WO2019020039A1 - 一种静电纺纤维改性复合膜及其制备方法 - Google Patents

一种静电纺纤维改性复合膜及其制备方法 Download PDF

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WO2019020039A1
WO2019020039A1 PCT/CN2018/096918 CN2018096918W WO2019020039A1 WO 2019020039 A1 WO2019020039 A1 WO 2019020039A1 CN 2018096918 W CN2018096918 W CN 2018096918W WO 2019020039 A1 WO2019020039 A1 WO 2019020039A1
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solution
composite film
electrospun fiber
modified composite
electrospun
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English (en)
French (fr)
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王林格
李卫昌
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华南理工大学
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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
    • 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
    • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • 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
    • 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
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • 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
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent

Definitions

  • the invention belongs to the field of biomedical materials, and particularly relates to an electrospun fiber modified composite film and a preparation method thereof.
  • biomedical materials medical metal materials, bioceramics, polymers and Composite materials, etc., applied to the diagnosis and treatment of different types of tissue and organ diseases, including: soft tissue materials such as skin, esophagus, breast, bladder, respiratory tract; bones such as teeth, bones, tendons, joints, etc. - Muscle system repair materials; cardiovascular system materials such as blood vessels, cardiovascular endotracheal tubes, artificial heart valves; drug release carrier materials; tissue adhesives and suture materials; clinical diagnostic and biosensor materials; separation membranes and blood purification membranes, corneas Contact lens, gas selective transmission of medical film materials such as fiber membranes, etc.
  • soft tissue materials such as skin, esophagus, breast, bladder, respiratory tract
  • bones such as teeth, bones, tendons, joints, etc.
  • - Muscle system repair materials such as blood vessels, cardiovascular endotracheal tubes, artificial heart valves
  • drug release carrier materials tissue adhesives and suture materials
  • clinical diagnostic and biosensor materials separation membranes and blood purification membranes, corneas Contact lens
  • medical polymer membrane materials have good biocompatibility, easy processing, good plasticity, and simple process; however, single-component polymer membrane materials generally have mechanical properties (tensile strength, tensile force, elastic force, The compression modulus is not high, the chemical stability is poor, the degradation rate is uncontrollable, and it is difficult to support the problem of tissue reconstruction. Therefore, how to improve the mechanical strength of such polymer film materials is a key issue in the current research of artificial tissue and even organ research.
  • the common solution to improve material properties is to compound materials with different properties to achieve the effect of 'complementary complementarity'. Therefore, there is a problem in that the existing biomedical polymer film material has poor mechanical strength and toughness.
  • the invention adopts a structural composite method similar to the 'reinforced steel cement' with the polymer fiber as the 'skeleton' and the conventionally prepared medical polymer film, improves the mechanical strength and stability of the polymer film, and further expands the application range thereof. Enhancement for biomedical polymer materials / Modification provides a new approach.
  • the present invention uses electrospun fibers and a polymer casting film to be composited.
  • the object of the present invention is to provide an electrospun fiber-modified composite film, which is integrated into the interior or surface of a polymer film of a casting process, so that the mechanical properties and stability of the prepared composite film are significantly improved.
  • Another object of the present invention is to provide a method for producing the above electrospun fiber-modified composite film.
  • the fiber membrane was prepared by electrospinning with good biocompatible polymer materials, and then the fiber membrane was composited with the polymer membrane prepared by the casting process to obtain the electrospun fiber modified composite membrane.
  • a method for preparing an electrospun fiber-modified composite film comprises the following steps:
  • Step 1 The spinning solution obtained in the method is put into a sample feeding device with a spinning needle, the spinning needle is connected to the positive high voltage of the static electricity, the flow rate of the spinning solution is controlled by the injection pump, and the static electricity is performed under certain spinning conditions and environment. Spinning, collecting the fiber by the wire collecting device, and obtaining the electrospun fiber after the solvent is evaporated and dried;
  • step (3) the pouring solution obtained in step (3) is injected into the mold, and then step 2 is The obtained electrospun fiber is laid on the surface of the casting solution, and after being left to be completely infiltrated, the pouring solution is injected again onto the surface of the electrospun fiber, so that the cycle is repeated for a certain number of times, and the film is formed into an electrospun fiber-modified composite film by drying into a film. .
  • step 1) and step 3 The spinning solution and the casting solution may be a one-component polymer or a multi-component polymer mixture.
  • the polymer material is a natural high molecular material and a derivative thereof (e.g., Collagen, chitosan, gelatin, cellulose, hyaluronic acid, silk fibroin, etc., or synthetic polymers (eg, polyethylene glycol, polycaprolactone, polylactide, polyanhydride, polystyrene, poly Lactic acid, polyglycolic acid, One or more of carrageenan, polyphosphazene, polyphosphate, poly- ⁇ -hydroxybutyl ester, polyvinylpyrrolidone, polyglycolide, polyvinyl alcohol, hydrogenated styrene-butadiene block copolymerization, etc. .
  • synthetic polymers eg, polyethylene glycol, polycaprolactone, polylactide, polyanhydride, polystyrene, poly Lactic acid, polyglycolic acid, One or more of carrageenan, polyphosphazene, polyphosphate, poly- ⁇ -hydroxy
  • the solvent is an organic solvent or an acidic aqueous solution
  • the organic solvent is N, N- dimethylformamide (DMF), tetrahydrofuran (THF), hexafluoroisopropanol (HFIP), chloroform (CHCl 3) , N,N-dimethylacetamide (DMAC), acetone (Acetone), methyl isobutyl ketone (MIBK), dichloromethane (DCM), dimethyl sulfoxide (DMSO), ethanol (Ethanol), A One or more of Acetonitrile and methyl acetate;
  • the acidic aqueous solution is one or more of hydrochloric acid, sulfuric acid and acetic acid, and the concentration of the acidic aqueous solution is 0 to 5 wt%.
  • the concentration of the spinning solution and the casting solution are both 1 to 30 wt%.
  • the stirring speed is 100-800 r/min, stirring The time is 2 to 48 h.
  • the positive electrostatic high voltage is 10 to 30 kV
  • the spinning needle is The distance from the wire receiving device is 10 to 50 cm
  • the flow rate of the spinning solution is 0.5 to 8 mL/h
  • the temperature in the electrospinning environment is 10 to 55 °C
  • the relative humidity is 10%. ⁇ 99%.
  • the step 2) is a flat wire receiving device or a drum wire collecting device, and the rotating speed of the drum wire collecting device is 100 ⁇ 3000 r/min.
  • the number of times of the repeated loop operation in step 4) is 1 ⁇ 100.
  • the drying method is natural drying or vacuum drying, and the drying temperature is 25 to 40 °C.
  • the electrospun fiber is first laid on the bottom of the mold, and then poured into the casting solution.
  • the present invention has the following advantages:
  • the electrospun fiber-modified composite film of the present invention is compared with a conventional single polymer film material.
  • the mechanical properties and stability are significantly improved.
  • the preparation method of the invention is simple and reproducible, and the prepared electrospun fiber-modified composite membrane can be effectively applied to biomedical related fields, and has the possibility of wide application in clinic.
  • Figure 1 is a schematic view showing the structure of an electrospun fiber-modified composite film.
  • Example 2 a is a macro photograph of the electrospun fiber-modified composite film prepared in Example 1;
  • Figure 2b is a scanning electron micrograph of the surface of the electrospun fiber-modified composite film of Example 1;
  • Example 3 is a sectional scanning electron micrograph of the electrospun fiber-modified composite film prepared in Example 2;
  • Figure 4a is a scanning electron micrograph of the electrospun fiber prepared in Example 3 before being combined with the casting film;
  • Figure 4b is a scanning electron micrograph of the electrospun fiber prepared in Example 3 after being combined with the casting film;
  • Figure 5a is a scanning electron micrograph of the surface of the electrospun fiber-modified composite film prepared in Example 4.
  • Figure 5b is a scanning electron micrograph of a cross section of the electrospun fiber-modified composite film prepared in Example 4.
  • Figure 6 is a bar graph showing the change of tensile strength before and after the electrospun fiber prepared in Example 5 is added to the cast film;
  • Fig. 7 is a graph showing the change rate of degradation rate of the electrospun fiber prepared in Example 6 before and after being added to the cast film.
  • Dissolve polylactic acid in DCM solvent to prepare a polymer solution with a mass fraction of 25 % at 800 r/min
  • the mixture was mechanically stirred at a speed of 2 h to fully dissolve to form a spinning solution.
  • the spinning solution was loaded into a sample-feeding device with a spinneret.
  • the flow rate of the spinning solution was controlled by a syringe pump to be 0.5 mL/h, and the spinneret was 10 kW.
  • the static electricity is connected to a high voltage, and the electrospinning is carried out under the condition of an ambient temperature of 55 ° C and a relative humidity of 99 %.
  • the fiber is collected by a flat wire collecting device, and the distance between the wire needle and the wire receiving plate is 10 cm.
  • the collected electrospun fibers are evaporated to dryness after use as a solvent.
  • the collagen was added to a 1 wt% hydrochloric acid solution and mechanically stirred at 100 r/min for 48 h to obtain a mass fraction of 1%.
  • Collagen solution The collagen solution is injected into the mold, the solution is laid flat on the bottom of the container, and then the electrospun fiber is laid on the surface of the solution, and after the fiber is completely infiltrated, the collagen solution is again injected on the surface of the electrospun fiber, and dried at room temperature.
  • Film formation is obtained by electrospinning fiber modified composite film; 1 is a schematic structural diagram of an electrospun fiber-modified composite film, which is formed by alternately superposing a fiber web and a casting film; The macroscopic photograph of the electrospun fiber-modified composite film is shown. It can be seen that the cast film covers the surface of the fiber web. The dense microscopic morphology of the deposited collagen film can be clearly observed by scanning electron microscopy, as shown in Fig. 2b. Shown.
  • Polycaprolactone and polyethylene glycol were blended into a mixed solvent of DMAC and CHCl 3 to prepare a blending solution with a mass fraction of 20%, and mechanical stirring at 400 r/min. h, fully dissolved to form a spinning solution.
  • the spinning solution was placed in a sample-feeding device with a spinneret.
  • the flow rate of the spinning solution was controlled by a syringe pump to be 0.5 mL/h, and the spinneret was connected to an electrostatic positive pressure of 30 kW at an ambient temperature of 10 °C.
  • Electrospinning was carried out under the condition of a relative humidity of 10%, and the fiber was collected by a roller take-up device (roller rotation speed of 100 r/min), and the distance between the wire needle and the take-up drum was 10 cm, and the obtained electrospun fiber was collected. After the solvent is evaporated and dried, it is reserved.
  • the collagen was added to a 0.75 wt% acetic acid solution and mechanically stirred at 300 r/min for 12 h to obtain a collagen solution having a mass fraction of 1.5%.
  • the collagen solution is injected into the mold, the solution is laid flat on the bottom of the container, and then the electrospun fiber is laid flat on the surface of the solution, and vacuum-dried to form a film at 40 ° C to obtain an electrospun fiber-modified composite film.
  • the cross-sectional microscopic scanning electron micrograph of the electrospun fiber-modified composite film is shown in Fig. 3, and the interface at the interface is good.
  • the spinning solution was placed in a sample-feeding device with a spinneret.
  • the flow rate of the spinning solution was controlled by a syringe pump to be 3 mL/h, and the spinneret was 20 kW.
  • the static electricity is connected to a high voltage, and the electrospinning is carried out under the condition of an ambient temperature of 25 ° C and a relative humidity of 50 %.
  • the fiber is collected by a flat wire collecting device, and the distance between the wire needle and the wire receiving plate is 20 cm. The collected electrospun fibers are evaporated to dryness after use as a solvent.
  • the gelatin was added to deionized water and mechanically stirred at 200 r/min for 12 h to obtain a mass fraction of 6 %.
  • Gelatin solution The electrospun fiber is placed on the bottom of the container, and then a gelatin solution is injected onto the surface of the fiber. After standing, the electrospun fiber is placed on the surface of the gelatin solution again.
  • the electrospun fiber-modified composite film was obtained by vacuum drying in a °C environment; the micro-morphologies of the electrospun fiber and the gelatin film before and after composite are shown in Fig. 4a and Fig. 4b, respectively.
  • the fiber web has a porous network structure composed of randomly arranged fibers, and the fiber network is embedded in the casting film after being combined with the casting film, and is integrated to achieve a modification effect.
  • Polylactic acid was added to DMF to prepare a solution with a mass fraction of 8 %, and mechanically stirred at 400 r/min for 8 h. , fully dissolved to form a spinning solution.
  • the spinning solution was placed in a sample-feeding device with a spinneret.
  • the flow rate of the spinning solution was controlled by a syringe pump to be 2 mL/h, and the spinneret was connected to a static positive pressure of 20 kW.
  • the ambient temperature was Electrospinning was carried out at 30 ° C and a relative humidity of 60 %.
  • the fiber was collected by a flat wire receiving device. The distance between the wire needle and the wire receiving plate was 15 cm. The collected electrospun fibers are evaporated to dryness after use as a solvent.
  • the electrospun fiber is placed on the bottom of the container, and then the gelatin and chitosan blending solution is injected onto the surface of the fiber. After standing, the electrospun fiber is placed on the surface of the gelatin solution again, and the film is naturally dried at room temperature to obtain an electrospun fiber.
  • Composite film; the surface morphology and cross-section of the electrospun fiber-modified composite film obtained in this embodiment are respectively shown in the figure 5a and 5b, the beaded fiber web is embedded in the cast film, and the combination is good.
  • the blended solution was mechanically stirred for 8 h at 400 r/min and fully dissolved to form a spinning solution.
  • the spinning solution is loaded into a sample introduction device with a spinneret, and the flow rate of the spinning solution is controlled by the syringe pump to be 1 mL/h, the spinneret is connected to a static positive pressure of 20 kW, electrospinning at an ambient temperature of 35 °C and a relative humidity of 75 %, using a roller collection device (roller speed is 3000) r/min)
  • the fibers were collected, and the distance between the wire needle and the take-up drum was 15 cm.
  • the collected electrospun fibers were evaporated to dryness and then used.
  • Add collagen to a 1.5 wt% hydrochloric acid solution, Mechanical stirring for 12 h at 350 r/min, giving a mass fraction of 1% Collagen solution.
  • the electrospun fiber is placed on the bottom of the container, and then the gelatin and chitosan blending solution is injected onto the surface of the electrospun fiber. After standing, the electrospun fiber is placed on the surface of the gelatin solution again, and the cycle is repeated.
  • the electrospinning fiber-modified composite film is obtained by naturally drying at room temperature; the composite film of the collagen film and the electrospun fiber (see b in Fig. 6) is significantly improved before the composite (see a in Fig. 6). .
  • the spinning solution was loaded into a sample-feeding device with a spinneret.
  • the flow rate of the spinning solution was controlled by a syringe pump to be 2 mL/h, and the spinneret was 15 kW.
  • the static electricity is connected to a high voltage, and the electrospinning is carried out under the condition of an ambient temperature of 25 ° C and a relative humidity of 55 %.
  • the fiber is collected by a flat wire collecting device, and the distance between the wire needle and the wire receiving plate is 12 cm.
  • the collected electrospun fibers are evaporated to dryness after use as a solvent.
  • the collagen was added to a 0.75 wt% hydrochloric acid solution and mechanically stirred at 350 r/min for 16 h to obtain a mass fraction of 0.8% blend solution.
  • the electrospun fiber is placed on the bottom of the container, and then the collagen solution is injected onto the surface of the electrospun fiber. After standing, the electrospun fiber is placed on the surface of the collagen solution again, and the cycle is repeated. Then, the electrospun fiber-modified composite film is obtained by naturally drying at room temperature; the collagen film is combined with the electrospun fiber (see b in Fig. 7) before compounding (see a in Fig. 7).
  • the degradation rate is significantly slower, indicating that the stability is improved.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
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Abstract

本发明公开了一种静电纺纤维改性复合膜及其制备方法，属于生物医用材料领域。该静电纺纤维改性复合膜主要是将静电纺纤维网膜与浇筑膜进行复合，通过控制纤维网膜在浇筑膜内的位置和层数，来调控复合膜的机械性能和稳定性。与传统单一高分子浇筑膜材料相比，本发明的静电纺纤维改性复合膜的力学性能得到显著提升且降解速率可控。本发明的制备方法简单、重复性好，制得的静电纺纤维改性复合膜可有效应用于生物医学相关领域，具有临床广泛应用的可能性。

Description

一种静电纺纤维改性复合膜及其制备方法
技术领域
本发明属于生物医用材料领域，具体涉及一种静电纺纤维改性复合膜及其制备方法 。
背景技术
自体或同种异体组织器官移植是治疗各种组织功能障碍的最有效手段，但是在实际临床应用中往往存在供体匮乏的问题。随着医疗水平和材料制备技术的不断提高，新型生物医用材料的出现为组织器官替代修复提供了新的途径，并有望从根本上改善上述治疗手段的局限。这些新治疗途径中，制备具有类似天然组织特征的修复体是一种具有重要应用价值的手段，目前，相关研究者已开发出逾千种生物医用材料（医用金属材料、生物陶瓷、高分子和复合材料等），应用于不同类型组织器官病变的诊断和治疗，这些材料包括：皮肤、食道、乳房、膀胱、呼吸道等软组织材料；牙、骨、肌腱、关节等骨骼 - 肌肉系统修复材料；血管、心血管内插管、人工心瓣膜等心血管系统材料；药物释放载体材料；组织粘合剂和缝线材料；临床诊断及生物传感器材料；分离膜和血液净化膜、角膜接触镜、气体选择性透过纤维膜等医用膜材料等。从材料上看，医用高分子膜材料具有良好的生物相容性、易加工、可塑性好、工艺简单等优点；然而，单一成分的高分子膜材料普遍存在机械性能（张力强度、拉力、弹力、压缩模量）不高、化学稳定性较差、降解速率不可控、难以支撑组织重建的问题。因此，如何改善此类高分子膜材料的机械强度是当前制备人工组织乃至器官研究的一个关键问题。
材料研究中，提高材料性能的常用的解决手段就是将不同性能的材料进行复合，达到'优势互补'的效果。因此，针对现有生物医用高分子膜材料存在的力学强度及韧性差的问题。本发明采用以高分子纤维作为'骨架'与现有常规制备的医用高分子膜进行类似'钢筋加强水泥'的结构复合方式，改善高分子膜的力学强度和稳定性，进而拓展其应用范围，为生物医用高分子材料的增强 / 改性提供了一种新的方法。
发明内容
为了改善传统单一高分子膜材料的稳定性，本发明采用电纺纤维与高分子浇筑膜进行复合。
本发明的目的在于提供一种静电纺纤维改性复合膜，将静电纺纤维网膜复合于浇筑工艺高分子膜的内部或表面，使所制备的复合膜的力学性能和稳定性得到显著改善。
本发明的另一目的在于提供上述一种静电纺纤维改性复合膜的制备方法。 选取具有良好生物相容性高分子材料，用静电纺丝工艺制备纤维网膜，然后将纤维网膜与采用浇筑工艺制备的高分子膜进行复合，得到静电纺纤维改性的复合膜。
本发明的目的通过以下技术方案实现。
一种静电纺纤维改性复合膜的制备方法， 包括以下 步骤：
1 ）纺丝溶液的配制：将高分子材料溶于溶剂中，搅拌至完全溶解，得到纺丝溶液；
2 ）静电纺纤维的制备：将步骤 1 ）中得到的纺丝溶液装入带有喷丝针头的给样装置中，将喷丝针头与静电正高压相连，由注射泵控制纺丝溶液的流速，在一定纺丝条件和环境下进行静电纺丝，用收丝装置收集纤维，待溶剂挥发干燥后即得静电纺纤维；
3 ）浇筑溶液的配制：将高分子材料加入到溶剂中，搅拌至完全溶解，得到浇筑溶液；
4 ）静电纺纤维改性复合膜的制备：将步骤（ 3 ）所得浇筑溶液注入模具中，随后将步骤 2 ）所得静电纺纤维平铺于浇筑溶液表面，静置待完全浸润后，再次注入浇筑溶液平铺于静电纺纤维表面，如此反复循环操作一定次数，干燥成膜即得静电纺纤维改性复合膜。
优选的， 步骤 1 ）和步骤 3 ）所述的纺丝溶液和浇筑溶液中，可以是单组份高分子也可以是多组分高分子混合物。
优选的， 所述高分子材料 为天然高分 子材料及其衍生物（如： 胶原、壳聚糖、明胶、纤维素、透明脂酸、丝素蛋白等） ，或合成高分子（如： 聚乙二醇、 聚己内酯、聚丙交酯、聚 酸酐、聚苯乙烯、 聚乳酸、聚羟基乙酸、 角叉胶、聚膦腈类、聚磷酸酯、 聚 β- 羟丁酯、 聚乙烯吡咯烷酮、 聚乙交酯、 聚乙烯醇、氢化苯乙烯 - 丁二烯嵌段共聚等） 中的 一种以上。
优选的， 所述 溶剂 为 有机溶剂 或酸性水溶液；所述 有机溶剂为 N,N- 二甲基甲酰胺（ DMF ）、四氢呋喃（ THF ）、六氟异丙醇（ HFIP ）、氯仿（ CHCl3 ）、 N,N- 二甲基乙酰胺（ DMAC ）、丙酮（ Acetone ）、甲基异丁酮（ MIBK ）、二氯甲烷（ DCM ）、二甲基亚砜（ DMSO ）、乙醇（ Ethanol ）、甲基氰（ Acetonitrile ）、醋酸甲酯（ methyl acetate ）中的一种以上 ； 所述 酸性水溶液 为盐酸、硫酸 和 醋酸中的一种或以上，所述 酸性水溶液的 浓度为 0 ~ 5 wt% 。
优选的， 所述纺丝溶液和浇筑溶液 的 浓度 均 为 1 ～ 30 wt% 。
优选的，步骤 1 ）和步骤 3 ）中， 所述搅拌 的 转速 均 为 100 ～ 800 r/min ，搅拌 的 时间 均 为 2 ～ 48 h 。
优选的，步骤 2 ） 所述 静电纺丝中， 静电正高压为 10 ～ 30 kV ，喷丝 针头 与收丝装置的间距为 10 ～ 50 cm ， 纺丝溶液的流速 为 0.5 ～ 8 mL/h ， 静电纺丝环境的温度为 10 ～ 55 ℃，相对湿度为 10 % ～ 99 % 。
优选的，步骤 2 ） 所述收丝装置为平板收丝装置或滚筒收丝装置，所述滚筒收丝装置的转速为 100 ～ 3000 r/min 。
优选的，步骤 4 ） 所述反复循环操作的次数为 1~100 次；所述干燥的方式为自然干燥或真空干燥，干燥的温度为 25~40 ℃。
优选的，步骤 4 ） 中，先将静电纺纤维平铺于模具底部，再注入浇筑溶液。
由以上所述的方法制得的 一种静电纺纤维改性复合膜 。
与现有技术相比，本发明具有如下优点：
1 、与 传统 单一高分子膜材料 相比，本发明的 静电纺纤维改性复合膜 的力学性能和稳定性得到显著改善。
2 、本发明的制备方法简单、重复性好，制得的静电纺纤维改性复合膜可有效应用于生物医学相关领域，具有临床广泛应用的可能性 。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图 1 为静电纺纤维改性复合膜的结构示意图。
图 2 a 为实施例 1 制备的静电纺纤维改性复合膜的宏观照片；
图 2 b 为实施例 1 静电纺纤维改性复合膜表面的扫描电镜图；
图 3 为实施例 2 制备的静电纺纤维改性复合膜的断面扫描电镜图；
图 4a 为实施例 3 制备的静电纺纤维与浇筑膜复合前的扫描电镜图；
图 4b 为实施例 3 制备的静电纺纤维与浇筑膜复合后的扫描电镜图；
图 5a 为实施例 4 制备的静电纺纤维改性复合膜表面的扫描电镜图；
图 5b 为实施例 4 制备的静电纺纤维改性复合膜截面的扫描电镜图；
图 6 为实施例 5 制备的静电纺纤维加入浇筑膜前后拉伸强度的变化柱形图；
图 7 为实施例 6 制备的静电纺纤维加入浇筑膜前后降解速率的变化曲线图。
具体实施方式
以下结合实例与附图对本发明作进一步的详细描述，但实施例并不对本发明做任何形式的限定。
实施例 1
将聚乳酸溶于 DCM 溶剂中，配制成质量分数为 25 % 的高分子溶液，在 800 r/min 转速下机械搅拌 2 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 0.5 mL/h ，喷丝头与 10 kW 的静电正高压相连，环境温度为 55 ℃、相对湿度为 99 % 条件下进行静电纺丝，采用平板收丝装置收集纤维，出丝针头与收丝板之间的距离为 10 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将胶原加入到 1 wt% 的盐酸溶液中， 100 r/min 转速下机械搅拌 48 h ，得到质量分数为 1 % 的胶原溶液。将胶原溶液注入模具中，使溶液平铺于容器底部，随后将静电纺纤维平铺于溶液表面，静置待纤维完全浸润后，再次注入胶原溶液平铺于静电纺纤维表面，室温条件下干燥成膜即得静电纺纤维改性复合膜；图 1 为静电纺纤维改性复合膜的结构示意图，复合膜是由纤维网膜和浇筑膜交替叠加形成的；图 2a 所示为静电纺纤维改性复合膜的宏观照片，可以看到浇筑膜覆盖在纤维网膜表面，通过扫描电子显微镜可以清楚观察到浇筑胶原膜表面致密的微观形貌，如图 2b 所示。
实施例 2
将聚己内酯和聚乙二醇（质量比为 10:1 ）共混加入到 DMAC 和 CHCl3 混合溶剂中配制成质量分数为 20 % 的共混溶液， 400 r/min 转速下机械搅拌 8 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 0.5 mL/h ，喷丝头与 30 kW 的静电正高压相连，环境温度为 10 ℃、相对湿度为 10 % 条件下进行静电纺丝，采用滚筒收丝装置（滚筒转速为 100 r/min ）收集纤维，出丝针头与收丝滚筒之间的距离为 10 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将胶原加入到 0.75 wt% 的醋酸溶液中， 300 r/min 转速下机械搅拌 12 h ，得到质量分数为 1.5 % 胶原溶液。将胶原溶液注入模具中，使溶液平铺于容器底部，随后将静电纺纤维平铺于溶液表面， 40 ℃环境下真空干燥成膜即得静电纺纤维改性复合膜。该静电纺纤维改性复合膜的断面微观扫描电子显微镜图如图 3 所示，二者界面处结合良好。
实施例 3
将聚乙交酯加入到 THF 中配制成质量分数为 30 % 的溶液， 500 r/min 转速下机械搅拌 6 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 3 mL/h ，喷丝头与 20 kW 的静电正高压相连，环境温度为 25 ℃、相对湿度为 50 % 条件下进行静电纺丝，采用平板收丝装置收集纤维，出丝针头与收丝板之间的距离为 20 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将明胶加入到去离子水中， 200 r/min 转速下机械搅拌 12 h ，得到质量分数为 6 % 明胶溶液。将静电纺纤维平铺于容器底部，随后注入明胶溶液于纤维表面，静置后再次将静电纺纤维置于明胶溶液表面， 25 ℃环境下真空干燥成膜即得静电纺纤维改性复合膜；静电纺纤维与明胶膜复合前后的微观形貌分别如图 4a 、图 4b 所示，纤维网膜具有纤维无规排列组成的多孔网状结构，与浇筑膜复合后纤维网络嵌入到浇筑膜内，融为一体，达到改性的效果。
实施例 4
将聚乳酸加入到 DMF 中配制成质量分数为 8 % 的溶液， 400 r/min 转速下机械搅拌 8 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 2 mL/h ，喷丝头与 20 kW 的静电正高压相连，环境温度为 30 ℃、相对湿度为 60 % 条件下进行静电纺丝，采用平板收丝装置收集纤维，出丝针头与收丝板之间的距离为 15 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将明胶和壳聚糖（质量比为 9:1 ）共混加入到 5 wt% 的盐酸溶液中， 250 r/min 转速下机械搅拌 8 h ，得到质量分数为 5 % 共混溶液。将静电纺纤维平铺于容器底部，随后注入明胶和壳聚糖共混溶液于纤维表面，静置后再次将静电纺纤维置于明胶溶液表面，室温自然干燥成膜即得静电纺纤维改性复合膜；本实施例所得的静电纺纤维改性复合膜表面和截面的微观形貌分别如图 5a 、图 5b 所示，串珠状纤维网膜嵌入到浇筑膜内，二者结合良好。
实施例 5
将明胶和丝素蛋白（质量比为 10:1 ）共混加入到 六氟异丙醇 中配制成质量分数为 15 % 的共混溶液， 400 r/min 转速下机械搅拌 8 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 1 mL/h ，喷丝头与 20 kW 的静电正高压相连，环境温度为 35 ℃、相对湿度为 75 % 条件下进行静电纺丝，采用滚筒收集装置（滚筒转速为 3000 r/min ）收集纤维，出丝针头与收丝滚筒之间的距离为 15 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将胶原加入到 1.5 wt% 的盐酸溶液中， 350 r/min 转速下机械搅拌 12 h ，得到质量分数为 1 % 胶原溶液。将静电纺纤维平铺于容器底部，随后注入明胶和壳聚糖共混溶液于静电纺纤维表面，静置后再次将静电纺纤维置于明胶溶液表面，如此反复循环操作 5 次，室温自然干燥成膜即得静电纺纤维改性复合膜；胶原膜与静电纺纤维复合后（见图 6 中的 b ）较复合前（见图 6 中的 a ）力学性能有了显著提高。
实施例 6
将明胶加入到六氟异丙醇中配制成质量分数为 15 % 的溶液， 400 r/min 转速下机械搅拌 10 h ，充分溶解形成纺丝溶液。将纺丝溶液装入带有喷丝针头的给样装置中，由注射泵控制纺丝液的流速为 2 mL/h ，喷丝头与 15 kW 的静电正高压相连，环境温度为 25 ℃、相对湿度为 55 % 条件下进行静电纺丝，采用平板收丝装置收集纤维，出丝针头与收丝板之间的距离为 12 cm ，收集得到的静电纺纤维待溶剂挥发干燥后备用。将胶原加入到 0.75 wt% 的盐酸溶液中， 350 r/min 转速下机械搅拌 16 h ，得到质量分数为 0.8 % 共混溶液。将静电纺纤维平铺于容器底部，随后注入胶原溶液于静电纺纤维表面，静置后再次将静电纺纤维置于胶原溶液表面，如此反复循环操作 100 次，室温自然干燥成膜即得静电纺纤维改性复合膜；胶原膜与静电纺纤维复合后（见图 7 中的 b ）较复合前（见图 7 中的 a ）降解速率明显减缓，说明稳定性得到了提高。

Claims (10)

  1. 一种静电纺纤维改性复合膜的制备方法，其特征在于，包括以下步骤：
    1）纺丝溶液的配制：将高分子材料溶于溶剂中，搅拌至完全溶解，得到纺丝溶液；
    2）静电纺纤维的制备：将步骤1）中得到的纺丝溶液装入带有喷丝针头的给样装置中，将喷丝针头与静电正高压相连，由注射泵控制纺丝溶液的流速，然后进行静电纺丝，用收丝装置收集纤维，待溶剂挥发干燥后即得静电纺纤维；
    3）浇筑溶液的配制：将高分子材料加入到溶剂中，搅拌至完全溶解，得到浇筑溶液；
    4）静电纺纤维改性复合膜的制备：将步骤（3）所得浇筑溶液注入模具中，随后将步骤2）所得静电纺纤维平铺于浇筑溶液表面，静置待完全浸润后，再次注入浇筑溶液平铺于静电纺纤维表面，如此反复循环操作，干燥成膜即得静电纺纤维改性复合膜。
  2. 根据权利要求1所述的方法，其特征在于，所述高分子材料为胶原、壳聚糖、明胶、纤维素、透明脂酸、丝素蛋白、聚乙二醇、聚己内酯、聚丙交酯、聚酸酐、聚苯乙烯、聚乳酸、聚羟基乙酸、角叉胶、聚膦腈类、聚磷酸酯、聚β-羟丁酯、聚乙烯吡咯烷酮、聚乙交酯、聚乙烯醇和氢化苯乙烯-丁二烯嵌段共聚中的一种以上。
  3. 根据权利要求1所述的方法，其特征在于，所述溶剂为有机溶剂或酸性水溶液；所述有机溶剂为N,N-二甲基甲酰胺、四氢呋喃、六氟异丙醇、氯仿、N,N-二甲基乙酰胺、丙酮、甲基异丁酮、二氯甲烷、二甲基亚砜、乙醇、甲基氰和醋酸甲酯中的一种以上；所述酸性水溶液为盐酸、硫酸和醋酸中的一种或以上，所述酸性水溶液的浓度为0 ~ 5 wt%。
  4. 根据权利要求1所述的方法，其特征在于，所述纺丝溶液和浇筑溶液的浓度均为1～30 wt%。
  5. 根据权利要求1所述的方法，其特征在于，步骤1）和步骤3）中，所述搅拌的转速均为100～800 r/min，搅拌的时间均为2～48 h。
  6. 根据权利要求1所述的方法，其特征在于，步骤2）所述静电纺丝中，静电正高压为10～30 kV，喷丝针头与收丝装置的间距为10～50 cm，纺丝溶液的流速为0.5～8 mL/h，静电纺丝环境的温度为10～55 ℃，相对湿度为10 %～99 %。
  7. 根据权利要求1所述的方法，其特征在于，步骤2）所述收丝装置为平板收丝装置或滚筒收丝装置，所述滚筒收丝装置的转速为100～3000 r/min。
  8. 根据权利要求1所述的方法，其特征在于，步骤4）所述反复循环操作的次数为1~100次；所述干燥的方式为自然干燥或真空干燥，干燥的温度为25~40 ℃。
  9. 根据权利要求1所述的方法，其特征在于，步骤4）中，先将静电纺纤维平铺于模具底部，再注入浇筑溶液。
  10. 由权利要求1-9任一项所述的方法制得的一种静电纺纤维改性复合膜。
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