CN102517689B - Lignin base skin core structure nanometer/micron fiber and preparation method thereof - Google Patents
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Abstract
本发明公开了一种木质素基皮芯结构纳/微米纤维的制备方法，包括以下步骤：(1)按质量份计，将木质素和石油基高分子的混合物1份加到1～20份有机溶剂中，混合均匀并使其完全溶解后，得到木质素混合溶液；将1份天然或合成高分子加到4～25份溶剂中，混合均匀并使其完全溶解后，得到高分子溶液；(2)进行同轴电纺，将木质素混合溶液和高分子溶液分别通入同轴针头的两层中，待溶液由同轴针头稳定挤出，在5～100kV的高压静电场作用下，得到木质素基皮芯结构纳/微米纤维。本发明纤维的制备方法简单，条件温和，同时降低了木质素向皮层扩散的程度，提高了芯层物质在纤维中的连续性和均匀性。
The invention discloses a preparation method of a lignin-based sheath-core structure nano/micron fiber, which comprises the following steps: (1) adding 1 part to 1 to 20 parts of a mixture of lignin and petroleum-based macromolecule in parts by mass In an organic solvent, mix evenly and dissolve completely to obtain a lignin mixed solution; add 1 part of natural or synthetic polymer to 4 to 25 parts of solvent, mix uniformly and completely dissolve to obtain a polymer solution; (2) Carry out coaxial electrospinning, pass the lignin mixed solution and the polymer solution into the two layers of the coaxial needle respectively, and wait for the solution to be stably extruded from the coaxial needle, under the action of a high-voltage electrostatic field of 5-100kV, A lignin-based sheath-core structure nano/micron fiber is obtained. The preparation method of the fiber of the invention is simple, the condition is mild, and at the same time, the diffusion degree of the lignin to the cortex is reduced, and the continuity and uniformity of the core material in the fiber are improved.
Description
技术领域 technical field
本发明属于材料领域，特别涉及一种木质素基皮芯结构纳/微米纤维及其制备方法。The invention belongs to the field of materials, in particular to a lignin-based skin-core structure nano/micron fiber and a preparation method thereof.
背景技术 Background technique
皮芯结构纳/微米纤维是一种纳/微米级的材料，因其芯层和皮层由不同材料组成，相对于传统的纳/微米纤维，不但具有尺度小、比表面积大和物理性能优异等特点，同时以皮芯结构复合两种或两种以上不同组成物质的优点，扩展了应用领域和提高了材料性能，其在膜技术、增强材料、纺织品、光学传感器、医药释放体系和组织工程等诸多领域具有非常广阔的应用前景。皮芯结构纳/微米纤维可以通过单轴电纺和同轴电纺的方法制得。其中，单轴电纺是将电纺溶液通过单轴针头喷出，在高压电场力作用下，溶液液滴经高频拉伸、弯曲甩动变形并固化为同轴纳/微米纤维的过程。同轴电纺法是制备皮芯结构纳/微米纤维最常用的方法，皮芯两层溶液从两个同轴但不同直径的针头中喷出，并在针头处汇合为皮芯结构的射流，在高压电场力作用下，经高频拉伸、弯曲甩动变形并固化为同轴纳/微米纤维。这种制备方法操作简单，纤维可以具有较好的连续性和均匀性。Skin-core structure nano/micron fiber is a nano/micron material, because the core layer and the skin layer are composed of different materials, compared with the traditional nano/micron fiber, it not only has the characteristics of small scale, large specific surface area and excellent physical properties. At the same time, the advantage of compounding two or more different components in a skin-core structure expands the application field and improves the material performance. The field has very broad application prospects. Nano/micro fiber with skin-core structure can be prepared by uniaxial electrospinning and coaxial electrospinning. Among them, uniaxial electrospinning is a process in which the electrospinning solution is sprayed through a uniaxial needle, and under the action of a high-voltage electric field, the solution droplets are deformed by high-frequency stretching, bending and shaking, and solidified into coaxial nano/micron fibers. The coaxial electrospinning method is the most commonly used method to prepare nano/micro fibers with skin-core structure. The two-layer solution of skin-core is sprayed from two coaxial needles with different diameters, and merges into a jet with skin-core structure at the needles. Under the action of high-voltage electric field force, it is deformed by high-frequency stretching, bending and shaking, and solidified into coaxial nano/micron fibers. The preparation method is simple to operate, and the fibers can have better continuity and uniformity.
根据现有文献资料，用于同轴纺丝制备皮芯结构纳/微米纤维的高分子原料包括聚丙烯腈、聚氧化乙烯、聚己内酯等石油化工原料和壳聚糖、醋酸纤维素、聚乳酸等长链天然高分子原料。上述原料具有平均相对分子质量大，分子结构规整，分子链长的共同特点，使其成为可纺性好的高分子材料。但是，石油基高分子材料生物可降解性差，长链天然高分子材料机械强度不高、使用寿命较短。这样皮芯结构纳/微米纤维的在某些方面的性能与人们的要求有一定差距。采用复合纤维则有可能使材料性能有较大改善。According to the existing literature, the polymer raw materials used for coaxial spinning to prepare nano/micro fibers with skin-core structure include polyacrylonitrile, polyethylene oxide, polycaprolactone and other petrochemical raw materials, as well as chitosan, cellulose acetate, Polylactic acid and other long-chain natural polymer raw materials. The above-mentioned raw materials have the common characteristics of large average relative molecular mass, regular molecular structure and long molecular chain, making them good polymer materials with good spinnability. However, petroleum-based polymer materials have poor biodegradability, and long-chain natural polymer materials have low mechanical strength and short service life. In some respects, the properties of the sheath-core structure nano/micron fibers have a certain gap with people's requirements. The use of composite fibers may greatly improve the performance of the material.
木质素是植物纤维原料的主要成分之一，在自然界中蕴藏量仅次于纤维素。它是一种网状结构的天然芳香族高分子。同时，木质素具有原料可再生、可生物降解的特点。在复合材料研究领域，木质素的添加可以改善高分子材料的机械性能、抗老化性能、疏水性能、生物可降解性能。因此，将木质素添加进纳/微米纤维是扩大纳/微米纤维应用范围的有效途径之一。然而，相对于常用的用于同轴电纺的高分子，木质素平均相对分子质量较小，其分子结构不规整，因而可纺性差。敖日格勒等在中国专利申请201010104518.1中提出了一种木质素基纳米碳纤维的制备方法，其中所使用的木质素通过单轴电纺法成功制得木质素基纳米纤维。但由于木质素可纺性差，该专利提出木质素必须按照分离方法的不同在酸或碱条件下精制，并且通过超滤分离出相对分子质量较适合电纺的木质素级分，木质素才能具有较好的可纺性，其过程较为复杂。由于该木质素溶液可纺性有限，因而只能形成单轴纤维。同时，木质素溶液本身的粘弹性和电导率仅能控制在一个较小的范围，不能达到制备木质素基皮芯结构纳/微米纤维所必需的条件，因此，并没有木质素基皮芯纤维的相关报道。Lignin is one of the main components of plant fiber raw materials, and its reserves in nature are second only to cellulose. It is a natural aromatic polymer with network structure. At the same time, lignin has the characteristics of renewable and biodegradable raw materials. In the field of composite material research, the addition of lignin can improve the mechanical properties, anti-aging properties, hydrophobic properties, and biodegradable properties of polymer materials. Therefore, adding lignin to nano/micron fibers is one of the effective ways to expand the application range of nano/micron fibers. However, compared with the commonly used polymers for coaxial electrospinning, the average relative molecular weight of lignin is relatively small, and its molecular structure is irregular, so the spinnability is poor. In Chinese patent application 201010104518.1, Ao Rigel et al. proposed a method for preparing lignin-based carbon nanofibers, in which the lignin used was successfully prepared by uniaxial electrospinning to obtain lignin-based nanofibers. However, due to the poor spinnability of lignin, the patent proposes that lignin must be refined under acid or alkali conditions according to different separation methods, and the lignin fraction with a relative molecular mass suitable for electrospinning is separated by ultrafiltration, so that lignin can have Better spinnability, the process is more complicated. Due to the limited spinnability of this lignin solution, only uniaxial fibers can be formed. At the same time, the viscoelasticity and electrical conductivity of the lignin solution itself can only be controlled in a small range, which cannot reach the conditions necessary for the preparation of lignin-based skin-core structure nano/micron fibers. Therefore, there is no lignin-based skin-core fiber related reports.
Sun等(Advanced Materials 2003，15，(22)：1929-1932)分别以聚氧化乙烯(PEO)和聚乳酸(PLA)为皮层材料，以十二烷基噻吩(PDT)、醋酸钯(Pd(OAc)2)、聚砜(PSU)、PEO为芯层材料，通过同轴电纺法制得具有皮芯纤维。研究结果表明，由于PDT相对分子质量小，其本身不能成纤，皮芯纤维可以通过皮层的PEO将PDT封装在芯层后获得。但是，PDT在纺丝过程中不够稳定，相对容易扩散到皮层的PEO中，因而破坏了芯层物质在皮层物质中的均匀性。Sun et al. (Advanced Materials 2003, 15, (22): 1929-1932) respectively used polyethylene oxide (PEO) and polylactic acid (PLA) as skin materials, and dodecylthiophene (PDT), palladium acetate (Pd( OAc)2), polysulfone (PSU), and PEO are core materials, and core-skin fibers are prepared by coaxial electrospinning. The research results show that due to the small relative molecular weight of PDT, it cannot form fibers by itself, and the skin-core fiber can be obtained by encapsulating PDT in the core layer with PEO in the skin layer. However, PDT is not stable enough in the spinning process, and it is relatively easy to diffuse into the PEO of the skin layer, thus destroying the uniformity of the core layer material in the skin layer material.
R.Ruiz-Rosas等(Advanced Materials.2007，19(23)：1292-1296)分别将乙醇法木质素(Alcell木质素)乙醇溶液作为芯层，乙醇溶剂作为皮层，通过同轴电纺法，制备出直径为400nm-1μm的木质素纤维。但是，该研究只是通过同轴电纺技术阻止木质素溶液挥发过快的缺陷。同时，由于木质素相对分子质量偏低，且为非链状结构，导致该木素溶液粘弹性有限；由于该溶液体系电导率偏低，使该溶液受到的电场力仅能拉伸木质素液滴本身形成纤维，而不能增加更大的载荷，从而使其不能形成木质素基皮芯纤维。R.Ruiz-Rosas et al. (Advanced Materials.2007, 19(23): 1292-1296) respectively use the ethanol method lignin (Alcell lignin) ethanol solution as the core layer, and the ethanol solvent as the cortex, through the coaxial electrospinning method, Lignin fibers with a diameter of 400nm-1μm were prepared. However, this study is only a flaw in preventing the lignin solution from volatilizing too quickly through coaxial electrospinning technology. At the same time, due to the low relative molecular weight of lignin and its non-chain structure, the viscoelasticity of the lignin solution is limited; due to the low conductivity of the solution system, the electric field force on the solution can only stretch the lignin solution. The drops form fibers by themselves, without being able to add a larger load, making it impossible to form lignin-based sheath-core fibers.
目前，现有技术的限制因素主要在于不能同时协调好木质素可纺性、溶液电导率和溶剂挥发的关系，使之形成具有皮芯结构的纳/微米纤维。At present, the limiting factor of the existing technology is mainly that the relationship between the spinnability of lignin, the conductivity of the solution and the volatilization of the solvent cannot be well coordinated at the same time, so that it can form nano/micro fibers with a skin-core structure.
发明内容 Contents of the invention
为克服上述现有技术的不足之处，本发明提供一种木质素基皮芯结构纳/微米纤维的制备方法。可在木质素中加入一定量线性长链的合成高分子物质，并溶于合适的有机溶剂，首先使木质素溶液在保证其具有较高电导率的同时，提高了其可纺性；其次由于高分子和木质素间存在氢键等作用，降低了木质素固化时向皮层扩散的程度，避免了因封装而出现的芯层物质分布不均匀的问题。在此基础上可以对其他电纺条件进行调控，制备出皮芯结构的纳/微米纤维。In order to overcome the shortcomings of the above-mentioned prior art, the present invention provides a method for preparing lignin-based skin-core structure nano/micro fibers. A certain amount of linear long-chain synthetic polymer substances can be added to lignin and dissolved in a suitable organic solvent. First, the lignin solution can improve its spinnability while ensuring its high electrical conductivity; secondly, due to There are hydrogen bonds between polymers and lignin, which reduces the degree of diffusion of lignin to the cortex when it is solidified, and avoids the problem of uneven distribution of core material due to encapsulation. On this basis, other electrospinning conditions can be adjusted to prepare nano/micro fibers with skin-core structure.
本发明的另一目的在于提供一种木质素基皮芯结构纳/微米纤维，该纳/微米纤维具有纳/微米级、皮芯结构的性质。Another object of the present invention is to provide a lignin-based skin-core structure nano/micro fiber, the nano/micro fiber has properties of nano/micro scale and skin-core structure.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved through the following technical solutions:
一种木质素基皮芯结构纳/微米纤维的制备方法，其特征在于，包括以下步骤：A method for preparing lignin-based sheath-core structure nano/micron fibers, characterized in that it comprises the following steps:
(1)按质量份计，将木质素和石油基高分子的混合物1份加到1～20份有机溶剂中，混合均匀并使其完全溶解后，得到木质素混合溶液，所述混合物中木质素与石油基高分子的质量比为1∶1～20∶1；将1份天然或合成高分子加到4～25份溶剂中，混合均匀并使其完全溶解后，得到高分子溶液；(1) In terms of parts by mass, add 1 part of the mixture of lignin and petroleum-based polymers to 1 to 20 parts of organic solvents, mix evenly and completely dissolve it, and obtain a lignin mixed solution, in which lignin The mass ratio of prime and petroleum-based polymers is 1:1 to 20:1; add 1 part of natural or synthetic polymers to 4 to 25 parts of solvents, mix evenly and completely dissolve them, and obtain a polymer solution;
(2)进行同轴电纺，环境温度为10～50℃，环境相对湿度为5～70％，将木质素混合溶液和高分子溶液分别通入同轴针头的两层中，待溶液由同轴针头稳定挤出，在5～100kV的高压静电场作用下，得到木质素基皮芯结构纳/微米纤维(直径为100nm～5μm)。(2) Carry out coaxial electrospinning, the ambient temperature is 10～50°C, and the relative humidity of the environment is 5～70%. The lignin mixed solution and the polymer solution are respectively passed into the two layers of the coaxial needle. Stable extruding from the needle head, and under the action of a high-voltage electrostatic field of 5-100kV, a lignin-based skin-core structure nano/micron fiber (with a diameter of 100nm-5μm) is obtained.
优选地，步骤(1)中所述木质素混合溶液中的石油基高分子是下述高分子的一种或两种以上：聚丙烯腈、聚丙烯酸酯、聚氨酯、聚氧化乙烯、聚乙烯醇、聚乙烯吡咯烷酮、聚己内酯、聚己二酸己二胺、聚碳酸酯、聚苯并咪唑、聚苯胺、聚苯乙烯、聚对苯二甲酸二乙酯、聚氯乙烯、聚二茂铁二甲基硅烷。Preferably, the petroleum-based macromolecule in the lignin mixed solution described in step (1) is one or more of the following macromolecules: polyacrylonitrile, polyacrylate, polyurethane, polyethylene oxide, polyvinyl alcohol , polyvinylpyrrolidone, polycaprolactone, polyhexamethylene adipate, polycarbonate, polybenzimidazole, polyaniline, polystyrene, polyethylene terephthalate, polyvinyl chloride, polydicene Iron Dimethylsilane.
优选地，步骤(1)中所述木质素混合溶液中的有机溶剂是下述溶剂中的一种或两种以上：甲酸、甲醇、丙酮、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、四氢呋喃、1，4-二氧六环、二氯甲烷、三氯甲烷、三氟乙酸。Preferably, the organic solvent in the lignin mixed solution described in step (1) is one or more than two of the following solvents: formic acid, methanol, acetone, N,N-dimethylformamide, N,N -Dimethylacetamide, tetrahydrofuran, 1,4-dioxane, dichloromethane, chloroform, trifluoroacetic acid.
优选地，步骤(1)中所述的天然或合成高分子是下述高分子中的一种或两种以上：聚乳酸、壳聚糖、纤维素、微晶纤维素、醋酸纤维素、羧甲基纤维素、羟丙基纤维素、醋酸丁酸纤维素、纤维素硝酸酯、纤维素磺酸酯、聚丙烯腈、聚丙烯酸酯、聚氨酯、聚氧化乙烯、聚乙烯醇、聚乙烯吡咯烷酮、聚己内酯、聚己二酸己二胺、聚碳酸酯、聚苯并咪唑、聚苯胺、聚苯乙烯、聚对苯二甲酸二乙酯、聚氯乙烯、聚二茂铁二甲基硅烷。Preferably, the natural or synthetic macromolecule described in step (1) is one or more than two of the following macromolecules: polylactic acid, chitosan, cellulose, microcrystalline cellulose, cellulose acetate, carboxylated Methylcellulose, hydroxypropylcellulose, cellulose acetate butyrate, cellulose nitrate, cellulose sulfonate, polyacrylonitrile, polyacrylate, polyurethane, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, Polycaprolactone, polyhexamethylene adipate, polycarbonate, polybenzimidazole, polyaniline, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyferrocenedimethylsilane .
优选地，步骤(1)中所述高分子溶液中的溶剂是下述溶剂中的一种或两种以上：水、氢氧化钠水溶液、乙酸、丙酮、氯化锂/二甲基乙酰胺(二者为离子液体溶剂的组成，氯化锂是固体，其本身不是溶剂，且两种物质要配合使用，其中氯化锂和二甲基乙酰胺的质量比为5∶95～9∶91)、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、乙酸乙酯。Preferably, the solvent in the polymer solution described in step (1) is one or more than two of the following solvents: water, aqueous sodium hydroxide solution, acetic acid, acetone, lithium chloride/dimethylacetamide ( The two are the composition of the ionic liquid solvent, lithium chloride is a solid, it is not a solvent itself, and the two substances should be used in conjunction, wherein the mass ratio of lithium chloride and dimethylacetamide is 5:95～9:91) , N,N-dimethylformamide, N,N-dimethylacetamide, ethyl acetate.
优选地，所述木质素混合溶液和高分子溶液挤出速率的范围均为30～1000μL/h，挤出速率比为10∶1～1∶10。Preferably, both the extrusion rates of the lignin mixed solution and the polymer solution are in the range of 30-1000 μL/h, and the extrusion rate ratio is 10:1-1:10.
优选地，所述同轴针头内层内径为0.1～1mm，外层内径为0.5～2.5mm，且针头外层内径始终大于内层内径0.4～2mm，内层针头顶端超出外层针头0.1mm～3mm。Preferably, the inner diameter of the inner layer of the coaxial needle is 0.1-1 mm, the inner diameter of the outer layer is 0.5-2.5 mm, and the inner diameter of the outer layer of the needle is always greater than the inner diameter of the inner layer by 0.4-2 mm, and the top of the inner needle exceeds the outer needle by 0.1-2 mm. 3mm.
优选地，所述同轴电纺采用的装置包括高压静电发生器、储液输液装置、同轴针头和金属接地的收集板四个部分，其中正、负极分别连接到一根或多根同轴针头和收集板上；其中设定同轴针头针尖和收集板之间距离为5～40cm。Preferably, the device used in the coaxial electrospinning includes four parts: a high-voltage electrostatic generator, a liquid storage and infusion device, a coaxial needle, and a metal-grounded collecting plate, wherein the positive and negative electrodes are respectively connected to one or more coaxial The needle and the collection plate; wherein the distance between the tip of the coaxial needle and the collection plate is set to be 5-40 cm.
本发明相对于现有技术具有以下优点：Compared with the prior art, the present invention has the following advantages:
1)纤维的制备方法简单，条件温和，无需考虑木质素精制和溶剂挥发过快对纤维形成的影响；1) The fiber preparation method is simple, the conditions are mild, and there is no need to consider the influence of lignin refining and fast solvent volatilization on fiber formation;
2)通过加入合适的高分子和选用合适的有机溶剂来提高木质素溶液的粘度和电导率，使溶液液滴在同轴电纺过程中具有足够大的粘弹性和导电性被拉成纳/微米纤维，从而可以制备出木质素基皮芯结构纳/微米纤维；2) Increase the viscosity and conductivity of the lignin solution by adding a suitable polymer and selecting a suitable organic solvent, so that the solution droplets have sufficient viscoelasticity and conductivity during the coaxial electrospinning process to be pulled into nano/ Micron fibers, so that lignin-based skin-core structure nano/micron fibers can be prepared;
3)由于高分子与木质素间存在氢键等作用，降低了木质素向皮层扩散的程度，提高了芯层物质在纤维中的连续性和均匀性。3) Due to the presence of hydrogen bonds between polymers and lignin, the degree of lignin diffusion to the cortex is reduced, and the continuity and uniformity of the core material in the fiber is improved.
附图说明 Description of drawings
图1为同轴电纺装置的结构示意图。Figure 1 is a schematic diagram of the structure of the coaxial electrospinning device.
图2为实施例1所述的木质素基皮芯结构纳/微米纤维的扫描电镜照片，其中(a)为纤维整体视图，(b)为单根纤维断面视图。2 is a scanning electron micrograph of the lignin-based skin-core structure nano/micro fiber described in Example 1, wherein (a) is an overall view of the fiber, and (b) is a cross-sectional view of a single fiber.
具体实施方式 Detailed ways
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
1.芯层溶液的制备：将2.5g木质素和2.5g聚丙烯腈的混合物投入到100gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 2.5g lignin and 2.5g polyacrylonitrile into 100g N, N-dimethylacetamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚乳酸投入到50gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polylactic acid into 50g of N,N-dimethylformamide, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为5cm，同轴针头4的内层内径为0.1mm，外层内径为0.5mm(即针头外层内径大于内层内径0.4mm)，内层针头顶端超出外层0.1mm，高压静电发生器6的电压为5kV，环境温度为10℃，环境相对湿度为5％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1均以30μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle 4 of the electrospinning device and the grounded collecting plate 7 is 5 cm, the inner inner diameter of the coaxial needle 4 is 0.1 mm, and the outer inner diameter is 0.5 mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 0.4 mm) , the top of the inner layer of needles exceeds the outer layer by 0.1mm, the voltage of the high-voltage electrostatic generator 6 is 5kV, the ambient temperature is 10°C, and the relative humidity of the environment is 5%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed In the two liquid storage containers 2 of the high-voltage electrospinning device, use the infusion pump 1 to extrude from the containers at an extrusion rate of 30 μL/h (that is, the extrusion rate ratio of the core-skin two-layer solution is 1:1) , and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning solution jet is solidified, The nanofibers are formed and arranged in a disordered manner on the collecting plate 7 to form a fibrous film similar to a non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例2Example 2
1.芯层溶液的制备：将3.25g木质素和1.75g聚氨酯混合物投入到50gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put 3.25g of lignin and 1.75g of polyurethane mixture into 50g of N, N-dimethylformamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g纤维素投入到25g质量比为7∶93的氯化锂/二甲基乙酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5 g of cellulose into 25 g of lithium chloride/dimethylacetamide with a mass ratio of 7:93, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例3Example 3
1.芯层溶液的制备：将4.5g木质素和0.5g聚氧化乙烯的混合物投入到5g丙酮中，搅拌使其完全溶解，成为高分子溶液成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4.5g lignin and 0.5g polyethylene oxide into 5g acetone, stir to dissolve it completely, and become a polymer solution and a lignin mixed solution;
2.皮层溶液的制备：将5g醋酸纤维素投入到50g乙酸中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of cellulose acetate into 50g of acetic acid, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为40cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为50kV，环境温度为25℃，环境相对湿度为70％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以50μL/h、皮层以500μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶10)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 40cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5mm, and the outer layer inner diameter is 1.5mm (that is, the outer layer inner diameter of the needle head is greater than the inner layer inner diameter 1mm), The tip of the inner layer needle is 1 mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 50 kV, the ambient temperature is 25° C., and the ambient relative humidity is 70%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 50 μL/h and the cortex at an extrusion rate of 500 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:10), and then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例4Example 4
1.芯层溶液的制备：将3.5g木质素和1.5g聚乙烯醇的混合物投入到30g1，4-二氧六环中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.5g lignin and 1.5g polyvinyl alcohol into 30g 1,4-dioxane, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g微晶纤维素投入到20g质量比为5∶95的氯化锂/二甲基乙酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5 g of microcrystalline cellulose into 20 g of lithium chloride/dimethylacetamide with a mass ratio of 5:95, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为20cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为20kV，环境温度为25℃，环境相对湿度为40％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以50μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为4∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 20 cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5 mm, and the outer layer inner diameter is 1.5 mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1 mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 20kV, the ambient temperature is 25°C, and the relative humidity of the environment is 40%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 50 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 4: 1), then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例5Example 5
1.芯层溶液的制备：将4.25g木质素和0.75g聚乙烯吡咯烷酮的混合物投入到25g四氢呋喃中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4.25g lignin and 0.75g polyvinylpyrrolidone into 25g tetrahydrofuran, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g羧甲基纤维素投入到125g体积比为60∶40的水/丙酮中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of carboxymethylcellulose into 125g of water/acetone with a volume ratio of 60:40, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为0.8mm，外层内径为2mm(即针头外层内径大于内层内径1.2mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为30kV，环境温度为20℃，环境相对湿度为30％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以1000μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶5)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 25cm, the inner layer inner diameter of the coaxial needle head 4 is 0.8mm, and the outer layer inner diameter is 2mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1.2mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 30kV, the ambient temperature is 20°C, and the ambient relative humidity is 30%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 1000 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:5), and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例6Example 6
1.芯层溶液的制备：将4g木质素和1g聚己内酯的混合物投入到20g体积比为3∶1的二氯甲烷/甲醇中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4g lignin and 1g polycaprolactone into 20g of dichloromethane/methanol with a volume ratio of 3:1, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g羟丙基纤维素投入到30gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of hydroxypropyl cellulose into 30g of N,N-dimethylacetamide, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为50％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以500μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为5∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The top of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 50%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 500 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 5:1), then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例7Example 7
1.芯层溶液的制备：将3.25g木质素和1.75g聚碳酸酯的混合物投入到40g二氯甲烷中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.25g lignin and 1.75g polycarbonate into 40g methylene chloride, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g醋酸丁酸纤维素投入到35g乙酸乙酯中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of cellulose acetate butyrate into 35g of ethyl acetate, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例8Example 8
1.芯层溶液的制备：将4.75g木质素和0.25g聚己二酸己二胺混合物投入到40g甲酸中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put 4.75g of lignin and 0.25g of polyhexamethylene adipate mixture into 40g of formic acid, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g纤维素硝酸酯投入到35g丙酮中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of cellulose nitrate into 35g of acetone, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为40cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为50kV，环境温度为25℃，环境相对湿度为70％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以50μL/h、皮层以500μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶10)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 40cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5mm, and the outer layer inner diameter is 1.5mm (that is, the outer layer inner diameter of the needle head is greater than the inner layer inner diameter 1mm), The tip of the inner layer needle is 1 mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 50 kV, the ambient temperature is 25° C., and the ambient relative humidity is 70%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 50 μL/h and the cortex at an extrusion rate of 500 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:10), and then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例9Example 9
1.芯层溶液的制备：将3.5g木质素和1.5g聚苯并咪唑的混合物投入到45gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.5g lignin and 1.5g polybenzimidazole into 45g N, N-dimethylacetamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g羧甲基纤维素投入到125g体积比为60∶40的水/丙酮中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of carboxymethylcellulose into 125g of water/acetone with a volume ratio of 60:40, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为20cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为20kV，环境温度为25℃，环境相对湿度为40％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以50μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为4∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 20 cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5 mm, and the outer layer inner diameter is 1.5 mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1 mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 20kV, the ambient temperature is 25°C, and the relative humidity of the environment is 40%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 50 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 4: 1), then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例10Example 10
1.芯层溶液的制备：将4g木质素、0.2g聚苯胺和0.8g聚苯乙烯的混合物投入到100g三氯甲烷中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4g lignin, 0.2g polyaniline and 0.8g polystyrene into 100g chloroform, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚乳酸投入到50gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polylactic acid into 50g of N,N-dimethylformamide, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为5cm，同轴针头4的内层内径为0.1mm，外层内径为0.5mm(即针头外层内径大于内层内径0.4mm)，内层针头顶端超出外层0.1mm，高压静电发生器6的电压为5kV，环境温度为10℃，环境相对湿度为5％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1均以30μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle 4 of the electrospinning device and the grounded collecting plate 7 is 5 cm, the inner inner diameter of the coaxial needle 4 is 0.1 mm, and the outer inner diameter is 0.5 mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 0.4 mm) , the top of the inner layer of needles exceeds the outer layer by 0.1mm, the voltage of the high-voltage electrostatic generator 6 is 5kV, the ambient temperature is 10°C, and the relative humidity of the environment is 5%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed In the two liquid storage containers 2 of the high-voltage electrospinning device, use the infusion pump 1 to extrude from the containers at an extrusion rate of 30 μL/h (that is, the extrusion rate ratio of the core-skin two-layer solution is 1:1) , and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning solution jet is solidified, The nanofibers are formed and arranged in a disordered manner on the collecting plate 7 to form a fibrous film similar to a non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例11Example 11
1.芯层溶液的制备：将4.25g木质素和0.75g聚对苯二甲酸二乙酯的混合物投入到30g体积比为1∶1的二氯乙烷/三氟乙酸中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: the mixture of 4.25g lignin and 0.75g polyethylene terephthalate is dropped into 30g of dichloroethane/trifluoroacetic acid with a volume ratio of 1:1, and stirred to make it completely Dissolved to become a lignin mixed solution;
2.皮层溶液的制备：将5g聚乳酸投入到50gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polylactic acid into 50g of N,N-dimethylformamide, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为0.8mm，外层内径为2mm(即针头外层内径大于内层内径1.2mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为30kV，环境温度为20℃，环境相对湿度为30％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以1000μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶5)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 25cm, the inner layer inner diameter of the coaxial needle head 4 is 0.8mm, and the outer layer inner diameter is 2mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1.2mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 30kV, the ambient temperature is 20°C, and the ambient relative humidity is 30%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 1000 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:5), and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例12Example 12
1.芯层溶液的制备：将4g木质素和1g聚氯乙烯的混合物投入到20g体积比为1∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put the mixture of 4g lignin and 1g polyvinyl chloride into 20g tetrahydrofuran/N,N-dimethylformamide with a volume ratio of 1:1, stir to make it completely dissolve, and become a lignin Primer mixed solution;
2.皮层溶液的制备：将5g纤维素磺酸酯投入到60g质量分数为20％的氢氧化钠水溶液中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5 g of cellulose sulfonate into 60 g of 20% sodium hydroxide aqueous solution, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为50％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以500μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为5∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The top of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 50%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 500 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 5:1), then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例13Example 13
1.芯层溶液的制备：将3.25g木质素和1.75g聚二茂铁二甲基硅烷的混合物投入到30g体积比为9∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: the mixture of 3.25g lignin and 1.75g polyferrocenedimethylsilane is dropped into 30g volume ratio of 9: 1 tetrahydrofuran/N, N-dimethylformamide, stirring Make it dissolve completely and become a lignin mixed solution;
2.皮层溶液的制备：将5g纤维素投入到35g质量比为9∶91的氯化锂/二甲基乙酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5 g of cellulose into 35 g of lithium chloride/dimethylacetamide with a mass ratio of 9:91, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例14Example 14
1.芯层溶液的制备：将2.5g木质素和2.5g聚丙烯腈的混合物投入到100gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 2.5g lignin and 2.5g polyacrylonitrile into 100g N, N-dimethylacetamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚碳酸酯投入到50g二氯甲烷中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polycarbonate into 50g of dichloromethane, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到两个尺寸相同的同轴针头4和收集板7上，两个同轴针头4同高度平行排列，两针头轴间距优选30mm，两个同轴针头4和收集板7均位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为5cm，同轴针头4的内层内径为0.1mm，外层内径为0.5mm(即针头外层内径大于内层内径0.4mm)，内层针头顶端超出外层0.1mm，高压静电发生器6的电压为5kV，环境温度为10℃，环境相对湿度为5％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1均以30μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative poles are respectively connected to two coaxial needles 4 and the collecting plate 7 of the same size, and the two coaxial needles 4 have the same height Arranged in parallel, the axial distance between the two needles is preferably 30 mm, and the two coaxial needles 4 and the collecting plate 7 are located in the constant temperature and humidity container 5 . The distance between the coaxial needle 4 of the electrospinning device and the grounded collecting plate 7 is 5 cm, the inner inner diameter of the coaxial needle 4 is 0.1 mm, and the outer inner diameter is 0.5 mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 0.4 mm) , the top of the inner layer of needles exceeds the outer layer by 0.1mm, the voltage of the high-voltage electrostatic generator 6 is 5kV, the ambient temperature is 10°C, and the relative humidity of the environment is 5%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed In the two liquid storage containers 2 of the high-voltage electrospinning device, use the infusion pump 1 to extrude from the containers at an extrusion rate of 30 μL/h (that is, the extrusion rate ratio of the core-skin two-layer solution is 1:1) , and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning solution jet is solidified, The nanofibers are formed and arranged in a disordered manner on the collecting plate 7 to form a fibrous film similar to a non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例15Example 15
1.芯层溶液的制备：将3.25g木质素和1.75g聚氨酯的混合物投入到80gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.25g lignin and 1.75g polyurethane into 80g N, N-dimethylformamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚己二酸己二胺投入到40g甲酸中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polyhexamethylene adipate into 40g of formic acid, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例16Example 16
1.芯层溶液的制备：将4.75木质素和0.25g聚氧化乙烯的混合物投入到50g丙酮中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4.75 g of lignin and 0.25 g of polyethylene oxide into 50 g of acetone, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚丙烯酸酯投入到30gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polyacrylate into 30g of N,N-dimethylformamide, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为40cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为50kV，环境温度为25℃，环境相对湿度为70％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以50μL/h、皮层以500μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶10)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 40cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5mm, and the outer layer inner diameter is 1.5mm (that is, the outer layer inner diameter of the needle head is greater than the inner layer inner diameter 1mm), The tip of the inner layer needle is 1 mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 50 kV, the ambient temperature is 25° C., and the ambient relative humidity is 70%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 50 μL/h and the cortex at an extrusion rate of 500 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:10), and then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例17Example 17
1.芯层溶液的制备：将3.5g木质素和1.5g聚乙烯醇的混合物投入到30g1，4-二氧六环中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.5g lignin and 1.5g polyvinyl alcohol into 30g 1,4-dioxane, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚苯胺和聚苯乙烯的混合物投入到100g三氯甲烷中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polyaniline and polystyrene mixture into 100g of chloroform, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为20cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为20kV，环境温度为25℃，环境相对湿度为40％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以50μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为4∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 20 cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5 mm, and the outer layer inner diameter is 1.5 mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1 mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 20kV, the ambient temperature is 25°C, and the relative humidity of the environment is 40%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 50 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 4: 1), then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例18Example 18
1.芯层溶液的制备：将4.25g木质素和1.75g聚乙烯吡咯烷酮的混合物投入到25g四氢呋喃中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4.25g lignin and 1.75g polyvinylpyrrolidone into 25g tetrahydrofuran, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚对苯二甲酸二乙酯投入到40g体积比为1∶1的二氯乙烷/三氟乙酸中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polyethylene terephthalate into 40g of dichloroethane/trifluoroacetic acid with a volume ratio of 1:1, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为0.8mm，外层内径为2mm(即针头外层内径大于内层内径1.2mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为30kV，环境温度为20℃，环境相对湿度为30％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以1000μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶5)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 25cm, the inner layer inner diameter of the coaxial needle head 4 is 0.8mm, and the outer layer inner diameter is 2mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1.2mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 30kV, the ambient temperature is 20°C, and the ambient relative humidity is 30%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 1000 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:5), and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例19Example 19
1.芯层溶液的制备：将4g木质素和1g聚己内酯的混合物投入到20g体积比为3∶1的二氯甲烷/甲醇中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4g lignin and 1g polycaprolactone into 20g of dichloromethane/methanol with a volume ratio of 3:1, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚氯乙烯投入到20g体积比为1∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polyvinyl chloride into 20g of tetrahydrofuran/N,N-dimethylformamide with a volume ratio of 1:1, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为50％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以500μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为5∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The top of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 50%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 500 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 5: 1), then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例20Example 20
1.芯层溶液的制备：将3.25g木质素和1.75g聚碳酸酯混合物投入到40g二氯甲烷中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put 3.25g of lignin and 1.75g of polycarbonate mixture into 40g of methylene chloride, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚二茂铁二甲基硅烷投入到36g体积比为9∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polyferrocenedimethylsilane into 36g of tetrahydrofuran/N,N-dimethylformamide with a volume ratio of 9:1, stir to make it completely dissolve, and become a polymer solution ;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例21Example 21
1.芯层溶液的制备：将4.75g木质素和0.25g聚己二酸己二胺混合物投入到40g甲酸中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put 4.75g of lignin and 0.25g of polyhexamethylene adipate mixture into 40g of formic acid, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚氨酯投入到80gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polyurethane into 80g of N,N-dimethylformamide, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为40cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为50kV，环境温度为25℃，环境相对湿度为70％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以50μL/h、皮层以500μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶10)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 40cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5mm, and the outer layer inner diameter is 1.5mm (that is, the outer layer inner diameter of the needle head is greater than the inner layer inner diameter 1mm), The tip of the inner layer needle is 1 mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 50 kV, the ambient temperature is 25° C., and the ambient relative humidity is 70%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 50 μL/h and the cortex at an extrusion rate of 500 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:10), and then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例22Example 22
1.芯层溶液的制备：将3.25g木质素和1.75g聚丙烯酸酯的混合物投入到25gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 3.25g lignin and 1.75g polyacrylate into 25g N, N-dimethylformamide, stir to make it completely dissolve, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚苯并咪唑投入到50gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polybenzimidazole into 50g of N,N-dimethylacetamide, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为20cm，同轴针头4的内层内径为0.5mm，外层内径为1.5mm(即针头外层内径大于内层内径1mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为20kV，环境温度为25℃，环境相对湿度为40％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以50μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为4∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 20 cm, the inner layer inner diameter of the coaxial needle head 4 is 0.5 mm, and the outer layer inner diameter is 1.5 mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1 mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 20kV, the ambient temperature is 25°C, and the relative humidity of the environment is 40%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 50 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 4: 1), then the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例23Example 23
1.芯层溶液的制备：将4g木质素、0.2g聚苯胺和0.8g聚苯乙烯的混合物投入到100g三氯甲烷中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put a mixture of 4g lignin, 0.2g polyaniline and 0.8g polystyrene into 100g chloroform, stir to dissolve it completely, and become a lignin mixed solution;
2.皮层溶液的制备：将5g聚乙烯醇投入到40g1，4-二氧六环中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polyvinyl alcohol into 40g of 1,4-dioxane, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为5cm，同轴针头4的内层内径为0.1mm，外层内径为0.5mm(即针头外层内径大于内层内径0.4mm)，内层针头顶端超出外层0.1mm，高压静电发生器6的电压为5kV，环境温度为10℃，环境相对湿度为5％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1均以30μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为500nm～3μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle 4 of the electrospinning device and the grounded collecting plate 7 is 5 cm, the inner inner diameter of the coaxial needle 4 is 0.1 mm, and the outer inner diameter is 0.5 mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 0.4 mm) , the top of the inner layer of needles exceeds the outer layer by 0.1mm, the voltage of the high-voltage electrostatic generator 6 is 5kV, the ambient temperature is 10°C, and the relative humidity of the environment is 5%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed In the two liquid storage containers 2 of the high-voltage electrospinning device, use the infusion pump 1 to extrude from the containers at an extrusion rate of 30 μL/h (that is, the extrusion rate ratio of the core-skin two-layer solution is 1:1) , and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning solution jet is solidified, The nanofibers are formed and arranged in a disordered manner on the collecting plate 7 to form a fibrous film similar to a non-woven fabric, which is the target product. The fiber diameter is 500nm～3μm.
实施例24Example 24
1.芯层溶液的制备：将4.25g木质素和0.75g聚对苯二甲酸二乙酯的混合物投入到30g体积比为1∶1的二氯乙烷/三氟乙酸中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: the mixture of 4.25g lignin and 0.75g polyethylene terephthalate is dropped into 30g of dichloroethane/trifluoroacetic acid with a volume ratio of 1:1, and stirred to make it completely Dissolved to become a lignin mixed solution;
2.皮层溶液的制备：将5g聚乙烯醇投入到40g1，4-二氧六环中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of the cortex solution: put 5g of polyvinyl alcohol into 40g of 1,4-dioxane, stir to dissolve it completely, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为0.8mm，外层内径为2mm(即针头外层内径大于内层内径1.2mm)，内层针头顶端超出外层1mm，高压静电发生器6的电压为30kV，环境温度为20℃，环境相对湿度为30％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以200μL/h、皮层以1000μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为1∶5)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the coaxial needle head 4 of the electrospinning device and the grounded collecting plate 7 is 25cm, the inner layer inner diameter of the coaxial needle head 4 is 0.8mm, and the outer layer inner diameter is 2mm (that is, the inner layer inner diameter of the needle head is greater than the inner layer inner diameter of 1.2mm), The tip of the inner layer needle is 1mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 30kV, the ambient temperature is 20°C, and the ambient relative humidity is 30%. The lignin mixed solution and polymer solution obtained in steps 1 and 2 are respectively placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 200 μL/h and the cortex at an extrusion rate of 1000 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 1:5), and then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例25Example 25
1.芯层溶液的制备：将4g木质素和1g聚氯乙烯的混合物投入到20g体积比为1∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: put the mixture of 4g lignin and 1g polyvinyl chloride into 20g tetrahydrofuran/N,N-dimethylformamide with a volume ratio of 1:1, stir to make it completely dissolve, and become a lignin Primer mixed solution;
2.皮层溶液的制备：将5g聚己内酯投入到25比为3∶1的二氯甲烷/甲醇中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 5g of polycaprolactone into 25 methylene chloride/methanol with a ratio of 3:1, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为50％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以500μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为5∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The top of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 50%. The lignin mixed solution and the polymer solution obtained in steps 1 and 2 are placed under high pressure In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 500 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 5:1), then make the skin-core two-layer solution (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) to be ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
实施例26Example 26
1.芯层溶液的制备：将3.25g木质素和1.75g聚二茂铁二甲基硅烷的混合物投入到30g体积比为9∶1的四氢呋喃/N，N-二甲基甲酰胺中，搅拌使其完全溶解，成为木质素混合溶液；1. Preparation of the core layer solution: the mixture of 3.25g lignin and 1.75g polyferrocenedimethylsilane is dropped into 30g volume ratio of 9: 1 tetrahydrofuran/N, N-dimethylformamide, stirring Make it dissolve completely and become a lignin mixed solution;
2.皮层溶液的制备：将4g聚丙烯腈投入到50gN，N-二甲基甲酰胺中，搅拌使其完全溶解，成为高分子溶液；2. Preparation of cortex solution: put 4g of polyacrylonitrile into 50g of N,N-dimethylformamide, stir to make it completely dissolve, and become a polymer solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为高分子溶液，芯层溶液为木质素混合溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为2μm～5μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), then the two-layer solutions of the skin and core (the skin layer solution is a polymer solution, and the core layer solution is a lignin mixed solution) are ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 2 μm to 5 μm.
实施例27Example 27
1.芯层溶液的制备：将3g聚氧化乙烯投入到50g丙酮中，搅拌使其完全溶解，成为高分子溶液；1. Preparation of the core layer solution: put 3g of polyethylene oxide into 50g of acetone, stir to dissolve it completely, and become a polymer solution;
2.皮层溶液的制备：将3.5g木质素和1.5g聚苯并咪唑的混合物投入到45gN，N-二甲基乙酰胺中，搅拌使其完全溶解，成为木质素混合溶液；2. Preparation of cortex solution: put the mixture of 3.5g lignin and 1.5g polybenzimidazole into 45g N, N-dimethylacetamide, stir to make it completely dissolve, and become lignin mixed solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为木质素混合溶液，芯层溶液为高分子溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), and then the skin-core two-layer solution (the skin layer solution is a lignin mixed solution, and the core layer solution is a polymer solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100nm-2μm.
实施例28Example 28
1.芯层溶液的制备：将5g质量比为65∶35的木质素和聚碳酸酯混合物投入到40g二氯甲烷中，搅拌使其完全溶解，成为高分子溶液；1. Preparation of the core layer solution: 5 g of a mixture of lignin and polycarbonate with a mass ratio of 65:35 are put into 40 g of methylene chloride, stirred to completely dissolve it, and become a polymer solution;
2.皮层溶液的制备：将4g木质素和1g聚乙烯醇的混合物投入到40g1，4-二氧六环中，搅拌使其完全溶解，成为木质素混合溶液；2. Preparation of the cortex solution: put a mixture of 4g lignin and 1g polyvinyl alcohol into 40g 1,4-dioxane, stir to make it completely dissolve, and become a lignin mixed solution;
3.同轴电纺：使用如图1所示的同轴电纺装置，其中正、负极分别连接到同轴针头4和收集板7上，同轴针头4和收集板7位于恒温恒湿容器5内。电纺装置同轴针头4和接地的收集板7之间距离为25cm，同轴针头4的内层内径为1mm，外层内径为2.5mm(即针头外层内径大于内层内径1.5mm)，内层针头顶端超出外层3mm，高压静电发生器6的电压为100kV，环境温度为50℃，环境相对湿度为10％，将步骤1、2所得木质素混合溶液和高分子溶液分别置于高压静电纺丝装置的两个贮液容器2中，用输液泵1芯层以1000μL/h、皮层以100μL/h的挤出速率从容器中挤出(即芯皮两层溶液的挤出速率比为10∶1)，然后使皮芯两层溶液(皮层溶液为木质素混合溶液，芯层溶液为高分子溶液)分别从同轴针头4的外层和内层喷出，喷出的纺丝溶液射流被固化，形成纳米纤维，以无序状排列在收集板7上，形成类似无纺布状的纤维膜，即为目的产物。纤维直径为100nm～2μm。3. Coaxial electrospinning: Use the coaxial electrospinning device shown in Figure 1, wherein the positive and negative electrodes are connected to the coaxial needle 4 and the collecting plate 7 respectively, and the coaxial needle 4 and the collecting plate 7 are located in a constant temperature and humidity container within 5. The distance between the electrospinning device coaxial needle 4 and the grounded collection plate 7 is 25cm, the inner inner diameter of the coaxial needle 4 is 1mm, and the outer inner diameter is 2.5mm (that is, the outer inner diameter of the needle is greater than the inner inner diameter of 1.5mm), The tip of the inner layer needle is 3mm beyond the outer layer, the voltage of the high-voltage electrostatic generator 6 is 100kV, the ambient temperature is 50°C, and the ambient relative humidity is 10%. In the two liquid storage containers 2 of the electrospinning device, use the infusion pump 1 to extrude the core layer from the container at an extrusion rate of 1000 μL/h and the cortex at an extrusion rate of 100 μL/h (that is, the ratio of the extrusion rate of the core-skin two-layer solution to 10:1), and then the skin-core two-layer solution (the skin layer solution is a lignin mixed solution, and the core layer solution is a polymer solution) is ejected from the outer layer and the inner layer of the coaxial needle 4 respectively, and the ejected spinning The solution jet is solidified to form nanofibers, which are randomly arranged on the collecting plate 7 to form a fibrous film similar to non-woven fabric, which is the target product. The fiber diameter is 100 nm to 2 μm.
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| CN103774276B (en) * | 2014-01-13 | 2016-05-04 | 东华大学 | Adopt physical blending to prepare the method for lignin/polyacrylonitrile blended melt spun fibre |
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| CN104593902B (en) * | 2015-02-15 | 2017-01-04 | 东华大学 | A kind of preparation method of carbon fiber precursor polyacrylonitrile/lignin fibre |
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| CN109537071A (en) * | 2018-12-06 | 2019-03-29 | 南通纺织丝绸产业技术研究院 | A method of preparing the nanofiber of multilayered structure |
| CN110318105B (en) * | 2019-05-28 | 2020-11-27 | 武汉纺织大学 | A centrifugal spraying device for bidirectional sheath-core fibers |
| CN111005092B (en) * | 2019-11-25 | 2022-10-21 | 东北林业大学 | Preparation method of alkali lignin-based porous carbon fibers and tin oxide composite nanomaterials |
| CN111235697A (en) * | 2020-02-28 | 2020-06-05 | 西安理工大学 | A kind of preparation method of high wave absorbing performance lignin-based carbon material |
| CN114351284A (en) * | 2022-01-18 | 2022-04-15 | 上海理工大学 | Method for preparing porous nano polymer fiber through improved coaxial electrospinning process |
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