维长丝束制备方法，属于特种纤维制备的技术领 域。 背景技术
随着社会的发展和人们生活水平的提高，纤维工业也面临着巨大的挑战，单 一纤维已经不能满足人们对多种功能的要求了， 于是开始出现皮芯型、 夹心型、 并列型、 海岛型和其他各种类型的复合纤维。 美国专利 （US 4， 717， 325 )设计了 一个复合纤维纺丝板，将熔融组分聚合物从挤出机中引出，经过复合纤维纺丝板 的纺丝孔得到多层复合纤维。
静电纺丝是通过在聚合物溶液中施加外电场来制造聚合物纳米纤维的一种 有效方法， 近年来受到格外重视。利用电紡纳米纤维的低密度、高孔隙率和大的 比表面积， 不仅可以制作高效过滤材料， 而且在生物医学材料、化学传感器、 防 护材料、 纳米复合材料等领域有广泛应用前景。
电纺纳米纤维的尺寸在纳米或亚微米级，在电纺过程中由于纤维带有同种电 荷相互排斥，纤维无规分布得到纳米纤维无纺布。并且常常存在纤维散失的情况， 所以不可避免地会出现不稳定的情况。
电纺制备取向纳米纤维长丝束是一个挑战。将电纺喷头喷出的纳米纤维用高 速旋转的转鼓接受可以获得少量取向的纳米纤维长丝束。有人将电纺喷头喷出的 纳米纤维沉积在水面上， 通过向水下牵引、抽出， 并卷绕得到取向长丝束。还有 人将电纺喷头喷出的纳米纤维沉积在不锈钢转鼓上， 通过聚集、牵引， 并卷绕得 到取向长丝束。
因此， 有必要发明一种更有效地制备复合纳米纤维长丝的方法。 发明内容
技术问题：本发明的目的是提供一种复合纳米纤维长丝束制备装置及其制备 方法， 该装置和方法能简单、 高效的生产复合纳米纤维长丝束。 技术方案：本发明的复合纳米纤维长丝束制备装置，其特征在于该装置由若 干对纺丝喷头对、 导丝辊对、支架、 固定杆、底座组成， 两列喷口相向的多对电 纺喷头对固定在支架上， 每对电纺喷头喷口可以在同一水平面或不同水平面上， 支架通过垂直底座的固定杆与底座相连，导丝辊对在支架下方的中间，支架所在 平面与固定杆之间成锐角。 支架同一列电纺喷头之间间距为 2- 50cm; 两列喷口 相向的电纺喷头对的两个喷头之间相距 10- 100cm。 支架所在平面与固定杆之间 所成的角度为 0-90°。
本发明的复合纳米纤维长丝束制备方法具体制备的步骤如下：
1 )将料液输送给支架上的电纺喷头对；
2) 喷口相向的电纺喷头对的每个喷头分别施加相反极性的直流高电压；
3)每对相向喷口喷出分别带相反电荷的纳米纤维， 并在空中相互吸引、 碰撞形成复合纳米纤维， 或沉积在在电纺喷头对的两个喷头之间沿支 架平面向下方牵引的作为接受体的高分子纤维长丝上， 经牵引、 拉伸 后形成复合纳米纤维长丝束；
4)第一对相向放置的电纺喷头纺丝形成的复合纳米纤维长丝束向下拉 伸， 并作为接受体与第二对电纺喷头喷出的分别带相反电荷并相互吸 引的纳米纤维在空中相遇， 被第二对电纺喷头喷出的纳米纤维包裹， 经牵引、 拉伸后形成两层复合纳米纤维长丝束；
5)依次类推， 上层形成的长丝束向下拉伸并作为接受体与下层电纺喷头 对纺丝形成的纳米纤维在空中相遇， 被下层电纺喷头对喷出的纳米纤 维包裹， 经牵引、 拉伸后形成复合纳米纤维长丝束， 最后经导丝辊对 牵引、 拉伸后得到多层复合纳米纤维长丝束。 - 对两列喷口相向的电纺喷头分别施加相反极性的直流髙电压 3KV-200KVo 料液是高分子溶液或含添加剂的高分子溶液或高分子与无机粒子的混合物体系。 高分子是聚烯烃、 聚卤代烯烃、聚硅氧垸、 聚醚、 聚酰胺、 聚酯、 聚碳酸酯、 聚 氨酯、环氧树脂、聚丙烯腈、聚丙烯酸类高分子、聚丙烯酸酯、聚苯醚、聚酸酐、 聚- α -氨基酸、聚苯硫醚， 或是其中两种或多种的共混物； 或是纤维素、纤维素 衍生物、葡聚糖、丝蛋白、壳聚糖、壳聚糖衍生物、透明质酸、透明质酸衍生物、 胶原、角叉胶、藻酸钠、藻酸钙、硫酸软骨素、 明胶、琼脂、葡聚糖、纤维蛋白、 纤维蛋白原、角质蛋白、酪蛋白、白蛋白、弹性蛋白中的一种或是它们的衍生物、 或是其中两种或多种的共混物;或是生物可吸收合成高分子聚- L-乳酸、聚 _(D, L) -乳酸、 聚羟基乙酸、 聚己内酯、 聚丁内酯、 聚戊内酯、 聚酯二氧杂环己烷、 聚 酸酐、聚 - a -氨基酸中的一种或者是至少以下两种单体的共聚物： L-乳酸、 D, L - 乳酸、羟基乙酸、 3-羟基丁酸、 3-羟基戊酸、 己内酯、丁内酯、戊内酯、氨基酸， 或是其中两种或多种的共混物。 无机粒子是纳米抗菌剂、 催化剂、 纳米碳管。
添加剂是抗生素、 免疫抑制剂、 抗菌剂、 激素、 维生素、 氨基酸、 多肽、 蛋 白质、 酶、 生长因子、 抗菌药物、 麻醉药物、 止血药物、 激素、 镇痛药物、 降压 药物、 抗肿瘤药物。
有益效果：
本发明与现有技术相比， 具有如下优点：
( 1 ) 本发明一种复合纳米纤维长丝束制备方法， 在喷口相对的电纺喷头 上分别施加相反极性直流高电压， 电纺喷头产生的带相反电荷的纳 米纤维在空中相互吸引、聚集、碰撞， 使纳米纤维所带的电荷消散， 有效地避免了纳米纤维在空中的飞散和损失， 提高了生产效率， 并 且可以不使用接地线的金属接受器。
(2) 本发明可以通过调节支架平面与地面的角度来避免了各种扰动引起 的不稳定喷射， 又方便操作， 大大提高生产效率。
(3) 本发明可以操作简单、 高效地制备出复合纳米纤维长丝束。
(4) 本发明向喷口相对的电纺喷头输不同的髙聚物溶液， 或是含添加剂 的高分子溶液， 可以高效地制备出多组分复合纳米纤维长丝束。
(5) 采用多对电纺喷头对制备的复合纳米纤维长丝束具有纤维组成、 纳 米结构可以控制， 丝束粗， 力学性能好的特点。
(6) 在电纺喷头对的两个喷头之间沿支架平面向下方牵引的作为接受体 的高分子纤维长丝上沉积带相反电荷的纳米纤维长丝束， 纳米纤维 无飞散， 可以进一步提高长丝束的力学性能， 形成表层是纳米纤维 层、 芯层是普通高分子纤维。
(7) 本发明将电纺制备纳米纤维长丝束与电喷雾制备纳米粒子结合起 来， 可以制得含有电喷雾纳米粒子的复合纳米纤维长丝束。
(8) 本发明的复合纳米纤维长丝束可以用于组织工程支架， 纺织品等。 附图说明
图 1为本发明的总体结构示意图。
图 2为本发明的工作原理图。
以上的图中有： 电纺喷头对 1、 导丝辊对 2、 支架 3、 固定杆 4、 底座 5。 图 3为本发明 PLLA (聚 -1-乳酸）纳米纤维长丝束的表观照片。
图 4为本发明 PLLA (聚- 1-乳酸） 复合纳米纤维长丝束的表观照片。
图 5为本发明 PLLA (聚- 1-乳酸）复合纳米纤维长丝束扫描电子显微镜图片。 图 6为本发明 PU/PVDF (聚氨酯 /聚偏氟乙烯） 复合纳米纤维长丝束扫描电 子显微镜图片。
图 7为本发明 PAN (聚丙烯腈） 复合纳米纤维长丝束扫描电子显微镜图片。 图 8为本发明 PVDF (聚偏氟乙烯）复合纳米纤维长丝束扫描电子显微镜图片。 具体实施方式
复合纳米纤维长丝束制备装置由若干对纺丝喷头对 1、 导丝辊对 2、支架 3、 固定杆 4、 底座 5组成， 两列喷口相向的多对电纺喷头对 1固定在支架 3上， 每 对电纺喷头喷口可以在同一水平面或不同水平面上，支架 3通过垂直底座的固定 杆 4与底座 5相连，导丝辊对 2在支架 3下方的中间，支架 3所在平面与固定杆 4之间成锐角。
具体制备的步骤如下：
1 )将料液输送给支架 3上的电纺喷头对 1
2 ) 喷口相向的电纺喷头对 1的每个喷头分别施加相反极性的直流高电压；
3 ) 每对相向喷口喷出分别带相反电荷的纳米纤维， 并在空中相互吸引、 碰 撞形成复合纳米纤维， 经牵引、 拉伸后形成复合纳米纤维长丝束；
4)第一对相向放置的电纺喷头纺丝形成的复合纳米纤维长丝束向下拉伸， 并作为接受体与第二对电纺喷头喷出的分别带相反电荷并相互吸引的纳 米纤维在空中相遇， 被第二对电纺喷头喷出的纳米纤维包裹， 经牵引、 拉伸后形成两层复合纳米纤维长丝束；
5 ) 依次类推， 上层形成的长丝束向下拉伸并作为接受体与下层电纺喷头对 纺丝形成的纳米纤维在空中相遇， 被下层电紡喷头对喷出的纳米纤维包 裹， 经牵引、 拉伸后形成复合纳米纤维长丝束， 最后经导丝辊对 2牵引、 拉伸后得到多层复合纳米纤维长丝束。
复合纳米纤维长丝束制备方法的具体步骤或者是： 1 )将料液输送给支架 3 上的电紡喷头对 1 ; 2) 喷口相向的电纺喷头对 1的每个喷头分别施加相反极性 的直流高电压； 3)每对相向喷口喷出分别带相反电荷的纳米纤维， 并在空中相 互吸引并沉积在在电纺喷头对 1 的两个喷头之间沿支架平面向下方牵引的作为 接受体的高分子纤维长丝上， 经牵引、 拉伸后形成复合纳米纤维长丝束。
支架 3同一列电纺喷头 1之间间距为 2- 50cm;两列喷口相向的电纺喷头对 1 的两个喷头之间相距 10-100cm。 支架 3所在平面与固定杆 4之间所成的角度为 0-90° 。 两列喷口相向的电紡喷头对 1 分别施加相反极性的直流髙电压 料液是高分子溶液或含添加剂的高分子溶液或髙分子与无机粒子的混合物 体系。 高分子是聚烯烃、 聚卤代烯烃、 聚硅氧烷、 聚醚、 聚酰胺、 聚酯、 聚碳酸 酯、 聚氨酯、 环氧树脂、 聚丙烯腈、 聚丙烯酸类高分子、 聚丙烯酸酯、 聚苯醚、 聚酸酐、聚 - a -氨基酸、聚苯硫醚，或是其中两种或多种的共混物；或是纤维素、 纤维素衍生物、 葡聚糖、丝蛋白、 壳聚糖、 壳聚糖衍生物、透明质酸、 透明质酸 衍生物、 胶原、 角叉胶、 藻酸钠、 藻酸钙、 硫酸软骨素、 明胶、 琼脂、 葡聚糖、 纤维蛋白、 纤维蛋白原、角质蛋白、 酪蛋白、 白蛋白、 弹性蛋白中的一种或是它 们的衍生物、 或是其中两种或多种的共混物； 或是生物可吸收合成高分子聚 -L - 乳酸、 聚-（D，L) -乳酸、 聚羟基乙酸、 聚己内酯、 聚丁内酯、 聚戊内酯、 聚酯 二氧杂环己烷、聚酸酐、聚- α -氨基酸中的一种或者是至少以下两种单体的共聚 物： L-乳酸、 D, L-乳酸、羟基乙酸、 3-羟基丁酸、 3-羟基戊酸、 己内酯、丁内酯、 戊内酯、 氨基酸， 或是其中两种或多种的共混物。 无机纳米材料是纳米抗菌剂、 催化剂、 纳米碳管。 添加剂是抗生素、 免疫抑制剂、 抗菌剂、 激素、 维生素、 氨 基酸、 多肽、 蛋白质、 酶、 生长因子、 抗菌药物、 麻醉药物、 止血药物、 激素、 镇痛药物、 降压药物、 抗肿瘤药物。
本发明的复合纳米纤维长丝束可以用于再生医学、 纺织品等许多领域。 实施例 1
聚- L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50ralN， N-二甲 基甲酰胺的混合溶剂中配成溶液 1号， 丙交酯-乙交酯共聚物 PLGA (其中质量组 基甲酰胺的混合溶剂中配成溶液 1号， 丙交酯-乙交酯共聚物 PLGA (其中质量组 成丙交酯 50%， 乙交酯 50%, 粘均分子量 10万） 15g溶于 50ml丙酮和 50mlN， N- 二甲基甲酰胺的混合溶剂中配成溶液 2号， 将 1号溶液输送给支架上同一列 3 个电纺喷头，将 2号溶液输送给支架上另一列 3个电纺喷头，支架上同一列相邻 电纺喷头之间的间距为 15ctn， 两列喷口相向的电纺喷头相距 40cm。 支架所在平 面与固定杆之间成 90° 角。 对两列喷口相向的电纺喷头分别施加相反极性的直 流高电压 ±20kV， 电纺喷头内径为 0. 5誦。导丝辊对牵引长丝束的速度为 8cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集 得到 PLLA/PLGA双组分三层复合纳米纤维长丝束。
实施例 2
聚 -L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲 基甲酰胺的混合溶剂中配成溶液 1号， 聚己内酯 PCL (分子量 9万） 10g溶于 100mlN， N-二甲基甲酰胺中配成溶液 2号， 将 1号溶液输送给支架上同一列 4 个电纺喷头，将 2号溶液输送给支架上另一列 4个电纺喷头，支架上同一列相邻 电纺喷头之间的间距为 15cm， 两列喷口相向的电纺喷头相距 40cm。 支架所在平 面与固定杆之间成 90° 角。 对两列喷口相向的电钫喷头分别施加相反极性的直 流高电压 ±20kV， 电纺喷头内径为 0. 5匪。导丝辊对牵引长丝束的速度为 8cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集 得到 PLLA/PCL双组分三层复合纳米纤维长丝束。
实施例 3
聚- L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲 基甲酰胺的混合溶剂中配成溶液 1号， 玉米蛋白 ZEIN (分子量 3. 5万） 35g溶于 100ml乙醇水溶液中（乙醇 /水体积比为 80/20)配成溶液 2号， 将 1号溶液输送 给支架上同一列 3个电纺喷头， 电纺喷头内径为 0. 8mm， 将 2号溶液输送给支架 上另一列 3个电纺喷头， 电纺喷头内径为 1. 2隱， 支架上同一列相邻电纺喷头之 间的间距为 15cm， 两列喷口相向的电纺喷头相距 40cm。 支架所在平面与固定杆 之间成 90° 角。 对两列喷口相向的电纺喷头分别施加相反极性的直流高电压士 25kV。 导丝辊对牵引长丝束的速度为 8cm/s。 电纺喷头顶端喷射出的纳米纤维经 导丝辊对牵引后形成长丝束并向前导出，收集得到 PLLA/ZEIN双组分三层复合纳 米纤维长丝束。 实施例 4
聚丙烯腈 PAN (平均分子量 13万） 10g溶于 100mlN， N-二甲基甲酰胺中配 成溶液 1号， 聚苯醚砜 PPES (熔融指数 3. 9克 /10分钟, 320 °C ) 10g溶于 100ml 二甲亚砜中配成溶液 2号， 将 1号溶液输送给支架上同一列 4个电纺喷头， 将 2 号溶液输送给支架上另一列 4个电纺喷头，支架上同一列相邻电纺喷头之间的间 距为 15cm， 两列喷口相向的电纺喷头相距 40cm。 支架所在平面与固定杆之间成 90° 角。对两列喷口相向的电纺喷头分别施加相反极性的直流高电压 ±20kV， 电 纺喷头内径为 0. 5mm。 导丝辊对牵引长丝束的速度为 8cm/s。 电纺喷头顶端喷射 出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出， 收集得到 PAN/PPES双 组分三层复合纳米纤维长丝束。
实施例 5
聚- L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲 基甲酰胺的混合溶剂中配成溶液 1号， 丙交酯-乙交酯共聚物 PLGA (其中质量组 成丙交酯 50%， 乙交酯 50°/。， 粘均分子量 10万） 15g溶于 50ml丙酮和 50mlN， N - 二甲基甲酰胺的混合溶剂中配成溶液 2号， 聚氨酯 PU15g溶于 lOOmlN, N-二甲 基甲酰胺中配成溶液 3号， 聚己内酯 PCL (分子量 9万） 10g溶于 lOOmlN, N-二 甲基甲酰胺中配成溶液 4号，充分溶解后将这些高聚物溶液分别输送给支架上的 两列共 4个不同的电纺喷头 （每列 2个电纺喷头）。 支架中各列中相邻电纺喷头 之间的间距为 15cm, 两列喷口相向的电纺喷头相距 40cm。 支架所在平面与固定 杆之间平行。 对两列喷口相向的电纺喷头分别施加相反极性的直流高电压士 20kv， 电纺喷头内径为 0. 8mm。 导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头 顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集得到四组 分复合纳米纤维长丝束。
实施例 6
透明质酸（分子量 10万） lg溶于 100ml水中配成溶液 1号， 壳聚糖 0. 5g 溶于 lOOmlO. 1M的稀醋酸中配成溶液 2号， 聚- L -乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲基甲酰胺的混合溶剂中成溶液 3号，丙交酯 -乙交酯共聚物 PLGA (其中质量组成丙交酯 50%， 乙交酯 50%，粘均分子量 10万） 15g溶于 50ml丙酮和 50ralN， N-二甲基甲酰胺的混合溶剂中成溶液 4号，聚氨酯 PU15g溶于 lOOmlN, N-二甲基甲酰胺中配成溶液 5号， 聚己内酯 PCL (分子量 9 万） lOg溶于 100mlN， N-二甲基甲酰胺中配成溶液 6号， 充分溶解后将这些高聚 物溶液分别输送给支架上的两列共 6个不同的电纺喷头 （每列 3个电纺喷头）。 支架中各列中相邻电纺喷头之间的间距为 10cm， 两列喷口相向的电纺喷头相距 30cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对两列喷口相向的电纺喷 头分别施加相反极性的直流高电压土 20kv， 电纺喷头内径为 0. 8ram。 导丝辊对牵 引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形 成长丝束并向前导出， 收集得到六组分复合纳米纤维长丝束。
实施例 7
透明质酸（分子量 10万） lg溶于 100ml水中配成溶液 1号，聚- L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲基甲酰胺的混合溶剂 中配成溶液 2 号， 充分溶解后将这些高聚物溶液分别输送给支架上的两列共 6 个的电纺喷头 （每列 3个电纺喷头， 同一列输送相同聚合物溶液）。 支架中各列 中相邻电纺喷头之间的间距为 10cm， 两列喷口相向的电纺喷头相距 30cm。 支架 所在平面与固定杆之间平行 （成 0° 角）。 对两列喷口相向的电纺喷头分别施加 相反极性的直流高电压 ±20kv， 电纺喷头内径为 0. 8匪。 导丝辊对牵引长丝束的 速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并 向前导出， 收集得到双组分复合纳米纤维长丝束。 ' 实施例 8
.透明质酸（分子量 10万） lg和布洛芬 0. 2克溶于 100ml水中配成溶液 1号， 聚 -L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲基甲 酰胺的混合溶剂中配成溶液 2号，充分溶解后将这些高聚物溶液分别输送给支架 上的两列共 6个的电纺喷头（每列 3个电纺喷头， 同一列输送相同聚合物溶液)。 支架中各列中相邻电纺喷头之间的间距为 lOcm, 两列喷口相向的电纺喷头相距 30cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对两列喷口相向的电纺喷 头分别施加相反极性的直流高电压 ±20kv， 电紡喷头内径为 0. 8mm。 导丝辊对牵 引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形 成长丝束并向前导出， 收集得到含布洛芬的双组分复合纳米纤维长丝束。
实施例 9
聚丙烯腈 PANlOg溶于 lOOmlN, N-二甲基甲酰胺中配成溶液 1号， 聚氨酯 PU15g溶于 lOOmlN, N-二甲基甲酰胺中配成溶液 2号，充分溶解后将这些高聚物 溶液分别输送给支架上的两列共 6个的电纺喷头（每列 3个电纺喷头， 同一列输 送相同聚合物溶液）。支架中各列中相邻电纺喷头之间的间距为 10cm, 两列喷口 相向的电纺喷头相距 30cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对两 列喷口相向的电纺喷头分别施加相反极性的直流高电压 ±20kv，电纺喷头内径为 0. 8匪。 导丝辊对牵引长丝束的速度为 5cm/s。 电紡喷头顶端喷射出的纳米纤维 相互吸引，并沉积在位于支架中间向下牵引的聚酯长丝上， 由导丝辊对牵引后芯 层是聚酯长丝， 皮层是 PAN/PU复合纳米纤维的纳米纤维长丝束。
实施例 10
聚氨酯 PU15g溶于 100mlN， N-二甲基甲酰胺中配成溶液 1 号， 聚己内酯 PCLlOg溶于 lOOmlN, N-二甲基甲酰胺中配成溶液 2号， 将溶液 1、 2分别输送两 列共 8个电纺喷头 （每列 4个电纺喷头， 同一列输送相同聚合物溶液）， 支架中 各列电纺喷头的间距为 10cm， 两列喷口相对的电纺喷头相距 30cm。 支架所在平 面与固定杆之间成 45° 角。 对两列喷口相对的电纺喷头分别施加相反极性的直 流高电压 ± 15kv， 电纺喷头内径为 1. 2mm。导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集 得到多层复合纳米纤维长丝束。
实施例 11
聚- L-乳酸 PLLA (粘均分子量 10万） 20g溶于 100ml丙酮和 50mlN， N-二甲 基甲酰胺的混合溶剂中配成溶液，将溶液分别输送给支架上两列共 4个电纺喷头 (每列 2个电纺喷头）。支架中各列中相邻电纺喷头之间的间距为 15cm, 两列喷 口相向的电纺喷头相距 40cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对 两列喷口相向的电纺喷头分别施加相反极性的直流高电压 ±20kv，电纺喷头内径 为 1. 2mm。 导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤 维经导丝辊对牵引后形成长丝束并向前导出， 收集得到 PLLA单组分复合纳米纤 维长丝束。
实施例 12
电纺支架上相向排列两列 4个电纺喷头（每列两个），聚己内酯 PCLlOg溶于 lOOralN, N-二甲基甲酰胺中， 将溶液输送给支架上第一对电纺喷头， 丙交酯 -乙 交酯共聚物 PLGA (其中质量组成丙交酯 50%， 乙交酯 50%， 粘均分子量 10万） 15g溶于 50ml丙酮及 50mlN， N-二甲基甲酰胺的混合溶剂中， 再加入 0. 3g布洛 芬，充分溶解后将溶液输送给支架上第二对电紡喷头，支架中各列中两个电纺喷 头的间距为 15cm， 两列喷口相对的电纺喷头相距 30cm。 支架所在平面与固定杆 之间平行 （成 0° 角）。 对两列喷口相对的电纺喷头分别施加相反极性的直流高 电压 ± 10kv， 电纺喷头内径为 0. 8mm。 导丝辊对牵引长丝束的速度为 5cm/s。 电 纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集得 到 PCL/PLGA双层复合纳米纤维长丝束。
实施例 13
电纺支架上相向排列两列 20个电纺喷头（每列 10个），聚- L-乳酸 PLLA (粘 均分子量 15万） 50g溶于 250ml丙酮及 250ralN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输送给支架上的一侧的 10个电纺喷头，透明质酸（分子量 100 万） 5g溶于 500ml水中， 充分溶解后将溶液输送给支架上的另一侧的 10个电纺 喷头，支架中各列电纺喷头的间距为 10cm，两列喷口相对的电纺喷头相距 30cm。 支架所在平面与固定杆之间成 30° 角。 对两列喷口相对的电纺喷头分别施加相 反极性的直流高电压 ±50kv， 电纺喷头内径为 0. 8誦。 导丝辊对牵引长丝束的速 度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向 前导出， 收集得到复合纳米纤维长丝束， 丝束直径约 150微米。
实施例 14
电纺支架上相向排列两列 6个电紡喷头 （每列 3个）， 壳聚糖 0. 5g溶于 lOOmlO. 1M稀醋酸中， 充分溶解后将溶液输送给支架上的一列的 3个电纺喷头， 聚己内酯 PCLlOg溶于 lOOmlN, N-二甲基甲酰胺中， 充分溶解后将溶液输送给支 架上的另一列的 3个电纺喷头， 支架中各列电纺喷头的间距为 10cm， 两列喷口 相对的电纺喷头相距 20cm。 支架所在平面与固定杆之间成 30° 角。 对两列喷口 相对的电纺喷头分别施加相反极性的直流高电压 ± 20kv， 电纺喷头内径为 0. 6醒。 导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维 经导丝辊对牵引后形成长丝束并向前导出， 收集得到双组分复合纳米纤维长丝 束。
实施例 15
聚碳酸酯 PC (平均分子量 10万） 10g溶于 lOOmlN, N-二甲基甲酰胺中配成 溶液 1号， 聚苯醚砜 PPES (熔融指数 3. 9克 /10分钟， 320°C ) 10g溶于 100ml 二甲亚砜中配成溶液 2号， 将 1号溶液输送给支架上同一列 4个电纺喷头， 将 2 号溶液输送给支架上另一列 4个电纺喷头，支架上同一列相邻电纺喷头之间的间 距为 15cm， 两列喷口相向的电纺喷头相距 40cm。 支架所在平面与固定杆之间成 90° 角。对两列喷口相向的电紡喷头分别施加相反极性的直流高电压 ±20kV， 电 纺喷头内径为 0. 5mm。 导丝辊对牵引长丝束的速度为 8cm/S。 电纺喷头顶端喷射 出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集得到 PC/PPES双组 分三层复合纳米纤维长丝束。
实施例 16
聚丙烯腈 PAN (平均分子量 13万） 10g溶于 lOOmlN, N-二甲基甲酰胺中， 并将 0. 1克单壁碳纳米管分散在其中， 配成溶液 1号， 聚苯醚砜 PPES (熔融指 数 3. 9克 /10分钟， 320°C ) 10g溶于 100ml二甲亚砜中配成溶液 2号， 将 1号溶 液输送给支架上同一列 4个电纺喷头，将 2号溶液输送给支架上另一列 4个电纺 喷头， 支架上同一列相邻电纺喷头之间的间距为 15cm， 两列喷口相向的电纺喷 头相距 40cm。 支架所在平面与固定杆之间成 30° 角。 对两列喷口相向的电纺喷 头分别施加相反极性的直流高电压 ±20kV， 电纺喷头内径为 0. 5匪。 导丝辊对牵 引长丝束的速度为 8cm/S。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形 成长丝束并向前导出，收集得到单壁碳纳米管增强的 PC/PPES双组分复合纳米纤 维长丝束。
实施例 17
透明质酸（分子量 10万） lg溶于 100ml水中，并将骨形成蛋白 10毫克分散 其中，配成溶液 1号， 聚- L-乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN， N-二甲基甲酰胺的混合溶剂中配成溶液 2号， 充分溶解后将这些高聚物 溶液分别输送给支架上的两列共 6个的电纺喷头（每列 3个电纺喷头， 同一列输 送相同聚合物溶液）。支架中各列中相邻电纺喷头之间的间距为 10cm， 两列喷口 相向的电纺喷头相距 30cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对两 列喷口相向的电纺喷头分别施加相反极性的直流高电压 ±20kv，电纺喷头内径为 0. 8画。 导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维 经导丝辊对牵引后形成长丝束并向前导出， 收集得到双组分复合纳米纤维长丝 束。
实施例 18
聚 -L-乳酸 PLLA (粘均分子量 10万） 20g溶于 100ml丙酮和 50mlN， N-二甲 基甲酰胺的混合溶剂中，并将粒子直径 300纳米的磷酸三钙 1克分散其中，配成溶 液， 将溶液分别输送给支架上两列共 4个电纺喷头 （每列 2个电纺喷头）。 支架 中各列中相邻电纺喷头之间的间距为 15cm，两列喷口相向的电纺喷头相距 40cm。 支架所在平面与固定杆之间平行 （成 0° 角）。 对两列喷口相向的电纺喷头分别 施加相反极性的直流高电压 ±50kV， 电纺喷头内径为 1. 2讓。 导丝辊对牵引长丝 束的速度为 5cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝 束并向前导出， 收集得到含磷酸三钙的 PLLA复合纳米纤维长丝束。
实施例 19
电纺支架上相向排列两列 50个电纺喷头（每列 25个），聚- L-乳酸 PLLA (粘 均分子量 15万） 100g溶于 500ml丙酮及 500mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输送给支架上的一侧的 25个电纺喷头，透明质酸（分子量 100 万） 10g溶于 1000ml水中， 充分溶解后将溶液输送给支架上的另一侧的 25个电 纺喷头， 支架中同一列相邻电纺喷头之间的距离为 2cm， 两列喷口相对的电纺喷 头相距 40cm。 支架所在平面与固定杆平行。 对两列喷口相对的电紡喷头分别施 加相反极性的直流高电压 ± 120kV， 电纺喷头内径为 1. 2mm。 导丝辊对牵引长丝 束的速度为 10cm/s。 电紡喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长 丝束并向前导出， 收集得到复合纳米纤维长丝束， 丝束直径约 200微米。
实施例 20
电纺支架上相向排列两列 20个电纺喷头（每列 10个），聚- L-乳酸 PLLA (粘 均分子量 15万） 50g溶于 250ml丙酮及 250mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输送给支架上的两侧的 20个电纺喷头， 支架中同一列相邻电 纺喷头之间的距离为 8cm，两列喷口相对的电纺喷头相距 40cm。支架所在平面与 固定杆平行。 对两列喷口相对的电紡喷头分别施加相反极性的直流高电压土 80kV, 电纺喷头内径为 1. 2mm。 导丝辊对牵引长丝束的速度为 5cm/s。 电纺喷头 顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集得到聚乳 酸复合纳米纤维长丝束， 丝束直径约 100微米。
实施例 21
电纺支架上相向排列两列 4个电纺喷头 （每列 2个）， 聚 -L-乳酸 PLLA (粘 均分子量 15万） 10g溶于 50ml丙酮及 50mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输送给支架上的一侧的 2个电纺喷头， 胶原 1. 5g溶于 30ml 六氟异丙醇中，充分溶解后将溶液输送给支架上的另一侧的 2个电纺喷头，支架 中同一列相邻电纺喷头之间的距离为 10cm，两列喷口相对的电纺喷头相距 30cm。 支架所在平面与固定杆平行。对两列喷口相对的电纺喷头分别施加相反极性的直 流高电压 ±30kV， 电纺喷头内径为 1. 2mm。导丝辊对牵引长丝束的速度为 3cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出，收集 得到 PLLA/胶原复合纳米纤维长丝束。
实施例 22
电纺支架上相向排列两列 4个电纺喷头 （每列 2个）， 聚偏氟乙烯 PVDFlOg 溶于 50ml丙酮和 50mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输 送给支架上的电纺喷头， 支架中同一列相邻电纺喷头之间的距离为 15Cm， 两列 喷口相对的电纺喷头相距 40cm， 支架所在平面与固定杆成 30度角。 对两列喷口 相对的电纺喷头分别施加相反极性的直流高电压 ± 30kV , 电纺喷头内径为 1. 2mm。 导丝辊对牵引长丝束的速度为 3Cm/S。 电纺喷头顶端喷射出的纳米纤维 经导丝辊对牵引后形成长丝束并向前导出，收集得到 PVDF复合纳米纤维长丝束。 实施例 23
电纺支架上相向排列两列 4个电纺喷头 （每列 2个）， 聚偏氟乙烯 PVDFlOg 溶于 50ml丙酮和 50mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输 送给支架上的一侧的 2个电纺喷头， 聚氨酯 PU15g溶于 lOOmlN, N-二甲基甲酰 胺中配成溶液并输送给支架上的另一侧的 2个电纺喷头，支架中同一列相邻电纺 喷头之间的距离为 10cm， 两列喷口相对的电纺喷头相距 30cm。 支架所在平面与 固定杆平行。 对两列喷口相对的电纺喷头分别施加相反极性的直流高电压土 20kV， 电纺喷头内径为 1. 2mm。 导丝辊对牵引长丝束的速度为 3cm/s。 电纺喷头 顶端喷射出的纳米纤维经导丝辊对牵引后形成长丝束并向前导出， 收集得到 PLLA/PU复合纳米纤维长丝束。
实施例 24
电纺支架上相向排列两列 4个电纺喷头 （每列 2个）， 聚- L-乳酸 PLLA (粘 均分子量 15万） 10g溶于 50ml丙酮及 50mlN， N-二甲基甲酰胺的混合溶剂中， 充分溶解后将溶液输送给支架上的一侧的 2个电纺喷头， 聚乙烯吡咯烷酮 PVP K60 (BASF公司产品） 10g溶于 50ml丙酮中， 充分溶解后将溶液输送给支架上的 另一侧的 2个电纺喷头， 支架中同一列相邻电纺喷头之间的距离为 10cm， 两列 喷口相对的电纺喷头相距 30cm。 支架所在平面与固定杆平行。 对两列喷口相对 的电纺喷头分别施加相反极性的直流高电压 ±20kV， 电纺喷头内径为 1. 2國。 导 丝辊对牵引长丝束的速度为 3cm/s。 电纺喷头顶端喷射出的纳米纤维经导丝辊对 牵引后形成长丝束并向前导出， 收集得到 PLLA/PVP复合纳米纤维长丝束。
实施例 25
聚- L -乳酸 PLLA (粘均分子量 10万） 10g溶于 50ml丙酮和 50mlN, N-二甲 基甲酰胺的混合溶剂中成溶液溶液 1号， 丙交酯-乙交酯共聚物 PLGA (其中质量 组成丙交酯 50°/。， 乙交酯 50%， 粘均分子量 10万） 15g溶于 50ml丙酮和 50mlN， N -二甲基甲酰胺的混合溶剂中配成溶液 2号， 透明质酸（分子量 10万） lg溶 于 100ml水中配成 3号，壳聚糖 0. 3g溶于 lOOmlO. 1M的稀醋酸中配成溶液 4号， 胶原 1. 5g溶于六氟异丙醇中配成溶液 5号， 聚己内酯 PCL (分子量 9万） 10g 溶于 lOOmlN, N-二甲基甲酰胺中配成溶液 6号， 充分溶解后将这些高聚物溶液 1-6号分别输送给支架上从上到下的两列共 6个不同的电纺喷头（每列 3个电纺 喷头）。支架中各列中相邻电纺喷头之间的间距为 10cm， 两列喷口相向的电紡喷 头相距 30cm。 支架所在平面与固定杆之间平行。 对两列喷口相向的电纺喷头分 别施加相反极性的直流高电压 ± 15kv， 电纺喷头内径为 0. 8匪。 1、 2号喷出纳米 纤维相互吸引、 聚集并向下牵引得到长丝束， 并作为 3、 4号溶液电喷雾粒子沉 积的载体， 表面附着电喷雾粒子的长丝束向下牵伸， 5、 6号溶液喷出的纳米纤 维继续沉积在表面附着电喷雾粒子的长丝束上，纳米纤维长丝束经导丝辊对牵引 后形成复杂组分复合纳米纤维长丝束。

Claims

权 利 要 求 书 、 一种复合纳米纤维长丝束制备装置，其特征在于该装置由若干对纺丝喷头对
( 1 )、 导丝辊对 （2)、 支架 （3)、 固定杆（4)、 底座 （5) 组成， 两列喷口 相向的多对电纺喷头对（1 ) 固定在支架（3)上， 每对电纺喷头喷口可以在 同一水平面或不同水平面上， 支架（3)通过垂直底座的固定杆 （4)与底座
(5)相连， 导丝辊对（2) 在支架 （3)下方的中间。
、 根据权利要求 1所述的复合纳米纤维长丝束制备方法， 其特征在于支架（3) 同一列电纺喷头 （1 ) 之间间距为 2_50cm; 两列喷口相向的电纺喷头对 （1 ) 的两个喷头之间相距 10-100cm。
、 根据权利要求 1所述的复合纳米纤维长丝束制备方法， 其特征在于支架（3 ) 所在平面与固定杆 （4) 之间所成的角度为 0-90°。
、 一种如权利要求 1所述装置的复合纳米纤维长丝束制备方法其特征在于具体 制备的步骤如下-
1 )将料液输送给支架 （3)上的电纺喷头对（1 );
2) 喷口相向的电纺喷头对（1 )的每个喷头分别施加相反极性的直流高电压;
3) 每对相向喷口喷出分别带相反电荷的纳米纤维， 并在空中相互吸引、 碰 撞形成复合纳米纤维， 或沉积在在电纺喷头对（1 ) 的两个喷头之间沿支 架平面向下方牵引的作为接受体的高分子纤维长丝上， 经牵引、 拉伸后 形成复合纳米纤维长丝束；
4)第一对相向放置的电纺喷头纺丝形成的复合纳米纤维长丝束向下拉伸， 并作为接受体与第二对电纺喷头喷出的分别带相反电荷并相互吸引的纳 米纤维在空中相遇， 被第二对电纺喷头喷出的纳米纤维包裹， 经牵引、 拉伸后形成两层复合纳米纤维长丝束；
5)依次类推， 上层形成的长丝束向下拉伸并作为接受体与下层电纺喷头对 紡丝形成的纳米纤维在空中相遇， 被下层电纺喷头对喷出的纳米纤维包 裹， 经牵引、 拉伸后形成复合纳米纤维长丝束， 最后经导丝辊对（2)牵 弓 I、 拉伸后得到多层复合纳米纤维长丝束。
、 根据权利要求 4所述的多层复合纳米纤维长丝束的制备方法，其特征在于对 两列喷口相向的电纺喷头（1 )分别施加相反极性的直流高电压 3KV-200KV。 、 根据权利要求 4所述的复合纳米纤维长丝束制备方法，其特征在于料液是高 分子溶液或含添加剂的高分子溶液或高分子与无机粒子的混合物体系。 、 根据权利要求 6所述的复合纳米纤维长丝束制备方法，其特征在于高分子是 聚烯烃、聚卤代烯烃、聚硅氧垸、聚醚、聚酰胺、聚酯、聚碳酸酯、聚氨酯、 环氧树脂、 聚丙烯腈、 聚丙烯酸类高分子、 聚丙烯酸酯、 聚苯醚、 聚酸酐、 聚- α -氨基酸、 聚苯硫醚， 或是其中两种或多种的共混物； 或是纤维素、 纤 维素衍生物、 葡聚糖、 丝蛋白、 壳聚糖、 壳聚糖衍生物、 透明质酸、 透明质 酸衍生物、 胶原、 角叉胶、 藻酸钠、 藻酸钙、 硫酸软骨素、 明胶、 琼脂、 葡 聚糖、 纤维蛋白、 纤维蛋白原、 角质蛋白、 酪蛋白、 白蛋白、 弹性蛋白中的 一种或是它们的衍生物、 或是其中两种或多种的共混物； 或是生物可吸收合 成高分子聚 -L-乳酸、聚- (D，L) -乳酸、聚羟基乙酸、聚己内酯、聚丁内酯、 聚戊内酯、 聚酯二氧杂环己垸、 聚酸酐、 聚- α -氨基酸中的一种或者是至少 以下两种单体的共聚物： L-乳酸、 D，L-乳酸、 羟基乙酸、 3-羟基丁酸、 3-羟 基戊酸、 己内酯、丁内酯、戊内酯、氨基酸， 或是其中两种或多种的共混物。 、 根据权利要求 6所述的复合纳米纤维长丝束制备方法，其特征在于无机粒子 是纳米抗菌剂、 催化剂、 纳米碳管。
、 根据权利要求 6所述的复合纳米纤维长丝束制备方法，其特征在于添加剂是 抗生素、 免疫抑制剂、抗菌剂、激素、维生素、氨基酸、 多肽、 蛋白质、酶、 生长因子、 抗菌药物、 麻醉药物、 止血药物、 激素、 镇痛药物、 降压药物、 抗肿瘤药物。
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