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CN106319687B - A kind of serialization electrospinning process of sodium alginate nano fiber - Google Patents

A kind of serialization electrospinning process of sodium alginate nano fiber
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CN106319687B
CN106319687BCN201610670070.7ACN201610670070ACN106319687BCN 106319687 BCN106319687 BCN 106319687BCN 201610670070 ACN201610670070 ACN 201610670070ACN 106319687 BCN106319687 BCN 106319687B
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sodium alginate
borax
electrospinning
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CN106319687A (en
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谭业强
隋坤艳
窦雪宇
夏延致
吴淑贤
张庆旭
桑震
王立斌
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Qingdao University
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本发明公开了一种海藻酸钠纳米纤维的连续化静电纺丝方法,其在现有技术的基础上,通过以硼砂为化学交联剂,对海藻酸钠进行化学交联,并采用液氮速冻与冻干相结合的方式,对交联后的海藻酸钠凝胶进行干燥处理,以控制可逆反应进行的方向,进一步强化交联效果,从而较好地解决了现有技术中,分子链交联度不高、不稳定,可纺性差,以及纺丝成形的纤维内部微观结构均匀性差等系列问题。更为重要的是,可有效保证纺丝液的粘度这一重要的可纺性指标始终稳定在一个较窄的理想范围,从而保证生产过程的连续化。本发明生产过程连续稳定、工艺控制简单、纤维粗细均匀、产品质量有保证且稳定性好。The invention discloses a continuous electrospinning method for sodium alginate nanofibers. On the basis of the prior art, sodium alginate is chemically crosslinked by using borax as a chemical crosslinking agent, and liquid nitrogen is used to Combining quick-freezing and freeze-drying, the cross-linked sodium alginate gel is dried to control the direction of the reversible reaction and further strengthen the cross-linking effect, thereby better solving the problem of molecular chain in the prior art. A series of problems such as low degree of crosslinking, instability, poor spinnability, and poor uniformity of the internal microstructure of the fiber formed by spinning. More importantly, it can effectively ensure that the viscosity of the spinning solution, which is an important spinnability index, is always stable in a narrow ideal range, thereby ensuring the continuity of the production process. The invention has continuous and stable production process, simple process control, uniform fiber thickness, guaranteed product quality and good stability.

Description

Translated fromChinese
一种海藻酸钠纳米纤维的连续化静电纺丝方法A continuous electrospinning method for sodium alginate nanofibers

技术领域technical field

本发明一种海藻酸钠纳米纤维的生产方法,尤其涉及一种海藻酸钠纳米纤维的连续化静电纺丝方法。The invention relates to a method for producing sodium alginate nanofibers, in particular to a continuous electrospinning method for sodium alginate nanofibers.

背景技术Background technique

静电纺丝具有制造装置简单、纺丝成本低廉、可纺物质种类繁多、工艺可控等优点,是一种高效的纳米纤维制备方法,可以纺制出直径为几十到几百的纳米纤维。Electrospinning has the advantages of simple manufacturing equipment, low spinning cost, a wide variety of spinnable materials, and controllable process. It is an efficient method for preparing nanofibers, and can spin nanofibers with diameters ranging from tens to hundreds.

采用静电纺丝工艺制备出的纳米纤维,具有很高的比表面积、高孔隙率及良好的延展性。目前,已有许多聚合物通过静电纺丝法成功地制备纳米纤维。Nanofibers prepared by electrospinning process have high specific surface area, high porosity and good ductility. At present, many polymers have been successfully prepared into nanofibers by electrospinning.

但是,现有研究表明:通过静电纺丝制备纯海藻酸钠纳米纤维是非常困难的(参见:Carbohydr Polym,20l1,85(1):276-279)。原因在于,海藻酸钠分子链段呈刚性,其分子链总是紧密地重叠在一起,不能形成牢固的、稳定程度较高的有效分子链缠结,因而,海藻酸钠纺丝液在喷射过程中因缺乏弹性,无法形成以稳定的电射流。However, existing studies have shown that it is very difficult to prepare pure sodium alginate nanofibers by electrospinning (see: Carbohydr Polym, 20l1, 85(1):276-279). The reason is that the molecular chain segment of sodium alginate is rigid, and its molecular chains are always tightly overlapped together, which cannot form a firm and highly stable effective molecular chain entanglement. Therefore, the sodium alginate spinning solution is Because of the lack of elasticity, it is impossible to form a stable electric jet.

现有技术中,为解决上述技术问题,人们普遍采用在海藻酸钠溶液/凝胶体系中加入二价金属盐(氯化钙或氯化镁等)溶液作为交联剂进行交联反应,以增加海藻酸盐分子链间的缠结度的技术手段,以适应静电纺丝工艺的需要,并取得了一定的效果。如:In the prior art, in order to solve the above-mentioned technical problems, it is generally adopted to add a divalent metal salt (calcium chloride or magnesium chloride, etc.) The technical means of the degree of entanglement between acid salt molecular chains is used to meet the needs of the electrospinning process, and certain effects have been achieved. like:

中国专利申请CN105457094A公开了一种氯化钙交联的海藻酸钠纳米纤维支架材料及其制备方法,其所使用的交联剂成分为氯化钙稀溶液。Chinese patent application CN105457094A discloses a sodium alginate nanofiber scaffold material crosslinked by calcium chloride and a preparation method thereof, and the crosslinking agent component used is dilute calcium chloride solution.

中国专利申请CN102071497A公开了一种海藻酸钠纳米纤维的制备方法,其采用将海藻酸钠粉末分散于乙醇和水的混合溶液中,再加入一定量的氯化钙或氯化镁作为交联剂,然后,通过静电纺丝制备轻度交联的海藻酸钠纳米纤维。Chinese patent application CN102071497A discloses a method for preparing sodium alginate nanofibers, which uses sodium alginate powder dispersed in a mixed solution of ethanol and water, and then adds a certain amount of calcium chloride or magnesium chloride as a crosslinking agent, and then , to prepare lightly crosslinked sodium alginate nanofibers by electrospinning.

上述这两种技术,均可一定程度地改善了海藻酸钠/盐的分子链缠结度,实现了海藻酸盐纳米纤维的静电纺丝成形。但是,由于都属于物理交联,因而存在共同的缺点:一是,交联之后的海藻酸钠/盐分子链的缠结牢度、均匀性和稳定性相对较差;二是,由于交联反应与分解反应是一对可逆反应,在(液相)反应体系中,很难获得较为满意的、适于静电纺丝工艺要求的交联程度,进而保证进入静电纺丝设备中的海藻酸钠/盐纺丝液良好的粘度指标;三是,由于只能通过延长交联反应的时间,以保证交联反应进行程度(金属离子置换率或缓慢释放效率),使得整个工艺步骤耗时长,制约了生产效率的提高。四是,物理交联所得的溶液的均一度较差,因为离子交联海藻酸钠一般比较迅速(除非三中提到的离子置换和缓慢释放),所以一般采用向海藻酸钠中缓慢滴加交联剂溶液的方法,但是这一方法也无法保证溶液的均一性。The above two technologies can improve the degree of molecular chain entanglement of sodium alginate/salt to a certain extent, and realize the electrospinning of alginate nanofibers. However, because they all belong to physical crosslinking, there are common disadvantages: first, the entanglement fastness, uniformity and stability of the sodium alginate/salt molecular chain after crosslinking are relatively poor; Reaction and decomposition reaction are a pair of reversible reactions. In the (liquid phase) reaction system, it is difficult to obtain a satisfactory cross-linking degree suitable for the requirements of the electrospinning process, thereby ensuring that the sodium alginate entering the electrospinning equipment /Salt spinning solution has a good viscosity index; the third is, because the cross-linking reaction can only be guaranteed by prolonging the time of the cross-linking reaction (metal ion replacement rate or slow release efficiency), the entire process step is time-consuming and restricts improved production efficiency. The fourth is that the homogeneity of the solution obtained by physical crosslinking is poor, because ionically crosslinked sodium alginate is generally relatively rapid (unless the ion replacement and slow release mentioned in the third), so it is generally used to slowly drop into sodium alginate The method of cross-linking agent solution, but this method can not guarantee the homogeneity of the solution.

正是由于这几个方面的不足,使得海藻酸钠纳米纤维的静电纺丝生产过程中,一方面,可纺性差,纤维硬而脆,极易出现断头,造成纺丝困难,无法实现真正意义上的静电纺丝连续化生产;另一方面,由于海藻酸盐分子链与分子链之间的“缠结”与“解缠”处处随机并存,使得所纺制出的纤维在微观结构上,也别是所纺制出的纳米纤维的直径波动大,粗细不均匀,并且在纤维长度方向上,海藻酸盐分子链结合牢度、分布密度与致密程度等方面存在较大的差异,导致纤维质量稳定性差。It is precisely because of these deficiencies that in the electrospinning production process of sodium alginate nanofibers, on the one hand, the spinnability is poor, the fibers are hard and brittle, and the fibers are prone to broken ends, which makes spinning difficult and cannot achieve true spinning. Electrospinning in the sense of continuous production; on the other hand, due to the random coexistence of "entanglement" and "untanglement" between the molecular chains of alginate, the fibers spun have a microstructure , especially the diameter of the spun nanofiber fluctuates greatly, the thickness is uneven, and in the fiber length direction, there are large differences in the binding fastness, distribution density and compactness of the alginate molecular chain, which leads to Fiber quality stability is poor.

一言以蔽之:微观上,所纺制出的海藻酸盐纳米纤维“各向异性”、纤维直径均匀性差,纤维质量稳定性差,成品率低,且其静电纺丝过程中,工艺控制难度大、成品率低。In a nutshell: Microscopically, the spun alginate nanofibers are "anisotropic", have poor fiber diameter uniformity, poor fiber quality stability, low yield, and difficult process control during the electrospinning process. Large, low yield.

发明内容Contents of the invention

本发明的目的是,提供一种海藻酸钠纳米纤维的连续化静电纺丝方法,其工艺控制简单、纺丝液的可纺性好,所纺制出的海藻酸钠纳米纤维粗细均匀、内部结构均一性好、产品质量稳定,生产成本相对较低。The object of the present invention is to provide a continuous electrospinning method for sodium alginate nanofibers, which has simple process control and good spinnability of the spinning solution, and the spun sodium alginate nanofibers are uniform in thickness and internal Good structural uniformity, stable product quality, and relatively low production costs.

本发明为实现上述目的需要解决的技术问题是,如何获得海藻酸钠理想化的分子链与分子链之间的牢靠地、稳定的、均匀的有效缠结(度),以稳定纺丝液的粘度性能指标,进而有效解决连续化静电纺丝成形困难的技术问题。The technical problem that the present invention needs to solve for realizing above-mentioned object is, how to obtain the idealized molecular chain of sodium alginate and between the molecular chains firmly, stable, uniform effective entanglement (degree), to stabilize the spinning solution Viscosity performance index, and then effectively solve the technical problem of continuous electrospinning forming difficulties.

本发明为解决上述技术问题所采用的技术方案是,一种海藻酸钠纳米纤维的连续化静电纺丝方法,其特征在于,包括以下步骤:The technical solution adopted by the present invention for solving the above-mentioned technical problems is, a kind of continuous electrospinning method of sodium alginate nanofiber, it is characterized in that, comprises the following steps:

第一步,原料准备The first step, raw material preparation

按质量份数,分别称取硼砂1-5份、海藻酸钠6-12份,备用;According to the number of parts by mass, take 1-5 parts of borax and 6-12 parts of sodium alginate respectively, and set aside;

第二步,纺丝液的制备The second step, the preparation of spinning solution

将所取硼砂加水配制成浓度为0.01-1M的硼砂水溶液;然后,在40-60℃下,边搅拌边缓慢将所取海藻酸钠加入到上述硼砂水溶液中,交联反应3h后,得到经过化学交联的海藻酸钠凝胶;The obtained borax is added with water to prepare a borax aqueous solution with a concentration of 0.01-1M; then, at 40-60°C, slowly add the obtained sodium alginate into the above-mentioned borax aqueous solution while stirring, and after a cross-linking reaction for 3 hours, the obtained Chemically cross-linked alginate gel;

将所得到的海藻酸钠凝胶用液氮冷冻成冰后,取出并置于冷冻干燥器中,在-20--50℃下冷冻1-2.5h,得到干燥的海藻酸钠固形物;Freeze the obtained sodium alginate gel into ice with liquid nitrogen, take it out and place it in a freeze dryer, and freeze it at -20--50°C for 1-2.5 hours to obtain dry sodium alginate solids;

将所得干燥的海藻酸钠固形物研磨成粉后,加入40-60℃去离子水溶解,配制成质量百分比浓度为1%-5%的溶液,静置脱泡或真空脱泡后,待粘度达到0.4-3Pa.s时,即成纺丝液;Grind the obtained dried sodium alginate solid into powder, add 40-60°C deionized water to dissolve, prepare a solution with a concentration of 1%-5% by mass percentage, and let it stand for defoaming or vacuum defoaming. When it reaches 0.4-3Pa.s, it becomes spinning solution;

第三步,海藻酸钠纳米纤维的纺制The third step, the spinning of sodium alginate nanofibers

将纺丝液加入到静电纺丝设备的注射器中,开启变压器进行静电纺丝,即可得到海藻酸钠纳米纤维。Add the spinning solution into the syringe of the electrospinning equipment, turn on the transformer and perform electrospinning to obtain sodium alginate nanofibers.

上述技术方案直接带来的技术效果是:1、采用化学交联的方法,由于交联反应所形成的是共价键,其结合牢度、稳定性,“天生地”远高于物理交联(氢键和/或分子间引力)的结合牢度和稳定性,具有物理交联无法实现的交联力度。2、采用化学交联的方法,交联反应需要一定的时间,不会立刻在局部交联,而物理交联一般交联速度较快,而且需采用滴加的方式,容易导致局部交联而交联不均匀,所以化学交联具有物理交联无法实现的交联缠绕的均匀性。The technical effects directly brought by the above technical solutions are: 1. Using the method of chemical cross-linking, since the cross-linking reaction forms a covalent bond, its binding fastness and stability are "naturally" much higher than physical cross-linking (Hydrogen bond and/or intermolecular attraction) binding fastness and stability, with cross-linking strength that cannot be achieved by physical cross-linking. 2. Using the method of chemical cross-linking, the cross-linking reaction takes a certain amount of time, and it will not be locally cross-linked immediately, while physical cross-linking generally has a faster cross-linking speed, and it needs to be added dropwise, which may easily lead to partial cross-linking and Cross-linking is not uniform, so chemical cross-linking has the uniformity of cross-linking that cannot be achieved by physical cross-linking.

为更好地本发明的技术特点,下面结合化学反应式,进行简单的解释与说明。In order to better understand the technical characteristics of the present invention, a simple explanation and description will be given below in conjunction with the chemical reaction formula.

上述技术方案中,化学交联过程的反应式如下:In the above technical scheme, the reaction formula of the chemical crosslinking process is as follows:

从上式中不难看出:海藻酸钠的羟基和硼砂发生缩合反应,从而达到交联的目的,均匀的增加了海藻酸钠分子链的有效链缠结,从而使海藻酸钠溶液可以用于静电纺丝。It is not difficult to see from the above formula that the hydroxyl group of sodium alginate and borax undergo a condensation reaction, thereby achieving the purpose of crosslinking, and uniformly increasing the effective chain entanglement of the molecular chains of sodium alginate, so that the sodium alginate solution can be used for Electrospinning.

上述技术方案中,为有效控制交联反应的进行的方向、降低/减少分解反应,采用将“经过化学交联的海藻酸钠凝胶(立即)用液氮冷冻成冰,然后置于冷冻干燥器中,在-20~-50℃下冷冻24h,得到干燥的海藻酸钠固形物”的技术手段,一方面,将化学交联后的海藻酸钠凝胶速冻成冰,可以有效抑制“分解反应”的进行;另一方面,在后续的冷冻干燥过程中,对继续交联具有一定的促进作用;In the above technical scheme, in order to effectively control the direction of the cross-linking reaction and reduce/reduce the decomposition reaction, the "chemically cross-linked sodium alginate gel (immediately) is frozen into ice with liquid nitrogen, and then placed in a freeze-drying freezer at -20~-50°C for 24 hours to obtain dry sodium alginate solids". On the other hand, in the subsequent freeze-drying process, it has a certain promotion effect on the continued cross-linking;

海藻酸钠纺丝液采用具有稳定的、均匀的分子链缠结度的海藻酸钠粉末,并采用在纺丝前“即用即制”的方式,进一步稳定了静电纺丝的核心技术指标:纺丝液粘度指标,确保了连续化生产的顺利实现;The sodium alginate spinning solution uses sodium alginate powder with stable and uniform molecular chain entanglement, and adopts the "ready-to-use" method before spinning, which further stabilizes the core technical indicators of electrospinning: The viscosity index of spinning solution ensures the smooth realization of continuous production;

上述技术方案中,由于采用化学交联剂,相应地,避免了物理交联反应所采用的二价金属离子的引入所导致的最终纤维产品存在的“硬而脆”的缺点。In the above technical solution, due to the use of a chemical crosslinking agent, correspondingly, the shortcoming of "hard and brittle" in the final fiber product caused by the introduction of divalent metal ions used in the physical crosslinking reaction is avoided.

上述技术方案中,之所以能制得交联程度均一的海藻酸钠溶液,是因为硼砂与海藻酸钠的交联反应是缓慢进行的,在加热并不断搅拌的反应条件下,溶液可以充分的进行均匀的交联,而物理交联一般会导致溶液中的局部交联而交联不均,此方案可以完美的解决这一问题。In the above technical scheme, the reason why the sodium alginate solution with uniform degree of crosslinking can be obtained is that the crosslinking reaction between borax and sodium alginate is carried out slowly, and under the reaction conditions of heating and constant stirring, the solution can fully Perform uniform cross-linking, while physical cross-linking generally leads to partial cross-linking in the solution and uneven cross-linking. This solution can perfectly solve this problem.

上述技术方案通过加酸对纺丝液的pH进行调节,可以适当的调整溶液的交联程度,得到各种交联度的纺丝液,简单可控。The above technical solution adjusts the pH of the spinning solution by adding acid, so that the degree of crosslinking of the solution can be properly adjusted to obtain spinning solutions with various degrees of crosslinking, which is simple and controllable.

优选为,上述海藻酸钠的平均分子量为5-50万。Preferably, the average molecular weight of the above-mentioned sodium alginate is 50,000-500,000.

该优选技术方案直接带来的技术效果是,我们的经验表明,选择平均分子量为的5-50万海藻酸钠,可以将纺丝液的粘度指标稳定在“0.4-3Pa.s”这样一个较窄的范围,从而更有利于静电纺丝工艺参数的控制和连续化生产的稳定进行。The technical effect directly brought by this optimal technical solution is that our experience shows that choosing sodium alginate with an average molecular weight of 50,000-500,000 can stabilize the viscosity index of the spinning solution at a relatively low level of "0.4-3Pa.s". Narrow range, which is more conducive to the control of electrospinning process parameters and the stability of continuous production.

进一步优选,上述静电纺丝的主要工艺参数如下:Further preferably, the main process parameters of the above-mentioned electrospinning are as follows:

电压:10-25kV;Voltage: 10-25kV;

喷头至接收器的距离:5-25cm;The distance from the nozzle to the receiver: 5-25cm;

喷射流量:0.1-1ml/h;Jet flow: 0.1-1ml/h;

相对湿度低于40%。The relative humidity is below 40%.

该优选技术方案直接带来的技术效果是,可以微调电纺纤维的粗细。The technical effect directly brought by this preferred technical solution is that the thickness of the electrospun fiber can be fine-tuned.

进一步优选,上述硼砂为分析纯。Further preferably, the above-mentioned borax is analytically pure.

该优选技术方案直接带来的技术效果是,所配溶液的纯度高,避免了杂质引入。The technical effect directly brought by the preferred technical solution is that the prepared solution has high purity and avoids the introduction of impurities.

综上所述,本发明相对于现有技术,具有所用试剂价格低廉、纺丝液交联程度均一、生产连续稳定、工艺控制简单、产品质量好、档次高等有益效果。In summary, compared with the prior art, the present invention has the beneficial effects of low reagent price, uniform crosslinking degree of spinning solution, continuous and stable production, simple process control, good product quality and high grade.

具体实施方式Detailed ways

下面结合实施例,对本发明进行详细说明。The present invention will be described in detail below in conjunction with the embodiments.

说明:illustrate:

下列各实施例中,所使用的硼砂均为市售产品(分析纯);In following each embodiment, the borax used is commercially available product (analytical pure);

海藻酸钠(原料)的平均分子量为5-50万。The average molecular weight of sodium alginate (raw material) is 50,000-500,000.

实施例1Example 1

海藻酸钠纳米纤维的连续化静电纺丝方法,包括以下步骤:The continuous electrospinning method of sodium alginate nanofiber comprises the following steps:

第一步,原料准备The first step, raw material preparation

按质量份数,分别称取硼砂1-5份、海藻酸钠6-12份,备用;According to the number of parts by mass, take 1-5 parts of borax and 6-12 parts of sodium alginate respectively, and set aside;

第二步,纺丝液的制备The second step, the preparation of spinning solution

将所取硼砂加水配制成浓度为0.01-1M的硼砂水溶液;然后,在40-60℃下,边搅拌边缓慢将所取海藻酸钠加入到上述硼砂水溶液中,交联反应3h后,得到经过化学交联的海藻酸钠凝胶;The obtained borax is added with water to prepare a borax aqueous solution with a concentration of 0.01-1M; then, at 40-60°C, slowly add the obtained sodium alginate into the above-mentioned borax aqueous solution while stirring, and after a cross-linking reaction for 3 hours, the obtained Chemically cross-linked alginate gel;

将所得到的海藻酸钠凝胶用液氮冷冻成冰后,取出并置于冷冻干燥器中,在-20--50℃下冷冻24h以上,得到干燥的海藻酸钠固形物;Freeze the obtained sodium alginate gel into ice with liquid nitrogen, take it out and place it in a freeze dryer, and freeze it at -20--50°C for more than 24 hours to obtain a dried sodium alginate solid;

将所得干燥的海藻酸钠固形物研磨成粉后,加入40-60℃去离子水溶解,配制成质量百分比浓度为1%-5%的溶液,静置脱泡或真空脱泡后,待粘度达到0.4-3Pa.s时,即成纺丝液;Grind the obtained dried sodium alginate solid into powder, add 40-60°C deionized water to dissolve, prepare a solution with a concentration of 1%-5% by mass percentage, and let it stand for defoaming or vacuum defoaming. When it reaches 0.4-3Pa.s, it becomes spinning solution;

第三步,海藻酸钠纳米纤维的纺制The third step, the spinning of sodium alginate nanofibers

将纺丝液加入到静电纺丝设备的注射器中,开启变压器进行静电纺丝,即可得到海藻酸钠纳米纤维。Add the spinning solution into the syringe of the electrospinning equipment, turn on the transformer and perform electrospinning to obtain sodium alginate nanofibers.

上述静电纺丝的主要工艺参数如下:The main process parameters of the above-mentioned electrospinning are as follows:

电压:10-25kV;Voltage: 10-25kV;

喷头至接收器的距离:5-25cm;The distance from the nozzle to the receiver: 5-25cm;

喷射流量:0.1-1ml/h;Jet flow: 0.1-1ml/h;

相对湿度低于40%。The relative humidity is below 40%.

经检测,所制得的海藻酸钠纳米纤维直径为:110nm±15nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 110nm±15nm.

实施例2Example 2

除“第一步,原料准备:按质量份数,分别称取硼砂5份、海藻酸钠12份,备用”之外;In addition to "the first step, raw material preparation: weigh 5 parts of borax and 12 parts of sodium alginate respectively according to the parts by mass, and set aside";

其余,均同实施例1。All the other are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:145nm±20nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 145nm±20nm.

实施例3Example 3

除“第一步,原料准备:按质量份数,分别称取硼砂3份、海藻酸钠10份,备用”之外;其余,均同实施例1。Except "the first step, raw material preparation: weigh 3 parts of borax and 10 parts of sodium alginate respectively according to the parts by mass, and set aside"; the rest are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:135nm±10nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 135nm±10nm.

实施例4Example 4

除第二步中:“纺丝液的制备:再将海藻酸钠溶液加入含有一定化学交联剂的溶液中,磁力搅拌,加热并保持在60℃下交联反应3h”之外;In addition to the second step: "Preparation of spinning solution: add sodium alginate solution to a solution containing a certain chemical crosslinking agent, stir magnetically, heat and keep at 60°C for 3h for crosslinking reaction";

其余,均同实施例1。All the other are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:130nm±20nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 130nm±20nm.

实施例5Example 5

除第二步中:“纺丝液的制备:将经过化学交联的海藻酸钠的粉末溶于去离子水中,制得质量百分比浓度5%的溶液,静置脱泡或真空脱泡后,待粘度达到时,即成纺丝液”之外;In addition to the second step: "Preparation of spinning solution: dissolve the powder of sodium alginate through chemical crosslinking in deionized water to obtain a solution with a concentration of 5% by mass percentage, and after static defoaming or vacuum defoaming, When the viscosity is reached, it becomes "spinning solution";

其余,均同实施例1。All the other are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:140nm±10nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 140nm±10nm.

实施例6Example 6

除“第一步,原料准备:按质量份数,分别称取硼砂2份、海藻酸钠11份,备用”与第二步中:“纺丝液的制备:将经过化学交联的海藻酸钠的粉末溶于去离子水中,制得质量百分比浓度10%的溶液,静置脱泡或真空脱泡后,待粘度达到时,即成纺丝液”之外;In addition to "the first step, raw material preparation: weigh 2 parts of borax and 11 parts of sodium alginate according to the parts by mass, and set aside" and the second step: "Preparation of spinning solution: chemically cross-linked alginic acid Sodium powder is dissolved in deionized water to prepare a solution with a concentration of 10% by mass, and after standing for defoaming or vacuum defoaming, when the viscosity reaches a certain value, it becomes a spinning solution;

其余,均同实施例1。All the other are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:115nm±20nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 115nm±20nm.

实施例7Example 7

除“第一步,原料准备:按质量份数,分别称取硼砂1份、海藻酸钠8份,备用;与第二步中:“纺丝液的制备:将经过化学交联的海藻酸钠的粉末溶于去离子水中,制得质量百分比浓度8%的溶液,静置脱泡或真空脱泡后,待粘度达到时,即成纺丝液”之外;In addition to "the first step, raw material preparation: weigh 1 part of borax and 8 parts of sodium alginate according to the parts by mass, and set aside; and in the second step: "Preparation of spinning solution: chemically cross-linked alginic acid Sodium powder is dissolved in deionized water to obtain a solution with a concentration of 8% by mass percentage, and after standing for defoaming or vacuum defoaming, when the viscosity reaches a certain value, it becomes a spinning solution;

其余,均同实施例1。All the other are the same as in Example 1.

经检测,所制得的海藻酸钠纳米纤维直径为:145nm±20nm。After testing, the diameter of the prepared sodium alginate nanofibers is: 145nm±20nm.

Claims (4)

Translated fromChinese
1.一种海藻酸钠纳米纤维的连续化静电纺丝方法,其特征在于,包括以下步骤:1. a continuous electrospinning method of sodium alginate nanofiber, is characterized in that, comprises the following steps:第一步,原料准备The first step, raw material preparation按质量份数,分别称取硼砂1-5份、海藻酸钠6-12份,备用;According to the number of parts by mass, take 1-5 parts of borax and 6-12 parts of sodium alginate respectively, and set aside;第二步,纺丝液的制备The second step, the preparation of spinning solution将所取硼砂加水配制成浓度为0.01-1M的硼砂水溶液;然后,在40-60℃下,边搅拌边缓慢将所取海藻酸钠加入到上述硼砂水溶液中,交联反应3h后,得到经过化学交联的海藻酸钠凝胶;The obtained borax is added with water to prepare a borax aqueous solution with a concentration of 0.01-1M; then, at 40-60°C, slowly add the obtained sodium alginate into the above-mentioned borax aqueous solution while stirring, and after a cross-linking reaction for 3 hours, the obtained Chemically cross-linked alginate gel;将所得到的海藻酸钠凝胶用液氮冷冻成冰后,取出并置于冷冻干燥器中,在-20--50℃下冷冻24h以上,得到干燥的海藻酸钠固形物;Freeze the obtained sodium alginate gel into ice with liquid nitrogen, take it out and place it in a freeze dryer, and freeze it at -20--50°C for more than 24 hours to obtain a dried sodium alginate solid;将所得干燥的海藻酸钠固形物研磨成粉后,加入40-60℃去离子水溶解,配制成质量百分比浓度为1%-10%的溶液,静置脱泡或真空脱泡后,待粘度达到0.4-3Pa.s时,即成纺丝液;Grind the obtained dried sodium alginate solid into powder, add 40-60°C deionized water to dissolve, prepare a solution with a concentration of 1%-10% by mass percentage, let it stand for defoaming or vacuum defoaming, and wait until the viscosity When it reaches 0.4-3Pa.s, it becomes spinning solution;第三步,海藻酸钠纳米纤维的纺制The third step, the spinning of sodium alginate nanofibers将纺丝液加入到静电纺丝设备的注射器中,开启变压器进行静电纺丝,即可得到海藻酸钠纳米纤维。Add the spinning solution into the syringe of the electrospinning equipment, turn on the transformer and perform electrospinning to obtain sodium alginate nanofibers.2.根据权利要求1所述的海藻酸钠纳米纤维的连续化静电纺丝方法,其特征在于,第一步中,所述海藻酸钠的平均分子量为5-50万。2. the continuous electrospinning method of sodium alginate nanofiber according to claim 1, is characterized in that, in the first step, the average molecular weight of described sodium alginate is 5-50 ten thousand.3.根据权利要求1或2所述的海藻酸钠纳米纤维的连续化静电纺丝方法,其特征在于,所述静电纺丝的主要工艺参数如下:3. according to the continuous electrospinning method of sodium alginate nanofiber described in claim 1 and 2, it is characterized in that, the main process parameter of described electrospinning is as follows:电压:10-25kV;Voltage: 10-25kV;喷头至接收器的距离:5-25cm;The distance from the nozzle to the receiver: 5-25cm;喷射流量:0.1-1mL /h;Injection flow: 0.1-1mL /h;相对湿度低于40%。The relative humidity is below 40%.4.根据权利要求1所述的海藻酸钠纳米纤维的连续化静电纺丝方法,其特征在于,所述硼砂为分析纯。4. the continuous electrospinning method of sodium alginate nanofiber according to claim 1, is characterized in that, described borax is analytically pure.
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